RESUMEN

In this paper, we present a new design for a chronoamperometric flow cell in which air bubbles do not interfere with the control of potential between the working and reference electrodes. The flow-through dual-detection cell consists of two independent parts: an upper compartment containing a quiescent supporting electrolyte solution and a channel that operates under hydrodynamically controlled conditions. In this system, the working and counter electrodes can be placed directly in contact with both compartments, whereas the reference electrode can be assembled to be either isolated or in contact with the flowing stream channel. The design ensures that the potential applied to the working electrode (controlled in the upper compartment) is similar to the potential applied in the flowing channel. The performance of the proposed flow cell in generating accurate results, even in the presence of air bubbles, was evaluated through successive air-analyte-air injections. In both series where the analyte was introduced, suitable reproducibility was achieved. The robustness of the design was definitively proven by performing a series of measurements in analytical applications for the determination of hydrogen peroxide in antiseptic samples, yielding very satisfactory results.

RESUMEN

Chitosan coatings, derived from crustacean shell waste, possess inherent biocompatibility and biodegradability, rendering them suitable for various biomedical and environmental applications, including electrochemical biosensing. Its amine and hydroxyl functional groups offer abundant sites for chemical modifications to boost the charge transfer kinetics and provide excellent adhesion, enabling the construction of robust electrode-coating interfaces for electroanalysis. This study explores the role of electrostatically-driven chemical interactions and crosslinking density originating from different chitosan (Cs) and glutaraldehyde (Ga) concentrations in this aspect. Studying anionic ([Fe(CN)6]3-/4-), neutral (FcDM0/+), and cationic ([Ru(NH3)6]2+/3+) redox probes highlights the influence of Coulombic interactions with chitosan chains containing positively-charged pathways, calculated by DFT analysis. Our study reveals how a proper Ch-to-Ga ratio has a superior influence on the cross-linking efficacy and resultant charge transfer kinetics, which is primarily boosted by up to 20× analyte preconcentration increase, due to electrostatically-driven migration of negatively charged ferrocyanide ions toward positively charged chitosan hydrogel. Notably the surface engineering approach allows for a two-orders of magnitude enhancement in [Fe(CN)6]4- limit of detection, from 0.1 µM for bare GCE down to even 0.2 nM upon an adequate hydrogel modification.

RESUMEN

A nanohybrid-modified glassy carbon electrode based on conducting polypyrrole doped with carbon quantum dots (QDs) was developed and used for the electrochemical detection of anti-tissue transglutaminase (anti-tTG) antibodies. To improve the polypyrrole conductivity, carrier mobility, and carrier concentration, four types of carbon nanoparticles were tested. Furthermore, a polypyrrole-modified electrode doped with QDs was functionalized with a PAMAM dendrimer and transglutaminase 2 protein by cross-linking with N-hydroxysuccinimide (NHS)/N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC). The steps of electrode surface modification were surveyed via electrochemical measurements (differential pulse voltammetry (DPV), impedance spectroscopy, and X-ray photoelectron spectroscopy (XPS)). The surface characteristics were observed by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and contact angle measurements. The obtained modified electrode exhibited good stability and repeatability. DPV between - 0.1 and 0.6 V (vs. Ag/AgCl 3 M KCl reference electrode) was used to evaluate the electrochemical alterations that occur after the antibody interacts with the antigen (transglutaminase 2 protein), for which the limit of detection was 0.79 U/mL. Without the use of a secondary label, (anti-tTG) antibodies may be detected at low concentrations because of these modified electrode features.

Asunto(s)

RESUMEN

Defects on nanomaterials can effectively enhance the performance of electrochemical detection, but an excessive number of defects may have an adverse effect. In this study, MoS2 nanosheets were synthesized using a hydrothermal synthesis method. By controlling the calcination temperature, MoS2-7H, calcined at 700 °C under H2/Ar2, exhibited an optimal ratio of "point" defects to "plane" defects, resulting in excellent detection performance for mercury ions (Hg(II)). In general, the sulfur vacancies (SV) and undercoordinated Mo generated after calcination of MoS2 significantly promotes the adsorption process and redox of Hg(II) by increasing surface chemical activity, providing additional adsorption sites and adjusting surface charge status to accelerate the catalytic redox of Hg(II). The prepared MoS2-7H-modified electrode showed a sensitivity of 18.25 µA µM-1 and a low limit of detection (LOD) of 6.60 nM towards Hg(II). MoS2-7H also demonstrated a good anti-interference, stability, and exhibited a strong current response in real water samples. The modulation to obtain appropriate number of defects in MoS2 holds promise as a prospective electrode modification material for the electroanalysis.

