Sensors & Actuators: B.

Chemical 329 (2021) 129115

Contents lists available at ScienceDirect

Sensors and Actuators: B. Chemical

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

Facile synthesis of CDs@ZIF-8 nanocomposites as excellent peroxidase

mimics for colorimetric detection of H2O2 and glutathione
Yufei Wang a, Xueshibojie Liu b, Mengke Wang c, Xiaoxue Wang a, Wenyan Ma a, Jiyang Li a, *
a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China
b
Department of Otolaryngology, Head and Neck Surgery, Second Hospital of Jilin University, Changchun 130000, PR China
c
Department of Analytical Chemistry, College of Chemistry, Jilin University, Changchun, 130012, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: CDs@ZIF-8 nanocomposites are designed and synthesized as nanoenzymes by a novel one-pot synthetic method
CDs in solvent-free system, in which ZIF-8 framework protects CDs from the aggregation and quenching, increasing
MOFs the participation of CDs for catalytic reactions. The embedding of CDs into ZIF-8 matrix is conducted to rapid
Facile synthesis
electron transfer, and their synergetic effect promotes the composite materials to have superior peroxidase-like
Nanozyme
Peroxidase-like activity
activity. CDs@ZIF-8 materials have catalyzed the oxidation of a typical colorimetric substrate 3,3′ ,5,5′ -tetra­
methylbenzydine (TMB) in the presence of H2O2 with the color changes from colorless to blue oxidized TMB (ox-
TMB). A colorimetric approach could be established to detect H2O2 and glutathione (GSH) due to the outstanding
peroxidase-like activity of CDs@ZIF-8-a. This work gives a feasible strategy for the synthesis of CDs-based
composite nanozyme with enhanced catalytic activity and thus broadens the application of CDs@MOFs mate­
rials in biological analytical field.

1. Introduction biocompatibility, excellent optical properties, and low toxicity [22].

Natural enzyme is a biocatalyst with better catalytic activity and
substrate specificity. Almost all reactions in the human body are cata­
lyzed by a certain natural enzymes [1]. Peroxidase is a natural enzyme
that can catalyze many oxidation reactions with hydrogen peroxide in
ecosystems. However, the rigorous storage conditions and extremely
high cost of production of them have prompted researchers to develop
new peroxidase enzyme mimetics with high cost-effectiveness, simple
synthesis, more stable structures, and easy to store and transport [2].
Over the past decades, many nanomaterials with comparable catalytic
properties to peroxidase have been explored, such as metal nano­
particles (NPs) [3], metal oxides [4,5], metal sulfides [2], carbon-based
materials [6–9], metal-organic frameworks (MOFs) [10–14], and many
composite materials [15–19]. However, the use of complicated chem­
icals makes them have high synthesis costs and cumbersome synthesis
steps [20].
Recently, carbon-based nanomaterials have attracted much attention
of researchers because of their cost-effective and eco-friendly syntheses
[9,21]. Among them, carbon dots (CDs) demonstrated excellent
peroxidase-like activity and have attracted wide attention due to their
relatively low cost, simple and gentle preparation process, good
Such materials have been widely used in ion detection, bioimaging,
sensing, anti-counterfeiting, catalysis, supercapacitors and other fields
[22–25]. CDs have the abundant surface sites with rich functional
groups, easily modifiable structures and excellent electron transport
properties, which endow them to become the good electron donor and
acceptor [23]. The outstanding electron transfer performance of CDs
makes them display excellent peroxidase-mimicking activity and are
used to detect H2O2 related bioactive molecules, such as dopamine [26],
glucose [27], ascorbic acid [8,28], cysteine (CySH) [6], glutathione
(GSH) [29], and homocysteine (HcySH) [30]. However, due to the easy
aggregation and fluorescence quenching of CDs, the electron transfer
process may not be well involved in their peroxidase-like catalytic,
which is necessary to modify the surface of CDs or introduce CDs into
other hosts to disperse them and enhance their peroxidase-like catalytic
activity.
Metal-organic frameworks (MOFs) as an important kind of porous
crystalline materials are widely used in gas adsorption, storage and
separation, catalysis and sensing [31–33]. The abundant metal ions or
clusters and organic linkers in MOFs make them to be ideal precursors or
templates to synthesize nanoenzyme materials [34–36]. They also have
large internal surface areas and uniform cavities, the confinement effect

