Search Results (21)

Nickel-based metal–organic frameworks (Ni-MOFs) have received enormous amounts of attention from the scientific community due to their excellent porosity, larger specific surface area, tunable structure, and intrinsic redox properties. In previous years, Ni-MOFs and their hybrid composite materials have been extensively explored for electrochemical sensing applications. As per the reported literature, Ni-MOF-based hybrid materials have been used in the fabrication of electrochemical sensors for the monitoring of ascorbic acid, glucose, L-tryptophan, bisphenol A, carbendazim, catechol, hydroquinone, 4-chlorophenol, uric acid, kaempferol, adenine, _L-cysteine, etc. The presence of synergistic effects in Ni-MOF-based hybrid materials plays a crucial role in the development of highly selective electrochemical sensors. Thus, Ni-MOF-based materials exhibited enhanced sensitivity and selectivity with reasonable real sample recovery, which suggested their potential for practical applications. In addition, Ni-MOF-based hybrid composites were also adopted as electrode modifiers for the development of supercapacitors. The Ni-MOF-based materials demonstrated excellent specific capacitance at low current densities with reasonable cyclic stability. This review article provides an overview of recent advancements in the utilization of Ni-MOF-based electrode modifiers with metal oxides, carbon-based materials, MXenes, polymers, and LDH, etc., for the electrochemical detection of environmental pollutants and biomolecules and for supercapacitor applications. In addition, Ni-based bimetallic and trimetallic catalysts and their composites have been reviewed for electrochemical sensing and supercapacitor applications. The key challenges, limitations, and future perspectives of Ni-MOF-based materials are discussed. We believe that the present review article may be beneficial for the scientific community working on the development of Ni-MOF-based materials for electrochemical sensing and supercapacitor applications. Full article

The rapid development of smart electronic skin has led researchers to design a variety of flexible and stretchable devices that can be used to monitor physiological and environmental signals. In this work, we successfully demonstrate a color-adjustable and conductive wearable optical–electronic skin (OE-skin) based on photonic crystal hydrogel that is capable of delivering both optical and electrical signal responses synchronously. The OE-skin is fabricated by incorporating a structural colored layer, composed of periodically aligned magnetic nanoparticles, into a polyacrylamide hydrogel matrix that contains tea polyphenols and borax. The dynamic boronate ester bonds formed between borax and the catechol groups of tea polyphenols are able to enhance the mechanical properties of the OE-skin, while also conferring excellent electrical conductivity, high sensitivity, and a rapid electrical response. Additionally, the tea polyphenols, which are natural active compounds derived from tea, possess diverse bioactive properties, thereby endowing the OE-skin with excellent antibacterial and biocompatibility characteristics. In addition, the developed electronic skin successfully demonstrates its capability in synergistic electronic and optical sensing during human motion monitoring, indicating broad application prospects in the field of smart wearable sensors. Full article

This study describes the development of catalytic surface immobilizing dopamine via cross-linking or tyrosinase through covalent bonds on an electrografted screen-printed carbon electrode with a 4-nitrobenzenediazonium ion. A simple electrochemical reduction approach was used to covalently graft aryldiazonium ions onto the surface of commercial electrodes. After functionalization with aminophenyl groups, dopamine, an important neurotransmitter, was immobilized by imine bond formation using glutaraldehyde as a bifunctional cross-linking molecule. The presence of immobilized dopamine was confirmed by cyclic voltammetry following the electrochemical response of the hydroquinone/quinone redox process from catechol functionalities on the surface, which are responsible for the catalytic activity. In addition, the surface was also characterized by cyclic voltammetry using the redox probe, [Fe(CN)₆]^3−/4−, obtaining a signal approximately 14 times higher than that of a bare electrode, achieving a dynamic concentration range spanning three orders of magnitude. Remarkable sensitivity was also obtained by combining the electrografting, in situ diazotation, to generate grafted aryl diazonium ions on the surface, and coupling reaction to anchor the tyrosinase enzyme to the electrode surface. The response of the TYR-biosensor towards catechol, using the redox probe as mediator, was 10 times higher than that obtained with the dopamine modified catalytic surface. These modified surfaces offer promising alternatives for the voltammetric quantification of catechol in environmental fields. Full article

