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Oxazine-Functionalized CdSe/ZnS Quantum Dots for Photochemical

pH Sensing
Hongxia Zhang,* Qingwen Jin, Xiaomin Song, Hongdi Li, Dagong Jia, and Tiegen Liu
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ABSTRACT: pH is the most important chemical parameter of an aqueous solution, and it is widely used in biochemistry,
environmental science, and other fields. In this article, we have successfully prepared an application-type ratiometric photochemical
pH sensor combining semiconductor nanomaterial CdSe/ZnS quantum dots (QDs) and oxazine 170 perchlorate (O170). This
sensor facilitated fluorescence resonance energy transfer (FRET) between CdSe/ZnS QDs (donor) and O170 (acceptor) due to the
dipole−dipole interaction. Molar absorption coefficient, Foster radius, and FRET efficiency were determined, and the experimental
FRET efficiency was found to be very close to the theoretical value. Thus, we utilized the interaction of QD nanomaterials and the
O170 dye to promote oxazine-functionalized CdSe/ZnS QDs and revealed the principle of the FRET-based sensor. We mixed these
two substances to form a sensitive film that covered the end face of an optical fiber. The experimental results showed that the FRET-
based fiber-optic pH sensor exhibited a large detection range and good performance in terms of linearity, sensitivity, and
repeatability. The pH sensor studied by the photochemical method has great application potential in the fields of marine monitoring
and environmental protection.
KEYWORDS: fiber-optic chemical sensor, pH detection, fluorescence spectrum, quantum dots, fluorescence resonance energy transfer

1. INTRODUCTION They are a new type of luminescent material, and owing to their
The pH scale indicates hydrogen ion activity in a solution, and it unique optical and photophysical properties, they are consid-
is an important parameter for characterizing the acidic and ered a potential candidate in the development of photo-
alkaline properties of solutions in industrial production and luminescence sensors.21 In addition, nanoparticles have been
biochemical applications.1 Further, pH is a key indicator in used in a wider range of fields, such as clinical medicine and
biochemical imaging, environmental science, clinical medicine, biological diagnosis.22
The fluorescence of QDs is attributed to the recombination of
marine monitoring, industry and agriculture, aquaculture, and
electron−hole pairs after band gap excitation; different pH
other fields.2−7
conditions can affect the efficiency of this recombination. Thus,
Traditional pH measurement methods include the use of a pH
we can determine the pH environment by observing the changes
test paper, pH indicator, electrochemistry, spectral analysis, and
in the fluorescence intensity of QDs. An organic or inorganic
chemical extraction. The development of fiber-optic chemical
coating on the shell of CdSe QDs can help eliminate a large
sensors has been popular because of their small size, high
number of nonradiative recombination centers on the surface
sensitivity, short response time, and good repeatability.8,9 They
caused by surface defects, thereby improving the fluorescence
can be used in various types of sensing devices such as in
quantum yield and enhancing the light emission stability.23 In
temperature,10 salinity,11 metal element,12 gas,13 and pH
sensors.14
Quantum dots (QDs) are a new type of semiconductor Received: August 17, 2020
nanomaterial with sizes that range between 2 and 20 nm.15 The Accepted: September 30, 2020
unique functions of QDs include being reflected in the wide
excitation and narrow emission spectra,16 high fluorescence
quantum yield,17 high stability to degradation and photo-
bleaching,18 quantum size effect,19 and confinement effect.20

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsanm.0c02219

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2014, Pankaj first studied the pH sensing phenomenon of a
core−shell CdSe/ZnS QD sensor in the electrolyte−insulator−
semiconductor structure.24 In 2019, Ting Liu designed an
optical fiber pH sensor based on a smartphone platform using a
cone-shaped optical fiber combination probe modified by
CdSe/ZnS QDs to realize remote and on-site pH detection.25
In practical applications, sensors that only rely on the
fluorescence intensity of QDs are easily affected by the
fluctuation of the excitation source, fading of the indicator
light, and drift of the detector. To overcome these shortcomings,
researchers have designed and developed a ratiometric
fluorescence sensor based on reference technology.26,27 In
2019, Chu et al. proposed a new optical fiber carbon dioxide
sensor based on the colorimetric changes of α-naphthol and
CIS/ZnS QDs.28
The study found that fluorescence resonance energy transfer
(FRET)29 occurs when the overlap of donor emission and
acceptor absorption exceeds 30% and the distance is less than 10
nm.30 The process results from the dipole−dipole interaction
(donor) and is extremely sensitive to the center-to-center
separation distance (acceptor); it has a remarkable influence on
the detection sensitivity of the sensors.31−33
In this study, O170-functionalized CdSe/ZnS QDs were used
to design a wide-range, high-sensitivity ratiometric fiber-optic
pH sensor. The FRET process between CdSe/ZnS QDs as a
donor and the O170 dye as an acceptor was discussed. A
ratiometric fiber-optic pH sensor was prepared, and the
performance of the sensor was tested. It is proved that the
sensor can be used in actual pH monitoring.
