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The development of low-cost, sensitive, and simple analytical tools for biomolecule detection in health status monitoring is nowadays a growing research topic. Sensing platforms integrating nanocomposite materials as recognition elements in the monitoring of various biomolecules and biomarkers are addressing this challenging objective. Herein, we have developed electrochemical sensing platforms by means of a novel fabrication procedure for biomolecule detection. The platforms are based on commercially available low-cost conductive substrates like glassy carbon and/or screen-printed carbon electrodes selectively functionalized with nanocomposite materials composed of Ag and Au metallic nanoparticles and an organic polymer, poly(3,4-ethylenedioxythiophene). The novel fabrication method made use of alternating currents with controlled amplitude and frequency. The frequency of the applied alternating current was 100 mHz for the polymer deposition, while a frequency value of 50 mHz was used for the in situ electrodeposition of Ag and Au nanoparticles. The selected frequency values ensured the successful preparation of the composite materials. The use of readily available composite materials is intended to produce cost-effective analytical tools. The judicious modification of the organic conductive matrix by various metallic nanoparticles, such as Ag and Au, extends the potential applications of the sensing platform toward a range of biomolecules like quercetin and epinephrine, chosen as benchmark analytes for proof-of-concept antioxidant and neurotransmitter detection. The sensing platforms were tested successfully for quercetin and epinephrine determination on synthetic and real samples. Wide linear response ranges and low limit-of-detection values were obtained for epinephrine and quercetin detection.

Neurotransmitters play important roles in the normal functioning of the central nervous system. The accurate and sensitive quantification of neurotransmitters using chromatographic and optical analytical methods is of key interest in the management of related neurodegenerative maladies. In this study, electrochemical sensors based on electrodes modified with composite nanomaterials were investigated as reliable, fast and low-cost analytical devices for direct neurotransmitter quantification. A sensing platform was developed by means of an innovative preparation method using alternating currents (ACs). Low-cost sensing materials based on gold nanoparticles (AuNPs) and poly(3,4-ethylenedioxythiophene) were synthesized in situ onto glassy carbon electrodes by means of AC. A polymeric matrix was prepared by applying an AC at a frequency of 100 mHz for 300 s, resulting in an increase in roughness. AuNPs were synthesized by applying an AC at a frequency of 50 mHz for 100 s. The use of AC enabled the preparation of AuNPs embedded in the polymeric matrix characterized by increased electroactive surface area. The sensing platform was tested and successfully validated in the detection of epinephrine, with good analytical performance, achieving a low detection limit of 0.5 µM and a wide linear response range of 1 to 100 μM epinephrine. The practical applicability of the electrochemical sensing platform was demonstrated in the detection of epinephrine in human serum samples with good accuracy and recovery. AC frequency modulated the electrodeposition process, resulting in enhanced roughness. Consequently, the novel AC-based method ensured an improved sensitivity of the sensing platform compared to other electrochemical epinephrine sensors produced by classical methods, like potentiostatic and galvanostatic ones.

Quercetin (QR-3,3′,4′,5,7-pentahydroxylflavone) is very well known as a strong antioxidant with anti-inflammatory, antiviral, antineoplastic, and antithrombotic properties that can act as a free radical scavenger in human beings. It can be found in vegetables such as capers, lovage, broccoli, lettuce, spinach, onions, tea, seeds, and fruit skins. QR is recognized as one of the most important nutrients in a person’s daily diet. Lipoic acid (LA), also known as 1,2-dithiolane-3-pentanoic acid, is synthesized by animal, plant, and human cells from fatty acids and cysteine. LA is often used in the treatment of oxidative stress, diabetes, cardiovascular and hepatitis diseases, and heavy metal poisoning. In the literature, several chromatographic and optical methods have been developed in order to determine the presence of lipoic acid and quercetin with a low detection limit, but these methods have drawbacks such as sample pretreatments, the use of hazardous and expansive chemicals, and sophisticated extraction procedures. In view of this, an alternate electrochemical method for the sensitive determination of LA and QR is required. In the present work, we have developed novel electrochemical platforms for LA and QR sensing based on PEDOT-PB (poly(3,4-ethylenedioxythiophene-Prussian Blue) and PEDOT-AgNPs. Both nanocomposite materials were synthesized using a sinusoidal currents (SCs) method. The amplitude and frequency of the SCs method have been optimized. The developed electrochemical sensing platforms that use PEDOT-PB and PEDOT-AgNPs were assessed and validated for their LA and QR determination in synthetic and real samples in terms of their limit of detection, limit of quantification, and linear response range. The proposed sensing platforms ensured a comparable, fast, simple, and reliable detection of the target analytes QR and LA without sample pretreatment, as is usually required by other analytical methodologies such as chromatographic and optical methods.