* Corresponding author.
E-mail address: lijiyang@jlu.edu.cn (J. Li).

https://doi.org/10.1016/j.snb.2020.129115
Received 2 September 2020; Received in revised form 16 October 2020; Accepted 24 October 2020
Available online 30 October 2020
0925-4005/© 2020 Elsevier B.V. All rights reserved.
Y. Wang et al.
of their channels may limit the aggregation and migration of introduced
guest species [37–39], which make MOFs to be a good matrix for
dispersing and protecting CDs to enhance their electron transfer effi­
ciency and peroxidase-like catalytic activity. ZIF-8 is a kind of MOFs
with simple synthesis process and stable structure. Many functional
guests have been introduced into ZIF-8 to obtain MOFs-based composite
materials with better performance, such as hemin/ZIF-8 [17],
CuNCs/ZIF-8 [40] Au@ZIF-8 [41], Pd NCs@ZIF-8 [42] and
UiO-66-NH2@ZIF-8 [43]. In addition, the structure of imidazole as
organic ligands in ZIF-8 framework is similar to the histidine residues on
peroxidase [17], thus the combination of CDs and ZIF-8 may provide a
platform to design the novel peroxidase nanoenzyme with enhanced
catalytic activity.
Herein, CDs@ZIF-8 composite materials are synthesized by a novel
one-pot synthetic method without solvent for the first time. They can
effectively catalyze the oxidation of colorless 3, 3′ , 5, 5′ -tetrame­
thylbenzidine (TMB) by H2O2 to form deep blue oxidized TMB (ox-
TMB). In the composite materials, CDs are formed by the carbonization
of excess organic ligands 2-methylimidazole (Hmin) in the ZIF-8 syn­
thesis system and dominate the catalytic process. ZIF-8 matrix protects
CDs from the aggregation and quenching, and the synergetic effect of
CDs and ZIF-8 promotes the electron transfer and makes the composites
have superior peroxidase-like activity. After adding glutathione (GSH)
in to the catalytic system, the ox-TMB is reduced, which cause the
absorbance decreasing, and the mixture changes from blue to colorless
again. Owing to the peroxidase mimetic activity of CDs@ZIF-8-a, a
sensitive and convenient colorimetric method for detecting H2O2 and
glutathione has been developed (Scheme 1).
2. Experimental section
2.1. Materials and instrumentation
Materials and instrumentation were represented in the Electronic
Supplementary Material.
2.2. Synthesis of CDs@ZIF-8
ZnO and Hmin were mixed in the ratio of 1:4 and grinded uniformly,
and then sealed in a Teflon stainless steel reactor at 180 ◦ C for 8 h. After
that, the products were washed with ethanol three times and separated
by centrifugation (10,000 rpm, 3 min). The solid was dried at 60 ◦ C
followed by natural cooling to room temperature and named as
CDs@ZIF-8-a. In addition, products with different reaction times (4 h,
12 h, 24 h) and different ZnO/Hmin ratios (1/2 and 1/6) were also
synthesized in the same way for comparative experiments, and named as
CDs@ZIF-8-b to CDs@ZIF-8-f. The synthetic conditions of CDs@ZIF-8
composites were listed in Table S1.
Scheme 1. Schematic graphic for the synthesis of CDs@ZIF-8-a nanocrystals as the colorimetric snesor for H2O2 and GSH.
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Sensors and Actuators: B. Chemical 329 (2021) 129115
2.3. Synthesis of ZIF-8
Due to the carbonization of Hmin to form CDs, pure ZIF-8 nano­
crystals could not be obtained by the above solvent-free heating method.
ZIF-8 nanocrystals were synthesized based on the previous literature
[44]. Typically, the metal precursors (ZnO) and organic ligand (Hmin)
were added to the 50 mL Teflon tank at a ratio of 1:4, then 1.0 mL of
liquid ethanol and four stainless steel balls of 5 mm and 8 mm each were
added. The mixture was ground for 45 min in a QM-3SP04 mill at 30 Hz.
Finally, the obtained ZIF-8 was washed with ethanol three times and
centrifuged at 10,000 rpm. The solid was dried at 60 ◦ C followed by
