Full Paper

1 DOI: 10.1002/elan.201800032
2
3
4
Development of an Aluminium Doped TiO2
5
6
Nanoparticles-Modified Screen Printed Carbon Electrode
7
8
for Electrochemical Sensing of Vanillin in Food Samples
9
10 Khaled Murtada,[a, b] Shehdeh Jodeh,[c] Mohammed Zougagh,[b, d] and Ángel Rı́os*[a, b]
11
12
13 Abstract: A new chemically modified electrode based on voltammetry (LSV) were used to optimize the analytical
14 titanium dioxide nanoparticles (TiO2-NPs) has been procedure. A detection limit of vanillin was 0.02 mM, and
15 developed. Aluminium was incorporated into the TiO2- the relative standard deviation (RSD) was 3.50 %,
16 NPs to prepare aluminium doped TiO2 nanoparticles (Al- obtained for a 5.0 mM concentration of vanillin. The
17 TiO2-NPs). Aluminium doped TiO2 nanoparticles-modi- electrochemical behaviour of several compounds, such as
18 fied screen printed carbon electrode (Al-TiO2-NPs/SPCE) vanillic acid, vanillic alcohol, p-hydroxybenzaldehyde and
19 was employed as easy, efficient and rapid sensor for p-hydroxybenzoic, etc., generally present in natural vanilla
20 electrochemical detection of vanillin in various types of samples, were also studied to check the interferences with
21 food samples. Al-TiO2-NPs were characterized by energy- respect to vanillin voltammetric signal. The applicability
22 dispersive X-ray (EDX), transmission electron microscopy was demonstrated by analysing food samples. The ob-
23 (TEM), and X-ray diffraction (XRD) and analyses tained results were compared with those provided by a
24 showing that the average particle sizes varied for the Al- previous method based on liquid chromatography for
25 NPs (7.63 nm) and Al-TiO2-NPs (7.47 nm) with spherical determination of vanillin.
26 crystal. Cyclic voltammetry (CV) and linear sweep
27 Keywords: Aluminium doped TiO2 nanoparticles · screen-printed carbon electrode · electrochemical detection · vanillin · food samples
28
29
30
1 Introduction
31 cules in various sectors, such as biomedical environmental
32 Vanillin (4-hydroxy-3-methoxybenzaldehyde, C8H8O3) is and agri-food [14, 15]. SPCE is planar shape, thus can be
33 one of the world’s flavour extracts obtained primarily used as droplet on sensor, using typically few microliters
34 from Vanilla, a specie of tropical climbing. Although the (mL) of the sample in miniaturized system. Moreover, it is
35 production of vanillin every year more than 12,000 tons, low-cost and can be used as a disposable sensor with
36 the natural vanillin from Vanilla is less than 1 %; the possibility used in large-scale implementation. The oxida-
37 remainder is synthesized cheaper using biochemical and/ tion of vanillin at SPCE and others most unmodified
38 or chemical processes [1]. For the time being, several electrode surfaces represents a serious problem which
39 analytical methods have been used for determination and arises from the poor reproducibility with high over-
40 detection of vanillin in various types of food samples or potential resulted from a fouling effect, which results in
41 vanilla extracts, including fluorescence [2], capillary elec- rather poor sensitivity and selectivity [16, 17]. To avoid
42 trophoresis (CE) [3], liquid chromatography [4], and GC- these problems, the modification of electrochemical work-
43 MS [5]. These have high cost and involve time-consuming ing electrode is an excellent alternative. In this sense,
44 sample pre-treatment processes. Because vanillin is an
45 electro-active compound and it is possible to measure the
[a] K. Murtada, . Ros
46 quantity of vanillin in vanilla and in the final products by
Department of Analytical Chemistry and Food Technology,
47 electrochemical detection (ECD) through the study of its University of Castilla-La Mancha, Ciudad Real 13071, Spain
48 oxidation. ECD is important method for quantitative E-mail: angel.rios@uclm.es
49 determination of vanillin due to its simplicity, fast [b] K. Murtada, M. Zougagh, . Ros
50 response, high sensitivity, and cheap instrumentation [6– Regional Institute for Applied Chemistry Research (IRICA),
51 11]. Various electrochemical methods, such as amperom- Ciudad Real 13071, Spain
52 etry, square-wave voltammetry (SWV) or differential [c] S. Jodeh
Department of Chemistry, An-Najah National University, P. O.