A sensing platform based on nanocomposite materials composed of gold metal nanoparticles (AuNPs) and conducting polymer (CP) matrix has been developed for serotonin and epinephrine detection. The CP-AuNPs nanocomposite materials have been synthesized onto glassy carbon electrodes (GCE) by using novel electrochemical procedures based on sinusoidal currents (SC). The SC procedures ensured good control of the metal nanoparticles distribution, increased electrochemical surface area, and enhanced analytical performance. The proposed sensing platform displayed good analytical performance toward serotonin and epinephrine detection. A wide linear analytical response toward epinephrine in the range from 10 to 640 μM and a low detection limit of 1.4 μM epinephrine has been obtained. The sensing platform has also displayed a linear response toward serotonin in the range from 10 to 320 μM, with a detection limit of 5.7 μM serotonin. The sensing platform has been successfully applied in the analysis of epinephrine and serotonin in real samples of tap water and urine with good accuracy.

Neurotransmitters (NTs) are known as endogenous chemical messengers with important roles in the normal functioning of central and peripheral nervous systems. Abnormal levels of certain NTs, such as dopamine, serotonin and epinephrine, have been linked with several neurodegenerative diseases (such as Alzheimer’s disease, Parkinson’s disease and Huntington’s disease). To date, various strategies have been employed for the quantitative determination of NTs, and nanocomposite materials based on conducting polymers and metal nanoparticles constitute a cornerstone for the development of electrochemical sensors with low costs, stability, fast response rates and high selectivity and sensitivity. The preparation and analytical applications of nanocomposite materials based on metal nanoparticles in the electrochemical sensing of neurotransmitters are discussed in this paper. Recent developments in the electrochemical sensing of neurotransmitters are also discussed with emphasis on the benefits brought by metal nanoparticles in improving the sensitivity of the analytical measurements. The electrochemical synthesis methods for the in situ generation of metal nanoparticles within conducting polymer layers are reviewed. The analytical applications of the nanocomposite-sensing materials towards the detection of neurotransmitters such as dopamine, epinephrine and serotonin are discussed in terms of detection and quantification limits, linear response range, sensitivity and selectivity.

Previous studies performed on 2-(azulen-1-yldiazenyl)-5-phenyl-1,3,4-thiadiazole (T) showed that T is a ligand with complexing properties towards heavy metals (HMs) in solution and can be attached to electrode surfaces. Films of T were deposited on glassy carbon to obtain chemically modified electrodes (T-CMEs), either through scanning or using controlled potential electrolysis in tetrabutylammonium perchlorate in acetonitrile. They were investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and spectroelectrochemistry. All methods provided evidence for showing the formation of insulating films, with properties depending on their electropolymerization potential. CV and EIS studies of T-CMEs in tetrabutylammonium perchlorate in acetonitrile as supporting electrolyte, and in the presence of a ferrocene redox probe resulted in a thickness of ~10 µm, an active surface area about 6 times higher than the geometrical one, and conductivity of about 10−6 S/cm. This characterization performed using voltammetric techniques reveals the symmetry of the reversible anodic and cathodic redox CV peaks for the polymer, while spectroelectrochemistry shows the intensification of the charge transport process through polarons, due to the anodic polarization of the film.