A graphene sample (EGr) was obtained in a single-step synthesis by electrochemical exfoliation of graphite rods. A combination of 0.05 M ammonium sulfate and 0.05 M ammonium thiocyanate was employed, leading to a graphene sample composed of few-layer, multi-layer and graphene oxide flakes. Due to the mild exfoliation conditions, large sheets with linear sizes in the range of tens to hundreds of micrometers were produced. The LSV technique gave information about the effect of catechol concentration on the electrochemical signal of bare and graphene-modified electrodes. Based on the resulting calibration plots, the corresponding analytical parameters (linear range, sensitivity, limit of quantification and limit of detection) were calculated for each electrode. In the case of the EGr/GC electrode the linear range was from 6 × 10⁻⁷ to 1 × 10⁻⁴ M catechol. The detection limit was low (1.82 × 10⁻⁷ M) while the quantification limit was 6 × 10⁻⁷ M. The sensitivity was five times higher than that corresponding to bare GC, proving the excellent electro-catalytic properties of the graphene-modified electrode. The practical applicability of the graphene-modified electrode was tested in tap water, obtaining an excellent recovery of 102%. Full article

Effectively detecting catechol (CC) and hydroquinone (HQ) simultaneously is crucial for environmental protection and human health monitoring. In the study presented herein, a novel electrochemical sensor for the sensitive simultaneous detection of CC and HQ was constructed based on an electrochemically reduced graphene oxide (ERGO)-modified multi-walled carbon nanotube paste electrode (MWCNTPE). Scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and electrochemical techniques were utilized to characterize the sensing interface and investigate the sensing mechanism. Under the optimal detection conditions, the oxidation peak currents of CC and HQ show a good linear relationship with their concentrations in the range of 0.4–400 μM with a detection limit of 0.083 μM for CC and 0.028 μM for HQ (S/N = 3). Moreover, the sensor exhibits good performance and can be applied successfully in the simultaneous detection of CC and HQ in tap water samples and urine samples with satisfactory results, indicating its promising application prospects. Full article

A cheap and disposable pencil graphite electrode (PGE) was developed by the incorporation of amine groups (Am-PGE-1). A further improvement in the performance was observed when the aminated electrode (Am-PGE-1) was activated by applying a negative potential scan (Am-PGE-2). The electrochemical transport properties were evaluated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The Nyquist plot showed a reduced charge transfer resistance value of 24.3 Ω for Am-PGE-2, while it was 95.1 Ω for bare PGE. Thus, Am-PGE-2 was used as a sensing platform for the detection of catechol. It was found that the electrochemical response of catechol oxidation at Am-PGE-2 was twice than the current obtained for bare PGE. Additionally, the effect of pH of the supporting electrolyte and reaction kinetic were studied. The heterogeneous electron transfer rate constant was calculated to be 0.01 s⁻¹. Moreover, CV study revealed that the redox reaction of catechol was a quasi-reversible and diffusion-controlled process. The square wave voltammetry (SWV) technique was applied for the quantitative determination of catechol. The peak current showed a linear dependency on the concentration of catechol from 3 to 150 µM. Furthermore, the analyte could be detected as low as 3.86 µM. Likewise, the sensor demonstrates a good selectivity towards the target analyte than the other possible interfering molecules or ions. Aiming to examine practical applicability, real samples, such as river and household tap water, were tested by using the proposed transducer, and the satisfactory recoveries demonstrate the effectiveness of Am-PGE-2 in real life applications. Full article

