Determination of 5-hydroxymethylfurfural using an electropolymerized molecularly imprinted polymer in combination with Salle.

Coffee, a beverage with a complex chemical composition, is appreciated for the sensory experience of its taste and aroma. The compound 5-(hydroxymethyl)-2-furfural (HMF) is essential for sensory characterization of the beverage, and is also used in the traceability of its production. In this work, a procedure combining salting-out assisted liquid-liquid extraction (SALLE) and an electropolymerized molecularly imprinted polymer (e-MIP) was developed for the detection and quantification of HMF in coffee samples. The sample preparation step using SALLE employed a combination of acetonitrile and phosphate-buffered saline, in a proportion of 70:30 (ACN:PBS), with addition of 0.02 g of NaCl. The new sensor (e-MIP) was prepared by electropolymerization of p-aminobenzoic acid onto a glassy carbon electrode (GCE) using cyclic voltammetry (CV). Analytical determinations were performed by differential pulse voltammetry (DPV). The linear regression correlation coefficient (r2) for the response was 0.9986. The limits of detection and quantification were 0.372 mg L-1 and 1.240 mg L-1, respectively. The repeatability and reproducibility values obtained were 6 and 10%, respectively. The recoveries for three concentration levels were between 97 and 101%. Analyses of different coffee samples showed that the HMF concentrations varied from 261.0 ± 41.0 to 770.2 ± 55.9 mg kg-1 in powdered coffee samples, and from 1510 ± 50 to 4445 ± 278 mg kg-1 in instant coffee samples. The advantages of this procedure, compared to other methods described in the literature, are its simplicity, easy operation, good selectivity and sensitivity, low cost, and minimal use of organic solvents.

Underwater Energy Harvesting to Extend Operation Time of Submersible Sensors.

A linear electromagnetic energy harvesting device for underwater applications, fabricated with a simple manufacturing process, was developed to operate with movement frequencies from 0.1 to 0.4 Hz. The generator has two coils, and the effect of the combination of the two coils was investigated. The experimental study has shown that the energy capture system was able to supply energy to several ocean sensors, producing 7.77 mJ per second with wave movements at 0.4 Hz. This study shows that this energy is enough to restore the energy used by the battery or the capacitor and continue supplying energy to the sensors used in the experimental work. For an ocean wave frequency of 0.4 Hz, the generator can supply power to 8 sensors or 48 sensors, depending on the energy consumed and its optimization.

Pervasive hybridization with local wild relatives in Western European grapevine varieties.

Grapevine (Vitis vinifera L.) diversity richness results from a complex domestication history over multiple historical periods. Here, we used whole-genome resequencing to elucidate different aspects of its recent evolutionary history. Our results support a model in which a central domestication event in grapevine was followed by postdomestication hybridization with local wild genotypes, leading to the presence of an introgression signature in modern wine varieties across Western Europe. The strongest signal was associated with a subset of Iberian grapevine varieties showing large introgression tracts. We targeted this study group for further analysis, demonstrating how regions under selection in wild populations from the Iberian Peninsula were preferentially passed on to the cultivated varieties by gene flow. Examination of underlying genes suggests that environmental adaptation played a fundamental role in both the evolution of wild genotypes and the outcome of hybridization with cultivated varieties, supporting a case of adaptive introgression in grapevine.

PtOEP-PDMS-Based Optical Oxygen Sensor.

