New Approach to Multivariate Standard Addition Based on Multivariate Curve Resolution by Alternating Least-Squares: Application to Voltammetric Data.

A multivariate version of the classical univariate standard addition method is proposed for the analysis of samples generating overlapping signals in the presence of notorious matrix effects. Unlike previous versions based on multivariate calibration by partial least-squares (PLS), the proposed strategy takes advantage of a self-modeling methodology: multivariate curve resolution by alternating least-squares (MCR-ALS) enhanced with signal shape constraints based on parametric functions. In this way, there is no need for the full multivariate response of a blank solution, and in multianalyte determinations, the standard additions can be made with a solution containing all of the analytes, which constitutes a clear advance as compared to PLS approach. The proposed method has been successfully tested in the voltammetric determination of hydroquinone and catechol in solutions of increasing complexity and appears to be a promising tool in the field of electroanalysis.

Electroanalysis from the past to the twenty-first century: challenges and perspectives.

A personal mini-review is presented on the history of electroanalysis and on their present achievements and future challenges. The manuscript is written from the subjective view of two generations of electroanalytical chemists that have witnessed for many years the evolution of this discipline.

Screen-Printed Electrodes for the Voltammetric Sensing of Benzotriazoles in Water.

Benzotriazoles (BZTs) are high production volume industrial chemicals that are used in various applications such as corrosion inhibitors, antifreeze agents, and UV radiation stabilizers. Given their potential ecotoxicological implications for different ecosystems and in human health, as well as their poor biodegradability, they are of increasing concern. In this study, a new voltammetric method using commercial screen-printed electrodes (SPEs) has been developed for the sensing of BZTs in water samples to help in their environmental monitoring. To this end, different types of SPEs based on carbon nanoallotropes and copper were tested under several experimental conditions to determine the two BZTs most frequently detected in the environment: 1H-benzotriazole (BZT) and 5-methyl-1H-benzotriazole (Me-BZT, tolyltriazole) as model compounds for BZTs. Carbon nanofibers electrodes exhibited the best performance, allowing detection limits as low as 0.4 mg L-1 for both BZTs, with repeatability and reproducibility of ca. 5%. The applicability of the method was tested through the determination of BZT in spiked drinking water samples, suggesting its suitability for the sensing of samples heavily polluted with BZTs.

Commercial Screen-Printed Electrodes Based on Carbon Nanomaterials for a Fast and Cost-Effective Voltammetric Determination of Paracetamol, Ibuprofen and Caffeine in Water Samples.

Carbon screen-printed electrode (SPCE), multi-walled carbon nanotubes modified screen-printed electrode (SPCNTE), carbon nanofibers modified screen-printed electrode (SPCNFE), and graphene modified screen-printed electrode (SPGPHE) were in a pioneer way tested as sensors for the simultaneous determination of the two most consumed pain-killers, paracetamol (PA) and ibuprofen (IB), and the stimulant caffeine (CF) in water by differential pulse voltammetry (DPV). Their analytical performances were compared, and the resulting sensitivities (2.50, 0.074, and 0.24 µA V mg-1 L for PA, IB, and CF, respectively), detection limits (0.03, 0.6, and 0.05 mg L-1 for PA, IB, and CF, respectively) and quantification limits (0.09, 2.2, and 0.2 mg L-1 for PA, IB, and CF, respectively) suggested that the SPCNFE was the most suitable carbon-based electrode for the voltammetric determination of the selected analytes in water at trace levels. The methodology was validated using both spiked tap water and hospital wastewater samples. The results were compared to those achieved by liquid chromatography-tandem mass spectrometry (LC-MS/MS), the technique of choice for the determination of the target analytes.

Voltammetric Electronic Tongues in Food Analysis.

A critical revision is made on recent applications of voltammetric electronic tongues in the field of food analysis. Relevant works are discussed dealing with the discrimination of food samples of different type, origin, age and quality and with the prediction of the concentration of key substances and significant indexes related to food quality.

Determination of HPLC-UV Fingerprints of Spanish Paprika (Capsicum annuum L.) for Its Classification by Linear Discriminant Analysis.

The development of a simple HPLC-UV method towards the evaluation of Spanish paprika's phenolic profile and their discrimination based on the former is reported herein. The approach is based on C18 reversed-phase chromatography to generate characteristic fingerprints, in combination with linear discriminant analysis (LDA) to achieve their classification. To this aim, chromatographic conditions were optimized so as to achieve the separation of major phenolic compounds already identified in paprika. Paprika samples were subjected to a sample extraction stage by sonication and centrifugation; extracting procedure and conditions were optimized to maximize the generation of enough discriminant fingerprints. Finally, chromatograms were baseline corrected, compressed employing fast Fourier transform (FFT), and then analyzed by means of principal component analysis (PCA) and LDA to carry out the classification of paprika samples. Under the developed procedure, a total of 96 paprika samples were analyzed, achieving a classification rate of 100% for the test subset (n = 25).