The aim of this study is the preparation of nanostructured copper(II) oxide-based materials (CuONPs) through a facile additive-free polyol procedure that consists of the hydrolysis of copper(II) acetate in 1,4-butane diol and its application in hydrogen peroxide sensing. The nonenzymatic electrochemical sensor for hydrogen peroxide determination was constructed by drop casting the CuONP sensing material on top of a glassy carbon electrode (GCE) modified by a layer of poly(3,4-ethylenedioxythiophene) conducting polymer (PEDOT). The PEDOT layer was prepared on GCE using the sinusoidal voltage method. The XRD pattern of the CuONPs reveals the formation of the monoclinic tenorite phase, CuO, with average crystallite sizes of 8.7 nm, while the estimated band gap from UV–vis spectroscopy is of 1.2 eV. The SEM, STEM, and BET analyses show the formation of quasi-prismatic microaggregates of nanoparticles, with dimensions ranging from 1 µm up to ca. 200 µm, with a mesoporous structure. The developed electrochemical sensor exhibited a linear response toward H2O2 in the concentration range from 0.04 to 10 mM, with a low detection limit of 8.5 μM of H2O2. Furthermore, the obtained sensor possessed an excellent anti-interference capability in H2O2 determination in the presence of interfering compounds such as KNO3 and KNO2.

Non-alcoholic fatty liver disease (NAFLD) includes a spectrum of liver alterations that can result in severe disease and even death. Consumption of ultra-processed foods (UPF) has been associated with obesity and related comorbidities. However, the link between UPF and NAFLD has not been sufficiently assessed. We aimed to investigate the prospective association between UPF consumption and liver health biomarkers. Methods: We followed for 1 year 5867 older participants with overweight/obesity and metabolic syndrome (MetS) from the PREDIMED-Plus trial. A validated 143-item semi-quantitative food frequency questionnaire was used to evaluate consumption of UPF at baseline, 6, and 12 months. The degree of processing for foods and beverages (g/day) was established according to the NOVA classification system. The non-invasive fatty liver index (FLI) and hepatic steatosis index (HSI) were used to evaluate liver health at three points in time. The associations between changes in UPF consumption (percentage of total daily dietary intake (g)) and liver biomarkers were assessed using mixed-effects linear models with repeated measurements. Results: In this cohort, UPF consumption at baseline was 8.19% (SD 6.95%) of total daily dietary intake in grams. In multivariable models, each 10% daily increment in UPF consumption in 1 year was associated with significantly greater FLI (β 1.60 points, 95% CI 1.24;1.96 points) and HSI (0.43, 0.29; 0.57) scores (all p-values < 0.001). These associations persisted statistically significant after adjusting for potential dietary confounders and NAFLD risk factors. Conclusions: A higher UPF consumption was associated with higher levels of NAFLD-related biomarkers in older adults with overweight/obesity and MetS.

Galectins are a family of glycan binding proteins that stand out for the wide range of biological phenomena in which they are involved. Most galectin functions are associated with their glycan binding capacities, which are generally well characterized at the oligosaccharide level, but not at the glycoprotein or glycolipid level. Glycolipids form the part of cell membranes where they can act as galectin cellular receptors. In this scenario, glycan presentation as well as the membrane chemical and structural features are expected to have a strong impact in these molecular association processes. Herein, liposomes were used as membrane mimicking scaffolds for the presentation of glycosphingolipids (GSLs) and to investigate their interaction with Galectin-3 and the N-domain of Galectin-8 (Gal8N). The binding towards GM3 and GM1 and their non-silaylated GSLs was compared to the binding to the free glycans, devoid of lipid. The analysis was carried out using a combination of NMR methods, membrane perturbation studies, and molecular modeling. Our results showed a different tendency of the two galectins in their binding capacities towards the glycans, depending on whether they were free oligosaccharides or as part of GSL inserted into a lipid bilayer, highlighting the significance of GSL glycan presentation on membranes in lectin binding.

In this work, the development of an electrochemical sensor for melatonin determination is presented. The sensor was based on Sonogel-Carbon electrode material (SNGCE) and Au nanoparticles (AuNPs). The low-cost and environmentally friendly SNGCE material was prepared by the ultrasound-assisted sonogel method. AuNPs were prepared by a chemical route and narrow size distribution was obtained. The electrochemical characterization of the SNGCE/AuNP sensor was carried out by cyclic voltammetry in the presence of a redox probe. The analytical performance of the SNGCE/AuNP sensor in terms of linear response range, repeatability, selectivity, and limit of detection was investigated. The optimized SNGCE/AuNP sensor displayed a low detection limit of 8.4 nM melatonin in synthetic samples assessed by means of the amperometry technique. The potential use of the proposed sensor in real sample analysis and the anti-matrix capability were assessed by a recovery study of melatonin detection in human peripheral blood serum with good accuracy.