natural cooling to room temperature.
2.4. Synthesis of pure CDs
A certain amount of Hmin powder were heated in oven at 180 ◦ C for
8 h. The obtained products were dissolved in distilled water and filtered
with a 0.22 m filter, then the solution was dialyzed for 24 h with a
dialysis membrane bag (1000 MWCO), spin-dried and finally dissolved
CDs in distilled water to make 10 mg/mL solution for further use.
2.5. Peroxidase-like activity measurements of CDs@ZIF-8
Base on the oxidation of TMB to ox-TMB in the presence of H2O2, the
peroxidase-like activity of CDs@ZIF-8-a was investigated. Typically,
100 μL of CDs@ZIF-8-a (1.0 mg/mL), 60 μL of TMB (10 mM, dissolved in
ethanol) and 40 μL of H2O2 (100 mM) were add into the 0.2 M acetate
buffer solution (pH 4.0). The final mixture was 2.0 mL, and incubated at
50 ℃ for 30 min. Then UV–vis absorption and the spectra absorbance
intensity at 652 nm were recorded, and the corresponding photographs
were taken. Other samples were tested in the same way after replacing
CDs@ZIF-8-a.
2.6. Steady-state kinetic analysis of CDs@ZIF-8-a
The steady-state kinetic analysis with TMB as a substrate was using
0.05 mg/mL CDs@ZIF-8-a with 2.0 mM H2O2 in 2.0 mL of reaction
buffer (0.2 M, pH 4.0), and altering the concentration of TMB. The
steady-state kinetic analysis with H2O2 as a substrate was almost the
same except using 0.3 mM TMB and varying the concentration of H2O2.
All of the reactions were tested with UV–vis absorption and recorded at
652 nm.
The Michaelis − Menten equation was used to describe the rate of
enzymatic catalytic reaction, and the double reciprocal curves was
drawn to fit the following equation.
V = Vmax[S]/(Km + [S]) (1)
1/V = (Km/Vmax) × (1/[S]) + 1/Vmax (2)
Where V, [S], Km and Vmax is the initial velocity, concentration of the
Y. Wang et al.
substrate, Michaelis- Menten constant and maximum reaction velocity,
respectively.
2.7. Colorimetric detection of H2O2 and GSH
Different amounts of H2O2 were mixed with acetate buffer solution
(0.2 M, pH 4.0) containing 0.05 mg/mL CDs@ZIF-8-a and 0.3 mM TMB.
The final volume of mixture was 2.0 mL. The mixture was incubated at
50 ℃ for 30 min. The UV–vis absorption and the spectra absorbance
intensity at 652 nm were recorded for quantitative detection of H2O2,
and the corresponding photographs were taken. The detection of GSH
was used the same method by fixing the amount of H2O2 to 2.0 mM.
3. Results and discussion
3.1. Morphology and chemical structure of CDs@ZIF-8 composites
Fig. 1a and Fig. S1 show the XRD patterns of as-synthesized
CDs@ZIF-8 composites and ZIF-8 materials, all of them can be
indexed to the standard ZIF-8 crystal. Notice that no obvious peaks of
CDs can be observed due to their ultra-small sizes or the low carbon
content [45,46]. Compared with pure ZIF-8, the intensities of XRD peaks
of CDs@ZIF-8 composites are significantly enhanced, indicating the
higher crystallization degree. SEM images show the spherical ZIF-8
nanocrystals with uniform particle size of about 200 nm, and
CDs@ZIF-8 composites present irregular nanocrystal particles (Fig. S2).
With the extension of reaction time and increased ligand content, the
composites gradually grown from fragments to larger crystals with un­
even distribution. TEM image of CDs@ZIF-8-a shows the rhombic do­
decahedron particles and some dot-like particles with the size of about
1.9 nm, suggesting the existence of CDs in ZIF-8 nanocrystals (Fig. 1b-c
and Fig.S3). According to the high-resolution TEM (HR-TEM) mea­
surement, the lattice spacing of CDs are 0.21 nm (Fig. 1c inset), which is
the same as the graphene (100) plane [47]. In addition, XPS and FT-IR
spectra are used to characterize the structure of CDs. The XPS survey
spectrum in Fig. 1d demonstrates that Zn, C, O and N elements can be
