Novel magnetic nickel telluride nanowires decorated with thorns: Synthesis and their intrinsic peroxidase-like activity for detection of glucose

Article abstract of DOI:10.1039/c4cc06684g

The magnetic nickel telluride with thorny nanostructure is directly synthesized for the first time via a hydrothermal method. It was used to detect H₂O₂ and glucose with a limit of detection of 25 nM (linear range = 0.1-0.5 μM) and 0.42 μM (linear range = 1-50 μM), respectively. This journal is

Full text of DOI:10.1039/c4cc06684g

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Novel magnetic nickel telluride nanowires
decorated with thorns: synthesis and their
intrinsic peroxidase-like activity for detection
of glucose†
Cite this: Chem. Commun., 2014,
50, 13589
Received 25th August 2014,
Accepted 17th September 2014
Lijuan Wan,ab Jinhuai Liub and Xing-Jiu Huang*b
DOI: 10.1039/c4cc06684g
www.rsc.org/chemcomm
The magnetic nickel telluride with thorny nanostructure is directly
In this study, novel magnetic nickel telluride nanowires
synthesized for the first time via a hydrothermal method. It was decorated with many thorns were prepared for the first time
used to detect H2O2 and glucose with a limit of detection of 25 nM through a hydrothermal method. In order to evaluate the
(linear range = 0.1–0.5 lM) and 0.42 lM (linear range = 1–50 lM), practical potential of the as-obtained NiTe thorny nanowires
respectively.
(TNWs), we investigated the peroxidase-like property by cata-
lyzing the oxidation of ABTS with H2O2. A colorimetric detec-
Hydrogen peroxide (H2O2) is produced in chemical, biological, tion system constructed with glucose oxidase (GOx), NiTe TNWs
pharmaceutical, clinical, and environmental processes.1,2 and ABTS was used for the determination of glucose. As we
Commonly, H2O2 and glucose were detected using the traditional know, few biological applications of CoTe and NiTe have been
optical3,4 and electrochemical5 approaches, most of which use reported.
natural peroxidases. Obviously, these methods have practical
drawbacks such as lack of sensitivity, time-consuming fabrication were estimated from their corresponding SEM and TEM images
procedures and the need for expensive reagents. to be B45 nm and B5 mm, respectively (Fig. 1a and b). In the
The diameter and length of the as-synthesized NiTe TNWs
Nanomaterials (NMs) such as Fe3O4,6 Au@Pt,7 and graphene8 TEM image, we clearly see many thorns around the nanowires.
have been used to detect H2O2 because their catalytic activity is The diffraction peaks of the XRD patterns (Fig. 1c) can be indexed
similar to that of natural peroxidases. For example, NMs could to a rhombohedral crystal structure (JCPDS No. 65-3665). The
catalyze the oxidation of the peroxidase substrates such as the detection of Te and Ni in the EDS spectrum (Fig. 1d) further
2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium confirms the formation of NiTe. It is necessary to point out that
salt (ABTS)9,10 and 3,30,5,50-tetramethylbenzidine (TMB)11 using the signal of the Sc element originates from the sample bar of the
the catalytic activity of the released metal ions. NMs meet the TEM device and does not affect our results.
requirements of low cost, ease of preparation, stability, and
sensitivity.
Semiconducting tellurides are widely used in various fields
due to their electrochemical,12 photoluminescence13 and
magnetic14 properties. Typical magnetic tellurides such as FeTe,15
CoTe16 and NiTe17 are regarded as environmentally friendly NMs
that could be further recycled and reused. Roy et al. reported that
FeTe nanorods were used as enzyme mimics to detect glucose9
and mercury18 in blood.
a Hefei Teacher’s College, Hefei, 230061, P. R. China
b Research Center for Biomimetic Functional Materials and Sensing Devices,
Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, 230031,
P. R. China. E-mail: xingjiuhuang@iim.ac.cn; Fax: +86 551 5592420;
Tel: +86 551 5591142
† Electronic supplementary information (ESI) available: Experimental details,
chemical reaction of NiTe NWs, the SEM image of the commercial NiTe powder,
pH–temperature response curves, time-dependent UV absorption spectra, and the
Michaelis–Menten constant. See DOI: 10.1039/c4cc06684g
Fig. 1 Characterization of the as-synthesized NiTe TNWs. (a, b) SEM and
TEM images, (c, d) XRD and EDS spectra, respectively.
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Fig. 2 Magnetic hysteresis curves measured at room temperature for
NiTe TNWs. The right inset shows local enlarged hysteresis loop with an
applied field between ꢀ3k and 3k Oe. The left inset is a photograph.
The saturation magnetization (Ms), remanent magnetization
(Mr), and coercivity (Hc) values of NiTe TNWs measured at room
temperature are 2.5, 0.61 emu gꢀ1, and 140 Oe, respectively
