Preparation and physico-biochemical characterization of (Fe, Co, Ni) oxide nanoparticles-decorated PANI-MWCNTs as peroxidase mimetics

Article abstract of DOI:10.1039/c7nj02645e

In this research, a novel multiwall carbon nanotube/polyaniline (PANI-MWCNTs)-based metal oxides nanocomplex as a peroxidase mimetic was fabricated and characterized. Finally the peroxidase-like catalytic activity of nanocatalyst was investigated with the

Full text of DOI:10.1039/c7nj02645e

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Preparation and physico-biochemical characterization of (Fe‚ Co‚
Ni) oxide nanoparticles-decorated PANI-MWCNTs as peroxidase
mimetics
a
a
b
c
Received 00th January 20xx,
Accepted 00th January 20xx
Navvabeh Salarizadeh, Minoo Sadri* , Farhood Heydari ‚ Seyyed Salman Seyyed Afghahi
DOI: 10.1039/x0xx00000x
“
In this research, a novel multiwall carbon environmental changes such as pH, temperature
3
nanotube/polyaniline (PANI-MWCNTs)-based and proteases. So far, design and synthesis of
metal oxides nanocomplex as a peroxidase artificial enzymes can be a suitable substitution to
mimetics was fabricated and characterized. natural enzymes. The nanoꢀbased materials are
4
Finally the peroxidase-like catalytic activity of one of the promising candidates as peroxidase
nanocatalyst was investigated with the oxidation mimetics. Peroxidaseꢀlike activity of metals (Co,
of peroxidase substrates: 4-aminoantipyrine (4- Cu, Ni, Ag, Au, etc), metal oxides, nanoferrites,
AAP)/phenol
system
and
3,3',5,5'- CNTs and carbonꢀbased nanostructures has been
5
tetramethylbenzidine (TMB) substrate in the widely studied. In recent years, design and
presence of H
2
O
2
reagent.”
synthesis of magnetic nanostructures as enzyme
mimetics and other applied purposes have been
6
Hydrogen peroxide (H
2 2
O
) is a waste product of a
studied by many researchers.
However,
broad range of biological processes and plays a
mediator role in biochemistry and clinical analysis.
aggregation of magnetic nanoparticles decreases
the catalytic activity of nanoparticles. Therefore,
supporting materials with a large specific surface
area such as PANI, CNTs and graphene reduces
2 2
H O is a reagent that is commonly used for
removal of environmental contamination such as
pesticides in agriculture and treatment of
their agglomeration and causes uniform
7
wastewaters. Unfortunately, H
2
O
2
is very toxic to
distributions. PANI is a conductive polymer has
organisms, so far the detection and catalysis of
been used in the design of biosensors.
Compositions of PANI and other materials such as
porphyrin, metals, metal oxides and carbonꢀbased8
materials have been studied for applied purposes.
Peroxidase activity of Fe–Co alloy NPs using TMB
1
2 2
H O has considerable importance. Generally,
horseradish peroxidase (HRP) catalyses the
oxidation of aromatic compounds by hydrogen
peroxide or alkyl hydroperoxide. Also, HRP is
applied for peroxide detection. This enzyme was
widely employed in the synthesis of polymers, and
1
c
substrate was reported by Huang and coworkers.
Various sensors based on HRP and peroxidase
mimetics, have been developed for the
the bioremediation of toxic organic compounds like
phenolic structures from wastewaters. In spite of
the important role of natural enzymes, it is
expensive the cost of their production, purification
and storage. Also stability and activity of natural
enzymes were decreased in the harsh
2
determination of glucose and H
2
O
2
, consisting
fluorescence,
electrochemical
The enzyme mimetic activity of
chemiluminescence,
spectrophotometric
and
1
b,8a,8c
methods.
PANI/MWCNTsꢀbased nanostructures has not been
considered until now. For the first time, we
evaluated peroxidaseꢀlike catalytic activity of (Fe‚
Co‚
Ni)
oxide
nanoparticlesꢀdecorated
PANIMWCNTs with colorimetric method using 4ꢀ
AAP/phenol system and TMB substrate in the
presence
of
H
2
O
2
reagent.
Biochemical
E-mail: sadri.mn313@gmail.com; Fax: +98 21 22974605; Tel: +98
characterizations of the nanocatalyst were
2
b
1 22974619; +98 9123846007
evaluated using phenol/4ꢀAAP as
a
new
Nanomaterials Group, Department of Materials Engineering, Tarbiat
Modares University, Tehran, Iran
colorimetric assay for peroxidase mimetics (Fig. 1).