detected in CDs@ZIF-8-a. As shown in C 1s spectrum (Fig. 1e), the
binding energy values of 284.2, 284.8 and 286.0 eV are assigned to the
Fig. 1. (a) XRD patterns of as-synthesized CDs@ZIF-8-a and ZIF-8. (b) TEM image of CDs@ZIF-8-a with the scale of 100 nm. (c) TEM image of CDs@ZIF-8-a with the
scale of 20 nm. Inset: HR-TEM image of lattice fringes and size of CDs in CDs@ZIF-8-a. XPS spectra of CDs@ZIF-8-a: (d) full survey spectrum and (e) C 1s spectra. (f)
FT-IR spectrum of CDs@ZIF-8-a.
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Sensors and Actuators: B. Chemical 329 (2021) 129115
C–– C, C–sp3 and C–N peak, respectively, which is consistent with C 1s
peaks of ZIF-8 matrix coming from the Hmin ligands (Fig. S4a) [48]. The
extra peak of C– – O at 287.2 eV may belong to the CDs encapsulated in
ZIF-8 nanocrystals. Most of the peaks in FT-IR spectrum come from the
organic ligand Hmin of ZIF-8 framework [49], but the peak at
1700 cm− 1 can ascribed to C– – O, which is not available in pure ZIF-8
nanocrystals and may attribute to CDs (Fig. 1f inset). C–– O groups can
also be observed in the C 1s spectra and FT-IR spectra of other
CDs@ZIF-8 composites (Fig. S4b-f, S5). These studies indicate the exis­
tence of CDs in composite materials, and different synthesis conditions
may affect the content of CDs.
Photoluminescence is a typical property of CDs [25,50], thus the
fluorescence property of the pure ZIF-8 and composite materials has
been studied. As shown in Fig. 2a, when excited at 360 nm, ZIF-8 ex­
hibits a blue luminescence at 433 nm due to the organic linkers [51], and
the composite materials show slightly red-shifted emissions at 450 nm,
which may because of the interaction between CDs and ZIF-8 nano­
crystals. When changing the excitation wavelength to 480 nm, the ZIF-8
nanoparticles have no fluorescence emission but the composite mate­
rials display the yellow luminescence at 560 nm, which can be attributed
to the presence of CDs (Fig. 2b). Moreover, the excitation-dependent
fluorescence behavior can be observed for CDs@ZIF-8-a (Fig. 2c),
which also confirms the existence of CDs in the composite materials.
To further verify the existence of CDs, the Hmin as precursor was
used to synthesize CDs under the same conditions of composite materials
without the addition of ZnO. TEM image in Fig. S6a and b displays the
spherical CDs with size in the range of 1.4–3.0 nm (av. 2.4 nm), a little
larger than those encapsulated in CDs@ZIF-8-a. This may attribute to
the confinement effect of ZIF-8 matrix which limits the growth of the
encapsulated CDs and make them smaller [52,53]. The XPS and FT-IR
spectra of CDs in Fig. S6c and Fig. S6d further confirm that the exis­
tence of C– – O bonds in CDs@ZIF-8-a comes from CDs. As with
CDs@ZIF-8-a, the excitation-dependent emissions of as-made CDs can be
seen in Fig. 2d, but the emission peaks are weaker than those of the
composites. The enhanced fluorescence behavior of CDs may due to the
limiting effect of ZIF-8 host matrix.
The above analysis indicates that CDs have been successfully
confined in ZIF-8 nanocrystals by a simple one-step solvent-free method.
Y. Wang et al.
Fig. 2. Fluorescence spectra of CDs@ZIF-8 composites and ZIF-8: (a) excited at 360 nm and (b) excited at 480 nm. Fluorescence spectra of (c) CDs@ZIF-8-a and (d)
CDs under various excitation wavelengths.
Such synthesis is quite different from most reported CDs@MOF com­
posite materials which were obtained through the reaction of MOFs
precursors and the pre-synthesized CDs [45,46,48,51,52,54–,55,56].
The formation process of CDs@ZIF-8 composites may be as follows:
Hmin as organic ligands in ZIF-8 should be excessive, some Hmin to
form the ZIF-8 framework, and others do not participate in the crystal­
lization of ZIF-8, while are carbonized during the solvent-free thermal
