A disposable electrochemical sensor for vanillin detection

A disposable electrochemical sensor was developed for the detection of vanillin in vanilla extracts and in commercial products. An analytical procedure based on square-wave voltammetry (SWV) was optimised and a detection limit of 0.4 μM for vanillin was found. A relative standard deviation of 2% was calculated for a vanillin concentration of 100 μM. The method was applied to the determination of vanillin in natural concentrated vanilla extracts and in final products such as yoghurt and compote. The obtained results were compared with those provided by a reference method based on HPLC. The electrochemical behaviour of other compounds (vanillic acid, p-hydroxybenzaldehyde, p-hydroxybenzoic acid, etc.), generally present in natural oleoresins, were also studied, to check for interferences with respect to the vanillin voltammetric signal.     

Multiwalled Carbon Nanotube Modified Electrodes for the Adsorptive Stripping Voltammetric Determination and Quantification of Curcumin in Turmeric

A sensitive electrochemical method for the determination and quantification of curcumin using adsorptive stripping voltammetry (AdsSV) at a multiwalled carbon nanotube modified basal plane pyrolytic graphite electrode (MWCNT‐BPPG electrode) is presented exploiting the high surface area of the latter. Next the voltammetric behaviour of curcumin on the modified electrode is examined and AdsSV shown to be a sensitive method for quantifying curcumin. The adsorption of curcumin on the electrode surface is evidenced to follow a Langmuir adsorption isotherm. Linear calibration for curcumin in the range of 2–100 μM was obtained with a detection limit of 0.45 μM and a limit of quantification of 1.49 μM. For application to real samples of turmeric, a one‐step sample preparation in ethanol has developed providing a simple and rapid extraction procedure. The MWCNT‐BPPG electrode with AdsSV allowed the determination of curcumin equivalent in turmeric powder sample with recoveries in the range of 92–108 %. This facile and fast method will be useful for monitoring the quality of curcumin containing in commercial turmeric products.     

Development of an Aluminium Doped TiO2 Nanoparticles‐modified Screen Printed Carbon Electrode for Electrochemical Sensing of Vanillin in Food Samples

A new chemically modified electrode based on titanium dioxide nanoparticles (TiO₂‐NPs) has been developed. Aluminium was incorporated into the TiO₂‐NPs to prepare aluminium doped TiO₂ nanoparticles (Al‐TiO₂‐NPs). Aluminium doped TiO₂ nanoparticles‐modified screen printed carbon electrode (Al‐TiO₂‐NPs/SPCE) was employed as easy, efficient and rapid sensor for electrochemical detection of vanillin in various types of food samples. Al‐TiO₂‐NPs were characterized by energy‐dispersive X‐ray (EDX), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) and analyses showing that the average particle sizes varied for the Al‐NPs (7.63 nm) and Al‐TiO₂‐NPs (7.47 nm) with spherical crystal. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to optimize the analytical procedure. A detection limit of vanillin was 0.02 μM, and the relative standard deviation (RSD) was 3.50 %, obtained for a 5.0 μM concentration of vanillin. The electrochemical behaviour of several compounds, such as vanillic acid, vanillic alcohol, p‐hydroxybenzaldehyde and p‐hydroxybenzoic, etc., generally present in natural vanilla samples, were also studied to check the interferences with respect to vanillin voltammetric signal. The applicability was demonstrated by analysing food samples. The obtained results were compared with those provided by a previous method based on liquid chromatography for determination of vanillin.     

Simple and Sensitive Determination of Sibutramine in Slimming Tea Beverages Using a Carbon Screen‐printed Electrode with Adsorptive Stripping Voltammetry

The stimulant sibutramine is an anorexic agent found as an adulterant in natural products and multivitamins supplements used for weight‐loss. In this work, a carbon graphite screen‐printed electrode (SPE‐Gr) with adsorptive stripping pulse differential voltammetry (AdSDPV) is presented for the sensitive and simple detection of sibutramine in slimming tea beverages. The proposed electrochemical method shows a linear working range from 2.0 to 120 μM with a low LOD (0.3 μM) for sibutramine determination in slimming tea samples. The analytical performance of the SPE‐Gr with AdSDPV for sibutramine detection suggests its possible application as an easy, fast and low‐cost method to analyse adulterated tea samples with this stimulant at low levels (<0.1 %).     