2. PRINCIPLE
2.1. Material Preparation. Chemical reagents required for
this experiment include oxazine 170 perchlorate (O170, a laser
dye; Tianjin Taitan Technology Co., Ltd.), ethyl cellulose (EC;
Tianjin Botai Yida Biotechnology Co., Ltd.), toluene (Tianjin
Yuanli Chemical Co., Ltd.), tetrahydrofuran (THF; Beijing
Inokay Technology Co., Ltd.), 1 mol/L concentrated hydro-
chloric acid (HCl; Tianjin Yuanli Chemical Co., Ltd.), oil-
soluble CdSe/ZnS QD solution (purchased from Suzhou
Xingshuo Nano Technology Co., Ltd.), absolute ethanol with
purity ≥ 99.8%, and a large amount of deionized water. All
chemical reagents were used without further purification. The
synthesis and manufacturing processes of O170-functionalized
CdSe/ZnS QD nanoparticles are shown in Scheme 1. Inorganic
Scheme 1. Schematic Representation of the Synthetic
Strategy of the CdSe/ZnS QD Functionalized with O170
ZnS is coated on the surface of CdSe QDs to eliminate surface
defects, and the surface of the core−shell QD is modified with a
DDT (1-dodecanethiol) ligand to dissolve it in toluene solution.
2.2. Characterization of CdSe/ZnS QDs. CdSe/ZnS QDs
are key materials in this pH sensing experiment. The QDs are
observed using a field emission transmission electron micro-
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scope (TEM, Tecnai G2 F20). Figure 1a−c shows the TEM
images of CdSe/ZnS QDs at resolutions of 50, 10, and 5 nm,
respectively. Figure 1d illustrates a selected region with uniform
distribution and no aggregation of QDs; Figure 1e shows the
combined mapping of three elements (Cd, Se, and Zn); Figure
1f−i shows the mapping of Cd, Se, S, and Zn, respectively; and
Figure 1j shows the energy-dispersive X-ray (EDX) spectrosco-
py results of CdSe/ZnS QD nanoparticles, where the x-axis
represents energy (keV) and the y-axis represents the count of
each electron per second (i.e., X-ray intensity). The selected
nanoparticles were composed of S, Zn, Se, and Cd, with atomic
proportions of 19.06, 23.24, 40.38, and 17.32%, respectively.
The physical size of CdSe/ZnS QDs was verified to be ∼10 nm,
and the content of each element was in accordance with the
proportion and showed a homogeneous distribution. Thus,
CdSe/ZnS QDs can be used for experiments.
2.3. Principle of pH Sensing Based on FRET. In this
experiment, CdSe/ZnS QDs were excited using an LD light
source with a center wavelength of about 405 nm. They emitted
fluorescence around 575 nm, and the fluorescence intensity
changed accordingly with the change in pH. Thus, we chose
QDs as sensitive materials; O170 was used as a type of reference
laser dye. The increase of buffer solution pH value containing
O170-functionalized CdSe/ZnS QDs allowed obtaining pH
information by observing the linear change in the fluorescence
intensity ratio.