53 pulse voltammetry (DPV) for the detection and determi-
Box 7, Nablus, Palestine
54 nation of vanillin in various types of food samples have [d] M. Zougagh
55 been reported and discussed in literature [12, 13]. Castilla-La Mancha Science and Technology Park, Albacete
56 In recent years, many reports on screen-printed carbon 02001, Spain
57 electrodes (SPCEs) technology have been used to develop Supporting information for this article is available on the
58 various electrochemical sensors that detect target mole- WWW under https://doi.org/10.1002/elan.201800032

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 1
These are not the final page numbers! ÞÞ
 Full Paper
1 many researchers have attempted to diminish the over- Real, Spain). These extracts were filtered through a
2 potentials by using various modified electrodes such as, sintered filter, and diluted directly in phosphate solution.
3 graphene [6, 18], silver nanoparticles (Ag-NPs) [8], gold
4 nanoparticles (Au-NPs) [9, 10], and multi-walled carbon
2.2 Apparatus, Instruments and Chromatographic
5 nanotubes (MWCNTs) [19]. However, the performance of
Conditions
6 some electrodes was still ineffective enough. Thus it is
7 necessary to develop new types of electrode devices by Electrochemical detection was carried out on a CH
8 the preparation synthesis and preparation of new materi- Instruments Model 800D Series (Austin, Texas, USA) all
9 als (modifiers). That regard, as modifiers for electrode the experiments were carried out using a screen-printed
10 surface, titanium dioxide nanoparticles (TiO2-NPs) had carbon electrodes (SPCEs) system (Dropsens
11 highly interest of many researchers and a many amount of DRP C110) housed in the home made electrochemical
12 research was applied in the previous decades [12, 13, 19]. flow cell. Transmission electron microscopy (TEM) micro-
13 The increase in the TiO2-NPs efficiency such as to ensnare graphs were measured on a Jeol JEM 2011 operating at
14 the charge carrier is accomplished by doping with 200 kV and equipped with an Orius Digital Camera (2 3
15 transition metals and transition metal oxides such as, 2 MPi). The digital analysis of the HRTEM micrographs
16 copper (Cu) [20], cadmium oxide nanoparticles (CdO- was done using Digital Micrograph TM 1.80.70 for GMS
17 NPs) [21], silver nanoparticles (Ag-NPs) [22], gold nano- 1.8.0 Gatan. The samples were prepared onto a lacey
18 particles (Au-NPs) [23] and ruthenium (Ru) [24]. carbon/format-coated copper grid by deposition of a drop
19 Here, the synthesis of aluminium doped TiO2 nano- of the synthesized material suspension. XRD patterns
20 particles (Al-TiO2-NPs) is carried out, which were charac- were measured on Philips model X’Pert MPD diffractom-
21 terized by TEM and XRD. The sensitivity of the eter using a CuKa source (l = 1.5418 Å), programmable
22 developed electrode is compared with SPCE, TiO2-NPs/ divergence slit, graphite mono-chromator and propor-
23 SPCE, and Al-TiO2-NPs/SPCE for vanillin detection. The tional sealed xenon gas detector. The samples were made
24 results show that a composite film of Al-TiO2-NPs/SPCE with a voltage of 40 KV, intensity 40 mA and an angular
25 is more sensitive compared to SPCE and TiO2-NPs/SPCE. range of 20 to 70 degrees (2q), a step of 0.02 degrees 2q
