María Cristina González

Approach to the content of total extractable phenolic compounds from different food samples by comparison of chromatographic and spectrophotometric methods

A new approach to the error sources in the spectrophotometric determination of total phenols in foods has been performed. The choice of the suitable phenolic standard and the influence of sugars and proteins as interfering compounds were carefully studied. The results obtained by the spectrophotometric method were compared with those found from the chromatographic method which was taken as reference method because it was free of interferences. The spectrophotometric method overestimates the phenolic content except in some fruit samples with a high polyphenolic content. Sugars did not show interference whereas protein showed a high influence on the total phenols at the concentration ranges found in the extracts. In green bean samples both methods gave the same total phenols when the interference was masked. This fact could constitute an useful way to find the real content of phenolics in foods.

Sensing colorimetric approaches based on gold and silver nanoparticles aggregation: Chemical creativity behind the assay. A review

Localized surface plasmon resonance (LSPR) is one of the most remarkable features of gold nanoparticles (Au NPs) and silver nanoparticles (Ag NPs). Due to these inherent optical properties, colloidal solutions of Au and Ag NPs have high extinction coefficients and different colour in the visible region of the spectrum when they are well-spaced in comparison with when they are aggregated. Therefore, a well-designed chemical interaction between the analyte and NPs surroundings leads to a change of colour (red to blue for Au NPs and yellow to brown for Ag NPs from well-spaced to aggregated ones, respectively) allowing the visual detection of the target analyte. These approaches have exhibited an excellent analytical performance with high sensitivities due to the strong LSPR and excellent selectivity strategically driven by the interaction analyte-NPs surroundings involving mainly electrostatic and hydrogen bond interactions as well as donor-acceptor chemical reactions, among others. In addition, this kind of colorimetric assays has received considerable attention in the analytical field because of their simplicity and low cost since they do not require any expensive or complex instrumentation. As a consequence of this, detection of molecules with a high significance in the bio-medical, clinical, food safety and environmental fields including DNA, proteins and a wide spectrum of organic molecules as well as inorganic ions have been impressively reported in the most relevant literature using these assays. This timely review offers a rational vision of the main achievements yielded in the relevant literature according to this exciting and creative analytical field.

An approach to the influence of nutrients and other food constituents on resistant starch formation

The influence of nutrients and other food constituents, such as dietary fibre components, catechin and phytic acid, on resistant starch (RS) formation was systematically investigated. This investigation was carried out under standardized gelatinization conditions by using a high pressure autoclave (HPA). Except for insoluble dietary fibre constituents (cellulose and lignin), all the tested food ingredients reduced the formation of RS. Calcium ions, potassium ions and catechin showed the highest reduction of RS formation, while the nutrients studied (albumin, olive oil and sucrose) as well as phytic acid affected it to a lesser extent. These results were not significantly changed by varying amounts of the studied dietary components.

Microchips for CE: Breakthroughs in real-world food analysis

The well‐known complexity of food matrices is approached using CE microchips with different strategies to improve the selectivity and sensitivity of the analysis by avoiding and/or making the sample preparation as simple as possible: (i) enhancing the peak capacity in order to perform direct injection, (ii) using the microchip platform to measure one target analyte/group of analytes with or without separating other related interferences, (iii) integrating sample preparation steps on the microchip platform, and (iv) integrating new analytical tools from nanotechnology in the detection stage. New analyte separations of food significance involving DNA probes, biogenic amines, vanilla flavors, and dyes have been reported as successfully breaking new barriers in areas of high impact in the market, such as transgenic food analysis, as well as the detection of frauds and toxins. Simple microchip layouts are still the most common designs used, though sophisticated new ones are emerging. In contrast to other application areas, electrochemical detection continues to be the most common detection route, followed by LIF, though non‐conventional detection routes are also emerging, such as chemiluminescence or UV. In terms of analytical performance, the integration of calibration and quality control on a microchip platform, and remarkable accuracy and precision are being obtained using creative analytical methodologies that enhance the analytical potency of microfluidic chips for their future commercialization. This review critically states the most important advances derived from work done in the field over the past 2–3 years.