Figure 2a,b shows the pH dependence of the fluorescence
spectrum of only CdSe/ZnS QDs and O170 doped in EC,
respectively. In both cases, the fluorescence intensity increased
with an increase in pH from 0.10 to 13.99. Figure 2c,d shows the
pH dependence of the relative fluorescence intensity peak.
Figure 2e shows the emission spectrum with O170-function-
alized CdSe/ZnS QDs. When the LD light source was used for
irradiation, two emission peaks were generated for CdSe/ZnS
QDs at 573 nm and O170 at 647 nm. Figure 2e clearly shows
that with the increase of pH, the fluorescence intensity of CdSe/
ZnS QDs gradually decreases, while the fluorescence intensity of
O170 decreases slightly. Therefore, FRET occurred between
CdSe/ZnS QDs and O170.
O170 is a laser dye with a wide excitation spectrum range
(300−550 nm), which strongly absorbs light with a wavelength
greater than 550 nm, and it emits fluorescence with a wavelength
of about 645 nm. When CdSe/ZnS QDs and the O170 dye were
mixed together, the emission spectrum of QDs overlapped the
absorption spectrum of the O170 dye, and therefore, the
excitation of QD fluorescent molecules induced O170
molecules to emit a specific fluorescence, which resulted in
FRET. To study the FRET principle further, Forster radius (R0)
and FRET efficiency (E(R))as introduced in the equations
beloware utilized.
J(pH) = ∫ εpH(λ)d(λ)λ 4dλ (1)
ij 9000(ln 10)κ 2Q J yz
R 0 = jjjj d z zz
zz
j
k {
5 4
128 π n N (2)
R 06
E (R ) =
R 0 + R6
6
(3)
where λ is the wavelength, εpH is the pH-dependent molar
absorption coefficient of the fluorescent dye, d(λ) is the
normalized fluorescence intensity of the donor (CdSe/ZnS
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Figure 1. Physical size and chemical composition of CdSe/ZnS QDs: (a) TEM images at a resolution of 50 nm; (b, c) high-resolution TEM images.
(d) Specific QD region selected at a resolution of 50 nm. (e) Mapping diagram of the four elements of QDs: (f) Cd, (g) Se, (h) S, and (i) Zn. (j) EDX
analysis results for CdSe/ZnS QDs.

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Figure 2. Fluorescence spectrum of (a) CdSe/ZnS QDs doped in EC and (b) O170 doped in EC. The pH dependence of the normalized fluorescence
intensity of (c) CdSe/ZnS QDs and (d) O170 doped in EC. (e) Fluorescence emission spectrum of the sensor with embedded O170-functionalized
CdSe/ZnS QDs.

QDs), κ2 is an orientation factor (we assumed a value of 2/3), Qd
is the quantum yield of the donor, n is the refractive index of the
medium (n = 1.33), and N is Avogadro’s number.34,35 Here, εpH
and d(λ) were determined from the experimental results in
Figures 3 and 2a; Qd was 68%. The dependence of pH on R0 is
shown in Figure 4a; R is the distance between the energy donor
and energy acceptor, and 8 nm is selected for R.
The molar absorption coefficient εpH is a key parameter. A
single-beam UV−visible spectrophotometer (UV-2700) was
used to estimate the molar absorption coefficient; it was
calculated by configuring 10 mL of O170 solution with a
concentration of 0.15 mg/mL. Subsequently, 8 mL was used as a
solvent for each pH solution (pH 0.10−13.99). Finally, 0.4 mL
of O170 solution was dissolved in 15 types of pH solutions for an
ultraviolet absorption experiment.
As shown in Figure 3a, when the pH was less than or equal to
5, the maximum absorption peak appeared at about 570 nm. As
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the pH increased, the molar absorption coefficient initially
increased and then decreased, and it reached the maximum value
at pH 2.9. Figure 3b shows that the maximum molar absorption
coefficient increased when the pH changed from 5.09 to 10.91.