26 Furthermore, the electrochemical behaviour of vanillin at and a time per step of 1.50 sec.
27 modified SPCE with Al-TiO2 (Al-TiO2-NPs/SPCE) was Agilent 1200 liquid chromatography system was used
28 investigated. The performance of the modified electrode as a chromatographic system. It was consisted from a LC
29 (Al-TiO2-NPs/SPCE) is also demonstrated for the deter- pump, a vacuum degasser, a micro well-plate autosampler
30 mination and detection of vanillin in various types of food (5 mL injection loop), a thermostatted column compart-
31 samples obtaining good selectivity, stability and high ment and a Diode-Array Detector (DAD). The data was
32 sensitivity. processed using the PC computer with ChemStation
33 Software. An appropriate reversed-phase C18 analytical
34 column Luna 5 mm PFP (2) 100 A (150 3 4.6 mm) was
35 2 Experimental used for the separation of the analytes present in vanillin
36 extract samples. Elution was done quite under isocratic
2.1 Reagents, Standards and Samples
37 conditions, by using a mixture of acetonitrile/phosphate
38 All the starting materials were purchased with very (20 : 80 v/v) as a mobile phase, 40 mL the injection volume
39 highly purity. Aluminium acetylacetonate (Al(acac)3, was injected and flow-rate was set at 1.0 mL min 1. The
40 99 %), lithium aluminium hydride (LiAlH4, 95 %), mesi- detection wavelength was at 265 nm.
41 tylene (97 %), titanium (IV) oxide (anatase, powder,
42 235 mesh), 4-hydroxybenzaldehyde (98 %) and 4-
2.3 Preparation of Aluminium Doped TiO2 Nanoparticles
43 hydroxy-3-methoxybenzyl alcohol (98 %) were pur-
(Al-TiO2-NPs)
44 chased from Sigma-Aldrich (St. Louis, MO, USA).
45 Nafion 117 solution (5 % in a mixture of lower aliphatic At first, Al-NPs were prepared according the previously
46 alcohols and water), vanillin, vanillic acid, 4-hydroxyben- described procedures [25], with inserting some changes.
47 zoic acid were purchased from Fluka Chemie (Buchs, The aluminium acetylacetonate (Al(acac)3, 10 mmol) was
48 UK). Ethanol and phosphoric acid were purchased from added to a three-neck round bottom which was already
49 Panreac Quimica S.L.U. (Barcelona, Spain). Vanillin contained mesitylene solution with magnetic bar. Then
50 solution was prepared in ethanol and stored while tightly lithium aluminium hydride (LiAlH4, 30 mmol) was added
51 covered in the dark until use. Vanillin stock solutions to the mixture. The reaction was purged with N2 gas
52 were frequently diluted to working standard solutions during reflux with stirring for 72 hours at 165 8C. After
53 with phosphate buffer at pH 6.3. The pure water was cooling to 25 8C, a gray-colored precipitate was formed
54 obtained by a Milli-Q system (Millipore). Ethanol and which was crushed and kept to dry under low pressure for
55 phosphoric acid were obtained from Panreac Quimica 5 hours. Wash the isolated solid product well with 25 ml
56 S.L.U. (Barcelona, Spain). portions of cold methanol three times, to avoid any high
57 Vanillin extract samples (sample A and sample B) temperatures (exothermic reaction) between solvent and
58 were purchased from different local markets (Ciudad Al-NPs. The unreacted materials were washed three times

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 2
These are not the final page numbers! ÞÞ
 Full Paper
1 with methanol. The resulting product was filtered and
2 dried at 25 8C under low pressure. The preparation of Al-
3 TiO2-NPs started by mixing of TiO2 (0.5 g) previously
4 digested in nitric acid (0.1 M, 25 mL) during 3 hours and
5 Al-NPs (0.5 g) previously prepared. The final product was
6 filtered and dried at 25 8C under low pressure, obtaining
7 an Al-TiO2-NPs as light-gray powder.
