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Cobalt titanatetitania composite oxide lms have been grown on FTO-coated glass substrates using a
single-source heterometallic complex [Co2Ti4(-O)6(TFA)8(THF)6]THF (1) which was obtained in quanti-
tative yield from the reaction of diacetatocobalt(II) tetrahydrate, tetraisopropoxytitanium(IV), and triuoroa-
cetic acid from a tetrahydrofuran solution. Physicochemical investigations of complex 1 have been carried
out by melting point, FT-IR, thermogravimetric and single-crystal X-ray diraction analyses. CoTiO3TiO2
lms composed of spherical objects of various sizes have been grown from 1 by aerosol-assisted chemi-
cal vapor deposition at dierent temperatures of 500, 550 and 600 C. Thin lms characterized by XRD,
Raman and X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray
Received 15th March 2016, analysis have been explored for electrochemical detection of dopamine (DA). The cyclic voltammetry
Accepted 15th May 2016
with the CoTiO3TiO2 electrode showed a DA oxidation peak at +0.215 V while linear sweep voltammetry
DOI: 10.1039/c6dt01016d displayed a detection limit (LoD) of 0.083 M and a linear concentration range of 20300 M for DA.
www.rsc.org/dalton Thus, the CoTiO3TiO2 electrode is a potential candidate for the sensitive and selective detection of DA.
the elements.14,15 The reaction pathway involves adsorption of Some well-characterized heterobimetallic SSPs [Sr(H2O)]7[Ti
the precursor without breaking the MO bond but with loss of (O2)(edta)]H2O,26 [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]2H2O27
the ancillary ligands, aording a thin film of the desired and [ZnMn2(Hcit)2]8H2O28 (where edta = ethylenediamine-
material.15 The advantages of the SSP approach are fourfold. tetraacetic acid; NC6H6O6 = nitrilotriacetato and Hcit = citric
Firstly, the elemental stoichiometry of the precursor can be acid) have been reported for the target synthesis of single
Published on 16 May 2016. Downloaded by King Fahd University of Petroleum and Minerals on 29/05/2016 06:04:40.
retained in the film.15 Secondly, the high deposition tempera- phase CaTiO3, SrTiO3 and ZnMn2O4 powders, respectively,
tures often associated with multi-source depositions are gene- however these molecular precursors were not utilized in
rally lowered.15 Thirdly, the precursor delivery system can be AACVD for thin film deposition. The choice of preparation of
simplified15 and finally a better homogeneity is possible since single phase or multi-phase oxides via a heterobimetallic SSP
the desired elements are eectively premixed at the molecular mainly depends upon the design and synthesis of the hetero-
level.15 Consequently, SSPs can provide a simple and clean metallic precursor with a certain metallic stoichiometry. The
route to films, eliminating the need for a mixture of precursors elemental composition of the resultant SSP compound can be
which can often be toxic and/or expensive, as well as involving tuned by changing the molar ratios of the reactant spices so
complicated gas-phase reaction dynamics which can result in that they can produce single phase or multiphase oxide
the formation of non-stoichiometric films.15 The consumption materials. For example, a 1 : 1 (Co : Ti) complex [Co(H2O)5]2[Ti
of these SSPs in an aerosol assisted chemical vapor deposition (O2)2O(nta)2]7H2O24 obtained by reacting CoCl26H2O with Ti
(AACVD) has become a well-established route for the design (OC4H9)4 in 1 : 1 stoichiometry produces single phase CoTiO3,
and synthesis of advanced material films. AACVD is a solution- while a 1 : 2 (Co : Ti) compound (NH4)2[Co(H2O)6][Ti
based process, which relies on the solubility of the pre- (H2cit)3]26H2O25 prepared by the interaction of CoCl26H2O
cursor.16,17 The process is scalable, allows for the formation of with Ti(OC4H9)4 in a 1 : 2 molar ratio generates a biphasic
multicomponent materials and the simplification of the pre- CoTiO3TiO2 composite on pyrolysis. Similarly, two com-
cursor delivery stage potentially reduces the cost of the depo- pounds with dierent Cd/Ti ratios, [Cd4Ti4(dmae)4(T-
sition process.18 Recently, we reported several well-defined FA)8(OAc)4O6]29 and [Cd2Ti4(-O)6(TFA)8(THF)6]1.5THF19 were
heterobimetallic compounds including [Cd2Ti4(-O)6(T- designed by dierent synthetic methods to generate single
FA)8(THF)6]1.5THF,19 [Zn2Ti4(-O)6(TFA)8(THF)6]THF,20 phase CdTiO3 and multi-phase CdTiO3TiO2 composites
[Cu4Zr2(4-O)2(dmae)4(OAc)8]2H2O21 and [Cu4Zr6(-O)8(dma- respectively.