Reduced Graphene Oxide/Carbon Nanotube/Gold Nanoparticles Nanocomposite Functionalized Screen‐Printed Electrode for Sensitive Electrochemical Detection of Endocrine Disruptor Bisphenol A

We fabricated a highly sensitive electrochemical sensor for the determination of bisphenol A (BPA) in aqueous solution by using reduced graphene oxide (RGO), carbon nanotubes (CNT), and gold nanoparticles (AuNPs)‐modified screen‐printed electrode (SPE). GO/CNT nanocomposite was directly reduced to RGO/CNT on SPE at room temperature. AuNPs were then electrochemically deposited in situ on RGO/CNT‐modified SPE. Under optimized conditions, differential pulse voltammetry (DPV) produced linear current responses for BPA concentrations of 1.45 to 20 and 20 to 1,490 nM, with a calculated detection limit of an ultralow 800 pM. The sensor response was unaffected by the presence of interferents such as phenol, p‐nitrophenol, pyrocatechol, 2,4‐dinitrophenol, and hydroquinone.     

Highly Sensitive Voltammetric Speciation and Determination of Inorganic Arsenic in Water and Alloy Samples Using Ammonium 2‐Amino‐1‐Cyclopentene‐1‐Dithiocarboxylate

A simple, fast, reproducible (2.5% RSD at 3.0 μg/L), and sensitive method is described for quantifying As(III) (0.3 μg/L detection limit, 0.5–440 μg/L dynamic range). Anodic stripping voltammetry (ASV) is performed after accumulating arsenic at a mercury film electrode at ?0.350 V vs. Ag/AgCl (saturated KCl) for 20 s in 0.2 M HCl containing 8 μM ammonium 2‐amino‐1‐cyclopentene‐1‐dithiocarboxylate (AACD), without oxygen removal. This is the first report of using AACD in ASV and in electrochemical quantification of As(III). Total arsenic is determined after sodium‐sulfite‐reduction of As(V) to As(III). Interferences are minimal. Method validation involved water and metal alloy samples.     

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid‐phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean reco‐veries of pesticides at each of the four spiking levels between 10–300 μg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 μg/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix‐matched calibration. The method was applied successfully using d‐SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.     

Rapid sample screening method for authenticity controlling vanilla flavors using a CE microchip approach with electrochemical detection

Five vanilla-related flavors of food significance, vanillic alcohol (VOH), ethyl maltol (EMA), maltol (MAL), ethyl vanillin (EVA) and vanillin (VAN), were separated using CE microchips with electrochemical detection (CE-ED microchips). A +2 kV driving voltage for both injection and separation operation steps, using a borate buffer (pH 9.5, 20 mM) and 1 M nitric acid in the detection reservoir allowed the selective and sensitive detection of the target analytes in less than 200 s with reproducible control of EOF (RSD(migration times)<3%). The analysis in selected real vanilla samples was focusing on VAN and EVA because VAN is a basic fragrance compound of the vanilla aroma, whereas EVA is an unequivocal proof of adulteration of vanilla flavors. Fast detection of all relevant flavors (200 s) with an acceptable resolution (R(s) >1.5) and a high accuracy (recoveries higher than 90%) were obtained with independence of the matrices and samples examined. These results showed the reliability of the method and the potential use of CE microchips in the food control field for fraudulent purposes.     

Derivative spectrum chromatographic method for the determination of trimethoprim in honey samples using an on-line solid-phase extraction technique

A simple, selective and rapid analytical method for determination of trimethoprim (TMP) in honey samples was developed and validated. This method is based on a SPE technique followed by HPLC with photodiode array detection. After dilution and filtration, aliquots of 500 μL honey samples were directly injected to an on-line SPE HPLC system. TMP was extracted on an RP SPE column, and separated on a hydrophilic interaction chromatography column during HPLC analysis. At the first detection step, the noise level of the photodiode array data was reduced with two-dimensional equalizer filtering, and then the smoothed data were subjected to derivative spectrum chromatography. On the second-derivative chromatogram at 254 nm, the limit of detection and the limit of quantification of TMP in a honey sample were 5 and 10 ng/g, respectively. The proposed method showed high accuracy (60-103%) with adequate sensitivity for TMP monitoring in honey samples.     