According to electrochemical properties of PANI
c
Department of Engineering, Imam Hossein University, Tehran, Iran
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and MWCNT, this nanostructure can be developed aggregated together to form large clusters. Plotted
for the design of the ultrasensitive biosensor for in Fig. 2d is
H
2
O
2
and glucose detection. Composition of the size distribution of particles on the surface of
MWCNT with PANI and metals (Fe‚ Co‚ Ni, etc.) PANIꢀMWCNTs nanocomposite.
improve their electromagnetic properties. The first,
in situ polymerization of PANI on MWCNT (coreꢀ
shell PANI/MWCNTs) was performed as follow: 175
3 2 4
mL of acid solution (HNO /H SO 2:5 v/v) was
prepared then 1g MWCNT was added to the
solution and ultrasonically agitated for 6 h at 90 °C.
Subsequently the suspension was filtered and
washed by deionized water until the pH value of 5
was achieved. Then MWCNT powder was
collected and dried under vacuum at 80 °C. Then Fig. 1 Schematic diagram of the catalyzed reaction by
MWCNT was dispersed in 50 ml aqueous solution peroxidaseꢀlike activity of (Fe‚ Co‚ Ni) oxide nanoparticles@
containing 3.77 ml HCl and then agitated in an PANIꢀMWCNTs with the oxidation of 4ꢀAAP/phenol, TMB
ultrasonic bath for 30 min, meanwhile 7.04 ml substrate and H O reagent: 4ꢀ AAP and TMB by H O in the
2
2
2
2
aniline was added dropwise to the suspension. The presence of peroxidase were oxidized to color pink and blue
mixture was then stirred continuously in an ice products, respectively.
bath. Polymerization was initiated by the dropwise
addition of ammonium persulfate (0.06g, A really narrow size distribution of the magnetic
(
NH ) S O in 100 ml distilled water) and mixing nanoparticles is found, with sizes mostly falling
4 2 2 8
was continued for 12 hours. The reaction mixture between 7.0 and 9.0 nm.
was then filtered and washed repeatedly with Utilizing of PANIꢀMWCNTs as the supporting
distilled water and ethanol. The obtained wet materials causes uniform distribution of (Fe‚ Co‚
MWCNTꢀ polymer cake was dried at 60 °C for 2 h Ni) oxide nanoparticles on the outer surface of
under dynamic vacuum conditions. Then in order to PANIꢀMWCNTs with rather uniform particle sizes.
prepare (Fe‚ Co‚ Ni) oxide nanoparticlesꢀdecorated As shown in Fig 2b and c‚ the surface of PANI
PANIꢀMWCNTs, appropriate amounts of PANIꢀ branches have favourite sites for nucleation and
MWCNTs (30 mg)‚ FeCl ꢀ6H O (73 mg), growing of (Fe‚ Co‚ Ni) oxide and render
3
2
Co(NO ) ꢀ6H O (73 mg) and Ni(NO ) ꢀ6H O (73 nanoparticles with beadꢀlike morphology. UVꢀVis
3
2
2
3 2
2
mg) were charged in to ethylene glycol (EG). absorbance spectra of MWCNT, PANI‚ PANIꢀ
Suspension agitating was done by bath ultrasonic. MWCNT and (Fe‚ Co‚ Ni) oxidesꢀPANIꢀ
Then, sodium hydroxide and sodium borohydride MWCNTs nanocomposite were recorded on a
were solved in EG and this solution was slowly spectrophotometer (Shimadzu UVꢀ2501 PC) (Fig.
added to the salt solution drop wise under argon 3). The peaks at 259 and 253 nm are related to
flow in 30 min. The reaction was performed at 80 MWCNT and PANI, respectively. The peak at 263
°
C for 2 h under stirring. The prepared precipitate nm assigned to PANIꢀMWCNTs composite, it was
was then centrifuged and washed with ethanol. shifted by 4 and 10 nm compared
Finally, the nanocomposite dried at 60 °C for 2 h
under dynamic vacuum. The dried sample was then
annealed at 600 °C for 1 h under argon atmosphere
to get the desired crystalline nanoparticles.
