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Articulo #1-Destrezas Info
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ABSTRACT: In this paper, we first discovered that Co3O4 nanoparticles (NPs) possess intrinsic oxidase-like activity and can
catalytically oxidize peroxidase substrates, such as 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt
(ABTS) and 3,3′,5,5′-tetramethylbenzidine (TMB), to form colored products, in the absence of exogenously added H2O2. The
presence of sulfite inhibited the TMB−O2−Co3O4 NPs reaction system and caused a change in color of the reaction system. On
the basis of this phenomenon, a colormetric approach to detect sulfite was established with a good linear relationship ranging
from 0.2 × 10−6 to 1.6 × 10−5 M and a detection limit of 5.3 × 10−8 M. The method was used to detect sulfite in foods. Good
recoveries ranging from 93.8% to 100.5% were obtained. Furthermore, the mechanism was studied and results showed that the
oxidase-like activity of the Co3O4 NPs was not from •OH or O2•− radical generated. It may probably originate from their ability
to transfer an electron between the peroxidase substrate and oxygen absorbed on the surface of the Co3O4 NPs.
KEYWORDS: Co3O4 nanoparticles, oxidase mimic, colorimetry, sulfite, mechanism of oxidase-like activity
■ INTRODUCTION
Sulfite is one of the oldest and most ubiquitous food additives,
nanomaterials,18,19 metal nanomaterials,13,20 carbon nanoma-
terials,13,20 nanocomposites,21−28 and other nanomaterials.29−31
These enzyme-like nanomaterials could be employed in
which has been widely used as blanching and preservative
colorimetry to detect nucleotides,32 H2O2,33−35 glucose,33−35
agents in a large variety of foodstuffs (dried fruit, vermicelli,
melamine,36 and so on. To the best of our knowledge, however,
preserves, etc.) to improve the appearance of food and prevent
the colorimetric detection of sulfite in food using the enzyme-
bacterial growth.1,2 However, the ingestion of foods containing like property of nanoparticles has not been explored up to now,
large amounts of sulfite can cause asthmatic attacks and allergic which might be attributed to the complication of food samples’
reactions in sensitive individuals.3,4 Owing to the potential matrices and the difficulties in constructing an effective
toxicity, the sulfite in foods is strictly limited in many nanoparticles-based enzyme mimic sensing platform to detect
countries.5 Hence, sulfite determination in food products is micro amounts of food additive.
essential for the purposes of public health, food assurance, and Herein, we have developed a TMB−O2−Co3O4 NPs
quality control. In recent years, numerous methods have been colorimetric system for detection of sulfite in foods, based on
developed for determining sulfite in foods, including titrimetry, the property of oxidase-like activity of Co3O4 NPs. In this
flow injection analysis, anodic stripping voltammetry, ion method, the existence of sulfite can cause a change in color of
chromatography, chemiluminescence, gas chromatography, the reaction system, and the color change can be visually
fluorometry, high-performance liquid chromatography, and observed directly. We also investigated the mechanism of
colorimetry.6−8 oxidase-like activity of Co3O4 NPs by XPS, contrast experi-
Colorimetric biosensing has become more attractive because ments, and cyclic voltammetry.
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of its low cost, simplicity, and practicality. However, the key
challenge for colorimetric sensors is transforming the detection EXPERIMENTAL PROCEDURES
events into color changes. Since color changes can be read by
Materials. Co(CH3COO)2·4H2O were obtained from Tianjin
the naked eye, a colorimetric sensor does not require expensive Guangfu Chemical Reagent Factory (Tianjin, China). 3,3′,5,5′-
or sophisticated instrumentation and can be applied to field Tetramethylbenzidine (TMB) and 2,2′-azinobis(3-ethylbenzothiazo-
analysis.9−11 To this end, enzyme-like nanomaterials-based line-6-sulfonic acid) diammonium salt (ABTS) were purchased from
sensors have emerged as an important colorimetric tool. Since Sigma-Aldrich. Ammonium hydroxide (25−28 wt %) was purchased
the first report of Fe3O4 magnetic nanoparticles (MNPs) from Baiyin Liangyou Chemical Reagent Factory (Baiyin, China).