8
9
2.4 Preparation of Modified Electrodes
10
11 Nanoparticles were ultrasonically dispersed in pure water
12 (with 0.5 % Nafion, v : v), The concentrations of 1 mg mL 1
13 were obtained individually. On the SPCE forming a layer
14 of thin films from nafion-solubilized nanoparticles are
15 more uniform distribution than those casted by organic
16 solvents [26]. TiO2-NPs and Al-TiO2-NPs were used.
Fig. 1. TEM and EDX micrographs of the two precursors: (a and
17 Dropsens SPCEs (DRP-110), with carbon as a working
c) Al-NPs and (b and d) Al-TiO2-NPs.
18 electrode with a disk-shaped of 4 mm of diameter, were
19 used to fabricate the electrode. So, 2 mL of the dispersed
20 NPs was casted onto the surface of the SPCE. After drying
21 the modified SPCE by using infrared light lamp for 15 min, Figure 2, shows XRD patterns measured for Al-NPs
22 rinsing with pure water. The electrode is ready for using. (Figure 2a) and Al-TiO2-NPs (Figure 2b). The XRD
23 patterns show that the nanoparticles involved aluminium
24 as a major component. The XRD patterns and all the
2.5 Electrochemical Measurements of Vanillin
25 positions of the peaks are attributed to face-centered
26 A 25 mL of H3PO4 electrolyte (0.1 M) with proper cubic (fcc) crystal structure of aluminium [25], and
27 concentration of vanillin was transferred to a cell, then anatase TiO2 [27], as shown in Figure 2. A closer look at
28 the SPCE was assembled on it. The potential range was the figure shows that the Al-TiO2-NPs involved alumi-
29 0.00–1.20 V, and the scan rate was 50 mV s 1. Before each nium as a major component mixed with TiO2-NPs as
30 measurement, the electrode was cycled between 0.00– minor components, as shown in Figure 2b [28]. Calcula-
31 1.20 V in a blank solution (H3PO4, 0.1 M) until no vanillin tions based on the Scherrer equation (D=Kl/bcosP) [29],
32 peak current was detected. After each run, the sensor was show that the average particle sizes varied for the Al-NPs
33 rinsed in methanol/acetic acid (9 : 1, v:v) and ultrapure (7.63 nm) and Al-TiO2-NPs (7.47 nm). The XRD results
34 water for 5 min to remove vanillin for reuse. confirm the TEM micrograph results discussed above.
35
36
3.2 Voltammetric Behaviour of Vanillin at the
37 3 Results and Discussion
Al-TiO2-NPs/SPCE
38
3.1 Characterization of Aluminium Doped TiO2
39 The modified screen printed carbon electrodes (SPCEs)
Nanoparticles (Al-TiO2-NPs)
40 by aluminium doped TiO2 nanoparticles (Al-TiO2-NPs/
41 Energy-dispersive X-ray (EDX) elemental mapping and SPCE) were first characterized by cyclic voltammetry
42 transmission electron microscopy (TEM) micrograph for (CV) to test their behaviour for the oxidation of vanillin,
43 the aluminium and aluminium doped titanium nano- as shown in Figure 3d. In order to find the role of Al-NPs,
44 particles (Al-TiO2-NPs) are shown in Figure 1. This figure the cyclic voltammograms of (b) SPCE, (c) TiO2-NPs/
45 shows that different materials have different surface SPCE, and (d) Al-TiO2-NPs/SPCE in the presence of
46 morphologies. Figure 1 (a and c), shows the TEM and 250 mM vanillin were recorded, as shown in Figure 3. The
47 EDX micrographs of the aluminium particles without electrochemical behaviours of the TiO2-NPs/SPCE and
48 doping (this image was obtained before aluminium was Al-TiO2-NPs/SPCE were studied by using the CV techni-
49 mixed with TiO2-NPs.), and a higher magnification is also que, as shown in Figure 3 (c and d). All cyclic voltammo-
50 presented. A large number of precipitates were distrib- grams reported here were obtained in the presence of
51 uted homogeneously in the aluminium grains. The distri- H3PO4 electrolyte (0.1 M and pH = 6.3) with 250 mM
52 bution of the precipitates for aluminium, which leads to vanillin and scan rate at 50 mV s 1. In contrast, the cyclic
53 increase in hardness and tensile properties. Figure 1 (b voltammograms observed for the TiO2-NPs/SPCE and Al-
54 and d), shows the TEM and EDX micrographs of the fully TiO2-NPs/SPCE modified electrode exhibited only an
55 mixed precursor. It shows two large particles in the lower oxidation peak in the presence of vanillin, within the
56 region, which are Al-NPs and TiO2-NPs, were distributed potential window between 0.00 and 1.20 V. The data
57 homogeneously, indicating that a large amount of Al-NPs suggest that the oxidation reaction on Al-TiO2-NPs/SPCE
58 has been doped in the TiO2-NPs. for vanillin is totally irreversible. The oxidation peak

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 3
These are not the final page numbers! ÞÞ
 Full Paper
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 Fig. 2. XRD patterns measured for different NPs: (a) Al-NPs and (b) Al-TiO2-NPs.