Differential Pulse Voltammetry Determination of Ofloxacin in Human Serum and Urine Based on a Novel Tryptophan‐graphene Oxide‐carbon Nanotube Electrochemical Sensor

The highly sensitive determination of ofloxacin (OFL) in human serum and urine was achieved on a novel tryptophan‐graphene oxide‐carbon nanotube (Trp‐GO‐CNT) composite modified glassy carbon electrode (Trp‐GO‐CNT/GCE). The Trp‐GO‐CNT composite was fabricated, and its morphologies and surface functional groups were characterized by field emission scanning electron microscopy (FE‐SEM) and Fourier transform infrared (FT‐IR) spectroscopy. The electrochemical properties of Trp‐GO‐CNT/GCE were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The superior electrochemical behaviors of Trp‐GO‐CNT/GCE toward OFL can be mainly assigned to the excellent electrocatalytic activity of Trp, the great conductivity and high surface area of GO and CNT, and the synergistic effect between Trp, GO and CNT. Under optimum conditions, a wide and valuable linear range (0.01–100 μM), a low detection limit (0.001 μM, S/N=3), a good linear relationship (R2>0.999), good stability and repeatability were obtained for the quantitative determination of OFL. Furthermore, the Trp‐GO‐CNT electrochemical sensor was successfully applied to the determination of OFL in human serum and urine samples, and satisfactory accuracy and recovery could be obtained.     

Rapid Sample Screening Method for Authenticity Controlling of Vanilla Flavours Using Liquid Chromatography with Electrochemical Detection Using Aluminium-Doped Zirconia Nanoparticles-Modified Electrode

A rapid and sensitive technique for frauds determination in vanilla flavors was developed. The method comprises separation by liquid chromatography followed by an electrochemical detection using a homemade screen-printed carbon electrode modified with aluminium-doped zirconia nanoparticles (Al-ZrO₂-NPs/SPCE). The prepared nanomaterials (Al-ZrO₂-NPs) were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray (EDX). This method allows for the determination of six phenolic compounds of vanilla flavors, namely, vanillin, p-hydroxybenzoic acid, p-hydroxybenzaldehyde, vanillyl alcohol, vanillic acid and ethyl vanillin in a linear range between 0.5 and 25 µg g⁻¹, with relative standard deviation values from 2.89 to 4.76%. Meanwhile, the limits of detection and quantification were in the range of 0.10 to 0.14 µg g⁻¹ and 0.33 to 0.48 µg g⁻¹, respectively. In addition, the Al-ZrO₂-NPs/SPCE method displayed a good reproducibility, high sensitivity, and good selectivity towards the determination of the vanilla phenolic compounds, making it suitable for the determination of vanilla phenolic compounds in vanilla real extracts products.     

Disposable Biosensor Based on Amidase/CeO2/GNR Modified Inkjet‐printed CNT Electrodes‐droplet Based Paracetamol Detection in Biological Fluids for “Point‐of‐care” Applications

A disposable acetaminophen biosensor based on inkjet‐printed CNT electrodes (IJPCNT) modified with amidase/cerium dioxide@graphene nanoribbons composite was developed (ACeO2@GNR/IJPCNT). The enzyme amidase A was used for the first time as a recognition element. Inkjet‐printed CNT electrodes served as a basis for the construction of a biosensor that enables droplet detection using 5 μL sample volume. The biosensor showed high selectivity, sensitivity, a low detection limit of 0.18 μM and a wide working linear range from 1 to 100 μM. The proposed approach allows fast and reliable detection of acetaminophen in biological fluids with negligible matrix effect and remarkable reproducibility.     

A Novel Sensitive and Selective Amperometric Detection Platform for the Vanillin Content in Real Samples

Accurate and sensitive determination of vanillin in commercial samples is significant for food safety & quality. In the proposed study, copper particles were coated on an indium tin oxide electrode (ITO) by cyclic voltammetry (CV) for the determination of vanillin in food samples. CV studies indicated that the electrodeposition of Cu particles provides a good electrocatalytic effect towards the oxidation of vanillin. The fabricated sensor determines vanillin linearly between 0.50 μM–2.0 mM (Limit of detection: 0.15 μM). The Cu/ITO was successfully tested on vanillin samples and the recommended method provides accurate and selective determination of vanillin in daily samples.     