Ag Nanoparticles Drop-Casting Modification of Screen-Printed Electrodes for the Simultaneous Voltammetric Determination of Cu(II) and Pb(II).

A new silver nanoparticle modified screen-printed electrode was developed and applied to the simultaneous determination of Pb(II) and Cu(II). Two different types of silver nanoparticles with different shapes and sizes, Ag nanoseeds and Ag nanoprisms, were microscopically characterized and three different carbon substrates, graphite, graphene and carbon nanofibers, were tested. The best analytical performance was achieved for the combination of Ag nanoseeds with a carbon nanofiber modified screen-printed electrode. The resulting sensor allowed the simultaneous determination of Pb(II) and Cu(II) at trace levels and its applicability to natural samples was successfully tested with a groundwater certified reference material, presenting high reproducibility and trueness.

Application of HPLC-UV combined with chemometrics for the detection and quantification of 'true cinnamon' adulteration.

Cinnamon is one of the most popular spices used in cuisines worldwide. Among its different species, Ceylon cinnamon ("true cinnamon") is the one with the most health benefits due to its high concentration in the antioxidant eugenol and the ultra-low content of the hepatotoxic compound coumarin. However, the higher price of Ceylon cinnamon makes it vulnerable to fraudulent adulteration with more economic species of cinnamon, such as Cassia and Saigon. Thus, for the detection of frauds in cinnamon samples, a HPLC-UV method was developed for the determination of 4 characteristic cinnamon compounds: eugenol, cinnamaldehyde, coumarin and cinnamic acid. The obtained data were analyzed by PLS to attain not only the authentication of cinnamon species but also the detection and quantification of partial adulterations. Several mixtures prepared in the laboratory using different cinnamon powder samples considered 'pure' Ceylon, Cassia or Saigon were tested, concluding that the proposed approach allows a clear identification of Ceylon cinnamon and a suitable quantification of the Ceylon: non-Ceylon ratio regardless of the commercial sample selected (RMSE <0.06 for both training and test sets).

Electrochemical Sensor Based on Glassy Carbon Electrode Modified with Carbon Nanohorns (SWCNH) for Determination of Cr(VI) via Adsorptive Cathodic Stripping Voltammetry (AdCSV) in Tap Water.

In this study, a new and simple glassy carbon electrode modified with carbon nanohorns (SWCNH/GCE) was used for the determination of Cr(VI) in aqueous matrices via adsorptive cathodic stripping voltammetry (AdCSV). The modified electrode was characterized via field emission scanning electron microscopy and cyclic voltammetry, which revealed a homogeneous distribution of spherical agglomerates of SWCNH on the electrode surface. The modification increased the electrochemically active area from 0.10 cm2 ± 0.01 (GCE) to 0.16 cm2 ± 0.01 (SWCNH/GCE). The optimized analytical conditions were as follows: a supporting electrolyte (0.15 mol L-1 HCl), an accumulation potential of 0.8 V versus Ag/AgCl, and an accumulation time of 240 s. Validation of the analytical methodology was performed, obtaining a linear range between 20 and 100 µg L-1, a limit of detection of 3.5 µg L-1, and a limit of quantification of 11.6 µg L-1 with good accuracy and precision. The method was applied to the analysis of spiked tap water samples, and the results were compared using a flame atomic absorption spectrophotometer (FAAS) with no significant statistical differences.

Parametric Signal Fitting by Gaussian Peak Adjustment: implementation of 2D transversal constraints and its application for the determination of pKa and complexation constants by differential pulse voltammetry.

A new method, GPA2D, is presented as a significant improvement of the previously described Gaussian Peak Adjustment (GPA) which includes, for the first time, transversal constraints to increase the consistency of the resolution along the different signals of a voltammetric dataset. The constraints deal with the evolution of peak potentials versus pH and with the implementation of chemical equilibrium constants. Moreover, pkavolt, a new tool for the pKa determination, is proposed as an example of the great versatility of the PSF-GPA (Parametric Signal Fitting by Gaussian Peak Adjustment) methodology. GPA2D and pkavolt have been successfully tested on the systems Cd(ii):phytochelatin, Cu(ii):6-benzylaminopurine, Cd(ii):1,10-phenanthroline, Zn(ii):oxalate and captopril drug by determining formation constants (metal complex systems) or pKa values (captopril).