p)4(OAc)12]H2O22 for the synthesis of composite oxide thin The protraction of a previous synthetic strategy23 enables us
films of CdTiO3TiO2, ZnTiO3TiO2, CuZrO3CuO and CuO to develop a new heterobimetallic assembly [Co2Ti4(-O)6(T-
1.5ZrO2, respectively, via the AACVD method and their possible FA)8(THF)6]THF (1) by reacting cobalt(II) acetate with titanium(IV)
technological applications were explored. For example, the isopropoxide in a 1 : 2 stoichiometry in the presence of trifluoro-
scope of a CdTiO3TiO2 composite thin film having a band acetic acid in THF. The resultant complex exhibits dierent
gap of 3.1 eV was investigated as a photoanode for dye-sensi- physicochemical properties from the previously reported [Co2Ti
tized solar cell applications.19 The ZnTiO3TiO2 films grown (3-O)(TFA)6(THF)3]23 complex and hence the single molecular
into a variety of spherical designs at 550 C using three potential of this complex generates a 1 : 1 CoTiO3 : TiO2 compo-
dierent solvents such as methanol, tetrahydrofuran and site oxide material. Thin films from complex 1 were grown on a
acetonitrile were tested for their electrochemical sensing capa- fluorinated tin oxide (FTO) conducting glass substrate in the
bility towards nitrite ions.20 Further, CuO1.5ZrO2 composite temperature range of 500600 C under an air atmosphere. The
films developed at 550 C from methanol and ethanol solvents deposited films were examined by XRD, SEM, EDX and XPS for
were found promising for the electrocatalytic oxidation of their phase, structural, textural and compositional recognition
methanol that indicated their potential for direct methanol and further the films were tested for their suitability for electro-
fuel cell application.22 In contrast to our previous work, we chemical determination of dopamine (DA).
expanded our studies towards biological applications and Dopamine (DA) is a well-known neurotransmitter which
hence prepared 1 : 1 CoTiO3 : TiO2 composite thin films by belongs to the catecholamine family of neurotransmitters. DA
thermolysis of an appropriate CoTi heterometallic assembly is one of the most abundant neurotransmitters in the body
on the substrate surface and the resultant films were explored fluids and plays a crucial role in controlling many physiologi-
for dopamine sensing. cal processes such as learning, memory and motivated beha-
The previously known heterobimetallic oxo complexes of viors. DA deficiency in the body can cause severe neurological
CoTi metals are not significantly large in numbers and disorders and diseases such as Parkinsons disease and
include [Co2Ti(3-O)(TFA)6(THF)3]23 and [Co(H2O)5]2[Ti(O2)2O Schizophrenia. Furthermore, the use of drugs also directly
(nta)2]7H2O.24 Earlier, we utilized the former compound as an aects the physiological pathways of DA release and trans-
SSP for deposition of CoTiO3CoO composite oxide thin films; mission in the human body.30,31 Thus, being such an impor-
however the thermolysis of the latter yielded CoTiO3 at 700 C. tant neurotransmitter with a wide range of implications,
Hexaaquacobalt titanium citrate (NH4)2[Co(H2O)6][Ti attempts for precise electrochemical determination of DA has
(H2cit)3]26H2O has been recognized as a class of molecular attracted much attention in recent research. One approach for
precursor compound for the single step synthesis of CoTiO3 the advancement of a DA sensor is to synthesize new materials
TiO2 nanocomposite powder at 600 C.25 which can catalyze DA oxidation.