The advanced and widespread use of microfluidic devices, which are usually fabricated in polydimethylsiloxane (PDMS), requires the integration of many sensors, always compatible with microfluidic fabrication processes. Moreover, current limitations of the existing optical and electrochemical oxygen sensors regarding long-term stability due to sensor degradation, biofouling, fabrication processes and cost have led to the development of new approaches. Thus, this manuscript reports the development, fabrication and characterization of a low-cost and highly sensitive dissolved oxygen optical sensor based on a membrane of PDMS doped with platinum octaethylporphyrin (PtOEP) film, fabricated using standard microfluidic materials and processes. The excellent mechanical and chemical properties (high permeability to oxygen, anti-biofouling characteristics) of PDMS result in membranes with superior sensitivity compared with other matrix materials. The wide use of PtOEP in sensing applications, due to its advantage of being easily synthesized using microtechnologies, its strong phosphorescence at room temperature with a quantum yield close to 50%, its excellent Strokes Shift as well as its relatively long lifetime (75 µs), provide the suitable conditions for the development of a miniaturized luminescence optical oxygen sensor allowing long-term applications. The influence of the PDMS film thickness (0.1-2.5 mm) and the PtOEP concentration (363, 545, 727 ppm) in luminescent properties are presented. This enables to achieve low detection levels in a gas media range from 0.5% up to 20%, and in liquid media from 0.5 mg/L up to 3.3 mg/L at 1 atm, 25 °C. As a result, we propose a simple and cost-effective system based on a LED membrane photodiode system to detect low oxygen concentrations for in situ applications.

All-Oxide p-n Junction Thermoelectric Generator Based on SnOx and ZnO Thin Films.

Achieving thermoelectric devices with high performance based on low-cost and nontoxic materials is extremely challenging. Moreover, as we move toward an Internet-of-Things society, a miniaturized local power source such as a thermoelectric generator (TEG) is desired to power increasing numbers of wireless sensors. Therefore, in this work, an all-oxide p-n junction TEG composed of low-cost, abundant, and nontoxic materials, such as n-type ZnO and p-type SnOx thin films, deposited on borosilicate glass substrate is proposed. A type II heterojunction between SnOx and ZnO films was predicted by density functional theory (DFT) calculations and confirmed experimentally by X-ray photoelectron spectroscopy (XPS). Moreover, scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDS) show a sharp interface between the SnOx and ZnO layers, confirming the high quality of the p-n junction even after annealing at 523 K. ZnO and SnOx thin films exhibit Seebeck coefficients (α) of ∼121 and ∼258 µV/K, respectively, at 298 K, resulting in power factors (PF) of 180 µW/m K2 (for ZnO) and 37 µW/m K2 (for SnOx). Moreover, the thermal conductivities of ZnO and SnOx films are 8.7 and 1.24 W/m K, respectively, at 298 K, with no significant changes until 575 K. The four pairs all-oxide TEG generated a maximum power output (Pout) of 1.8 nW (≈126 µW/cm2) at a temperature difference of 160 K. The output voltage (Vout) and output current (Iout) at the maximum power output of the TEG are 124 mV and 0.0146 µA, respectively. This work paves the way for achieving a high-performance TEG device based on oxide thin films.

NS1 glycoprotein detection in serum and urine as an electrochemical screening immunosensor for dengue and Zika virus.

The incidence of infection by the dengue virus (DENV) has grown dramatically, reaching 128 countries in tropical and subtropical regions worldwide, with a pattern of hyper-endemicity. DENV is a mosquito-borne disease having four serotypes, one or two circulating in epidemic outbreaks. The diagnosis of DENV is challenging mainly due to the circulation of new viruses with remarkable similarities, such as Zika (ZIKV) that may cause fetal microcephaly. DENV affects 390 million people per year, but these numbers may be higher due to the underreported and misclassified cases. Recently, the NS1 nonstructural protein has been described in serum and urine of DENV and ZIKV patients, suggesting its use as a biomarker for screening since a negative NS1 sample confirms the absence of these infections. Herein, a label-free immunosensor comprising an assembled nanostructured thin film of carbon nanotube-ethylenediamine is described. The advantage of in situ electrosynthesis of polymer film is to allow major control of thickness and conductivity, in addition to designing the reactive groups for functionalization. A quartz crystal microbalance system was used to estimate the thickness of the polymeric film obtained. The anti-NS1 monoclonal antibodies were immobilized to carbon nanotubes by covalent linkage, permitting a high stability during measurements. Analytical responses to NS1 were obtained by differential pulse voltammetry (DPV), showing a linear range from 20 to 800 ng mL-1 and reproducibility of 3.0%, with a limit of detection (LOD) of 6.8 ng mL- 1. This immunosensor was capable of detecting ZIKV and DENV NS1 in spiked urine and real serum in a clinical range.Graphical abstract.