The morphology of the nanocomposites was
observed using scanning electron microscopy
(SEM) (Leo 440, UK) and transmission electron
microscopy (TEM) (Zeiss EM900, Germany). In
Fig. 2a, the SEM images show that PANIꢀMWCNT
nanocomposites have uniform morphology. These
results obviously show that the PANIꢀMWCNT
nanocomposites have coaxially tube shaped
structures with a coating on the surface of tube
perimeter. From the TEM images (Fig. 2b and c)
and results achieved from XRF testing (table 1), it
could be seen that on the surface of PANIꢀ
MWCNT; (Fe‚ Co‚ Ni) oxide nanoparticles were
2
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NP lee wa s eJ od uo r nn oa tl aod fj uC s ht em ma ri sg it nr ys
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Fig. 2 (a) SEM image of PANIꢀMWCNT coreꢀ shell nanocatalyst in the absence of substrates, exhibited
nanostructure‚ (b,c) TEM images of metal oxidesꢀ PANIꢀ no absorption peaks at 510 nm. Also, colorimetric
MWCNTs nanostructure‚ (d) size distribution histogram of assay of nanocomposite was investigated in the
nanoparticles coated on the surface of PANIꢀMWCNTs.
presence of TMB and H
2 2
O as substrates, exhibited
no absorption peaks at 510 nm.
Table 1. XRF analysis of metal oxides ꢀ PANIꢀMWCNT nanocomposite
XRF L.O.I
Na
2
O
Al
2
O
3
SiO
2
SO
3
Cl
CaO
Fe
2
O
3
Co
Ni
Zn
%
8
6.72
1.575
0.034
0.22
0077 0.106
0.069
10.022
0.795
0.333
0.049
to MWCNT and PANI spectra, respectively; which
can be due to the interplay interfacial between
MWCNT and PANI. These data approve the
grafting of functionalized MWCNTs and PANI
chains. The UVꢀVis spectrophotometric results of
Fe‚ Co‚ Ni and O doped PANIꢀMWCNTs showed
2
peaks in 203 and 227 nm‚ indicating augmentation
of light absorption in the UV range and increase of
band gap energy of PANIꢀMWCNT by
incorporation of transition metals (Fe‚ Co‚ Ni) and
O2 under UV light irradiation. Xꢀray diffraction
(
D8 ADVANCE, Bruker, Ltd., Germany, with Cu
Kα radiation MWCNT in (Fe‚ Co‚ Ni) oxideꢀ
8
d
PANIꢀMWCNT hybrids.
It is observed from a diffraction pattern of the
annealed samples that the characteristic peaks at 2ꢀ
=
18.23° (440), 30.28° (511), 43.24° (400)‚ 53.74° Fig. 3 UVꢀVis spectra of MWCNT, PANI‚ PANIꢀMWCNT
(
311) and 62.89° (111) can be assigned to the and (Fe‚ Co‚ Ni) oxideꢀ PANIꢀ MWCNT nanocomposite.
CoFe2O4 NPs characteristic peaks. These data are
consistent to the PDF2 00ꢀ001ꢀ1121. The peaks at
2
ꢀ = 30.24° (220), 35.72° (311), 43.19° (400) are
matched well with the PDF2 00ꢀ003ꢀ0875 and can
be assigned to the faceꢀcentered cubic structured
NiFe2O4 characteristic peaks. The peaks at 2ꢀ =
4
3.13° (222), 62.62° (311) and 75° (220) are
consisting to the PDF2 00ꢀ003ꢀ0997 and can be
assigned to the faceꢀcentered cubic structured
CoO.7NiO characteristic peaks. These patterns
reveal a good crystallinity and rather broad peaks
due to smaller particle size. The colorimetric assay
of nanocomposite was performed in the presence of
4
ꢀAA/Phenol and H O2 as substrates at room
2
Fig. 4 XRD patterns of synthesized nanocomposite before
and after annealing.
temperature according to Worthington method for
peroxidase (Fig. 1). A solution of (Fe‚ Co‚ Ni)
oxide nanoparticles@ PANIꢀMWCNT could Also, colorimetric assay of nanocomposite was
catalyze the oxidation of 4ꢀ AAP in the presence of investigated in the presence of TMB and H
2 2
O as
2 2
H O
to produce a pink colored quinoneimine dye substrates in acetate buffer pH 4.0 at room
resulting from oxidation of 4ꢀAAP showed a temperature (Fig. 6b). In colorimetric assay in
maximum absorbance at 510 nm (Fig. 5a,c). There acetate buffer the optimum pH of catalytic activity
wasn’t any catalytic activity in the 4ꢀ was obtained at the range of 3.0ꢀ4.0. (Fig. 6a).