using a Schlenk tube fitted with vacuum line and hot plate
arrangements. Tetrahydrofuran was rigorously dried over 2.4. Deposition of thin films by AACVD
sodium benzophenoate and distilled immediately before use. An in-house designed AACVD set up was used for the growth
The melting point was determined in a capillary tube using an of the CoTiO3TiO2 oxide composite on commercially available
electrothermal melting point apparatus; model MP.D Mita- FTO conducting glass substrates. The substrates were cleaned
mura Riken Kogyo (Japan). The Fourier transform infra-red with a detergent, distilled water, acetone and ethyl alcohol, to
(FT-IR) spectrum was recorded on a single reflectance ATR remove surface grease, then placed inside the reactor tube and
instrument (4000400 cm1, resolution 4 cm1). The con- furnace (Carbolite, model no. 10/25/130) (6L 1D) and heated
trolled thermal analysis was investigated using a Perkin Elmer up to the desired deposition temperature for 10 minutes. Thin
TGA 4000 thermogravimetric analyzer with a computer inter- film deposition experiments were performed at three dierent
face. The thermal measurements were carried out using a temperatures of 500, 550 and 600 C, respectively, from 20 mL
ceramic crucible under an atmosphere of flowing nitrogen of 0.1 M solutions of precursor 1 in ethanol. In a typical depo-
(50 mL min1) with a heating rate of 10 C min1. sition experiment, a precursor solution was taken in a 50 mL
round bottom flask which was immersed in a water bath above
2.2. Synthesis of [Co2Ti4(-O)6(TFA)8(THF)6]THF (1) the piezoelectric modulator of an ultrasonic humidifier (model
Complex 1 was prepared by mixing stoichiometric amounts of no. Cool Mist-plus serial no. ADV-CMP-85956). Air at a flow rate
0.50 g (2.0 mmol) of Co(CH3COO)2(H2O)4 and 1.19 mL of 100 mL min1 was used as the carrier gas and the flow rate
(4.0 mmol) of Ti(OCH(CH3)2)4 followed by the addition of was controlled by using an L1X linear flow meter. The generated
1.21 mL (16.0 mmol) of CF3COOH in 25 mL of THF in a 50 mL aerosol droplets were then transferred into the hot wall zone of
Schlenk tube. The reaction mixture was stirred for 4 h and the the reactor by using the carrier gas. Both the solvent and pre-
solvent was evacuated under vacuum to obtain a red powder cursor were evaporated and the precursor vapour reached the
which was re-dissolved in THF. The resulting transparent solution heated substrate surface where thermally induced reactions and
was cannula-filtered and placed at room temperature for 2 days to subsequent film deposition took place.
obtain the red block shape crystals of complex 1 in 75% yield.
Mp: 195 C (decomposition). IR: max/cm1 2989w, 2904w, 2.5. Thin film analysis
1717s, 1681s, 1469s, 1388w, 1329w, 1198s, 1148s, 1025w, X-ray diraction (XRD) measurements were obtained using a
1038w, 899w, 792s, 722s, 681w, 654w, 618s, 585w, 493s, 474s. PANanalytical, XPert HighScore diractometer with primary
TGA: 5095 C (1.53 wt% loss); 100180 C (7.2 wt% loss); monochromatic high intensity CuK ( = 1.5418 ) radiation
181225 C (23.6 wt% loss), 250500 C (40.17 wt% loss) over Bragg angles ranging from 10 to 90 in a step size of
(residual mass of 27.50%); (Cal. for CoTiO3TiO2 25.80%). 0.026 while the operating voltage and current were main-
tained at 30 kV and 40 mA respectively. Raman spectroscopic
2.3. Single-crystal X-ray crystallography measurements were carried out on a Renishaw InVia Raman
Diraction data for the crystal were collected on an Agilent microscope and excitation was performed using the 514 nm
SuperNova Dual diractometer with an Atlas detector (graph- line of an argon laser with a 0.01 mW output power. Scanning
ite-monochromatized Mo-K radiation, = 0.71073 ) at 100(2) K. electron microscopy (Hitachi FESEM SU 8000) equipped with
The data were processed using CrysAlisPro, Agilent Techno- an energy dispersive X-ray spectrometer EDX (INCA Energy
logies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171. 200, Oxford Inst.) was used to determine the film morphology
NET) and empirical absorption correction using spherical har- and elemental stoichiometry. X-ray photoelectron spectroscopy
monics implemented in the SCALE3 ABSPACK scaling algor- (XPS) analysis of the films was carried out using an ULVAC-PHI
ithm. The structure was solved using the program SHELXT and Quantera II with a 32-channel spherical capacitor energy analy-
was refined by the full matrix least-squares method on F2 with zer under vacuum (1 106 Pa) using monochromated Al K
SHELXL-2014/7.32 All the non-hydrogen atoms were refined radiation (1486.8 eV) and a natural energy width of 680 meV.
anisotropically. All the hydrogen atoms were placed at calcu- The carbonaceous C 1s line (284.6 eV) was used as a reference
lated positions and were treated as riding on their parent to calibrate the binding energies.