Application of different chemometric strategies to voltammetric and UV-vis spectroscopic data to obtain a complexation model: study of the Cu(II) binding with the phytohormone 6-benzylaminopurine.

The complexation processes of Cu(II) by the phytohormone and the possible antitumoral agent 6-benzylaminopurine (BAP) were studied by Differential Pulse Polarography (DPP) and ultraviolet-visible spectroscopy (UV-vis) in combination with chemometric programs such as Multivariate Curve Resolution by Alternating Least-Squares (MCR-ALS) and Gaussian Peak Adjustment (GPA). All data confirm the formation of the predominant 1 : 1 and 1 : 2 Cu(2+) : BAP complexes. The corroboration of the presented stoichiometries was performed by ElectroSpray Ionization-Mass Spectrometric (ESI-MS) experiments of the Cu(II)-BAP system at different ratios.

A hybrid sensing system combining simultaneous optical and electrochemical measurements: Application to beer discrimination.

A hybrid sensing system, which combines simultaneous cyclic voltammetric (CV) and UV-vis absorbance measurements using a commercial carbon screen-printed electrode and a set of optical fibres in disposable cuvettes, is proposed. The hybrid system approach was applied to 27 samples of recognized beer brands, improving the classification power as compared to only voltammetric or only spectrophotometric measurements. The developed partial least squares discriminant analysis (PLS-DA) model was able to discriminate between five types of beer (lager, marzen, black/stout, alcohol-free and white/ale). The model was also successfully applied to 28 beer samples of white-label brands sold in local supermarkets, demonstrating their similarity to recognized brand beers.

Enhanced voltammetric performance of sensors based on oxidized 2D layered black phosphorus.

The exceptional properties of 2D layered black phosphorus (BP) make it a promising candidate for electrochemical sensing applications and, even though BP is considered unstable and tends to degrade by the presence of oxygen and moisture, its oxidation can be beneficial in some situations. In this work, we present an unequivocal demonstration that the exposition of BP-based working electrodes to normal ambient conditions can indeed be advantageous, leading to an enhancement of voltammetric sensing applications. This point was proved using a BP modified screen-printed carbon electrode (BP-SPCE) for the voltammetric determination of dopamine (DA) as a model target analyte. Oxidized BP-SPCE (up to 35% of PxOy at the surface) presented an enhanced analytical performance with a 5-fold and 2-fold increase in sensitivity, as compared to bare-SPCE and non-oxidized BP-SPCE stored in anhydrous atmosphere, respectively. Good detection limit, repeatability, reproducibility, stability, selectivity, and accuracy were also achieved. Overall, the results presented herein display the prominent possibilities of preparing and working with BP based-sensors in normal ambient settings and showcase their implementation under physiological conditions.

Vibrating boron-doped diamond electrode: A new, durable and highly sensitive tool for the detection of cadmium.

In this paper, a vibrating boron-doped diamond (BDD) electrode electroanalytical device and respective method for the analysis of ultralow concentrations of Cd(II) in water were studied. The enhanced mass transfer on the electrode surface was studied using Ru(NH3)6Cl3. Vibration with 133 Hz frequency enhanced the Ru(III) to Ru(II) reduction by 92.6% compared to a static electrode. The peak current of the anodic stripping voltammetry (ASV) method employed was increased by a factor of 5.3 and 4.7 for 10 and 30 µg L-1 Cd(II) concentrations, respectively, when a frequency of 200 Hz was used. A calibration plot with two linear regions was resolved between 0.01 and 1 µg L-1 and 1-30 µg L-1 with the LOD and LOQ of 0.04 µg L-1 and 0.12 µg L-1, respectively. The applicability of the device and the respective method in the analysis of real environmental samples was successfully verified by analysis of river samples and comparing the results with the ICP analysis presenting high reproducibility and trueness. According to the results of this research, the vibrating BDD electrode with the ASV method has excellent analytical performance without surface modification or regular replacement or polishing of the electrode surface. Combining the exceptional electrochemical and chemical properties of BDD with enhanced mass transfer and signal strength of vibrating electrodes makes the system especially suitable for on-site and online analysis of heavy metals.

Stripping analysis of heavy metals in tap water using the bismuth film electrode.

A commercially available screen-printed carbon electrode coated with an ex situ deposited bismuth film (BiSPCE) has been applied to the determination of Pb(II) and Zn(II) ions in tap water (Barcelona water distribution network) by means of stripping voltammetry (SV) and stripping chronopotentiometry (SCP). A good reproducibility of the measurements and a satisfactory agreement between SV and SCP data were observed for both heavy metal ions. Although, in principle, the procedure could be also suited to the determination of Cd(II), this species was not detected. The results were also consistent with the routine ICP-OES measurements of the water distribution company, thus confirming the potential usefulness of such BiSPCE disposable devices for the analysis of heavy metals in natural waters.