possessing intrinsic peroxidase-like activity,12 nanoparticles- Sodium acetate, glacial acetic acid, anhydrous sodium sulfite, sodium
based enzyme mimics have received great attention due to their
merits relative to native enzymes (e.g., low cost, high stability, Received: February 23, 2014
and tunability in catalytic activity). More and more nano- Revised: May 28, 2014
particles have been found as enzymatic mimics, such as metal Accepted: June 2, 2014
oxide nanomaterials,13 sulfide nanomaterials,14−17 selenide Published: June 2, 2014
© 2014 American Chemical Society 5827 dx.doi.org/10.1021/jf500950p | J. Agric. Food Chem. 2014, 62, 5827−5834
Journal of Agricultural and Food Chemistry Article
Figure 1. Images of the oxidation color reaction of TMB and ABTS by Co3O4 NPs (a). UV/vis spectra of TMB solution in 0.2 M acetic acid−acetate
buffer (pH 4.0) at 40 °C for 10 min. The TMB and Co3O4 NPs concentrations were 0.25 mM and 40 μg mL−1, respectively (b). UV/vis spectra of
an ABTS solution in 0.2 M acetic acid−acetate buffer (pH 4.0) at 40 °C for 10 min. The ABTS and Co3O4 NPs concentrations were 0.25 mM and
40 μg mL−1, respectively (c).
Figure 2. Survey XP spectra of Co3O4 NPs before and after reaction (a and d). Deconvoluted high-resolution Co 2p3/2 XP spectra of Co3O4 NPs
before and after reaction (b and e). Deconvoluted high-resolution O 1s XP spectra of Co3O4 NPs before and after reaction (c and f).
dihydrogen phosphate, and other regents were obtained from Tianjin D/Max-2400 X-ray diffractometer with Cu Kα radiation (λ =
Guangfu Chemical Reagent Factory (Tianjin, China). A sulfite 0.154056). The chemical state of the coating surface was analyzed
solution was prepared daily by dissolving anhydrous sodium sulfite using X-ray photoelectron spectroscopy (XPS, PerkinElmer PHI-5702
in water and was standardized by iodimetric titration when needed. All multifunctional photoelectron spectrometer). Element determination
other chemicals were of analytical reagent grade and used without was measured by a 4300 DV inductively coupled plasma−atomic
further purification. Deionized water was used throughout the emission spectrometer (ICP-AES). Zeta potential measurements of
experiment. Co3O4 NPs were performed with a Malvern Nano-ZS apparatus. ESR
Apparatus and Characterization. A TU-1901 double-beam spectra were acquired using a JES-FA200 electron spin resonance
UV−vis spectrophotometer (Beijing Purkine General Instrument Co. spectrometer. Electrochemical experiments were performed on a CHI
Ltd., China) was used to record absorption spectra and measure 832 electrochemical workstation (Shanghai Chenhua Instrument Co.,
absorbance. A FEI Tecnai G2 F30 microscope (TEM) was used for China) and a conventional three-electrode system. The conventional
measuring the morphologies and size of Co3O4 NPs. The X-ray three-electrode system contained a Pt wire counter electrode, a
diffraction (XRD) pattern of Co3O4 NPs was determined on a Rigaku saturated calomel electrode as reference electrode, and an as-prepared
■
change before or after the reaction. These results confirmed
that Co3O4 NPs exhibited intrinsic oxidase-like activity.