Carbon nanotube disposable detectors in microchip capillary electrophoresis for water-soluble vitamin determination : Analytical possibilities in pharmaceutical quality control

In this work, the synergy of one mature example from “lab‐on‐chip” domain, such as CE microchips with emerging miniaturized carbon nanotube detectors in analytical science, is presented. Two different carbon electrodes (glassy carbon electrode (GCE) 3 mm diameter, and screen‐printed electrode (SPE) 0.3 mm×2.5 mm) were modified with multiwalled carbon nanotubes (MWCNTs) and their electrochemical behavior was evaluated as detectors in CE microchip using water‐soluble vitamins (pyridoxine, ascorbic acid, and folic acid) in pharmaceutical preparations as representative examples. The SPE modified with MWCNT was the best electrode for the vitamin analysis in terms of analytical performance. In addition, accurate determination of the three vitamins in four different pharmaceuticals was obtained (systematic error less than 9%) in only 400 s using a protocol that combined the sample analysis and the methodological calibration.

Design of a composite amperometric enzyme electrode for the control of the benzoic acid content in food

A graphite-Teflon-tyrosinase composite biosensor for the determination of benzoic acid in foodstuffs is reported. The biosensor functioning is based on the inhibition effect of benzoic acid on the biocatalytic activity of the enzyme in a reversed micelle working medium formed with ethyl acetate as the continuous phase, a 0.05 moll(-1) phosphate buffer solution of pH 7.4 (5%) as the aqueous dispersed phase, and 0.10 moll(-1) dioctyl sulfosuccinate (AOT) as the emulsifying agent. A potential value of -0.10 V, and a constant enzyme-substrate (phenol) concentration of 2.0x10(-4) moll(-1) were selected to carry out the amperometric inhibition measurements. The tyrosinase inhibition process by benzoic acid is reversible and of the competitive type, with an apparent inhibition constant of 0.016 mmoll(-1). The composite bioelectrodes allow the regeneration of the electrode surface by polishing and exhibit long-term operation and stability. A limit of detection of 9.0x10(-7) moll(-1) benzoic acid was obtained. An interference study from other substances which can be found in foodstuffs together with benzoic acid was performed. Taking advantage of the capabilities of reversed micelles as universal solubilization media, the composite tyrosinase electrode was used for the determination of benzoic acid in two different kind of samples: mayonnaise sauce, which is a highly hydrophobic matrix, and Cola soft drinks, a hydrophilic matrix for which practically no sample treatment is necessary.

Carbon Nanotubes Press-Transferred on PMMA Substrates as Exclusive Transducers for Electrochemical Microfluidic Sensing

Novel single-walled carbon nanotube press-transfer electrodes (SW-PTEs) for microfluidic sensing are proposed. In this approach, carbon nanotubes are press-transferred on poly(methyl methacrylate) (PMMA) substrates and are easily coupled to microfluidic chips and act as the exclusive transducer in electrochemical sensing. The detector design consisted of a press-transferred SW film (7 mm × 1 mm) positioned and centered on the PMMA substrate (33 mm × 9 mm). The analytical performance of the SW-PTEs was deeply evaluated using two commercial SWs sources and employing a mixture of dopamine and catechol as model analytes. Analyte detection was influenced by the volume of commercial SW dispersion used in the fabrication of SW-PTEs, with 5 mL taken from a dispersion of 0.5 mg/100 mL being the most favorable volume. In addition, excellent repeatability (relative standard deviation (RSD) of ≤7%, n = 5), interelectrodes reproducibility (RSD ≤ 9%, n = 5), and an extreme resistance to fouling were obtained even after 1 h of microchip analysis with RSD values of ≤4% and ≤9% (n = 15) for migration times and peak heights, respectively. Good sensitivity, remarkable signal-to-noise characteristics, and a well-defined linear concentration dependence (r ≥ 0.990) was also obtained, which allowed these novel detectors to be considered as valuable tools for quantitative analysis. Analytical characterization of the SW-PTEs by field-emission scanning electron microscopy (FESEM) revealed individual bundles of SWs that were highly ordered over the PMMA at the background where the SW bundles were embedded on the PMMA substrate, giving the electrode a high stability. Furthermore, the laboratory-fabricated SW-PTEs can be afforded in any laboratory since they do not require clean-room facilities and are highly compatible with microfluidic scale, mass production, and disposability. In addition, the proposed approach draws new and exciting horizons for electrochemical microfluidic sensing, such as the use of other pure or hybrid nanomaterials and also the possibilities to incorporate biomolecules for highly selective sensing.

