Preparation of Fe2O3-Clorprenaline/Tetraphenylborate Nanospheres and Their Application as Ion Selective Electrode for Determination of Clorprenaline in Pork
© Shao et al. 2016
Received: 16 January 2016
Accepted: 22 March 2016
Published: 5 April 2016
A novel modified ion selective electrode based on Fe2O3-clorprenaline/tetraphenylborate nanospheres (Fe2O3-CLPT NSs) as electroactive materials for the determination of clorprenaline hydrochloride (CLP) is described. The α-Fe2O3 nanoparticles (NPs) were prepared by hydrothermal synthesis, then self-assembled on CLP/tetraphenylborate (TPB) to form Fe2O3-CLPT NSs, which were used as a potentiometric electrode for analyte determination innovatively. The Fe2O3-CLPT NSs modified electrode exhibited a wider concentration range from 1.0 × 10−7 to 1.0 × 10−1 mol/L and a lower detection limit of 3.7 × 10−8 mol/L compared with unmodified electrodes. The selectivity of the modified electrode was evaluated by fixed interference method. The good performance of the modified electrode such as wide pH range (2.4–6.7), fast response time (15 s), and adequate lifetime (14 weeks) indicate the utility of the modified electrode for evaluation of CLP content in various real samples. Finally, the modified electrode was successfully employed to detect CLP in pork samples with satisfactory results. These results demonstrated the Fe2O3-CLPT NSs modified electrode to be a functional and convenient method to the field of potentiometry determination of CLP in real samples.
Potentiometric sensors were recently developed and are currently widely used in environmental monitoring, medicine detection, and biotechnology [9–11]. Potentiometric sensors possess advantages such as fast response times, simple instrumentation, ease of operation, low cost, and reasonable selectivity. For these reasons, the potentiometric sensor is a promising potential method for the determination of CLP. However, most of the reported sensors may have either of the problems such as a high detection limit or a narrow working concentration range or limited pH range. [12–14]. Therefore, finding a suitable modifier may play a crucial role in improving the detection characteristics of potentiometric sensors.
Nanomaterials have severed as promising candidates for modifiers and are commonly used in the construction of potentiometric sensors. As reported in the literatures, the linear range and detection limits of potentiometric sensors modified with nanomaterials have been improved by several orders of magnitudes compared to their unmodified counterparts [15–17]. Hematite (α-Fe2O3) is one of the most promising nanomaterials with high electric conductivity, large surface area, and good photocatalytic activity [18–20], which has received considerable attention due to its versatile applications in fabricating gas sensors [21, 22]. However, its application in constructing potentiometric sensors for analyte determination has not been reported. Thus, we present a strategy for the use of Fe2O3 nanoparticles (NPs) as modifiers of potentiometric sensors for CLP determination.
In this work, the α-Fe2O3 NPs were prepared by hydrothermal synthesis and then self-assembled on CLP/tetraphenylborate (TPB) to form Fe2O3-CLPT nanospheres (NSs). The Fe2O3-CLPT NSs were used as electroactive materials in the construction of modified electrodes. Finally, the modified electrode was applied as an indicator electrode for the convenient and rapid potentiometric determination of CLP in pork samples.
In this work, all the chemical reagents were analytical grade. CLP was purchased from National Institutes for Food and Drug Control (Beijing, China), and FeCl3 and anhydrous CH3COONa were purchased from Sigma-Aldrich (St. Louis, MO, USA). Distilled water was used throughout.
Preparation of α-Fe2O3NPs
Fe2O3 NPs were prepared by hydrothermal synthesis following the reported literature [23, 24]: a mixture of 1 mmol FeCl3, 3 mmol CH3COONa, and 50 mL distilled water was heated under stirring to form a transparent solution. Then, the obtained solution was transferred and sealed into a Teflon-lined autoclave and maintained at 180 °C for 12 h. After cooling to room temperature, the resulting red precipitate was separated by centrifuging (10,000 r/min, 10 min), repeatedly rinsed with distilled water, and finally dried at 60 °C under vacuum for further characterization and application.
Preparation of Fe2O3-CLPT NSs
In a typical synthesis, 1 mmol Fe2O3 NPs was uniformly dispersed into a 50 mL 0.02 mol/L CLP solution after ultrasonic treatment, followed by the addition of a TPB solution (50 mL, 0.02 mol/L) into the above mixed solution drop by drop under continuous stirring. The formed precipitate was filtered with no. 3 sand core funnel and thoroughly rinsed by distilled water for 3~5 times, then stored in a desiccator until constant weight gotten. Consequently, the Fe2O3-CLPT NSs were received and used as electroactive materials of the electrode.