RESULTS AND DISCUSSION
It is important to confirm the possibility that the observed
Oxidase-like Activity of Co3O4 NPs. The oxidase-like activity was not caused by cobalt ions leaching from Co3O4 NPs
activity of Co3O4 NPs was evaluated in the catalysis of typical in acidic solution. To test this, Co3O4 NPs were incubated in
substrates TMB and ABTS in the absence of H2O2. As can be the reaction buffer (pH 4.0) for 2 h and then removed from the
seen from Figure 1a, Co3O4 NPs catalyzed the oxidation of solution by centrifugation. As shown in Figure S5, comparing
TMB and ABTS to produce the typical colored products. the activity of the leaching solution with that of Co3O4 NPs
under the same conditions, the leaching solution had no
activity, showing that the observed oxidase-like activity was due
to intact Co3O4 NPs. Figure S6 shows the amount of cobalt
ions leaked from Co3O4 NPs in the buffer solutions (pH 3.0−
7.0) for 2 h, which was implemented by ICP-OES. The ICP
results exhibited that there were few cobalt ions in the leaching
solution. They probably came from residual Co3O4 NPs after
centrifugation.
Figure 3. Photographs of TMB solutions in the absence and presence
Possible Mechanism of Oxidase-like Activity of Co3O4
of an O2 oxidation reaction catalyzed by Co3O4 NPs (a). Photographs NPs. As an oxidase mimic, Co3O4 NPs catalyze an oxidation−
of a TMB solution oxidation reaction catalyzed by Co3O4 NPs without reduction reaction involving oxygen (O2) as the electron
degassing and Co3O4 NPs degassed by three freeze−pump−thaw acceptor. However, in the reaction system of TMB−O2−Co3O4
cycles (b). Photographs of the oxidation color reaction of TMB, TMB- NPs, oxygen is present in the aqueous solution and also exists
SO32−, and TMB-SO42− catalyzed by Co3O4 NPs, respectively (c). on the surface of Co3O4 NPs due to the high specific surface
5829 dx.doi.org/10.1021/jf500950p | J. Agric. Food Chem. 2014, 62, 5827−5834
Journal of Agricultural and Food Chemistry Article
Figure 5. Michaelis−Menten curve of Co3O4 NPs with TMB (a). Michaelis−Menten curve of Co3O4 NPs with ABTS (b). Details are included in
the Experimental Procedures.
area of nanomaterials. In order to determine whether the bond strength of Co3O4 and the larger surface energy of
oxygen in the solution played a role in the TMB−O2−Co3O4 nanomaterials caused by a large surface to volume ratio.39 In
NPs system, two sets of experiments were conducted: the first addition, the O 1s peak at 533.0 eV in the XPS spectrum shown
one was carried out in the presence of oxygen; the other was in Figure 2c indicated that there was chemisorbed oxygen on
performed under high-purity nitrogen and the solution was the surface of Co3O4 NPs.40 It is indicated that both the
degassed before the reaction, as in the photograph shown in physically absorbed and chemisorbed oxygen on the surface of
Figure 3a. It was found that they exhibited the same color. The Co3O4 NPs played a key role in the TMB−O2−Co3O4 NPs
absorbance of the first one was 0.747; the other was 0.770 at system. In order to further confirm the above conclusion,
652 nm. The absorbance of the latter was higher than the oxidation experiments of TMB, TMB-SO32−, and TMB-SO42−
former; one possible reason was that nitrogen played a role in catalyzed by Co3O4 NPs were carried out. The results are
mixing and speeded up the reaction. This indicated that the shown in Figure 3c. TMB-SO32− system presented a lower
oxygen in the solution had no effect on the reaction, which was absorbance than the other two systems. Since the volume of
different from the behavior of some nanoparticles-based oxidase SO32− is smaller than TMB, and Co3O4 NPs have a positive
mimics reported.8,38 For further study, the Co3O4 NPs without charge at pH 4.0 (Supporting Information), SO32− is more
degassing and Co3O4 NPs degassed by three freeze−pump− easily adsorbed on the surface of Co3O4 NPs. Then SO32−
thaw cycles that catalyze the oxidation of TMB were consumed oxygen absorbed on the surface of the Co3O4 NPs
implemented in the degassed solutions. They produced and interfered with the TMB−O2−Co3O4 NPs system. This
different colors, as in the photograph shown in Figure 3b, supported the above result that the oxygen absorbed on the
and the degassed Co3O4 NPs also catalyzed the oxidation of surface of the Co3O4 NPs oxidized TMB in this system.
