Discrimination of Olive Oil and Extra-Virgin Olive Oil from Other Vegetable Oils by Targeted and Untargeted HRMS Profiling of Phenolic and Triterpenic Compounds Combined with Chemometrics.

Extra-virgin olive oil (EVOO) and virgin olive oil (VOO) are valuable natural products of great economic interest for their producing countries, and therefore, it is necessary to establish methods capable of proving the authenticity of these oils on the market. This work presents a methodology for the discrimination of olive oil and extra-virgin olive oil from other vegetable oils based on targeted and untargeted high-resolution mass spectrometry (HRMS) profiling of phenolic and triterpenic compounds coupled with multivariate statistical analysis of the data. Some phenolic compounds (cinnamic acid, coumaric acids, apigenin, pinocembrin, hydroxytyrosol and maslinic acid), secoiridoids (elenolic acid, ligstroside and oleocanthal) and lignans (pinoresinol and hydroxy and acetoxy derivatives) could be olive oil biomarkers, whereby these compounds are quantified in higher amounts in EVOO compared to other vegetable oils. The principal component analysis (PCA) performed based on the targeted compounds from the oil samples confirmed that cinnamic acid, coumaric acids, apigenin, pinocembrin, hydroxytyrosol and maslinic acid could be considered as tracers for olive oils authentication. The heat map profiles based on the untargeted HRMS data indicate a clear discrimination of the olive oils from the other vegetable oils. The proposed methodology could be extended to the authentication and classification of EVOOs depending on the variety, geographical origin, or adulteration practices.

Development of a Novel Biosensor Based on Tyrosinase/Platinum Nanoparticles/Chitosan/Graphene Nanostructured Layer with Applicability in Bioanalysis.

The present paper describes the preparation and characterization of a graphene, chitosan, platinum nanoparticles and tyrosinase-based bionanocomposite film deposited on the surface of a screen-printed carbon electrode for the detection of L-tyrosine by voltammetry. The redox process on the biosensor surface is associated with the enzymatic oxidation of L-tyrosine, which is favoured by graphene and platinum nanoparticles that increase electrical conductivity and the electron transfer rate. Chitosan ensures the biocompatibility between the tyrosinase enzyme and the solid matrix, as well as a series of complex interactions for an efficient immobilization of the biocatalyst. Experimental conditions were optimized so that the analytical performances of the biosensor were maximal for L-tyrosine detection. By using square wave voltammetry as the detection method, a very low detection limit (4.75 × 10-8 M), a vast linearity domain (0.1⁻100 µM) and a high affinity of the enzyme for the substrate (KMapp is 53.4 µM) were obtained. The repeatability of the voltammetric response, the stability, and the reduced interference of the chemical species present in the sample prove that this biosensor is an excellent tool to be used in bioanalysis. L-tyrosine detection in medical and pharmaceutical samples was performed with very good results, the analytical recovery values obtained being between 99.5% and 101%. The analytical method based on biosensor was validated by the standard method of analysis, the differences observed being statistically insignificant at the 99% confidence level.

Highly sensitive voltamperometric determination of pyritinol using carbon nanofiber/gold nanoparticle composite screen-printed carbon electrode.

A novel and highly sensitive electrochemical method for the detection of pyritinol in pharmaceutical products and serum samples has been accomplished based on voltamperometric response of pyritinol in carbon nanofiber-gold nanoparticle (CNF-GNP)-modified screen-printed carbon electrode (SPCE). The electrochemical response of pyritinol to CNF-GNP-modified SPCE was studied by cyclic voltammetry and square-wave voltammetry (SWV). Under optimized working conditions, the novel sensor shows excellent voltamperometric response toward pyritinol. The SWV study shows significantly enhanced electrochemical response for pyritinol in CNF-GNP-modified SPCE providing high sensitivity to the novel sensor for pyritinol detection. The peak current for pyritinol is found to be linear with the concentration in the range 1.0×10-8-5.0×10-5 M with a detection limit of 6.23×10-9 M using SWV as the detection method. The viability of the new developed sensor for the analytical purposes was studied by performing experiments on various commercial pharmaceutical products and blood serum samples, which yielded adequate recoveries of pyritinol. The novel electrochemical sensor provides high sensitivity, enhanced selectivity, good reproducibility and practical applicability.