When the pH reached 12 and a color reaction occurred, the
maximum absorption peak changed from about 570 nm to about
450 nm. The molar absorption coefficient increases with pH, as
shown in Figure 3c. The εpH value reflects the degree of light
absorption by the absorption medium. For the same measured
dye, the sensitivity of the color development reaction increased
with an increase in the εpH value. The theoretical basis for
measuring absorbance by spectrophotometry is the Lambert−
Beer law, which is an ideal model and ignores the interaction
between molecules. However, the interaction between these dye
molecules and between the dye and water molecules in the
aqueous solution cannot be ignored. This interaction can change
their absorbance. Therefore, the molar absorption coefficient of
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Figure 3. Analysis of molar ultraviolet−visible (UV−vis) absorption coefficients of oxazine-170 (O170): (a) less than or equal to 5, (b) between 5 and
11, and (c) greater than 12.

Figure 4. FRET efficiency. (a) Variation in Forster radius under different pH values, (b) theoretically calculated value, and (c) comparison of
theoretical and experimental values.

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the O170 dye in Figure 3 changes nonlinearly with an increase in
pH value.
Figure 4a shows the trend of changes in R0 with pH between
0.10 and 13.99. With an increase in pH (pH from 0.10 to 10.91),
the molar absorption coefficient of the O170 dye increased
gradually, which suggested that the FRET efficiency was
enhanced at high pH values. When the pH was greater than or
equal to 12, the concentration of the O170 dye decreased
because of the aggravation of the color reaction, and therefore,
the molar absorption coefficient of the O170 dye decreased. The
molar absorption coefficient of the dye increased with the
increase in pH value (pH = 0.10−10.91), which resulted in an
efficient FRET process from CdSe/ZnS QDs to the dye to occur
under high pH conditions.
Based on R0, we calculated the change curve for FRET
efficiency at different pH values. The FRET efficiency is closely
related to the R0. When the pH was between 0.10 and 10.91, the
FRET efficiency increased with an increase in pH. When the pH
was between 11.92 and 13.99, the FRET efficiency changed
abruptly owing to the influence of the color reaction.
Meanwhile, we calculated the real FRET efficiency E(pH)
with experimental data and compared it with the theoretical
value E(R). The results are shown in Figure 4b. The formula for
E(pH) is
IQDs − IQDs − O170
E(pH) =
IQDs (4)
where IQDs and IQDs‑O170 represent the relative fluorescence
intensity of only QDs and those of CdSe/ZnS QDs-O170,
respectively. It can be seen from Figure 4c that the experimental
value E(pH) is generally lower than the theoretical value E(R).
This may be because the fluorescence efficiency of quantum dots
is 68% in the theoretical calculation, but the actual fluorescence
excitation efficiency is not so high. Moreover, through
calculation, the correlation between the two curves is 99.05%.
This numerical value has a great reference significance and has a
strong influence on the correctness of the experimental results.
Figure 5a shows the fluorescence emission of QDs and O170
when the light source separately excites them. Figure 5b shows
the FRET schematic diagram of the pH sensor combining
CdSe/ZnS QDs and O170 organic dyes. It can be seen that in
the environment of increasing hydrogen ion concentration, the
FRET efficiency decreases and the fluorescence intensity of QDs
increases.