TMB to produce the typical color reaction. It is suggested that The oxidation of TMB is an electron transfer process.41 The
the oxygen on the surface of Co3O4 NPs was due not only to electrocatalytic behavior of a Co3O4 NP modified glassy carbon
physical adsorption. Chemisorbed oxygen probably existed on electrode (GCE) toward the electrochemical oxidation of TMB
the surface of Co3O4 NPs because of the low oxygen Co−O was studied using cyclic voltammetry (CV), in order to
5830 dx.doi.org/10.1021/jf500950p | J. Agric. Food Chem. 2014, 62, 5827−5834
Journal of Agricultural and Food Chemistry Article
Figure 6. A pH−ΔA curve (a), a temperature−ΔA curve (b), a TMB concentration−ΔA curve (c), and a Co3O4 NPs concentration−ΔA curve (d)
for 6 μM sulfite detection, where ΔA = A(blank,652nm) − A(sulfite,652nm), in 0.2 M acetic acid−acetate buffer solutions incubated for 10 min with the as-
prepared Co3O4 NPs as oxidase mimics.
It is suggested that TMB was not oxidized by O2•− and •OH graphs for the determination of sulfite were constructed under
radicals in the TMB−O2−Co3O4 NPs system, which was the optimum conditions described above. The calibration data
different from the behavior of CoFe2O4 NPs.8 Therefore, the of ΔA versus sulfite concentration are shown in Figure 7. The
nature of oxidase-like activity of the Co3O4 NPs does not results indicated that the concentration of detectible sulfite
originate from the O2•− and •OH radicals generated. could be 0.2 × 10−6 M with a linear range from 0.2 × 10−6 to
Taken together, although the detailed mechanism remains 1.6 × 10−5 M. The limit of detection (LOD) for sulfite was 5.3
unclear, these observations demonstrated that Co3O4 NPs × 10−8 M. (LOD = KS0/S, where K is a numerical factor chosen
accelerated the electron transfer from the peroxidase substrate according to the confidence level desired, S0 is the standard
to oxygen absorbed on the surface of the Co3O4 NPs. The deviation (SD) of the blank measurements (n = 10, K = 3), and
possible mechanism of oxidase-like activity of Co3O4 NPs is S is the slope of the calibration curve.44)
presented in Scheme 1; that is, TMB was absorbed on the Effect of Foreign Substances. The effect of foreign
surface of the Co3O4 NPs and donated electrons to the Co3O4 substances was tested by analyzing the mixed solution and
NPs, resulting in an increase in electron density and mobility in standard solution of sulfite (12 μM). The molar ratio of other
the Co3O4 NPs, thus accelerating the electron transfer to ion and sulfite was 20 in the mixed solution. The relative ΔA
oxygen absorbed on the surface of the Co3O4 NPs. After the values ((ΔAtotal − ΔAsulfite)/ΔAsulfite) are presented in Figure 8.
completion of the electron transfer, the Co3O4 NPs reverted to As can be seen, Fe and Cu were the main interferences for
their original state. sulfite determination, since trace amounts of heavy metal ions
Steady-State Kinetic Assay of Co3O4 NPs. Since Co3O4 in the water are believed to act as the catalyst in the oxidation
NPs exhibited oxidase-like activity, the kinetic parameters of of sulfite by oxygen.45 EDTA was selected as a chelate reagent
only TMB/ABTS were determined by changing the concen- for the present study to eliminate the interferences derived
tration of TMB/ABTS. A typical Michaelis−Menten curve from Fe, Cu, and other coexisting transient metals in the
(Figure 5a,b) was obtained with TMB/ABTS by monitoring samples.
the absorbance change at 652/417 nm for 4 min (Figure Detection of Sulfite in Real Samples. As an illustration
S8a,b). The Michaelis−Menten constant (Km) and maximum of analytical application, the proposed method was used to
initial velocity (Vmax) were obtained using a Lineweaver−Burk determine sulfite in real samples under the optimal
plot. The values of Km and Vmax for the Co3O4 NPs with TMB experimental conditions. The results are listed in Table 1.