25
26
27 indicating that the Al-TiO2-NPs/SPCE can be used to
28 determine vanillin.
29
30
3.3 Optimization of Experimental Parameters
31
32 The electrochemical response of the modified Al-TiO2-
33 NPs/SPCE toward the determination of vanillin were
34 optimized by analyzing a standard solution (10 mM) of
35 vanillin using linear sweep voltammetry (LSV) technique.
36 The parameters affecting the determination of vanillin,
37 such as electrolyte, pH, Al-TiO2-NPs amount, scan rates,
38 adsorption time, accumulation conditions and stability of
39 the electrodes, were investigated. In order to find the
40 optimal parameters, one parameter was varied and the
41 other parameters were held fixed at their reference
42 values.
43 Fig. 3. Cyclic voltammograms of different electrodes: (a) blank, The influence of various supporting electrolytes were
44 (b) SPCE, (c) TiO2-NPs/SPCE, and (d) Al-TiO2-NPs/SPCE, at tested, such as NH4Ac, HCl, H3PO4, HNO3, H2SO4 and
250 mM vanillin solution in 0.1 M H3PO4.
45 NaOH. The results indicated that when H3PO4 solution
46 (0.1 M) was used, the oxidation peak current was a higher
47 sensitivity than other. For this study, 0.1 M H3PO4 solution
48 current at the SPCE electrode for vanillin (Figure 3b), we was chosen to act as supporting electrolyte. On the other
49 therefore have a rather low and broad peak current. The hand, the effect of 0.1 M H3PO4 supporting electrolyte pH
50 oxidation current of vanillin (0.58 V) on Al-TiO2-NPs/ on the electrochemical behaviour of the modified Al-
51 SPCE (Figure 3d) was better than that on the bare TiO2-NPs/SPCE for the vanillin determination was
52 SPCE. Compared with the SPCE, TiO2-NPs/SPCE and studied. The variations of the oxidation peak potential as
53 Al-TiO2-NPs/SPCE, a significant enhancement in the well as the peak current with respect to changes in the pH
54 anodic current (0.58 V) was achieved at the Al-TiO2- of the electrolyte in range (1.40–6.30), with an increase
55 NPs/SPCE (Figure 3d), indicating that the high con- the pH, manifesting that protons have taken part in the
56 ductivity and high surface area of the TiO2-NPs/SPCE electrode reaction processes. Figure S1 (Supporting In-
57 improve the catalytic activity and increase the effective formation) shows, the relation between the oxidation
58 electrode area toward the vanillin oxidation obviously peak potential and supporting electrolyte pH. The effect

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 4
These are not the final page numbers! ÞÞ
 Full Paper
1 of modification amount of Al-TiO2-NPs on the SPCE Table 2. Comparison of different electrochemical electrodes for
2 surface for the determination of vanillin was also studied vanillin determination.
3 by using LSV, different modification volumes were tested:
Electrode Electrochemical Detection Ref.