Preparation of the Fe2O3-CLPT NSs Modified Graphite Electrode
A mixture containing 5 mg Fe2O3-CLPT NSs, 200 mg polyvinylchloride, 5 mL tetrahydrofuran, and 0.6 mLl dibutyl phthalate was prepared and dealt with sonicate dissolution until a clarified solution is obtained. Subsequently, the mixture was coated onto the surface of a graphite electrode, which has been polished to a mirror-like and allowed to dry under ambient condition for 2~3 days until a dried membrane formed on the surface of the electrode. Therefore, the Fe2O3-CLPT NSs modified graphite electrode for a working electrode was gotten. Before use, the electrode was soaked in a 1.0 × 10−3 mol/L CLP solution for 30 min to be active.
The preparation of pork samples follows several reported methods [25, 26]. A 2.00-g homogenized pork sample was transferred to a 50-mL centrifuge tube and mixed with 8 mL amine acetate (0.2 mol/L, pH 5.2). After the addition of 40 μL of β-glucuronidase-arylsulfatase, the sample was incubated for 6 h at 42 °C in water bath. After being cooled down to room temperature, the mixture was vortexed for 10 min and centrifuged at 10,000 r/min for 10 min. The supernatant was transferred to another tube and mixed with 5 mL of 0.1 mol/L perchloric acid; then, the pH was adjusted to 1.0 with 1.0 mol/L perchloric acid, followed by centrifugation at 10,000 r/min for 10 min. The supernatant was transferred to another tube, and the pH was adjusted to 9.5 with 10 mol/L NaOH solution. Ten milliliter saturated NaCl solution and 10 mL isopropanol-ethyl acetate (6:4, v/v) was added, followed by vortexing for 1 min and centrifugation at 10,000 r/min for 10 min. The supernatant was collected and evaporated under a stream of nitrogen at 50 °C, after which the residue was dissolved in 10 mL HAc-NaAc buffer solution, followed by sonication for 5 min. Spiked samples were prepared in the same steps, except a known amount of CLP standard were added to the pork samples before treatment.
Preparation of Standard CLP Solutions
A stock solution of 0.1 mol/L CLP solution was prepared using an HAc-NaAc buffer as solvent. The working solutions with concentration from 10−1 to 10−9 mol/L were completed by stepwise dilution of the stock solution.
SCE, KCl (3 M) | CLP solution | the Fe2O3-CLPT NSs modified graphite electrode or the unmodified graphite electrode.
Results and Discussion
Electrochemical Behaviors of Electrodes
Calibration Graph and Measuring Range
The Effect of Scan Rate on the Oxidation CLP at Electrodes
Effect of pH
Response Time and Lifetime of the Modified Electrode
Selectivity of the Modified Electrode
Selectivity coefficient values for Fe2O3-CLPT NSs modified electrode for various interfering ions
3.5 × 10−4
6.9 × 10−4
1.4 × 10−4
2.6 × 10−4
4.5 × 10−4
8.3 × 10−3
2.7 × 10−4
3.4 × 10−4
6.1 × 10−4
9.4 × 10−3
2.3 × 10−5
5.1 × 10−4
8.6 × 10−3
4.2 × 10−4
4.6 × 10−5
Reproducibility and Repeatability Stability of the Modified Electrode
The parameters of the reproducibility and repeatability were investigated in order to assess the precision of the method. For the repeatability, the relative standard deviation of ten replicate measurements with one modified electrode was 1.8 %. To evaluate the reproducibility of this modified electrode, a series of modified electrodes (six) were prepared with the same method and the responses of these modified electrodes were tested to CLP concentrations. The results showed that the standard deviation of measurements of the 1.0 × 10−4 mol/L CLP solution was ±2.3 mV with these six modified electrodes.
Determination of CLP in Pork Samples
Measurement results of CLP in pork samples (n = 5)
0.97 ± 0.11
4.89 ± 0.16
9.83 ± 0.21
19.70 ± 0.24
In the present work, a new electroactive material with a nano-size and large specific surface area has been prepared and characterized using FTIR, XRD, and SEM. The obtained Fe2O3-CLPT NSs were efficiently applied for construction of CLP ion selective electrodes. Satisfactory results were received from the application of the modified electrode to the determination of CLP in pure solutions and pork samples. The modified electrode displayed a wide concentration range and a low detection limit, providing comparable optical selectivity toward CLP with better response time of 15 s. These results indicated that the Fe2O3-CLPT NSs modified electrode offered a viable technique for the determination of CLP in the real samples, with its inherent advantages of high selectivity, rapid response, simple operation, precise results, and low cost. However, compared with other instrumental techniques such as HPLC-MS, the disparity in a detection limit also existed. Therefore, further improvements on electrode performance, like reducing the detection limit and increasing the speed of response, should be the future research focuses.
This work is supported by Liaoning S&T Project (No. 2013225305), Liaoning Medical University Principal Fund (No. 2014D17), National Natural Science Foundation of China (No. 51202199), Natural Science Foundation of Liaoning Province (No. 2014022038), and Excellent Talents program of Liaoning Provincial Universities (No. LJQ2013089).
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