The QD−dye inorganic−organic hybrid system is a complex
system. Dye molecules interact with QDs and aggregate states
between them. When the combined fluorescent material satisfies
the conditions of FRET, the emission peak reaches a peak when
excited at a single wavelength, where FRET occurs between QDs
and the dye. Given that the molar extinction coefficient of the
dye depends on pH, the fluorescence intensity ratio at a constant
excitation of the donor molecule (CdSe/ZnS QDs) is expected
to change with the change in pH. When the concentration of the
selected dye molecules is high, due to the homogeneous FRET
process, the dye molecules aggregate on the surface of the QDs,
and fluorescence quenching of the dye occurs. For this
experiment, we select a high concentration of the O170 dye as
a reference material. Self-aggregation occurred when the dye was
in an aqueous solution with increasing pH. Although the O170
dye as a receptor absorbed energy from the donor, its
fluorescence intensity did not increase significantly. This is
why the emission intensity of the O170 substance decreased
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Figure 5. Schematic diagram of the principle of the ratiometric pH
sensor (a CdSe/ZnS QD conjugated to O170 dye molecule): (a)
separate excitation of QDs and O170 and (b) principle of ratiometric
pH sensing based on the FRET process.
after it absorbed fluorescence; therefore, the observed change in
the fluorescence spectrum of the synthetic pH sensor was caused
by the FRET process between the CdSe/ZnS QD and the dye.
The experimental results revealed that the relative fluo-
rescence intensities of CdSe/ZnS QDs and O170 doped in the
EC matrix increased with increasing pH. Given that the response
occurred over a wide pH range, the compound substance could
provide a wide dynamic range for pH-dependent proportional
sensing devices. A dipole−dipole interaction occurred between
CdSe/ZnS QDs as a donor and O170 as an acceptor, followed
by a specific intensity transfer phenomenon that could influence
the sensitivity of the sensor. As shown in the R0 curve in Figure
4a, in a certain pH range, the FRET process between the QDs
and the reference dye increased gradually. The O170 dye
considerably absorbed the fluorescence from the QDs, while the
fluorescence emission of the absorbed O170 dye itself did not
increase, thereby greatly improving the sensitivity of the sensor.
The dipole−dipole interaction between the donor (QDs) and
the acceptor (O170) affected FRET, and therefore, the
magnitude of the dipole moment between the donor and
acceptor affected the energy transfer efficiency. The dipole
moment varies with the size, shape, surface reconstruction, and
chemical composition of the donor/acceptor. For the
mechanism of this experiment, we inferred that this may be
because of the surface reconstruction of the O170 dye when the
pH gradually increased (0.10−10.91). During surface recon-
struction, the molecular chains or groups on the molecular
surface rearranged to achieve a stable state with the highest
interface energy, thereby increasing the dipole moment of the
single excited state of the dye and resulting in a strong
electrostatic dipole−dipole interaction with the QDs, thus
promoting high FRET efficiency between them. However, when
the pH exceeded 11, the color reaction changed the molecular
form of the O170 dye, which significantly weakened the dipole−
dipole interaction and decreased the FRET efficiency between
O170 and QDs.
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In this experiment, priority was given to the use of cadmium-
based QDs. Although cadmium is toxic, its stability and
luminous efficiency are higher than those of other QDs (such
as InP or carbon QDs). Single-core CdSe QDs have poor
stability, short warranty period, and low luminous efficiency.
Therefore, we used alloy CdSe/ZnS core−shell QDs to
compensate for the deficiency of CdSe QD surface defects and
further improve the extinction coefficient of QDs. Free-growing
CdSe and ZnS will result in a lattice mismatch, which affects its
luminous efficiency and optical stability to a large extent. Alloy
QDs have strong lattice strength and stable performance, and
this can realize lattice transition gradually and effectively reduce
internal pressure caused by QD lattice defects, which results in
high luminous efficiency and stability. Therefore, alloy CdSe/
ZnS core−shell QDs were used in this experiment.
The concentration of QDs is the key to influence fluorescence
intensity. We used three QD concentrations for comparison and
analysis in the next experiment to achieve a wide range and high
sensitivity.
3. FRET-BASED FIBER-OPTIC PH SENSOR
3.1. Preparation of the Sensitive Membrane and Test
Samples. The specific preparation of the pH-sensitive
membrane is as follows: First, 1 g of EC was dissolved in 4
mL of ethanol and 10 mL of toluene to prepare the carrier matrix
(solution A), as shown in Figure 6a. Second, the reference dye
Figure 6. Chemical reagent and coating images of three optical fibers
with different quantum dot concentrations: (a) carrier matrix, (b)
reference dye, (c) sensitive composite solution, (d) 1.5, (e) 3.0, and (f)
4.5 mg/mL.