A recently synthesized azulene-tetrazole molecular receptor is proposed in this paper to continue the series of azulene substituted compounds that have been developed to build polyazulene-based materials for heavy metal (HM) ion detection. This study focuses on characterization of (E)-5-((6-t-butyl-4,8-dimethylazulen-1-yl) diazenyl)-1H-tetrazole (L) by electrochemical techniques in view of its use for designing electrochemical sensors for HM ion complexation. The character of redox processes was proved by cyclic, differential pulse, and rotating disk electrode voltammetry. An in-depth thermodynamic study of the complexation properties of the free ligand with Pb(II) and Cd(II) from aqueous solutions was performed, and the stoichiometry and stability constant values were determined. Chemically modified electrodes (CMEs) based on L (L-CMEs) prepared by controlled potential electrolysis (CPE) at different applied potentials and charges were characterized by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Their surface morphology was examined by scanning electron microscopy (SEM). The complexing properties of L-CMEs were investigated towards the detection of HM ions by anodic stripping and compared to the stability constants of the complexes in solution. Voltametric curves showed well-defined peaks for Pb (II), Cd (II), Cu (II) and Hg (II), but the responses differ from each other and vary depending on the ion concentrations in the accumulation solutions. The best results were obtained for Pb(II) and Cd(II) ions. The results obtained for Pb(II) are promising and can be used for its analysis in water solutions (detection limit of about 10−9 M).

The interaction of multi-LacNAc (Galβ1-4GlcNAc)-containing N-(2-hydroxypropyl) methacrylamide (HPMA) copolymers with human galectin-1 (Gal-1) and the carbohydrate recognition domain (CRD) of human galectin-3 (Gal-3) was analyzed using NMR methods in addition to cryo-electron-microscopy and dynamic light scattering (DLS) experiments. The interaction with individual LacNAc-containing components of the polymer was studied for comparison purposes. For Gal-3 CRD, the NMR data suggest a canonical interaction of the individual small-molecule bi- and trivalent ligands with the lectin binding site and better affinity for the trivalent arrangement due to statistical effects. For the glycopolymers, the interaction was stronger, although no evidence for forming a large supramolecule was obtained. In contrast, for Gal-1, the results indicate the formation of large cross-linked supramolecules in the presence of multivalent LacNAc entities for both the individual building blocks and the polymers. Interestingly, the bivalent and trivalent presentation of LacNAc in the polymer did not produce such an increase, indicating that the multivalency provided by the polymer is sufficient for triggering an efficient binding between the glycopolymer and Gal-1. This hypothesis was further demonstrated by electron microscopy and DLS methods.

Carotenoids are pigments contained mainly in fruit and vegetables (F&V) that have beneficial effects on cardiometabolic health. Due to their lipophilic nature, co-ingestion of fat appears to increase their bioavailability via facilitating transfer to the aqueous micellar phase during digestion. However, the extent to which high fat intake may contribute to increased carotenoid plasma concentrations is still unclear. The objective was to examine the degree to which the consumption of different amounts of both carotenoid-rich foods and fats is associated with plasma carotenoid concentrations within a Mediterranean lifestyle context (subsample from the PREDIMED-Plus study baseline) where consumption of F&V and fat is high. The study population was categorized into four groups according to their self-reported consumption of F&V and fat. Carotenoids were extracted from plasma samples and analyzed by HPLC-UV-VIS-QqQ-MS/MS. Carotenoid systemic concentrations were greater in high consumers of F&V than in low consumers of these foods (+3.04 μmol/L (95% CI: 0.90, 5.17), p-value = 0.005), but circulating concentrations seemed to decrease when total fat intake was very high (−2.69 μmol/L (−5.54; 0.16), p-value = 0.064). High consumption of F&V is associated with greater systemic levels of total carotenoids, in particular when fat intake is low-to-moderate rather than very high.