Enzyme-based microfluidic chip coupled to graphene electrodes for the detection of D-amino acid enantiomer-biomarkers.

An electrochemical microfluidic strategy for the separation and enantiomeric detection of D-methionine (D-Met) and D-leucine (D-Leu) is presented. These D-amino acids (D-AAs) act as biomarkers involved in relevant diseases caused by Vibrio cholerae. On a single layout microfluidic chip (MC), highly compatible with extremely low biological sample consumption, the strategy allowed the controlled microfluidic D-AA separation and the specific reaction between D-amino acid oxidase (DAAO) and each D-AA biomarker avoiding the use of additives (i.e., cyclodextrins) for enantiomeric separation as well as any covalent immobilization of the enzyme into the wall channels or on the electrode surface such as in the biosensor-based approaches. Hybrid polymer/graphene-based electrodes were end-channel coupled to the microfluidic system to improve the analytical performance. D-Met and D-Leu were successfully detected becoming this proof-of-the-concept a promising principle for the development of point-of-care (POC) devices for in situ screening of V. cholerae related diseases.

Multidimensional carbon allotropes as electrochemical detectors in capillary and microchip electrophoresis.

The main multidimensional carbon allotropes could be classified into carbon nanotubes as 1D material, graphene as 2D material, as well as graphite and diamond as 3D carbon materials. Along with this review, a discussion using these four structures as electrochemical detectors in CE and ME will permit us to explore the recent advances in this field.

Gold Nanoparticles-based Extraction-Free Colorimetric Assay in Organic Media: An Optical Index for Determination of Total Polyphenols in Fat-Rich Samples

In this work, a rapid and simple gold nanoparticle (AuNPs)-based colorimetric assay meets a new type of synthesis of AuNPs in organic medium requiring no sample extraction. The AuNPs synthesis extraction-free approach strategically involves the use of dimethyl sulfoxide (DMSO) acting as an organic solvent for simultaneous sample analyte solubilization and AuNPs stabilization. Moreover, DMSO works as a cryogenic protector avoiding solidification at the temperatures used to block the synthesis. In addition, the chemical function as AuNPs stabilizers of the sample endogenous fatty acids is also exploited, avoiding the use of common surfactant AuNPs stabilizers, which, in an organic/aqueous medium, rise to the formation of undesirable emulsions. This is controlled by adding a fat analyte free sample (sample blank). The method was exhaustively applied for the determination of total polyphenols in two selected kinds of fat-rich liquid and solid samples with high antioxidant activity and economic impact: olive oil (n = 28) and chocolate (n = 16) samples. Fatty sample absorbance is easily followed by the absorption band of localized surface plasmon resonance (LSPR) at 540 nm and quantitation is refereed to gallic acid equivalents. A rigorous evaluation of the method was performed by comparison with the well and traditionally established Folin-Ciocalteu (FC) method, obtaining an excellent correlation for olive oil samples (R = 0.990, n = 28) and for chocolate samples (R = 0.905, n = 16). Additionally, it was also found that the proposed approach was selective (vs other endogenous sample tocopherols and pigments), fast (15-20 min), cheap and simple (does not require expensive/complex equipment), with a very limited amount of sample (30 μL) needed and a significant lower solvent consumption (250 μL in 500 μL total reaction volume) compared to classical methods.