RESUMEN

In the era of liquid biopsy, microRNAs emerge as promising candidates for the early diagnosis and prognosis of cancer, offering valuable insights into the disease's development. Among all the existing analytical approaches, even if traditional approaches such as the nucleic acid amplification ones have the advantages to be highly sensitive, they cannot be used at the point-of-care, while sensors might be poorly sensitive despite their portability. In order to improve the analytical performance of existing electroanalytical systems, we demonstrate how a simple chromatographic paper-based disk might be useful to rationally improve the sensitivity, depending on the number of preconcentration cycles. A paper-based electrochemical platform for miRNA detection has been developed by modifying a paper-based electrode with a methylene blue (MB)-modified single-stranded sequence (ssDNA) complementary to the chosen miRNA, namely miR-224 that is associated with lung cancer. A detection limit of ca. 0.6 nM has been obtained in spiked human serum samples. To further enhance the sensitivity, an external chromatographic wax-patterned paper-based disk has been adopted to preconcentrate the sample, and this has been demonstrated both in standard and in serum solutions. For each solution, three miR-224 levels have been preconcentrated, obtaining a satisfactory lowering detection limit of ca. 50 pM using a simple and sustainable procedure. This approach opens wide possibilities in the field of analytical and bioanalytical chemistry, being useful not only for electrochemistry but also for other architectures of detection and transduction.

Asunto(s)

RESUMEN

The production, optimisation, physicochemical, and electroanalytical characterisation of a low-cost electrically conductive additive manufacturing filament made with recycled poly(lactic acid) (rPLA), castor oil, carbon black, and graphite (CB-G/PLA) is reported. Through optimising the carbon black and graphite loading, the best ratio for conductivity, low material cost, and printability was found to be 60% carbon black to 40% graphite. The maximum composition within the rPLA with 10 wt% castor oil was found to be an overall nanocarbon loading of 35 wt% which produced a price of less than £0.01 per electrode whilst still offering excellent low-temperature flexibility and reproducible printing. The additive manufactured electrodes produced from this filament offered excellent electrochemical performance, with a heterogeneous electron (charge) transfer rate constant, k0 calculated to be (2.6 ± 0.1) × 10-3 cm s-1 compared to (0.46 ± 0.03) × 10-3 cm s-1 for the commercial PLA benchmark. The additive manufactured electrodes were applied to the determination of ß-estradiol, achieving a sensitivity of 400 nA µM-1, a limit of quantification of 70 nM, and a limit of detection of 21 nM, which compared excellently to other reports in the literature. The system was then applied to the detection of ß-estradiol within four real water samples, including tap, bottled, river, and lake water, where recoveries between 95 and 109% were obtained. Due to the ability to create high-performance filament at a low material cost (£0.06 per gram) and through the use of more sustainable materials such as recycled polymers, bio-based plasticisers, and naturally occurring graphite, additive manufacturing will have a permanent place within the electroanalysis arsenal in the future.

RESUMEN

A sensing interface co-constructed from the two-dimensional conductive material (Ag@MXene) and an antifouling cyclic multifunctional peptide (CP) is described. While the large surface area of Ag@MXene loads more CP probes, CP binds to Ag@MXene to form a fouling barrier and ensure the structural rigidity of the targeting sequence. This strategy synergistically enhances the biosensor's sensitivity and resistance to contamination. The SPR results showed that the binding affinity of the CP to the target was 6.23 times higher than that of the antifouling straight-chain multifunctional peptide (SP) to the target. In the 10 mg/mL BSA electrochemical fouling test, the fouling resistance of Ag@MXene + CP (composite sensing interface of CP combined with Ag@MXene) was 30 times higher than that of the bare electrode. The designed electrochemical sensor exhibited good selectivity and wide dynamic response range at PD-L1 concentrations from 0.1 to 50 ng/mL. The lowest detection limit was 24.54 pg/mL (S/N = 3). Antifouling 2D materials with a substantial specific surface area, coupled with non-straight chain antifouling multifunctional peptides, offer a wide scope for investigating the sensitivity and antifouling properties of electrochemical sensors.

Asunto(s)

RESUMEN

3D-printable composites have become an attractive option used for the design and manufacture of electrochemical sensors. However, to ensure proper charge-transfer kinetics at the electrode/electrolyte interface, activation is often required, with this step consisting of polymer removal to reveal the conductive nanofiller. In this work, we present a novel effective method for the activation of composites consisting of poly(lactic acid) filled with carbon black (CB-PLA) using microwave radiation. A microwave synthesizer used in chemical laboratories (CEM, Matthews, NC, USA) was used for this purpose, establishing that the appropriate activation time for CB-PLA electrodes is 15 min at 70 °C with a microwave power of 100 W. However, the usefulness of an 80 W kitchen microwave oven is also presented for the first time and discussed as a more sustainable approach to CB-PLA electrode activation. It has been established that 10 min in a kitchen microwave oven is adequate to activate the electrode. The electrochemical properties of the microwave-activated electrodes were determined by electrochemical techniques, and their topography was characterized using scanning electron microscopy (SEM), Raman spectroscopy, and contact-angle measurements. This study confirms that during microwave activation, PLAs decompose to uncover the conductive carbon-black filler. We deliver a proof-of-concept of the utility of kitchen microwave-oven activation of a 3D-printed, free-standing electrochemical cell (FSEC) in paracetamol electroanalysis in aqueous electrolyte solution. We established satisfactory limits of linearity for paracetamol detection using voltammetry, ranging from 1.9 µM to 1 mM, with a detection limit (LOD) of 1.31 µM.