were 0.051 mM and 3.30 × 10−8 M s−1. The values of Km and The recoveries of the three samples ranged from 93.8% to
Vmax for the Co3O4 NPs with ABTS were 0.037 mM and 3.20 × 100.5%. Hence, the proposed method can be considered a
10−8 M s−1. The Km value of Co3O4 NPs with ABTS was useful tool for the quantification of sulfites in real samples.
smaller than that with TMB. It is suggested that Co3O4 NPs In summary, Co3O4 NPs were first found to possess oxidase-
have higher affinity toward ABTS than TMB, because ABTS like activity and could catalyze the oxidation of TMB and ABTS
has a higher affinity toward a positively charged nanoparticle to produce the typical color reaction in the absence of
surface and TMB has a stronger affinity toward a negatively exogenously added H2O2. It was found that the oxygen
charged nanoparticle surface.43 absorbed on the surface of the Co3O4 NPs oxidizes the
Optimization of Experimental Conditions. The reaction peroxidase substrate, rather than the oxygen dissolved in the
conditions were optimized to establish the optimum analytical solution. The oxidase-like activity of Co3O4 NPs was not from
conditions. The pH value not only decides the charge of the the generated O2•− or •OH radical, probably originating from
surface of Co3O4 NPs (Supporting Information), which affects their ability to transfer an electron between the peroxidase
the interaction between Co3O4 NPs and sulfite, but also affects substrate and oxygen absorbed on the surface of the Co3O4
the catalytic activity of Co3O4 NPs. The catalytic activity of NPs. Moreover, as the existence of sulfite inhibited TMB−O2−
Co3O4 NPs is also dependent on the incubation temperature. Co3O4 NPs system and caused a change in color of the reaction
In addition, the concentrations of TMB and Co3O4 NPs system, a new colorimetric method for detecting sulfite was
determine the color level of the reaction system. Therefore, developed. The colorimetric method showed a good response
they were investigated in this study as influencing factors. toward sulfite detection with a linear range from 0.2 × 10−6 to
Figure 6a indicates that ΔA, where ΔA = A(blank,652nm) − 1.6 × 10−5 M and good recoveries ranging from 93.8% to
A(sulfite,652nm), increased and then decreased with increasing pH 100.5% in three real samples using Co3O4 NPs as an oxidase
and had a maximum at 4.0. The reaction temperature- mimic. The detection platform showed great potential
dependent response curve is shown in Figure 6b. It showed applications in reducing substrates. In addition, Co3O4 NPs
that ΔA of the reaction system had a peak value at 40 °C. can be expected to provide potential applications for chemical
Therefore, 4.0 and 40 °C were taken as the optimal pH and sensing, biochemical analysis, electrochemical biosensing, and
temperature. The concentrations of TMB and Co3O4 NPs even clinical chemistry.
■
response curves are shown in Figure 6c and d; the optimal
concentrations of TMB and Co3O4 NPs were 0.25 mM and 40
μg mL−1, respectively.
ASSOCIATED CONTENT
Analytical Performance for Sulfite Determination. As * Supporting Information
S
an oxidase mimic, Co3O4 NPs can catalyze TMB to form This material is available free of charge via the Internet at
colored product in the absence of H2O2. The sulfite inhibits the http://pubs.acs.org.
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TMB−O2−Co3O4 NPs system and causes a change in color of
the reaction system, which suggested that sulfite can be AUTHOR INFORMATION
indirectly detected. Since sulfite is easily adsorbed on the
surface of Co3O4 NPs and consumes absorbed oxygen more Corresponding Author
easily than dissolved oxygen, the sulfite that is consumed by *E-mail: chenxg@lzu.edu.cn (X.-G. Chen). Tel: 86-931-
dissolved oxygen is neglected in the reaction. The calibration 8912763 Fax: 86-931-8912582.
5832 dx.doi.org/10.1021/jf500950p | J. Agric. Food Chem. 2014, 62, 5827−5834
Journal of Agricultural and Food Chemistry Article
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