Wearable Inertial Sensor System Towards Daily Human Kinematic Gait Analysis: Benchmarking Analysis to MVN BIOMECH.

This paper presents a cost- and time-effective wearable inertial sensor system, the InertialLAB. It includes gyroscopes and accelerometers for the real-time monitoring of 3D-angular velocity and 3D-acceleration of up to six lower limbs and trunk segment and sagittal joint angle up to six joints. InertialLAB followed an open architecture with a low computational load to be executed by wearable processing units up to 200 Hz for fostering kinematic gait data to third-party systems, advancing similar commercial systems. For joint angle estimation, we developed a trigonometric method based on the segments' orientation previously computed by fusion-based methods. The validation covered healthy gait patterns in varying speed and terrain (flat, ramp, and stairs) and including turns, extending the experiments approached in the literature. The benchmarking analysis to MVN BIOMECH reported that InertialLAB provides more reliable measures in stairs than in flat terrain and ramp. The joint angle time-series of InertialLAB showed good waveform similarity (>0.898) with MVN BIOMECH, resulting in high reliability and excellent validity. User-independent neural network regression models successfully minimized the drift errors observed in InertialLAB's joint angles (NRMSE < 0.092). Further, users ranked InertialLAB as good in terms of usability. InertialLAB shows promise for daily kinematic gait analysis and real-time kinematic feedback for wearable third-party systems.

Erratum: Martins, M.S., et al. Wideband and Wide Beam Polyvinylidene Difluoride (PVDF) Acoustic Transducer for Broadband Underwater. Sensors 2019, 19, 3991.

The authors wish to make the following erratum to this paper [...].

Wideband and Wide Beam Polyvinylidene Difluoride (PVDF) Acoustic Transducer for Broadband Underwater Communications.

The advances in wireless communications are still very limited when intended to be used on Underwater Communication Systems mainly due to the adverse proprieties of the submarine channel to the acoustic and radio frequency (RF) waves propagation. This work describes the development and characterization of a polyvinylidene difluoride ultrasound transducer to be used as an emitter in underwater wireless communications. The transducer has a beam up to 10° × 70° degrees and a usable frequency band up to 1 MHz. The transducer was designed using Finite Elements Methods and compared with real measurements. Pool trials show a transmitting voltage response (TVR) of approximately 150 dB re µPa/V@1 m from 750 kHz to 1 MHz. Sea trials were carried in Ria Formosa, Faro (Portugal) over a 15 m source-receiver communication link. All the signals were successfully detected by cross-correlation using 10 chirp signals between 10 to 900 kHz.

Voltammetric determination of trace amounts of diacetyl at a mercury meniscus modified silver solid amalgam electrode following gas-diffusion microextraction.