Laccase is an enzyme belonging to the oxidoreductase class and has copper atoms in the catalytic centre. The catalytic property of this enzyme consists of the enzymatic oxidation of the phenolic compounds, in the corresponding quinones, with the concomitant reduction of molecular oxygen to water. There is growing interest in developing innovative sensing methods for detecting phenolic substrates, such as catechol. Preliminary absorption and fluorescence measurements were carried out in the UV-visible range to evaluate the possibility of using the variations produced in the spectra of laccase and/or catechol to monitor the presence of this substrate. The absorption and fluorescence emission increase upon UV excitation was detected. By monitoring the time course of the fluorescence signal, an evident increase in the signal detected in the UV range is observed until a saturation level is reached. The observed variations in the spectra, in the presence of the catechol, are discussed also in terms of the interactions between the enzyme and the phenolic compound. The results are very promising for the design of new optical detection methods for polyphenol pollutants. Full article

High sensitivity and a wide detection range are always the pursuit of sensor design. In this work, gold nanostars (Au NSs) featuring the shape of sea urchins with an absorption peak at the near infrared region (822 nm) were prepared. We proposed a Au NSs-based plasmonic colorimetric sensing platform for ultrasensitive catechol (CC) detection with a wide detection range from 3.33 nM to 107 μM and a limit of detection (LOD) at 1 nM. The target analyte, CC, was used to reduce silver ions (Ag⁺) to form silver (Ag) coating on the surface of Au NSs, which caused a blue-shift in the localized surface plasmon resonance (LSPR) of Au NSs. With the gradual increase in CC concentration, the Ag coating on the surface was gradually nucleated, and the LSPR blue-shift carried on. This strategy yields a wide LSPR shift by as much as 276 nm for plasmonic effects, enabling an ultra-wide range and the ultrasensitive detection of CC. This work will facilitate the research of target-mediated LSPR sensors and their wide application in environmental monitoring, food safety, and disease diagnosis. Full article

Metallic nanoparticles potentially have wide practical applications in various fields of science and industry. In biosensorics, they usually act as catalysts or nanozymes (NZs) and as mediators of electron transfer. We describe here the development of amperometric biosensors (ABSs) based on purified oxidases, synthesized nanoparticles of CuCe (nCuCe), and micro/nanoporous gold (pAu), which were electro-deposited on a graphite electrode (GE). As an effective peroxidase (PO)-like NZ, nCuCe was used here as a hydrogen-peroxide-sensing platform in ABSs that were based on glucose oxidase, alcohol oxidase, methylamine oxidase, and L-arginine oxidase. At the same time, nCuCe is an electroactive mediator and has been used in laccase-based ABSs. As a result, the ABSs we constructed and characterized were based on glucose, methanol, methyl amine, L-arginine, and catechol, respectively. The developed nCuCe-based ABSs exhibited improved analytical characteristics in comparison with the corresponding PO-based ABSs. Additionally, the presence of pAu, with its extremely advanced chemo-sensing surface layer, was shown to significantly increase the sensitivities of all constructed ABSs. As an example, the bioelectrodes containing laccase/GE, laccase/nCuCe/GE, and laccase/nCuCe/pAu/GE exhibited sensitivities to catechol at 2300, 5055, and 9280 A·M⁻¹·m⁻², respectively. We demonstrate here that pAu is an effective carrier of electroactive nanomaterials coupled with oxidases, which may be promising in biosensors. Full article