atoms. The structure exhibits a whole molecule disorder with
the two components being connected by a pseudo-inversion 2.6. Electrochemical studies for dopamine sensing
center. The occupancy of the main component was refined to All the electrochemical experiments were performed in a
0.640(2). The structure was also refined as a racemic twin with single compartment three-electrode cell at room temperature
the twin parameter of 0.46(4). Drawing of the molecule was using a PAR-VersaSTAT-3 electrochemical workstation. The
produced with Mercury.33 Crystal data: C44H56Co2F24O29Ti4, Mr CoTiO3TiO2 composite film and a platinum wire were used as
= 1814.34, pink block, 0.49 0.28 0.26 mm3, orthorhombic, working and counter electrodes, respectively. A silver/silver
Table 1 Coordination bond lengths for [Co2Ti4(-O)6(TFA)8(THF)6]THF (1) ments were carried out on a FTO glass substrate at three
dierent temperatures of 500, 550 and 600 C using the etha-
Co(1)O(1) 2.175(6) Ti(2)O(13) 2.080(12)
Co(1)O(7) 2.111(7) Ti(2)O(15) 2.108(10)
nolic solution of complex 1 in ambient air.
Co(1)O(8) 2.039(8) Ti(2)O(17) 2.168(9) The structural characterization of the crystalline deposit
Co(1)O(10) 2.064(7) Ti(3)O(2) 1.860(8) was made by XRD analysis and the resultant patterns as a
Published on 16 May 2016. Downloaded by King Fahd University of Petroleum and Minerals on 29/05/2016 06:04:40.
Fig. 3 TG (red) and DTG (dotted black) traces of the thermal decompo-
sition of complex 1 as a function of temperature.
that the films grown at dierent temperatures 500, 550 and 2p3/2 and Ti 2p1/2 respectively which correspond to Ti4+ and
600 C retain the same metallic ratio as found in complex 1. match well with the published data for TiO2.36,37 Fig. 7(c) rep-
Further the heterogeneity and distribution of cobalt, tita- resents O 1s spectra where a primary peak at 530 eV can be
nium and oxygen atoms in CoTiO3TiO2 composite films was further divided into subpeaks centered at 529.7 and 530.2 eV
examined by EDX mapping and the results are shown in ESI attributing to TiO and CoO in CoTiO3, respectively.36,37 Two
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Fig. 2(ac), which reveal that these atoms are evenly distribu- peaks at 531.4 and 532.6 eV are assigned to the adsorbed
ted throughout the film matrix confirming the composite oxygen and hydroxyl oxygen, respectively.
nature of all films prepared at dierent temperatures. The high resolution Co 2p spectrum is shown in Fig. 7(d).
All CoTiO3TiO2 films were translucent and light green in Two main peaks at binding energies of 781.5 and 797.3 eV
colour. The films deposited at lower temperatures of 500 and correspond to Co 2p3/2 and Co 2p1/2. The dierence ()
550 C were robust and adhered strongly on the FTO substrate between Co 2p1/2 and Co 2p3/2 orbitals is nearly 16 eV, which
as verified by the Scotch tape test while the film prepared at implies the fundamental oxidation state of high-spin Co2+, and
600 C showed poor adhesive properties and was failed to is very similar to those reported earlier for CoTiO3.10,13 More-
qualify the adherence test. over, the splitting of the Co 2p1/2Co 2p3/2 orbital com-
ponents is usually 15 eV for the low-spin Co3+. Toward the
3.7. XPS analysis left of each main peak is a satellite peak known as a shake-up
The CoTiO3TiO2 composite film prepared at 550 C was line which occurs when Co(II) resides in a high spin state.
further examined by X-ray photoelectron spectroscopy (XPS) Thus, the XPS results strongly suggest the formation of phase
and the results are presented in Fig. 7. The XPS survey scan pure CoTiO3TiO2 composite oxide films.
spectrum in Fig. 7(a) indicates that cobalt, titanium, and
oxygen are the major components at the surface of the film. 3.8. Electrochemical detection of dopamine (DA) by using a
After identification of the elements, their chemical and CoTiO3TiO2 film electrode
valence states were analyzed by narrow scans and the results 3.8.1. CV behavior of DA. The CoTiO3TiO2 composite film
are shown in Fig. 7(bd). deposited at 550 C was used for the electrocatalysis and
In the high resolution Ti 2p spectrum, Fig. 7(b), the sensing of dopamine (DA) in 0.1 M phosphate buer solution
binding energies of 458.7 and 464.4 eV are indicative of Ti (PBS) ( pH 7.0). Fig. 8(a) represents cyclic voltammograms
Fig. 7 (a) XPS spectra of CoTiO3TiO2 composite thin lms prepared at 550 C from ethanol solutions of precursor 1; high resolution spectra
CoTiO3TiO2 for (b) Ti 2p (c) O 1s and (d) Co 2p.