A new approach was developed for the determination of trace amounts of diacetyl in food products using gas-diffusion microextraction (GDME) and subsequent detection by differential pulse voltammetry (DPV) at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). Diacetyl is a vicinal diketone responsible for the buttery aroma in many fermented foods and beverages. Its determination is important not only for evaluation of the final product quality (note of mention: health related concerns were associated with continuous diacetyl exposure) but also to monitor fermentation. GDME, a technique combining gas-diffusion and microextraction, particularly aimed to volatile and semi-volatile analytes, seemed the best way to selective extract diacetyl. A solution of 0.05% o-phenylenediamine (OPDA) prepared in a Britton-Robinson buffer (pH 5.0) was chosen as the extracting solution. This solution simultaneously extracts, pre-concentrates and derivatizes diacetyl to 2,3-dimethylquinoxaline (DMQ), enhancing the extraction selectivity and making the analyte electroactive. After finding the optimum conditions for the extraction process (10min at 60°C with 1.0mL of OPDA at pH 5.0), the DPV measurements at the m-AgSAE were conducted with a scan rate of 7mVs-1, a modulation amplitude of 50mV and a modulation time of 100ms. Under these conditions, the resulting DMQ could be easily measured at a potential of -0.6V vs. Ag|AgCl (3molL-1 KCl). The amalgam electrode keeps the advantages of classic mercury electrodes, like high sensitivity, while being environmentally friendly. The GDME/m-AgSAE produced suitable method features for the determination of low amounts of diacetyl (as DMQ) in alcoholic beverages, and in fact, to the best of our knowledge, the limit of quantification of 0.18µgL-1 is one of the lowest reported in literature.

An Insight on Salting-out Assisted Liquid-Liquid Extraction for Phytoanalysis.

INTRODUCTION: Salting-out assisted liquid-liquid extraction (SALLE) is a technique that, although simple and not requiring any complex equipment, is very powerful and versatile. It has obtained growing interest in bioanalysis particularly when combined with chromatographic techniques. OBJECTIVES: Herein, fennel seeds (Foeniculum vulgare Mill.) were used as a case-study to show the application of SALLE in phytochemical analysis. MATERIAL AND METHODS: SALLE combined with HPLC-UV-MS/MS and GC-MS. RESULTS: By HPLC-UV-MS/MS analysis of the organic extract it was possible to identify various phenolic compounds, including quercetin derivatives, caffeic acid, p-coumaric acid and chlorogenic acid. The main compounds identified by GC-MS were estragole, fenchone, anisaldehyde, anethole, benzaldehyde, camphor and apiole. CONCLUSION: HPLC and GC analysis of the extracts showed that it is possible to isolate, in only one step, a wide range of compounds with distinct properties, allowing a detailed phytochemical analysis. Copyright © 2017 John Wiley & Sons, Ltd.

Overall Antioxidant Properties of Malt and How They Are Influenced by the Individual Constituents of Barley and the Malting Process.

In the past several years researchers have focused on the study of the antioxidant properties of barley and barley malt as well as their influence on beer quality. Some malt constituents have been reported as potent antioxidants due to their radical-scavenging and reducing properties, with a positive effect on beer oxidative stability. However, barley and malt can suffer some serious modifications during malting and roasting, namely on the levels of phenolic compounds and the development of Maillard reaction products, which may have a great impact on the overall antioxidant properties of malt. Although some studies have reported an increase of the antioxidant capacity during malting, others have mentioned an opposite effect. Recently, researchers have shown that compounds developed in malt during heat treatment at high temperature and long periods of time, as result of the Maillard reaction, can also exhibit pro-oxidant properties involving the metal-catalyzed Fenton reaction due to its reductive properties. This paper reviews important information and recent data regarding the chemical changes malting and roasting undergo along with their influence on the different anti- and pro-oxidant properties described for barley and malt. The contribution of individual components to the overall antioxidant capacity of malt is also discussed.

Diarylferrocene tweezers for cation binding.

The host-guest chemistry of ferrocene derivatives was explored by a combined experimental and theoretical study. Several 1-arylferrocenes and 1,1'-diarylferrocenes were synthesized by the Suzuki-Miyaura cross-coupling reaction. The ability of these compounds to bind small cations in the gas phase was investigated experimentally by electrospray ionization mass spectrometry (ESI-MS). The results evidenced a noticeable ability of all 1,1'-diarylferrocenes studied to bind cations, while the same was not observed for the corresponding 1-arylferrocenes nor ferrocene. The 1,1'-diarylferrocenecation relative interaction energies were evaluated by ESI-MS and quantum chemical calculations and showed that cation binding in these systems follows electrostatic trends. It was found that, due to their unique molecular shape and smooth torsional potentials, 1,1'-diarylferrocenes can act as molecular tweezers of small-sized cations in the gas phase.