reaction to form CDs. The formation of ZIF-8 matrix and CDs are carried
out simultaneously, thus some of CDs are wrapped in the crystals of ZIF-
8 to form CDs@ZIF-8 nanocomposites and other CDs are stayed on the
crystal surface and can be washed away by ethanol. This synthesis
method has the following advantages: 1) The synthesis requires only two
raw materials, and no solvent is involved, which reduce the synthesis
costs and environmental pollution. 2) The reaction can be completed in
one step with simple and easy operation, and can obtain abundant
products. 3) The thermal reaction and the inherent properties of ZIF-8
matrix make the composite materials have excellent stability, and the
solid raw materials and products are easy to store and transport.
Therefore, the composite materials synthesized by this method have
great advantages as nanoenzymes.
3.2. Peroxidase-like activity of CDs@ZIF-8-a
The peroxidase-like catalytic activity of CDs@ZIF-8-a is explored by
using a typical colorimetric substrate 3,3′ ,5,5′ -tetramethylbenzidine
(TMB) in the presence of H2O2. The color of the mixture of CDs@ZIF-8-a,
TMB and H2O2 (blue line) is turned to deep blue and a characteristic
absorption peak at 652 nm is observed (Fig. 3a). This phenomenon in­
dicates that the colorless TMB is oxidized to blue ox-TMB. It is noted that
there is only a little color and a much lower absorbance intensity
without the presence of CDs@ZIF-8-a (red line), which may be due to the
⋅OH produced by the decomposition of H2O2 oxidizes TMB. In addition,
no significant color and intensity changes for TMB and CDs@ZIF-8-a
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Sensors and Actuators: B. Chemical 329 (2021) 129115
solution (black line), implied that the composite materials cannot
oxidize TMB and has no oxidase-mimicking activity. The XRD patterns
and TEM image in Fig. S7 and Fig. S8 display no changes for CDs@ZIF-8-
a after the reaction, suggesting that CDs@ZIF-8-a indeed plays a role as a
catalyst and has better stability. Meanwhile, the UV–vis absorption
spectrum of CDs@ZIF-8-a in Fig. S9a shows no absorbance between
500− 800 nm. These results indicate that the CDs@ZIF-8-a composites
can effectively promote the decomposition of H2O2 and proceed
oxidation reaction due to their inherent peroxidase-like activity.
Furthermore, Fig. S10 shows the catalytic performance of CDs, ZIF-8 and
composite materials synthesized under different conditions, it is found
that CDs@ZIF-8-a has the best catalytic performance. In addition,
CDs@ZIF-8-a has the good catalytic repeatability with different batches,
which descriptions that the particle size uniformity of the composite
does not affect its catalytic activity (Fig.S11).
Like other peroxidase, the peroxidase-like activity of CDs@ZIF-8-a is
determined by the enzyme dosage, buffer pH, reaction temperature and
time [12,57,58]. Fig. S12 shows that the peroxidase-like catalytic ac­
tivity increased with increasing CDs@ZIF-8-a dosage from 10 to
50 μg/mL and then decreased, and the catalytic reaction has the highest
catalytic activity at pH 4.0, which might be due to the excessive catalyst
and higher pH would accelerate the decomposition of H2O2, resulting in
the decrease of its oxidation activity. Besides, the catalytic reaction
optimal temperature is about 50 ℃ and the absorbance signal reach a
plateau after 30 min. The stability of CDs@ZIF-8 composites has been
studied by storing CDs@ZIF-8-a in solution of pH 4.0 for different times.
Fig. S13a shows their UV–vis absorption intensity at 652 nm and there is
slight decline after storage for 5 day. XRD patterns in Fig. S13b show no
changed for CDs@ZIF-8-a stored in solution after 5 days. This suggests
CDs@ZIF-8 has good stability in solution with low pH value.
Y. Wang et al. Sensors and Actuators: B. Chemical 329 (2021) 129115