4 2.0, 4.0 and 6.0 mg. The 2.0 mg gave the best result of technique limit
5 oxidation peak current sensitivity than other counterparts. (mM)
6 The effect of scan rate on the oxidation peak current of
7 vanillin (10 mM) by using LSV was studied. Different scan SPCE SWV 0.40 [17]
GCE LSV and SWV 16 [16]
8 rates were tested 20, 30, 50 and 70 mV s 1. The 50 mV s 1
PVC/graphite Amperometric 290 [12]
9 scan rate gave the best result of oxidation peak current electrode
10 sensitivity than other counterparts. In this study, 50 mV s 1 Graphene/GCE DPV 0.056 [6]
11 scan rate was used. The accumulation step of 10 mM MIP-SWNTs-COOH/ DPV 0.2 [31]
12 vanillin after 120 second was performed under 0.0 V, at a GCE
13 fixed accumulation potential 0.0 V, the peak current Al-TiO2-NPs/SPCE LSV 0.02 This
14 increased progressively with accumulation time up to 120. work
15 Thereafter, the peak current increased much slightly as LSV: linear sweep voltammetry; SWV: square-wave voltammetry;
16 further increasing the accumulation time, also shown in DPV: differential pulse voltammetry; GCE: glass carbon elec-
17 Figure S2 (Supporting Information). This phenomenon trode; and MIP-SWNTs-COOH: molecularly imprinted ionic
18 could be explained to the saturated adsorption of vanillin liquid polymer-carboxyl single-walled carbon nanotubes compo-
site.
19 on the surface of the electrode. Then, the stability of the
20 modified electrodes was examined under the best con-
21 ditions. Five electrodes were made by the same procedure.
22 Moreover, the stability of the modified electrode was also 0.02 mM are expressed as the analyte concentration giving
23 studied. When the modified electrode (Al-TiO2-NPs/ a signal equivalent to the blank signal plus three times its
24 SPCE) was studied with eight segments, the peak current standard deviation (3s). The developed method provides
25 kept 99.0 % of the original peak is also shown in Figure S3 clear and good advantages in terms of sensitivity with
26 (Supporting Information). method previously-published reports for the electrochem-
27 ical determination of vanillin [6, 12, 16, 17, 31] that involve
28 the use of others vanillin sensors and electrochemical
3.4 Analytical Application
29 detection (see Table 2).
30 According to the previous optimum conditions, the The influence of some components in the determina-
31 analytical purposes parameters of the method were tion of vanillin was studied for various common interfer-
32 recorded by linear sweep voltammetry (LSV) technique, ing substances in the samples to be analyzed, including
33 with (50 mV s 1) scan rate. The calibration graph showed a vanillic acid, vanillic alcohol, p-hydroxybenzaldehyde and
34 linear range for standard vanillin solutions of 0.07 to p-hydroxybenzoic acid. These substances were chosen
35 20 mM. The LSV voltammograms obtained for different because they are known to be present in natural vanilla. A
36 concentrations of vanillin. Table 1, shows the results of compound was considered as interference if it caused an
37 linear range, slope, intercept and the regression coefficient analytical variation of more than 5 % when compared to
38 (R2) of the calibration curve for vanillin. the analytical signal obtained in the absence of the
39 The precision of the method for standard solutions interfering compound. The results were showed that no
40 (investigated after analyzing 10 series of 10 replicates) interferences were appeared for the interference analyte
41 and the relative standard deviation (RSD) was calculated (w/w) ratios investigated (Table 3).