An Optimized Firefly Luciferase Bioluminescent Assay for the Analysis of Free Fatty Acids.

A firefly luciferase (LUC)-based bioluminescent assay for total free fatty acids (FFA) is presented. It is based on LUC's capability of converting FFA into fatty acyl-adenylates with consumption of adenosine 5'-triphosphate (ATP). Since ATP is a cosubstrate in LUC's bioluminescent reaction, together with firefly D-luciferin (D-LH2 ) and atmospheric oxygen (O2 ), any reduction in the assay's ATP content will lead to a decrease in the bioluminescent signal, which is proportional to the amount of FFA. Using FFA mixtures containing myristic (14:0), palmitic (16:0), stearic (18:0), oleic (18:1) and arachidonic acid (20:4) in ethanol, the assay was optimized through statistical experimental design methodology, namely fractional factorial (screening) and central composite (optimization) designs. The optimized method requires 2 µL of sample per tube in a final reaction volume of 50 µL. It is linear in the concentration range from 1 to 20 µm, with limits of detection (LOD) and quantitation (LOQ) of 1.3 and 4.5 µm, respectively. The method proved to be simple to perform, demands low reagent volumes, it is sensitive and robust and may be adapted to high-throughput screening.

Chromatographic analysis of methylglyoxal and other α-dicarbonyls using gas-diffusion microextraction.

Many α-dicarbonyl compounds such as methylglyoxal, diacetyl and pentane-2,3-dione are important quality markers of processed foods. They are produced by enzymatic and chemical processes, the Maillard reaction is the most known chemical route for α-dicarbonyl formation. In the case of methylglyoxal, there are obstacles to be overcome when analysing this compound due to its high reactivity, low volatility and low concentration. The use of extraction techniques based on the volatilization of methylglyoxal (like solid-phase microextraction) showed to be ineffective for the methylglyoxal extraction from aqueous solutions. Therefore, derivatization is typically applied to increase analyte's volatility. In this work a new methodology for the extraction and analysis of methylglyoxal and also diacetyl and pentane-2,3-dione from selected food matrices is presented. It is based on a gas-diffusion microextraction step followed by high performance liquid chromatographic analysis. It was successfully applied to port wines, black tea and soy sauce. Methylglyoxal, diacetyl and pentane-2,3-dione were quantified in the following concentration ranges: 0.24-1.74 mg L(-1), 0.1-1.85 mg L(-1) and 0.023-0.15 mg L(-1), respectively. The main advantages over existing methodologies are its simplicity in terms of sample handling, not requiring any chemical modification of the α-dicarbonyls prior to the extraction, low reagent consumption and short time of analysis.

Analysis of cardamonin by square wave voltammetry.

INTRODUCTION: Several biochemical studies have already shown that cardamonin has health promoting properties, such is in agreement with typical characteristics of chalcones. Although being a very promising compound for the nutraceutical field there is a lack of studies concerning its electroanalytical properties. OBJECTIVE: To develop an electroanalytical methodology for the quantification of cardamonin in cardamom. METHODOLOGY: Cardamonin was analysed electrochemically by means of a hanging mercury drop electrode (HMDE) using square wave voltammetry (SWV). It was extracted from cardamom spice and quantified thereafter using the standard additions method to overcome matrix effects. RESULTS: A limit of detection (LOD) of 0.15 mg/L and good linearity (r² = 0.9998) were obtained. Decoction using ethanol as the extraction solvent appears to be the simplest extraction technique. Spectrophotometric analysis (maximum absorbance peak was found in ethanol at 344 nm with a value of molar extinction coefficient of (2.8 ± 0.1) × 104 L mol⁻¹ cm⁻¹) and mass spectrometry analysis by electrospray in the positive ion mode were also performed. CONCLUSION: Cardamonin was detected voltammetrically. The LOD and limit of quantification (LOQ) of the proposed voltammetric methodology are adequate for trace analysis of this compound in several phytochemical matrices.