Fig. 3. (a) UV–vis absorption spectra of reaction system with different reagents: TMB + CDs@ZIF-8-a (black line), TMB+H2O2 (red line) and TMB+H2O2+CDs@ZIF-
8-a (blue line). Inset: photographs of corresponding samples. (b) The fluorescence spectra of TA and H2O2 with different concentration of CDs@ZIF-8-a. (c) and (d)
The kinetic analysis of CDs@ZIF-8-a according to the Michaelis-Menten model with substrates of TMB and H2O2, respectively. Insets are the corresponding double
reciprocal plots (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).

3.3. Catalytic mechanism
The mechanism of this catalytic reaction is usually interpreted as the
⋅OH produced by the decomposition of H2O2 oxidizes colorless TMB and
then generated blue ox-TMB [2,13]. The catalyst can greatly promote
the decomposition of H2O2 to release ⋅OH. According to the literature
[59], terephthalic acid (TA) can easily react with ⋅OH to form 2-hydroxy
terephthalic acid, which displays a strong fluorescence emission peak at
425 nm. Therefore, a photoluminescence (PL) method can be used as
follows: different amounts of CDs@ZIF-8-a from 0 to 0.5 mg/mL,
0.5 mM TA and 50 mM H2O2 incubate in acetate buffer (0.2 M, pH 4.0)
at 50 ℃ for 30 min are used as the experimental conditions.
Fig. 3b shows that the fluorescence intensity gradually increased
with the dosage of CDs@ZIF-8-a rising, implying the catalytic mecha­
nism is attributed to the formation of ⋅OH radicals indeed, and the
generation of ⋅OH depends on the concentration of CDs@ZIF-8-a. After
replacing CDs@ZIF-8-a with other materials, there is no significant
fluorescence emission at 425 nm for pure ZIF-8 nanocrystals in such
system, and a weak emission peak of CDs can be observed (Fig. S14).
These phenomena prove that the peroxidase-like activity of CDs@ZIF-8-
a is attributed to the presence of CDs. Furthermore, the fluorescence
intensities of all CDs@ZIF-8 composite materials are higher than that of
pure CDs, indicating that the encapsulation of CDs in ZIF-8 nanocrystals
promotes its catalytic effect on the decomposition of H2O2 and produced
more ⋅OH radicals. This is consistent with our pre-design, which may
because the confinement effect of ZIF-8 nanocrystals can effectively
disperse CDs from aggregation and protect their surface functional
groups. Meanwhile, CDs@ZIF-8-a has the largest fluorescence intensity,
suggesting that its synthesis condition can obtain the best catalytic effect
with the optimal CDs content.
For further exploring the reaction mechanism of CDs@ZIF-8-a,
UV–vis DRS spectra and the Mott-Schottky measurement are conduct­
ed for CDs, ZIF-8 and CDs@ZIF-8-a. A sharp absorption at around
220 nm can be observed from ZIF-8 and CDs@ZIF-8-a (Fig. S9a), which
may be originated from the organic ligands of ZIF-8 [51]. At around
350 nm, a broad absorption band in CDs@ZIF-8-a can be observed and
may due to the n–π* transition of C– – O bonds of CDs [52]. The corre­
sponding Tauc plots in Fig. S9b-d show that the band-gap energy of
CDs@ZIF-8 is 2.64 V, which is similar with the CDs (2.65 eV) and much
lower than that of ZIF-8 (5.08 eV). This result shows that the interaction
of CDs and ZIF-8 framework decreases band-gap energy. The Mott–­
Schottky measurements of CDs, ZIF-8 and CDs@ZIF-8-a are used to
determine their conduction band (Ecb), those are about -0.14 V, -0.27 V
and -0.29 V, respectively (Fig. S15). Although the Ecb positions of ZIF-8
and CDs@ZIF-8-a are almost similar, the lower slope of CDs@ZIF-8-a
sample means a higher concentration of electron donors (ND) [60],
which are the CDs encapsulated in the ZIF-8 framework.
The illustration of the catalytic mechanism of CDs@ZIF-8-a nano­
particles is shown in Scheme 2. The photoinduced electrons transfer
from the LUMO of ZIF-8 framework to CDs, which are acted as an
acceptor of the photoinduced electrons from the matrix. The suppressed
recombination of electron-hole pairs in CDs@ZIF-8-a system, especially
those on CDs leave many charge carriers to form reactive species, pro­
moting the decomposition of H2O2 to H2O and generating the reactive
substances (⋅OH). ZIF-8 framework protects CDs from the aggregation
and quenching, which increases the participation of CDs for catalytic
reactions. The combination of CDs and ZIF-8 is conducted to rapid
electron transfer, and their synergetic effect promotes the composite
materials to have superior peroxidase-like activity.