42 to be 3.5 % at the 5 mM concentration of vanillin. The The applicability of the proposed methodology for the
43 theoretical limit of detection (LOD) was found to be determination of vanillin in two vanillin extract samples
44 (sample A and sample B) was investigated. These vanillin
45
46 Table 1. Analytical parameters of electrochemical detection of
47 vanillin by aluminium doped TiO2 nanoparticles-modified screen
printed carbon electrode. Table 3. Interference study in the detection of vanillin by
48
aluminum doped TiO2 nanoparticles-modified screen printed
49 Parameter Vanillin carbon electrode.
50
Linear dynamic range/mM 0.07–20 Interferents Tolerated interferent analyte
51 Calibration graph:
52 (w/w) ratio
Intercept 0.2868
53 Slope 2.7213 vanillic acid > 5b
54 Correlation coefficient 0.9977 vanillic alcohol > 10b
55 Detection limit/mM 0.02 p-hydroxybenzaldehyde and > 50b
56 Quantification limit/mM 0.07 p-hydroxybenzoic acid
RSD (%) (n = 10)a 3.5
57 a
For 5 mM vanillin concentration
a b
58 5 mM vanillin Maximum ratio tested

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 5
These are not the final page numbers! ÞÞ
 Full Paper
1 Table 4. Analysis of vanilla extract samples by the proposed and HPLC-DAD [30] methods.
2
Vanillin content (mM)
3
LSV method at Al-TiO2-NPs/SPCE electrode HPLC-DAD [30] Recovery (%)
4
5 Vanilla extract A 12.7  1.3 11.9  0.6 93.7
6 Vanilla extract B 8.4  0.9 7.9  0.3 94.0
7
8
[4] J. Wei, Z. Jiang, R. Li, J. Tan, Anal. Lett. 2012, 45, 1724–
9 extract samples were purchased from local markets and 1735.
10 prepared according the section 2.1. Sample A and sample [5] Z. Wang, G. Zeng, X. Wei, B. Ding, C. Huang, B. Xu, Food
11 B were found to contain vanillin. The results obtained are Anal. Methods 2016, 9, 3360–3366.
12 shown in Table 4. This was compared with a blind analysis [6] J. Peng, C. Hou, X. Hu, Int. J. Electrochem. Sci. 2012, 7,
13 of the vanillin extract samples using the modified HPLC- 1724–1733.
14 DAD method [30] described in the section 2.2. The results [7] L. Jiang, Y. Ding, F. Jiang, L. Li, F. Mo, Anal. Chim. Acta
2014, 883, 22–28.
15 showed, both methods are in close agreement for support-
[8] L. Huang, K. Hou, X. Jia, H. Pan, M. Du, Mater. Sci. Eng. C.
16 ing the validity of this method (Table 4). 2014, 38, 39–45.
17 [9] L. Shang, F. Zhao, B. Zeng, Food Chem. 2014, 151, 53–57.
18 [10] T. R. Silva, D. Brondani, E. Zapp, I. Cruz, Electroanalysis
4 Conclusion
19 2015, 27, 465–472.
20 The development of an aluminium doped TiO2 nano- [11] S. Luo, Y. Liu, Int. J. Electrochem. Sci. 2012, 7, 6396–6405.
21 particles have been described, and the prepared hybrid [12] M. Luque, E. Luque-Pérez, A. Rı́os, M. Valcárcel, Anal.
Chim. Acta 2000, 410, 127–134.
22 nanoparticles have been checked in SPCE, as new work-
[13] L. Agui, J. E. Lopez-Guzman, A. Gonzalez-Cortes, P. Yanez-
23 ing electrode for detection of vanillin in extract vanilla Sedeno, J. M. Pingarron, Anal. Chim. Acta 1999, 385, 241–
24 samples with good analytical performance. The use of the 248.
25 developed working electrode (Al-TiO2-NPs/SPCE) allows [14] P. Ekabutr, O. Chailapakul, P. Supaphol, J. Appl. Polym. Sci.
26 implementing a simple, effective and rapid method for 2013, 130, 3885–3893.
27 electrochemical detection of vanillin in extract vanilla [15] G. Hughes, K. Westmacott, K. C. Honeychurch, A. Crew,
28 samples. The Al-TiO2-NPs/SPCE electrode was found to R. M. Pemberton, J. P. Hart, Biosensors 2016, 6, 50.
[16] J. L. Hardcastle, C. J. Paterson, R. G. Compton, Electro-
29 increase the sensitivity higher than the commercial
analysis 2001, 13, 899–905.