Electrochemical Behaviour of Microwave‐assisted Oxidized MWCNTs Based Disposable Electrodes: Proposal of a NADH Electrochemical Sensor

The effect of the oxidation degree of multiwalled carbon nanotubes (MWCNTs) for the detection of NADH was evaluated in this paper. MWCNTs were oxidized by microwave‐assisted sulfonitic treatment at different times (5, 10, 15, and 30 min) and deposited onto a graphite screen printed electrodes. Oxidized MWCNTs were characterized and the electrochemical performance evaluated. The best sensor in terms of sensitivity and stability was obtained after 15 minutes of oxidation (SPE/CNT15). A significant reduction of the NADH oxidation potential was recorded for oxidized MWCNTs compared with unmodified MWCNTs (0.270 V and 0.500 V, respectively vs. Ag/AgCl pseudo reference electrode), increasing the selectivity of the system. Chronoamperometric calibration curves carried out applying a potential of 0.3 V for 1 min were linear in the 4–35 μM range of NADH. A limit of detection of 1 μM was achieved with negligible surface fouling (three consecutive calibration curves, 30 total measurements: slope decrease 5.9 %). Inter electrode reproducibility (n=13) was good resulting in RSD of 15.2 % and 5.0 % for the peak intensity and the oxidation potential, respectively. Quantification of glucose in white wine samples was carried out to demonstrate the ability of the NADH sensor to work in real samples. A good correlation with a spectrophotometric kit for the glucose quantification was achieved.     

Electrochemical Characteristics and Electrosensing of an Antiviral Drug,Entecavir via Synergic Effect of Graphene Oxide Nanoribbons and Ceria Nanorods

A sensitive electrochemical sensor was fabricated based on ceria‐graphene oxide nanoribbons composite (CeO₂‐GONRs) for an antiviral drug, entecavir (ETV). It was characterized by SEM, EDAX, AFM, IR and Raman spectroscopic techniques. The electrochemical behaviour of ETV was investigated by cyclic voltammetric, differential pulse voltammetric (DPV), linear sweep voltammetric (LSV) and square wave voltammetric (SWV) methods at CeO₂‐GONRs modified glassy carbon electrode. Good linearity was observed between the peak current and concentration of ETV in the range of 0.51 ‐ 100 μM with a detection limit of 0.042 μM in DPV method, 2.1 – 61.1 μM with a detection limit of 0.7 μM in LSV method and 0.1 ‐ 80 μM with a detection limit of 68.1 nM in SWV method. The proposed sensitive DPV method was successfully applied for the determination ETV in tablets and biological samples.     

One‐Step Electrodeposited Carbon Nanotube/Zirconia/Myoglobin Film for Direct Electron Transfer and Electrocatalysis

A nanobiocomposite film consisted of zirconia, multiwalled carbon nanotubes (MWNTs) and Myoglobin (Mb) was electrochemically deposited on the electrode. Direct electron transfer for the immobilized Mb was realized and high electrocatalytic efficiency toward H₂O₂ was observed. The proposed biosensor via a simple one‐step electrodeposition method displayed a broader linear range and a lower detection limit for H₂O₂, as compared with those CNT or ZrO₂ based biosensor. The linear range is from 2 × 10^?6 M to 1 × 10^?3 M with the detection limit of 6 × 10^?7 M. The present strategy provides a simple and effective method to assemble CNT, ZrO₂ and enzyme nanohybrid on the electrode and expands the scope of CNT‐based electrochemical devices.     

Simultaneous determination of sibutramine and its active metabolites in human plasma by LC‐MS/MS and its application to a pharmacokinetic study

A simple and sensitive liquid chromatography–electrospray ionization–tandem mass spectrometry (LC‐ESI‐MS/MS) technique was developed and validated for the determination of sibutramine and its N‐desmethyl metabolites (M1 and M2) in human plasma. After extraction with methyl t‐butyl ether, chromatographic separation of analytes in human plasma was performed using a reverse‐phase Luna C₁₈ column with a mobile phase of acetonitrile–10 mm ammonium formate buffer (50:50, v/v) and quantified by ESI‐MS/MS detection in positive ion mode. The flow rate of the mobile phase was 200 μL/min and the retention times of sibutramine, M1, M2 and internal standard (chlorpheniramine) were 1.5, 1.4, 1.3 and 0.9 min, respectively. The calibration curves were linear over the range 0.05–20 ng/mL, for sibutramine, M1 and M2. The lower limit of quantification was 0.05 ng/mL using 500 μL of human plasma. The mean accuracy and the precision in the intra‐ and inter‐day validation for sibutramine, M1 and M2 were acceptable. This LC‐MS/MS method showed improved sensitivity and a short run time for the quantification of sibutramine and its two active metabolites in plasma. The validated method was successfully applied to a pharmacokinetic study in human. Copyright © 2011 John Wiley & Sons, Ltd.     