5
Y. Wang et al.
Scheme 2. Illustration of the catalytic mechanism of CDs@ZIF-8-a nanocrystals.
3.4. Steady-state kinetic analysis
The steady-state kinetic analysis of CDs@ZIF-8-a-based catalytic
system is studied by varying the concentration of TMB or H2O2 under
optimal conditions (pH 4.0, 50 ℃ and incubate for 30 min). A typical
Michaelis–Menten curves are shown in Fig. 3c and d, and the double
reciprocal curves are fitted to the oxidation reaction catalyzed by
CDs@ZIF-8-a. The Vmax and Km value are calculated and listed in
Table S2. According to the literature, the affinity between the enzyme
mimics (catalysts) and the substrates is inversely proportional to Km
[14]. As shown in Table S2, the Km value of CDs@ZIF-8-a with 3,3′ ,5,
5′ -tetramethylbenzydine (TMB) is 0.232 mM, which is lower than that of
nature horseradish peroxidase (HRP) (0.434 mM) [58] and some pre­
viously reported artificial peroxidase mimics [6,10,11,18], implying the
stronger affinity between CDs@ZIF-8-a and TMB. When taking H2O2 as
the substrate, the Km value of CDs@ZIF-8-a is 0.737 mM, which also
possesses good affinity compared with those reported ones [10,11,17,
61,63]. The lower Km value is beneficial for enhancing the catalytic
activity of CDs@ZIF-8-a [64].
3.5. Detection of H2O2 and GSH
We establish a colorimetric method to detect H2O2 and GSH due to
the peroxidase-like catalytic activity of CDs@ZIF-8-a composite. Under
optimal conditions, the UV–vis absorbance intensities of H2O2 varied
Fig. 4. (a) UV–vis absorption curves and the photographs (inset) of 0.05 mg/mL CDs@ZIF-8-a with 0.3 mM TMB and different concentration of H2O2 at pH of 4.0. (b)
The absorbance intensity at 652 nm with increasing concentration of H2O2. Inset: the linear calibration plot for H2O2 sensing.
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Sensors and Actuators: B. Chemical 329 (2021) 129115
from 0.1 mM to 2.25 mM are shown in Fig. 4a. It can be seen that the
absorption intensity is proportional to the concentration of H2O2, and
the colorless mixtures gradually turns to deep blue (Fig. 4a inset), which
indicates the generation of ox-TMB. The corresponding intensity curve
at 625 nm is recorded in Fig. 4b, and at the range of 0.1–1.0 mM, a linear
relationship between H2O2 and generated ox-TMB are shown. The limit
of detection (LOD) is calculated by the following equation:
LOD = 3σ/k (3)
Where σ is the relative standard deviation and k is the slope.
The calculated LOD of H2O2 is 3.6 μM, lower than some artificial
peroxidase mimics listed in Table S3, such as M-CQDs [8], ZIF-67 [10],
FePPOP-1 [63] and H2TCPP/Co(OH)2/GO [62].
As the basic polypeptide in human body, GSH is important in
defensing against free radicals and toxins [65]. It can convert the blue
ox-TMB to colorless TMB due to the thiol in its structure. Based on these,
a sample colorimetric method can establish to detect GSH through the
peroxidase active CDs@ZIF-8-a system. Fig. 5a shows that the absor­
bance intensity at 652 nm decreases with the increasing dosage of GSH
and finally a colorless solution is obtained (Fig. 5a inset). The corre­
sponding absorbance value ΔA (ΔA = Ablank − AGSH) reaches a plateau
when the GSH dose is up to 100 μM (Fig. 5b), and at the range of
0− 100 μM, a linear relationship can be seen between ΔA and the con­
centration of GSH (Fig. 5b inset).
Calculated by the equation LOD = 3σ/k, the LOD of GSH is 1.04 μM.
Y. Wang et al. Sensors and Actuators: B. Chemical 329 (2021) 129115