Voltammetric determination of melatonin using a graphene-based sensor in pharmaceutical products.

Melatonin can be sensitively detected in pharmaceuticals by cyclic voltammetry and fixed-potential amperometry using a graphene-based sensor. The sensor characterization of cyclic voltammetry constantly provides high values of electrode active area and heterogeneous rate constant. In optimal conditions, the sensor was applied for the determination of melatonin in different pharmaceutical samples. The sensitivity to melatonin was 0.0371 A M(-1), and the limit of detection was 0.87×10(-6) M. The data obtained by using the graphene-based sensor for the detection of melatonin in pharmaceutical products were in good agreement with the data provided by the producer. Since no interferences from the excipients were found, using a separation technique was not necessary. Additionally, the low price, ease of handling, small amount of sample, short time per analysis, and possibility of automation are the important advantages that recommend this methodology for quality control of pharmaceuticals.

Amperometric Biosensor Based on Diamine Oxidase/Platinum Nanoparticles/Graphene/Chitosan Modified Screen-Printed Carbon Electrode for Histamine Detection.

This work describes the development and optimization studies of a novel biosensor employed in the detection and quantification of histamine in freshwater fish samples. The proposed biosensor is based on a modified carbon screen-printed electrode with diamineoxidase, graphene and platinum nanoparticles, which detects the hydrogen peroxide formed by the chemical process biocatalysed by the enzyme diamine oxidase and immobilized onto the nanostructurated surface of the receptor element. The amperometric measurements with the biosensor have been implemented in buffer solution of pH 7.4, applying an optimal low potential of +0.4 V. The novel biosensor shows high sensitivity (0.0631 µA·µM), low detection limit (2.54 × 10(-8) M) and a broad linear domain from 0.1 to 300 µM. The applicability in natural complex samples and the analytical parameters of this enzyme sensor have been performed in the quantification of histamine in freshwater fish. An excellent correlation among results achieved with the developed biosensor and results found with the standard method for all freshwater fish samples has been achieved.

Biosensor based on tyrosinase immobilized on a single-walled carbon nanotube-modified glassy carbon electrode for detection of epinephrine.

A biosensor comprising tyrosinase immobilized on a single-walled carbon nanotube-modified glassy carbon electrode has been developed. The sensitive element, ie, tyrosinase, was immobilized using a drop-and-dry method followed by cross-linking. Tyrosinase maintained high bioactivity on this nanomaterial, catalyzing the oxidation of epinephrine to epinephrine-quinone, which was electrochemically reduced (-0.07 V versus Ag/AgCl) on the biosensor surface. Under optimum conditions, the biosensor showed a linear response in the range of 10-110 µM. The limit of detection was calculated to be 2.54 µM with a correlation coefficient of 0.977. The repeatability, expressed as the relative standard deviation for five consecutive determinations of 10(-5) M epinephrine solution was 3.4%. A good correlation was obtained between results obtained by the biosensor and those obtained by ultraviolet spectrophotometric methods.

Carbon paste electrodes made from different carbonaceous materials: application in the study of antioxidants.

This work describes the sensing properties of carbon paste electrodes (CPES) prepared from three different types of carbonaceous materials: graphite, carbon microspheres and carbon nanotubes. The electrochemical responses towards antioxidants including vanillic acid, catechol, gallic acid, L-ascorbic acid and L-glutathione have been analyzed and compared. It has been demonstrated that the electrodes based on carbon microspheres show the best performances in terms of kinetics and stability, whereas G-CPEs presented the smallest detection limit for all the antioxidants analyzed. An array of electrodes has been constructed using the three types of electrodes. As demonstrated by means of Principal Component Analysis, the system is able to discriminate among antioxidants as a function of their chemical structure and reactivity.