(Fig. 2). So, it is believed that the as-prepared NiTe with relatively
high coercivity could be utilized as recycle and reuse material.
To our knowledge, the hysteresis loops of NiTe were not reported
in the previous literature yet. NiTe NWs were formed through a
coreduction reaction in alkaline solution (ESI†).
We determined the peroxidase-like activity of NiTe TNWs
that catalyze the reaction of H2O2 with substrate ABTS (eqn (1)).
The reaction mechanism follows the oxidation reaction of ABTS
to the radical-cation ABTS+ in the presence of H2O2. Bi et al.
explained the reaction process by using magnetic graphene
oxide-supported hemin as a peroxidase probe to detect sensi-
tively thiols in the extracts of cancer cells.19 Because the amount
of the colored oxidized product of ABTS (lmax = 418 nm) pro-
duced is proportional to the concentration of H2O2 present in
the solution, the concentration of H2O2 can be determined by
recording the absorbance at 418 nm of the solution according to
Beer’s law.9
Fig. 3 (a) Absorption spectra of solution containing (1) NiTe TNWs + ABTS +
H2O2, (2) commercial NiTe + ABTS + H2O2, (3) ABTS, (4) NiTe TNWs + ABTS
and (5) NiTe TNWs + H2O2. Inset: photograph. Concentrations: ABTS
(60 mM), H2O2 (100 mM), commercial NiTe (2.0 mg mlꢀ1), and NiTe TNWs
(2.0 mg mlꢀ1). Acetate buffer: (0.2 M, pH 4.0). (b) A dose–response curve
for H2O2 detection when using NiTe TNWs. Inset: linearity of absorbance
(Y) against H2O2 concentration (X) ranging over 0.1–0.5 mM.
leading to loss of its oxidation activity toward ABTS. Therein, an
insufficient amount of Ni2+ ions available in the solution also
accounts for low activity. In the presence of the NiTe TNWs, the
absorbance increased when the reaction temperatures were
increased from 20 to 60 1C. We plotted the differential absor-
bance (DA) values against reaction temperature in the range
NiTe TNWs
H O þ ABTS
Oxidized ABTS þ 2H O
(1)
ƒƒƒƒƒ!
2
2
2
The as-prepared NiTe TNWs provided about a 24-fold absor- 20–60 1C (Fig. S3, ESI†), in which DA = A418 nm (NiTe TNWs) ꢀ
bance value at 418 nm compared to that in the absence of the A418 nm (Blank); the maximum value of DA for the NiTe TNWs
NiTe TNWs (Fig. 3a). Under these conditions, the catalytic occurred at 30 1C.
activity of NiTe TNWs is 3 times higher than that of the
According to the proportional relationship between the
commercial NiTe powder. The morphology and size of com- catalytic activity and amount of released Ni2+, it is speculated
mercial NiTe samples are given in Fig. S1 (ESI†). In order to that the released Ni2+ from NiTe TNWs reached a maximum
exclude other possibilities, absorption spectra of solution con- value at 30 1C. The peroxidase-like activities of NiTe TNWs in
taining NiTe TNWs in the presence of ABTS or H2O2 are also acetonitrile and isopropanol organic solvents were studied. The
shown in Fig. 3a.
maximal absorbance appeared blue shifted at B396 nm in
The catalytic activity is related to the solution pH, reaction acetonitrile solvent (Fig. S4a, ESI†) compared with 418 nm in
temperature, and the kind of solvent.11,20 Fig. S2 (ESI†) shows acetate buffer solution. The time-dependent UV absorption
the response curves in acetate buffer solutions (0.2 M) con- spectra indicated that the catalytic oxidation of ABTS by NiTe
taining 100 mM H2O2 over a pH range of 3.0–8.0 at 30 1C. TNWs followed the Michaelis–Menten behavior (Fig. S4b, ESI†).
Decomposition of H2O2 occurs rapidly at a pH higher than 5.0, Additionally, there was no absorbance peak in isopropanol solvent.
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of 0.42 mM is found. Control experiments were carried out to test
the specificity of the developed system by using 5 mM fructose,
lactose, maltose, dopamine and ascorbic acid, all instead of
glucose (Fig. 4b).
GOx
O þ Glucose
H O þ Gluconic acid
(2)
ƒƒ!
2
2
2
In contrast to electrochemical biosensors and colorimetric
sensors constructed using the PtPd–Fe3O4 dumbbell,21,22 the
NiTe TNW system shows comparable sensitivity, selectivity and
acceptable recyclability (Fig. S6, ESI†).
In summary, the magnetic NiTe TNWs with novel nano-
structure were directly synthesized for the first time through
the hydrothermal method. The as-prepared NiTe TNWs have a
higher catalytic activity toward H2O2-mediated ABTS reaction
than that of commercial NiTe powder. The catalytic activity of
NiTe TNWs is related to pH, temperature and the kind of solvent.
Under the optimized conditions (pH 4.0, 30 1C) using GOx and the
NiTe TNW system, the assay provided relatively high sensitivity
and selectivity for the detection of glucose.
This study was supported by the Science Foundation of the
Education Committee of Anhui Province (KJ2014A204).
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