(solution B) was prepared by dissolving 2.5 mg of O170 in 8 mL
of THF, as shown in Figure 6b. Approximately 0.5 mL of
solution A and 0.5 mL of solution B were mixed into 1.5 mL of
CdSe/ZnS QD solution and then used as a pH-sensitive
composite solution after being stirred uniformly, as shown in
Figure 6c. For the above operations, a magnetic stirrer (MS-
H280-Pro, purchased from Beijing Southeast Yicheng Labo-
ratory Equipment Co., Ltd.) was used to stir the solution at 40 r/
min. Finally, a dipping−pulling coating machine (HT-DC300,
purchased from Beijing Huotong Experimental Instrument Co.,
Ltd.) was used to dip-coat at a speed of 15 mm/min, and
therefore, the sensitive composite material was deposited at the
end of the optical fiber. After the operation was completed, the
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coated optical fiber was placed in a dark, airtight, and dry
environment for 1 week.
For the reagent preparation, only the QD concentrations were
changed (1.5, 3.0, and 4.5 mg/mL). A polarizing microscope
(CX40P) was used to observe the coating on the end face of the
optical fiber with an objective magnification of 10×. The coating
thickness of the three optical fibers is 545, 556, and 563 μm, as
shown in Figure 6d−f, and the scale has been marked in Figure 6.
A total of 16 sample solutions were formulated, and the pH
range was 0.28−12.97, which was measured using a commercial
pH meter. The test sample was obtained by diluting 1 mol/L
concentrated HCl and 1 mol/L KOH solution with deionized
water.
3.2. Instrumentation and Experiment Procedure. The
system setup (Figure 7) includes an LD light source (MW-GX-
Figure 7. System setup: (a) schematic and (b) physical pictures.
405/150 mW, Changchun Leishi Optoelectronics Technology
Co., Ltd.), a Y-branch optical fiber (UV400, Beijing Shouliang
Technology Co., Ltd.), a 1000-μm-diameter infrared plastic
optical fiber (FC/PC-BGUV1000-0.6, Beijing Technology Co.,
Ltd.), a commercial pH meter (pH5 pen-type pH meter,
Yasuwang Trading Co., Ltd.), an Ocean Optical USB4000
miniature fiber spectrometer (Shanghai Bose Intelligent
Technology Co., Ltd.), and a personal computer.
As shown in Figure 7, the LD light source with a center
wavelength of 405 nm was used as the excitation light, which
entered the pH-sensitive membrane through one end of the Y-
type optical fiber. After fluorescence excitation, emission light
was emitted from the other end of the bifurcated optical fiber,
and the emission end was coupled with the spectrometer probe.
Spectral data were collected and saved by special computer
software.
4. RESULTS AND DISCUSSION
4.1. pH Sensing Properties of the Ratiometric Optical
Fiber Sensor. The ratio of the relative fluorescence intensities
of CdSe/ZnS QDs and O170 was used to reflect the change in
the pH of the solution. The formula is
ICdSe/ZnS
ratio =
IO170 (5)
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Figure 8. Relative fluorescence intensity of QDs and O170 with different concentrations: (a) 1.5, (b) 3.0, and (c) 4.5 mg/mL. (d) Linear correlation
curve and (e) sensitivity comparison of QDs without and with O170.
where ICdSe/ZnS and IO170 represent the steady-state fluorescence
intensity of CdSe/ZnS QDs and O170 at a certain pH solution,
respectively, under the same power.
Figure 8a−c shows the relative fluorescence intensity of the
O170-functionalized CdSe/ZnS QD at CdSe/ZnS QD
concentrations of 1.5, 3.0, and 4.5 mg/mL, respectively. It can
be seen that with the increase of the concentration, the
fluorescence intensity fluctuation of QDs gradually increases.