Polyphenol oxidase (PPO) mimics have advantage of detection and remediation of polyphenols. This work demonstrates rapid and sensitive colorimetric detection of phenolic compounds using nanocomposite of magnesium ferrite (MgFe₂O₄) and manganese oxide (Mn₃O₄) nanoparticles as PPO mimic. The catalytic properties of MgFe₂O₄ and Mn₃O₄ displayed synergistic effect in the nanocomposite. The synthesized nanocomposite and nanoparticles were fully characterized using various analytical techniques. The ratio of MgFe₂O₄ and Mn₃O₄ in the nanocomposite was optimized. Catechol and resorcinol were taken as model polyphenols. The best PPO-activity was shown by MgFe₂O₄@Mn₃O₄ nanocomposite with of w/w ratio 1:2. The results correlated with its higher surface area. Reaction parameters viz. pH, temperature, contact time, substrate concentration, and nanoparticles dose were studied. The synthesized MgFe₂O₄@Mn₃O₄ nanocomposite was used for the detection of catechol in the linear range of 0.1–0.8 mM with the detection limit of 0.20 mM, and resorcinol in the range of 0.01–0.08 mM with the detection limit of 0.03 mM. The estimated total phenolic content of green and black tea correlated well with the conventional method. These results authenticate promising future potential of MgFe₂O₄@Mn₃O₄ nanocomposite as PPO-mimic Full article

Polyurethane nanocomposites were prepared with a nanosized high surface area graphite (HSAG) functionalized on its edges with hydroxyl groups as a building block. Edge functionalization of HSAG was obtained through reaction with KOH. The addition of OH groups was demonstrated by means of infrared (FTIR) and thermogravimetric analysis (TGA), and the Boehm titration allowed estimation of a level of about 5.0 mmol_OH/g_HSAG. Results from wide-angle X-ray diffraction (WAXD) and Raman spectroscopy suggested that functionalization of the graphene layers occurred on the edges. The evaluation of the Hansen solubility parameters of G-OH revealed a substantial increase of δ_P and δ_H parameters with respect to HSAG. In line with these findings, homogeneous and stable dispersions of G-OH in a polyol were obtained. PU were prepared by mixing a dispersion of G-OH in cis-1,4-butenediol with hexamethylene diisocyanate. A model reaction between catechol, 1,4-butanediol, and hexamethylene diisocyanate demonstrated the reactivity of hydroxylated aromatic rings with isocyanate groups. PU-based G-OH, characterized with WAXD and differential scanning calorimetry (DSC), revealed lower T_g, higher T_c, T_m, and crystallinity than PU without G-OH. These results could be due to the higher flexibility of the polymer chains, likely a consequence of the dilution of the urethane bonds by the carbon substrate. Hence, G-OH allowed the preparation of PU with a larger temperature range between T_g and T_m, with potential positive impact on material applications. The model reaction between butylisocyanate and 1-butanol revealed that HSAG and G-OH promote efficient formation of the urethane bond, even in the absence of a catalyst. The effect of high surface area carbon on the nucleophilic oxygen attack to the isocyanate group can be hypothesized. The results here reported lead us to comment that a reactive nanosized sp² carbon allotrope, such as G-OH, can be used as a multifunctional building block of PU. Indeed, G-OH is a comonomer of PU, a promoter of the polymerization reaction, and can definitely act as reinforcing filler by tuning its amount in the final nanocomposite leading to highly versatile materials. The larger temperature range between T_g and T_m, together with the presence of G-OH acting as a reinforcing agent, could allow the production of piezoresistive sensing, shape-memory PU with good mechanical features. Full article

Metallic nanoparticles are usually applied in biosensors as catalysts and/or mediators of electron transfer. We describe the development of amperometric biosensors (ABSs) based on oxidases and nanoparticles of CuCe (nCuCe). nCuCe, being an electro-active mediator and active peroxidase (PO) mimetic, was used as an H₂O₂-sensing platform in oxidase-based ABSs. ABSs for glucose, primary alcohols, methyl amine, catechol, and L-arginine, which are based on corresponding oxidases and nCuCe, were developed. These ABSs exhibited improved analytical characteristics in comparison with the appropriate bi-enzyme ABSs containing natural PO. Including electrodeposited porous gold in the chemo-sensing layer was shown to increase significantly the sensitivities of all constructed ABSs. Full article