AAP/phenol/H
2
O
2
reaction without nanocatalyst According to obtained data from two reaction
system without 4ꢀ system, no obvious absorption peak was observed
and /nanozyme
2 2
H O
AAP/phenol. The 4ꢀAAP/phenol/nanozyme system from a solution in the absence of nanocatalyst.
exhibited a weak color variation, but in the When nanocatalyst was added to the solution, a
presence of nanozyme and two substrates, indicated strong response was appeared with monitoring of
deep color changes. These data demonstrate that obvious peaks at 510 and 652 nm. The Fig 5c,
both of substrate required for reaction progress and shows the progress curve of nanocatalyst at 510 nm
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in different situations. Also, the absorbance reported for peroxidase mimetics until now. This
changes of the reaction mixture investigated under new type of enzyme mimics shows high affinity to
different concentrations of H
ꢀ AAP/phenol (Fig. 5a).
2 2 2 2
O in the presence of H O similar to reported peroxidase mimetics.
4
Thus, this catalyst material demonstrates the
potential application in nonꢀenzymatic detection of
2 2
H O and glucose. Electrochemical tests were
examined in future works.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
We would like to thank Mohammad Javad
Taghizadeh from Chemistry Department of Imam
Hossein University.
Notes and References
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by (Fe‚ Co‚ Ni) oxidesꢀPANIꢀMWCNTs nanocomposite in Chem. Commun., 2013, 49, 5013ꢀ5015.
phosphate buffer pH
concentrations of H O : (C ꢀC : 400, 200, 100, 50, 25 and
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in the presence of different 2. (a) H. Wang, S. Li, Y. Si, Z. Sun, S. Lia, and Y. Lin, J.
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12.5 mM); (b) The absorption intensity at 510 nm against
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different concentrations of H O (c) The relative activity of
2
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Wu, Nanoscale., 2014, 6, 8107ꢀ8116; (b) J. Deng, X. Wen
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UVꢀVis absorption spectra of the oxidized phenol/4ꢀAAP in
H O (400 mM) and phosphate buffer pH 7 for (Fe‚ Co‚ Ni)
4
.(a) J. Shu, Z. Qiu, Q. Wei, J. Zhuang and D. Tang, Sci.
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2
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Fig. 6 (a) The relative activity of nanocatalyst using TMB in 41ꢀ60; (b) S. Mandal, K. Chaudhuri, In Complex Magnetic
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4
25ꢀ453; (c) Z. Chen, H Ji, C Liu, W Bing, Z Wang, X Qu.
absorption spectra of TMB using (Fe‚ Co‚ Ni) oxidesꢀPANIꢀ
MWCNTs nanocomposite with different pH values.
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7
2
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Also prepared nanocomposite exhibited higher
catalytic activity compared to pure PANIꢀ
MWCNTs (Fig. 5d). Since H O is the main
2 2
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8
. (a) Q. Zhang, A. Prabhu, A. San, J. F. AlꢀSharab and K.
product of the glucose oxidaseꢀcatalyzed reaction;
therefore the nanocatalyst with peroxidaseꢀlike
activity were also applied in the colorimetric and
quantitative detection of glucose. In summary, a
new enzymeꢀmimic activity (Fe‚ Co‚ Ni) oxidesꢀ
Levon. Biosens. Bioelectron., 2015, 72, 100ꢀ106; (b) S. Bao,
M. Du, M. Zhang, H. Zhu, P. Wang, T. Yang and M. Zou,
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P.A., Shaikh, R.C.,Kambale, A.V. Rao, and , Y.D., Kolekar.
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PANIꢀMWCNT
peroxidaseꢀlike activity, and could catalytically
oxidize TMB, and 4ꢀAAP using H to produce a
nanocomposite
exhibited
2
O
2
color reaction. Also, biochemical characterizations
of nanocatalyst were performed using phenol/ 4ꢀ
aminoantipyrine (4ꢀAAP) which has not been
4
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A nanocomposite of multiwalled carbon nanotubes/polyaniline and magnetic metal oxide
nanoparticles can used to catalyze the oxidation of peroxidase substrates.