This is because under the excitation of the same light source, the
fluorescence intensity generated from the high-concentration
quantum dots is greater and is more susceptible to the
fluctuation of the light source. Figure 8d shows the scatter
plot calculated from the ratio of the two fluorescence intensities.
Figure 8e shows the sensor sensitivity using QDs with and
without O170 when the concentration of QDs was 3.0 mg/mL.
When only QDs and O170-functionalized QDs act separately,
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the sensitivity of the sensor exhibits positive and negative slopes,
respectively. After the calculation, we found that the sensitivity
of the pH sensor for O170-functionalized QDs was 3.87 times
higher than that with only QDs.
As shown in Figure 8d, the fluorescence intensity ratios of the
three QD concentrations presented a good linear correlation.
The linearity was 94.93, 97.62, and 97.92%, and the sensitivity
was 0.079/pH unit, 0.107/pH unit, and 0.128/pH unit.
Therefore, the sensitivity of the sensor increased as the QD
concentration increased.
4.2. Performance of the Sensor. The repeatability of the
sensors was measured (Figure 9). The sensors were repeatedly
measured after 3, 5, 7 h, 1, 3, and 5 days at the first test; seven
groups of data were obtained.
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Figure 9. Sensor repeatability. (a) Relative fluorescence intensity fluctuation of QDs and O170. (b) Fluctuation in ratio intensity. (c) Three linearity
experiments with a quantum dot concentration of 3.0 mg/mL.
Figure 9a shows the relative fluorescence intensity of QDs and
O170. Figure 9b shows the ratio intensity fluctuation. A
nonlinear error was introduced as shown below.
ΔLmax
γL = ± × 100%
YFS
where ΔLmax represents the maximum nonrepetition error of the
output. Therefore, the nonlinear errors of the three pH solutions
were 4.04, 3.71, and 3.85%. It can be seen from the data that the
sensor has good repeatability under three pH solutions, and no
obvious mutation occurs in a certain period of time. To ensure
that the experimental data is true and reliable, we repeated the
experiment three times every three days on the optical fiber with
a quantum dot concentration of 3.0 mg/mL. The experimental
results are shown in Figure 9c. It can be seen from the fitting
curve that the sensitivities of the three measurements are 0.107,
0.112, and 0.111/pH unit.
4.3. Discussion. CdSe/ZnS QDs, as a kind of nanomaterial,
are combined with the O170 dye to form O170-functionalized
QDs, thereby fabricating a photochemical sensor based on the
FRET principle. We confirmed that FRET occurred between the
CdSe/ZnS QDs and the O170 reference dye, which resulted in
the attenuation of QD nanomaterials’ fluorescence intensity.
In practical applications, only QDs are used as materials for
pH sensing experiments, which limit the measurement range.
However, when only QDs were used as sensitive materials under
a strong alkaline environment (pH 11.92−13.99), the
fluorescence of QDs was highly unstable and quickly decayed.
Therefore, the use of the reference method greatly improves the
stability and detection range of the sensor. When Figure 8 is
compared with Figure 2e, the linear variation tendency of the
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fluorescence intensity of only CdSe/ZnS-QDs doped in EC and
O170-functionalized CdSe/ZnS QDs doped in EC at 573 nm
was found to be opposite as the pH increased. Simultaneously, as
the pH increased, the linear variation tendency of the
fluorescence intensity was different between only O170 doped
(6) in EC and O170-functionalized CdSe/ZnS QDs doped in EC at
647 nm. This is the result of the FRET principle and the O170
dye being an absorbing dye.
This work explains the mechanism of the pH sensors. When
the two substances were excited using an LD light source, the
fluorescence excited by the QDs as a donor was absorbed by the
O170 dye as the acceptor; the energy transfer efficiency was
closely related to the molar absorption coefficient of the O170
dye. The molar absorption coefficient has a correlation in a
certain range of pH values (pH 0.10−10.91). In the experiment
to verify the FRET principle, the results showed that the color
reaction affected only R0, not the sensor performance.