Catecholamines are an important class of neurotransmitters responsible for regularizing, controlling, and treating neural diseases. Based on control and diseases treatment, the development of methodology and dives to sensing is a promissory technology area. This work evaluated the role of iron phthalocyanine coordination (FePc) with the specific groups from catecholamine molecules (L-dopa, dopamine, epinephrine, and the amino acid tyrosine) and the effect of this coordination on electrochemical behavior. The in situ coordination analysis was performed through isotherms π-A of FePc Langmuir films in the absence and presence of catecholamines. The π-A isotherm indicates a strong interaction between FePc monolayer and L-Dopa and DA, which present a catechol group and a side chain with a protonated amino group (-NH₃⁺). These strong interactions with catechol and amine groups were confirmed by characterization at the molecular level using the surface-enhanced Raman spectroscopy (SERS) from a Langmuir–Schaefer monolayer deposited onto Ag surfaces. The electrochemical measurements present a similar tendency, with lower oxidation potential observed to DA>L-Dopa>Ep. The results corroborate that the coordination of the analyte on the electron mediator surface plays an essential role in an electrochemical sensing application. The FePc LS film was applied as a sensor in tablet drug samples, showing a uniformity of content of 96% for detecting active compounds present in the L-Dopa drug samples. Full article

The intake of sugar-sweetened beverages has been associated with an augmented prevalence of metabolic diseases, namely, obesity, type II diabetes, and metabolic syndrome. On the other hand, nowadays, it is broadly accepted that foods and beverages rich in (poly)phenols could contribute to reducing the incidence of these pathologies. In this sense, the objective of the work was to revalue second quality citrus fruits for the development of new beverages, rich in anthocyanins and flavanones (maqui berry and second qualities citrus-based), and evaluate the influence of alternative sweeteners (sucralose, sucrose, or stevia), regarding the bioaccessibility and bioavailability of these bioactive compounds in the frame of a chronic (longitudinal) intervention. To fulfill this objective, a longitudinal study of the urinary excretion of anthocyanins and flavanones, after 2-months of ingestion of the developed maqui-citrus beverage, by 138 volunteers (n = 46 per beverage) and the analysis of the resulting phenolic metabolites by ultra-high performance liquid chromatography coupled to mass spectrometry (UHPLC-ESI-QqQ-MS/MS) was carried out. As major results, the bioavailable metabolites of caffeic acid (CA), catechol (CAT), 3,4-di-hydroxyphenylacetic acid (DHPAA), eriodictyol (E), homoeriodictyol (HE), hippuric acid (HA), naringenin (N), trans-ferulic acid (TFA), 2,4,6-tri-hydroxybenzaldehyde (THBA), trans-isoferulic acid (TIFA), and vanillic acid (VA) were detected. Accordingly, significantly different bioavailability was dependent on the sweetener used, allowing proposing stevia and, to a lower extent, sucralose, as valuable alternatives to sucrose. Full article

Iron acquisition pathways have often been considered to be gateways for the uptake of antibiotics into bacteria. Bacteria excrete chelators, called siderophores, to access iron. Antibiotic molecules can be covalently attached to siderophores for their transport into pathogens during the iron-uptake process. P. aeruginosa produces two siderophores and is also able to use many siderophores produced by other bacteria. We investigated the phenotypic plasticity of iron-uptake pathway expression in an epithelial cell infection assay in the presence of two different siderophore–antibiotic conjugates, one with a hydroxamate siderophore and the second with a tris-catechol. Proteomic and RT-qPCR approaches showed that P. aeruginosa was able to sense the presence of both compounds in its environment and adapt the expression of its iron uptake pathways to access iron via them. Moreover, the catechol-type siderophore–antibiotic was clearly more efficient in inducing the expression of its corresponding transporter than the hydroxamate compound when both were simultaneously present. In parallel, the expression of the proteins of the two iron uptake pathways using siderophores produced by P. aeruginosa was significantly repressed in the presence of both conjugates. Altogether, the data indicate that catechol-type siderophores are more promising vectors for antibiotic vectorization using a Trojan-horse strategy. Full article