30 electrodes checked for vanillin determination, thus evalu- [17] F. Bettazzi, I. Palchetti, S. Sisalli, M. Mascini, Anal. Chim.
31 ating the effectiveness of the proposed approach for Acta 2006, 555, 134–138.
32 sensitivity improvement of the working electrodes in [18] P. Deng, Z. Xu, R. Zeng, C. Ding, Food Chem. 2015, 180,
33 screen printed carbon electrodes. This modification also 156–163.
34 introduces higher stability and appropriated selectivity, [19] F. Lopes, J. G. Pacheco, P. Rebelo, C. Delerue-Matos, Sens.
35 and the simplicity of the method allows to be used as a Actuators B 2017, 243, 745–752.
[20] S. Zhang, H. Ma, L. Yan, W. Cao, T. Yan, Q. Wei, B. Du,
36 rapid screening test for vanillin, very useful for routine
Biosens. Bioelectron. 2014, 59, 335–341.
37 analytical works. On the other hand, some limitations of [21] R. Jain, P. Pandey, J. Electrochem. Soc. 2013, 160, 687–692.
38 the use of Al-TiO2-NPs/SPCE have short electrode life- [22] W. Wang, Y. Xie, C. Xia, H. Du, F. Tian, Microchim. Acta
39 time, poor inter-electrode reproducibility and not being 2014, 181, 1325–1331.
40 user-friendly. [23] M. G. Hosseini, M. Faraji, M. M. Momeni, S. Ershad, Micro-
41 chim. Acta 2011, 172, 103–108.
42 [24] N. P. Shetti, D. S. Nayak, S. J. Malode, R. M. Kulkarni, Sens.
Acknowledgements Actuators B 2017, 247, 858–867.
43
[25] S. Reddy, G. Krishnamurthi, J. Nanopart. Res. 2013, 15, 175.
44 The Spanish Ministry of Economy and Competitiveness [26] V. Moreno, E. J. Llorent-Martı́nez, M. Zougagh, A. Rı́os,
45 (MINECO) and JJCC Castilla-La Mancha are gratefully Talanta 2016, 161, 775–779.
46 acknowledged for funding this work with Grants [27] H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith,
47 CTQ2016-78793-P and JCCM PEIC-2014-001-P, respec- H. M. Cheng, G. Q. Lu, Nature 2008, 453, 638–641.
48 tively. The support given through an “INCRECYT” [28] M. Gao, C. Chen, Y. Gu, X. Zeng, Materials 2014, 7, 1590–
1602.
49 research contract to M. Zougagh is also acknowledged.
[29] S. M. H. Al-Jawad, Mater. Sci. Semicond. Process. 2017, 67,
50
75–83.
51 [30] L. S. de Jager, G. A. Perfetti, G. W. Diachenko, J. Chroma-
52 References togr. A. 2007, 1145, 83–88.
53 [31] W. Wu, H. Wang, L. Yang, F. Zhao, B. Zeng, Int. J.
[1] N. J. Walton, M. J. Mayer, A. Narbad, Phytochemistry 2003,
54 Electrochem. Sci. 2016, 11, 6009–6022.
63, 505–515.
55 [2] G. M. Durán, A. M. Contento, Á. Rı́os, Talanta 2015, 131,
56 286–291. Received: January 14, 2018
57 [3] S. Minematsu, G. Xuan, X. Wu, J. Environ. Sci. 2013, 25, S8– Accepted: February 13, 2018
58 S14. Published online on &&&, &&&&

www.electroanalysis.wiley-vch.de  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2018, 30, 1 – 7 6
These are not the final page numbers! ÞÞ
 1
2
FULL PAPER
3
K. Murtada, S. Jodeh, M. Zougagh,
4
Á. Rı́os*
5
6 1–7
7
8 Development of an Aluminium
9 Doped TiO2 Nanoparticles-
10 Modified Screen Printed Carbon
11 Electrode for Electrochemical
12 Sensing of Vanillin in Food Samples
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58