In ref 5, the authors utilize the charge transfer process between
CdSe/ZnS QD−dopamine−peptide bioconjugates to realize in
vitro and intracellular pH sensors. Based on the principle of QD
fluorescence quenching, the reliability and stability of the pH
sensor are verified from the steady-state emission, fluorescence
lifetime, and absorption of quantum dots. In this article, the
FRET process between CdSe/ZnS QDs and O170 dyes was
deeply studied, and the ratio of fluorescence intensities of the
two substances at different pH values was used to achieve the
purpose of wide range and high sensitivity. Therefore, the
ratiometric fiber-optic pH sensor manufactured based on the
FRET principle exhibited a wide range and high sensitivity. The
results proved that the sensor showed good performance and
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ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
practical value from the aspects of repeatability and temperature
stability.
5. CONCLUSIONS
In this study, we used photochemical research methods to
design a wide-range, high-sensitivity ratiometric pH fiber-optic
chemical sensor with an O170-functionalized CdSe/ZnS QD
semiconductor nanomaterial. The molar absorption coefficient,
R0, and FRET efficiency were obtained through experiments,
which explained the mechanism of the pH sensor based on
FRET and proved the occurrence of the FRET process.
Experimental results showed that the sensor could achieve a
pH range of 0.28−12.97, sensitivity of 0.107/pH unit, and
linearity of 97.62%. The sensor was proven to have good
repeatability, indicating its wide use in many fields such as
industrial and agricultural applications, environmental protec-
tion, and marine monitoring.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsanm.0c02219.
Materials and experimental methods (characteristics of
quantum dots, preparation of sensitive materials); in-
depth analysis of experimental principles; fabrication of
sensors and system devices; and performance analysis and
multivariate evaluation (details of linearity and sensitivity,
details of temperature stability experiments, details of
repeatability and reversibility) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Hongxia Zhang − College of Precision Instrument and Opto-
Electronics Engineering, Tianjin University, Tianjin 300072,
China; Key Laboratory of Optoelectronics Information Technical
Science, EMC, Tianjin 300072, China; orcid.org/0000-
0002-6766-1263; Phone: 86-22-27403147;
Email: hxzhang@tju.edu.cn
Authors
Qingwen Jin − College of Precision Instrument and Opto-
Electronics Engineering, Tianjin University, Tianjin 300072,
China; Key Laboratory of Optoelectronics Information Technical
Science, EMC, Tianjin 300072, China
Xiaomin Song − College of Precision Instrument and Opto-
Electronics Engineering, Tianjin University, Tianjin 300072,
China; Key Laboratory of Optoelectronics Information Technical
Science, EMC, Tianjin 300072, China
Hongdi Li − College of Precision Instrument and Opto-Electronics
Engineering, Tianjin University, Tianjin 300072, China; Key
Laboratory of Optoelectronics Information Technical Science,
EMC, Tianjin 300072, China
Dagong Jia − College of Precision Instrument and Opto-Electronics
Engineering, Tianjin University, Tianjin 300072, China; Key
Laboratory of Optoelectronics Information Technical Science,
EMC, Tianjin 300072, China
Tiegen Liu − College of Precision Instrument and Opto-Electronics
Engineering, Tianjin University, Tianjin 300072, China; Key
Laboratory of Optoelectronics Information Technical Science,
EMC, Tianjin 300072, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.0c02219
J https://dx.doi.org/10.1021/acsanm.0c02219
www.acsanm.org Article
Author Contributions
X.S., H.L., D.J., and T.L. contributed equally. The manuscript
was written through contributions of H.Z. and Q.J. All authors
have given approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (NSFC) (61675153). We thank Dr.
Chuanxi Li at the School of Chemical Engineering for helping us
to perform UV−visible absorption experiments of the dye. We
also thank Dr. Yubing Hu at the School of Chemical Engineering
for helping with TEM imaging of QD materials.
■
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