Di(hetero)aryl ketones are important motifs present in natural products, pharmaceuticals or agrochemicals. In recent years, Pd(II)-catalyzed acylation of (hetero)arenes in the presence of an oxidant has emerged as a catalytic alternative to classical acylation methods, reducing the production of toxic metal waste. Different directing groups and acyl sources are being studied for this purpose, although further development is required to face mainly selectivity problems in order to be applied in the synthesis of more complex molecules. Selected recent developments and applications are covered in this review.

The aim of the study was to evaluate sleep duration and sleep variability in relation to serum uric acid (SUA) concentrations and SUA to creatinine ratio. This is a cross-sectional analysis of baseline data from 1842 elderly participants with overweight/obesity and metabolic syndrome in the (Prevención con Dieta Mediterránea) PREDIMED-Plus trial. Accelerometry-derived sleep duration and sleep variability were measured. Linear regression models were fitted to examine the aforementioned associations. A 1 hour/night increment in sleep duration was inversely associated with SUA concentrations (β = −0.07, p = 0.047). Further adjustment for leukocytes attenuated this association (p = 0.050). Each 1-hour increment in sleep duration was inversely associated with SUA to creatinine ratio (β = −0.15, p = 0.001). The findings of this study suggest that longer sleep duration is associated with lower SUA concentrations and lower SUA to creatinine ratio.

The application of a novel Poly(3,4-ethylenedioxythiophene)-Tyrosinase/Sonogel-Carbon electrode (PEDOT-Tyr/SNGC) biosensor to beers and wines analysis is proposed. This biosensor implies a new Sinusoidal Current (SC) electrodeposition method to immobilize the enzyme generating a nanostructure surface. The biosensors were characterized electrochemically, employing cyclic voltammetry and electrochemical impedance spectroscopy. Sensitivity, limit of detection, and correlation coefficients of the linear fitting were 2.40 × 10−4 µA·µM−1, 4.33 µM, and R2 = 0.9987, respectively. Caffeic acid is used as the reference polyphenol. A sampling of nine beers (four lager, three stout, and two non-alcoholic beers), and four wines (three red and one white wine) purchased in a local store was performed. The Polyphenol indeces for beers and wines have been assessed using the proposed biosensor, and the obtained values are in agreement with the literature data. Antioxidant properties of the samples using the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) radical spectrophotometric method were also evaluated. The correlation between the polyphenol index and the antioxidant capacity was obtained for beers and wines.

Bio-composite coatings consisting of poly(3,4-ethylenedioxythiophene) (PEDOT) and tyrosinase (Ty) were successfully electrodeposited on conventional size gold (Au) disk electrodes and microelectrode arrays using sinusoidal voltages. Electrochemical polymerization of the corresponding monomer was carried out in the presence of various Ty amounts in aqueous buffered solutions. The bio-composite coatings prepared using sinusoidal voltages and potentiostatic electrodeposition methods were compared in terms of morphology, electrochemical properties, and biocatalytic activity towards various analytes. The amperometric biosensors were tested in dopamine (DA) and catechol (CT) electroanalysis in aqueous buffered solutions. The analytical performance of the developed biosensors was investigated in terms of linear response range, detection limit, sensitivity, and repeatability. A semi-quantitative multi-analyte procedure for simultaneous determination of DA and CT was developed. The amperometric biosensor prepared using sinusoidal voltages showed much better analytical performance. The Au disk biosensor obtained by 50 mV alternating voltage amplitude displayed a linear response for DA concentrations ranging from 10 to 300 μM, with a detection limit of 4.18 μM.

Palladium-catalyzed dehydrogenative coupling is an efficient synthetic strategy for the construction of quinoline scaffolds, a privileged structure and prevalent motif in many natural and biologically active products, in particular in marine alkaloids. Thus, quinolines and 1,2-dihydroquinolines can be selectively obtained in moderate-to-good yields via intramolecular C–H alkenylation reactions, by choosing the reaction conditions. This methodology provides a direct method for the construction of this type of quinoline through an efficient and atom economical procedure, and constitutes significant advance over the existing procedures that require preactivated reaction partners.