(CVs) both in the absence and presence of DA in a phosphate relationship between the peak currents (Ip) and the square root
buer solution, also containing 10 mM of ascorbic acid (AA), a of the scan rate was observed for both oxidation and reduction
common interfering species for DA. processes as shown in the inset of Fig. 9. It is evident that the
The potential was scanned between 0.2 and +0.6 V. It is anodic peak currents (Ipa) for the 10 M DA varied linearly
evident from Fig. 8(a) that no redox peaks were observed in the with the square root of the scan rate (1/2), with a linear
absence of DA, which also infers that AA was not electrochemi- regression equation, for anodic peak current Ipa (A) =
cally active in this potential window. Fig. 8(b) represents that 0.05631/2 + 11.40 and a correlation coecient R2 = 0.985. This
the CoTiO3TiO2 composite electrode displayed an intense and behavior suggests that the electrode kinetics is mainly a
sharp anodic peak current at +0.215 V due to the electro- diusion controlled electrochemical reaction.
catalytic oxidation of dopamine when 15 M of DA was present 3.8.3. Eect of pH. pH plays a crucial role in the redox be-
in the buer solution. The corresponding reduction peak haviour of DA at the CoTiO3TiO2 film electrode surface. In
appeared at +0.075 V but with much less current density repre- fact, in CV experiments, the redox couple of DA shifted
senting the quasi-reversible redox behavior of DA. The sharp towards the negative direction upon increasing the pH from
peak for DA oxidation at +0.215 V was also indicative of fast 59, ESI Fig. 3. This infers that the electrocatalytic behaviour
electrode kinetics for the DA oxidation.40,41 To observe the con- of DA is pH dependent. For practicality purposes, pH 7 was
tribution from FTO towards DA oxidation, CVs in the presence chosen for further analysis of DA with the CoTiO3TiO2 com-
and absence of DA were recorded with a bare FTO electrode as posite electrode.
shown in Fig. 8c. The voltammograms indicate that in the 3.8.4. Analytical utilization. A series of linear scan voltam-
absence of DA no redox peaks were observed and the back- metry (LSV) curves were recorded in 0.1 M PBS ( pH = 7.0) with
ground current was higher than the CoTiO3TiO2 composite dierent DA concentrations of the CoTiO3TiO2 composite as
electrode. In the presence of 50 M of DA and AA, only a slight shown in Fig. 10a. It could be observed that the anodic peak
increase in current was observed with a broad oxidation peak current increased linearly with an increase in the concen-
starting from approximately 0.22 V and extending up to tration of DA in the range of 20 to 300 M, with R2 = 0.993
0.6 V. These results clearly indicate that the CoTiO3TiO2 com- (Fig. 10b). The sensitivity is determined from the slope of the
posite electrode is capable of oxidizing DA catalytically with a calibration plot. Fig. 10b shows the standard addition line
sharp oxidation peak within the tested potential window. with a linear regression equation. The detection limit found
3.8.2. Eect of the scan rate on CV studies. Further, the was 0.083 M (S/N = 6) by LSV. The sensitivity found from the
influence of the potential scan rate on the electrocatalytic slope was 0.325 A M1 cm2.
activity of DA at the CoTiO3TiO2 film electrode surface was 3.8.5. Selectivity and stability studies. The selectivity of the
studied in PBS ( pH = 7.0) using CV, as shown in Fig. 9. The CoTiO3TiO2 electrode towards DA oxidation was also investi-
increase in the scan rate from 25 to 200 mV s1 led to the gated by LSV. Common interfering species such as AA, uric
increase in both DA oxidation and reduction peaks with a acid (UA), glucose, sulphate, nitrate and chloride were chosen
slight shift in the peak potential. The shift in the peak poten- and their eect on the DA oxidation signal was evaluated as
tial was due to the quasi-reversible redox process.42 The linear represented in Fig. 11. It is evident that even when a 100-fold
Fig. 10 (a) LSV curves obtained with the CoTiO3TiO2 composite electrode for various concentrations of DA 0.1 M PBS ( pH 7) at a scan rate of
50 mV s1. (b) Correlation between the concentration of DA and peak current for the CoTiO3TiO2 electrode.
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