Fig. 5. (a) UV–vis absorption curves and the photographs (inset) of 0.05 mg/mL CDs@ZIF-8-a with 0.3 mM TMB and 2.0 mM H2O2 in the presence of different
concentration of GSH at pH 4.0. The mixture was incubated at 50 ℃ for 30 min. (b) The absorbance change (ΔA = Ablank − AGSH) with increasing concentration of
GSH. Inset: the linear calibration plot for GSH sensing.

And a broader linear range is shown in our method than that found in Declaration of Competing Interest
other detection methods, including spectrophotometric assay, capillary
electrophoresis, bioluminescence assay, electrochemistry and HPLC The authors declare that they have no known competing financial
methods [66]. Compared with other peroxidase-like mimics (N/S CDs interests or personal relationships that could have appeared to influence
[9], CB-CQDs [6], CQDs [29] and MXene@NiFe-LDH [15]), our method the work reported in this paper.
has a broader linear range and are listed in Table S4.
Acknowledgments

3.6. Selectivity analysis

This work is supported by the National Natural Science Foundation
of China (Grant Nos. 21671075, 21621001) and the 111 Project (No.
The great specificity is essential for an excellent biosensor. Thus, the
B17020).
selectivity of GSH detection based on CDs@ZIF-8-a system has been
investigated by using some metal ions and amino acids of 0.5 mg/mL as
Appendix A. Supplementary data
control samples, such as Ca2+, K+, Na+, proline (Pro), arginine (Arg),-D-
serine (Ser), DL-tryptophan (Try), Isoleucine (Iso), histidine (His), uric
Supplementary material related to this article can be found, in the
acid (UA), glutamine (Glu), cysteine (Cys), ascorbic acid (Asc), NADH
online version, at doi:https://doi.org/10.1016/j.snb.2020.129115.
and FADH. As shown in Fig. S16, an excellent selectivity of GSH can be
observed, and other substances can’t significantly suppress the oxida­
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Yufei Wang is currently carrying out her Doctor’s degree under the guidance of Professor
Y. Wang et al.
Xueshibojie Liu is a doctor of medicine and an attending physician of otorhinolaryn­
gology head and neck surgery in Jilin University Second Hospital. His research is mainly
focused on diagnosis and treatment of head and neck tumors.
Mengke Wang is currently carrying out her Doctor’s degree under the guidance of
Professor
Xiaoxue Wang is currently carrying out her Doctor’s degree under the guidance of
Professor
Sensors and Actuators: B. Chemical 329 (2021) 129115
Wenyan Ma is currently carrying out her Doctor’s degree under the guidance of Professor
Jiyang Li in Jilin University (China). Her research is mainly focused on the synthesis and
application of chiral carbon dots. Jiyang Li is a professor at State Key Laboratory of
Inorganic Synthesis and Preparative Chemistry at the College of Chemistry, Jilin Univer­
sity. She received her PhD degree from Jilin University (China) in 1999. Her research
focuses on the synthesis and new properties of porous functional materials.