Application of gas-diffusion microextraction to the analysis of free and bound acetaldehyde in wines by HPLC-UV and characterization of the extracted compounds by MS/MS detection.

In wines, the presence of high levels of acetaldehyde (AA) not only is responsible for undesirable characteristic odours but can also cause health adverse effects. Such sensorial activity of AA can be overcome by adding sulphites during winemaking, due to the formation of adducts between AA and sulphites, which lower the sensorial impact of AA. Nevertheless, bound AA can be released during wine storage; therefore, the knowledge of its total amount can be important to estimate the long-term wine quality. The proposed methodology is based on the extraction of AA from wines using gas-diffusion microextraction and determination by liquid chromatography. Free and bound forms of AA could be differentiated and determined using an alkaline hydrolysis step to dissociate the sulphites-AA adducts. This methodology was successfully applied to different wine types, with free AA values ranging between 5 and 26 mg L(-1) and total form between 154 and 906 mg L(-1). Bound AA was above 90% of the total content determined for all samples analysed, and higher amounts were obtained for white wines (around 98%). Other carbonyl compounds were also identified in the extracts using mass spectrometry.

Increased sensitivity of anodic stripping voltammetry at the hanging mercury drop electrode by ultracathodic deposition.

An improved approach to the anodic stripping voltammetric (ASV) determination of heavy metals, using the hanging mercury drop electrode (HMDE), is reported. It was discovered that using very cathodic accumulation potentials, at which the solvent reduction occurs (overpotential deposition), the voltammetric signals of zinc(II), cadmium(II), lead(II) and copper(II) increase. When compared with the classical methodology a 5 to 10-fold signal increase is obtained. This effect is likely due to both mercury drop oscillation at such cathodic potentials and added local convection at the mercury drop surface caused by the evolution of hydrogen bubbles.

Novel application of square-wave adsorptive-stripping voltammetry for the determination of xanthohumol in spent hops.

This paper reports the development of a novel electrochemical assay for xanthohumol (XN) by square-wave adsorptive-stripping voltammetry (SWAdSV) with a hanging mercury drop electrode. The method showed good repeatability (CV < 2%) and linearity (between 10 and 250 µg L(-1)), as well as suitable limits of detection (2.6 µg L(-1)) and quantification (8.8 µg L(-1)). The method was applied for the quantification of this compound in spent hops, and the results obtained were compared with the HPLC-UV method. XN contents determined by the SWAdSV method were 16 ± 1 and 100 ± 4 µg L(-1) for aqueous and methanolic extracts, respectively. The developed new methodology considerably reduces the analysis time, approximately from 25 min (HPLC-UV method) to 7 min, enabling a high sample throughput. In addition, the detection and quantification limits were approximately 5-fold lower than those obtained with the chromatographic method.

The indirect electrochemical detection and quantification of DNA through its co-adsorption with anthraquinone monosulphonate on graphitic and multi-walled carbon nanotube screen printed electrodes.

The voltammetric responses arising from the co-adsorption of anthraquinone monosulfonate and DNA on to a graphitic electrode are reported. The electrochemical responses of these two species show that the adsorbed species are non-interacting and further they occupy similar sites upon the electrode surface. Consequently it is demonstrated that there is an inverse linear relationship between the surface concentrations of the two species, such that it is possible to indirectly measure the quantity of adsorbed DNA to the electrode through the voltammetric signal of the co-adsorbed anthraquinone monosulfonate. This system is developed through the use of multiwalled carbon nanotube screen-printed electrodes to provide a proof-of-concept analytical methodology via which it is possible to accurately analyse the concentration of a DNA solution, where the limit of detection is shown to be 8.8 µM (equivalent to 5.9 µg/mL).