Direct As(V) Determination Using Screen-Printed Electrodes Modified with Silver Manoparticles.

Carbon-nanofiber-based screen-printed electrodes modified with silver nanoparticles (Ag-NP-SPCNFEs) were tested in a pioneering manner for the direct determination of As(V) at low µg L-1 levels by means of differential pulse anodic stripping voltammetry. Screen-printed electrodes were modified with two different types of Ag-NPs, nanoseeds (NS), and nanoprisms (NPr) and characterized both microscopically and electrochemically. Furthermore, after optimizing the direct voltammetric determination of As(V), the analytical performance of considered sensors was compared for the direct determination of As(V). These results suggest that Ag-NS offer a better analytical response compared to Ag-NPr, with a detection and quantification limit of 0.6 and 1.9 µg L-1, respectively. The proposed methodology was validated using a spiked tap water sample with a very high reproducibility and good agreement with inductively coupled plasma - mass spectrometry (ICP-MS) measurements.

New discrimination tools for harvest year and varieties of white wines based on hydrophilic interaction liquid chromatography with amperometric detection.

A simple HPLC-EC method based on hydrophilic interaction liquid chromatography with amperometric detection through gold screen-printed electrodes has been developed and applied for the first time to the determination of aminothiols in white wines. Moreover, the coupling of the method with partial least squares discriminant analysis (PLS-DA) using the analysed aminothiols as biomarkers provides wine discrimination in terms of harvest year. White wine samples were directly injected and chromatographic areas, together with pH and redox potential values, allowed a successful discrimination of wines from different harvest years with a global classification rate of 97.8%. The developed HPLC-EC method also generated characteristic fingerprints that were combined with PLS-DA to classify wines according to three wine varieties, with a global classification rate of 95.3%.

First application of carbon-based screen-printed electrodes for the voltammetric determination of the organic UV filters oxybenzone and octocrylene.

A new voltammetric methodology is proposed for the simultaneous determination of the organic UV filters oxybenzone (benzophenone 3, BP3) and octocrylene (OC) in personal care products and in wastewater extracts. It is based on previous adsorptive stripping voltammetric (AdSV) methods developed for hanging mercury drop electrodes, adapted to the special characteristics of carbon-based screen-printed electrodes. Among the carbon substrates tested, regular carbon screen-printed devices exhibited the best performance, with detection limits of 4.8 and 6.6 µmol L-1 and linearity ranges of 16-400 and 22-400 µmol L-1 for BP3 and OC, respectively, and, as compared to mercury electrodes, with the advantages of environmental safety, easy of use, low cost and compatibility with automation and flow measurements. The methodology has been successfully tested in real samples and compared to the standard methodology by liquid chromatography - tandem mass spectrometry (LC-MS/MS).

A new multivariate standard addition strategy for stripping voltammetric electronic tongues: Application to the determination of Tl(I) and In(III) in samples with complex matrices.

A new multivariate standard addition strategy applicable to stripping methods was proposed as an extention of the classical univariate standard addition method for the resolution of complex samples involving overlapped peaks and complex matrices. The proposed strategy consists in alternate additions of the considered analytes and the further extrapolation to a simulated blank solution measured by skipping the preconcentration step (deposition time = 0). This calibration approach was successfully tested in tonic water samples spiked with Tl(I) and In(III) using a sensor array based on a SeCyst-SPCNFE and an ex-situ-BiSPCE, providing good concordance between replicates and much better accuracy than the usual multivariate external calibration method.

Characterization and classification of Spanish paprika (Capsicum annuum L.) by liquid chromatography coupled to electrochemical detection with screen-printed carbon-based nanomaterials electrodes.

Screen-printed electrodes based on graphite, carbon nanotubes, carbon nanofibers, and graphene were tested as amperometric detectors for the determination of phenolic compounds by high performance liquid chromatography (HPLC). The chromatographic performance as well as the obtained sensitivity, detection and quantification limits suggest that carbon nanofibers modified screen-printed electrode (SPCE-CNF) is the amperometric sensor that provides the best analytical performance. Upon this confirmation, chromatographic data obtained using SPCE-CNF were exploited by means of linear discriminant analysis (LDA) to successfully characterize and classify 96 Spanish paprika (Capsicum annuum L.) samples with different origin and type: from La Vera (including sweet, bittersweet and spicy types) and from Murcia (including sweet and spicy types).