Simultaneous determination of seven phthalic acid esters in beverages using ultrasound and vortex‐assisted dispersive liquid–liquid microextraction followed by high‐performance liquid chromatography

A sensitive, rapid, and simple high‐performance liquid chromatography with UV detection method was developed for the simultaneous determination of seven phthalic acid esters (dimethyl phthalate, dipropyl phthalate, di‐n‐butyl phthalate, benzyl butyl phthalate, dicyclohexyl phthalate, di‐(2‐ethylhexyl) phthalate, and di‐n‐octyl phthalate) in several kinds of beverage samples. Ultrasound and vortex‐assisted dispersive liquid–liquid microextraction method was used. The separation was performed using an Intersil ODS‐3 column (C₁₈, 250 × 4.6 mm, 5.0 μm) and a gradient elution with a mobile phase consisting of MeOH/ACN (50:50) and 0.2 M KH₂PO₄ buffer. Analytes were detected by a UV detector at 230 nm. The developed method was validated in terms of linearity, limit of detection, limit of quantification, repeatability, accuracy, and recovery. Calibration equations and correlation coefficients (> 0.99) were calculated by least squares method with weighting factor. The limit of detection and quantification were in the range of 0.019–0.208 and 0.072–0.483 μg/L. The repeatability and intermediate precision were determined in terms of relative standard deviation to be within 0.03–3.93 and 0.02–4.74%, respectively. The accuracy was found to be in the range of –14.55 to 15.57% in terms of relative error. Seventeen different beverage samples in plastic bottles were successfully analyzed, and ten of them were found to be contaminated by different phthalic acid esters.     

Fabrication of the Enzyme‐less Voltammetric Bilirubin Sensor Based on Sol‐gel Imprinted Polymer

Measuring the serum bilirubin (BR) level is part of the common test for newborns, since high concentrations of bilirubin in the blood can cause brain damage and even death for them. Therefore, achieving a fast, accurate and cost effective method for bilirubin assay in medical diagnosis and Medical management of patients with jaundice, especially neonates, is very important. In this study, an electrochemical sensor was developed to detect low amounts of bilirubin in serum samples. The basis of the work is the BR imprinted polymer synthesis and the use of this polymer as a recognition element in the production of the bilirubin voltammetric sensor. For this purpose, bilirubin imprinted polymer was synthesized using the simple sol gel method and the prepared polymer is characterized by SEM and FT‐IR. In the next step, this polymer was applied to modify the carbon paste electrode and provide a sensitive and selective sensor for the BR molecule. The proposed sensor was able to measure the bilirubin in the concentration range of 1 to 100 μM after optimizing the operating conditions. The limit of detection (LOD) and limit of quantification (LOQ) was calculated 0.75 μM and 2.5 μM respectively. It is also applicable to bilirubin assay in serum samples.     

Solid-phase extraction and ultra high-performance liquid chromatography tandem mass spectrometry analysis of the gastrointestinal absorption of emodin in different digestive segments of rats

A rapid, simple and sensitive ultra high‐performance liquid chromatography (UHPLC‐MS/MS) method was established for determining the absorption amount of emodin in the five digestive segments of rat. Plasma samples were pre‐purified by solid‐phase extraction (SPE) with Oasis MAX cartridge. Separation of emodin and 1,8‐dihydroxyanthraquinone (internal standard) was performed on an Acquity BEH UHPLC C₁₈ column (100 mm×2.1 mm, 1.7 μm) with gradient elution of methanol and 0.1% formic acid aqueous solution. The LC/MS system was operated under multiple reaction monitoring mode using electrospray ionization (ESI) in negative ion mode. The results showed that this established method was valid and sensitive for emodin within 0.04–16.4 μg/mL, with low limits of detection and quantification of 0.6 ng/mL and 2.4 ng/mL, respectively and upper limit of quantification of 220.0 ng/mL. The intra‐ and interday variations were below 4.9% of RSD. The extraction recoveries were 98.9–106.1% with RSD of 1.9–3.2%. The plasma concentration‐time relationship showed that the absorption of emodin in stomach was faster than in intestine segments. The sequence of absorption amount was: ileum>jejunum>colon≈duodenum>stomach. Most of emodin was absorbed in ileum, and the absorption amount was increased with prolonged retention of drug form in intestine, especially in ileum and jejunum. The developed UHPLC‐ESI‐MS/MS method was appropriate for determining the in vivo absorption of emodin in other herbal medicines or preparations containing this compound.