RESUMEN

Neonicotinoids, as the fastest-growing class of insecticides, currently account for over 25% of the global pesticide market. Their effectiveness in controlling a wide range of pests that pose a threat to croplands, home yards/gardens, and golf course greens cannot be denied. However, the extensive use of neonicotinoids has resulted in significant declines in nontarget organisms such as pollinators, insects, and birds. Furthermore, the potential chronic, sublethal effects of these compounds on human health remain largely unknown. To address these pressing issues, it is crucial to explore and understand the capabilities of electrochemical sensors in detecting neonicotinoid residues. Surprisingly, despite the increasing importance of this topic, no comprehensive review article currently exists in the literature. Therefore, our proposed review aims to bridge this gap by providing a thorough analysis of the use of electrochemical methods for neonicotinoid determination. In this review article, we will delve into various aspects of electrochemical analysis, including the influence of electrode materials, employed techniques, and the different types of electrode mechanisms utilized. By synthesizing and analysing the existing research in this field, our review will offer valuable insights and guidance to researchers, scientists, and policymakers alike.

Asunto(s)

RESUMEN

The review discusses electrochemical methods for analysis of drug interactions with DNA. The electroanalysis method is based on the registration of interaction-induced changes in the electrochemical oxidation potential of heterocyclic nitrogenous bases in the DNA molecule and in the maximum oxidation current amplitude. The mechanisms of DNA-drug interactions can be identified based on the shift in the electrooxidation potential of heterocyclic nitrogenous bases toward more negative (cathodic) or positive (anodic) values. Drug intercalation into DNA shifts the electrochemical oxidation potential to positive values, indicating thermodynamically unfavorable process that hinders oxidation of nitrogenous bases in DNA. The potential shift toward the negative values indicates electrostatic interactions, e.g., drug binding in the DNA minor groove, since this process does not interfere with the electrochemical oxidation of bases. The concentration-dependent decrease in the intensity of electrochemical oxidation of DNA bases allows to quantify the type of interaction and calculate the binding constants.

Asunto(s)

RESUMEN

This paper presents a low-cost disposable sensor for gallic acid (GA) detection in non-alcoholic and alcoholic beverages using a screen-printed cell (SPC) whose working electrode (in graphite) is modified with electrosynthesized molecularly imprinted polypyrrole (eMIP). Our preliminary characterization of the electrochemical process shows that gallic acid (GA) undergoes irreversible oxidation at potentials of about +0.3 V. The peak potential is not affected by the presence of the eMIP film and alcohol percentages (ethanol) up to 20%. The GA determination is based on a differential pulse voltammetry (DPV) analysis leveraging its oxidation peak. The calibration data and the figures of merit of the analytical method (LOD, LOQ, and linear range) are calculated. To validate the feasibility of the sensor's application for the dosing of GA in real matrices, some non-alcoholic and alcoholic beverages are analyzed. The results are then compared with those reported in the literature and with the total polyphenol content determined by the Folin-Ciocalteu method. In all cases, the concentrations of GA align with those previously found in the literature for the beverages examined. Notably, the values are consistently lower than the total polyphenol content, demonstrating the sensor's selectivity in discriminating the target molecule from other polyphenols present.

RESUMEN

Improving novel and efficient biosensors for determining organic/inorganic compounds is a challenge in analytical chemistry for clinical diagnosis and research in biomedical sciences. Electrochemical enzyme-based biosensors are one of the commercially successful groups of biosensors that make them highly appealing because of their low cost, high selectivity, and sensitivity. Core/shell nanoparticles have emerged as versatile platforms for developing enzyme-based electrochemical biosensors due to their unique physicochemical properties and tunable surface characteristics. This study provides a comprehensive review of recent trends and advancements in the utilization of core/shell nanoparticles for the development of enzyme-based electrochemical biosensors. Moreover, a statistical evaluation of the studies carried out in this field between 2007 and 2023 is made according to the preferred electrochemical techniques. The recent applications of core/shell nanoparticles in enzyme-based electrochemical biosensors were summarized to quantify environmental pollutants, food contaminants, and clinical biomarkers. Additionally, the review highlights recent innovations and strategies to improve the performance of enzyme-based electrochemical biosensors using core/shell nanoparticles. These include the integration of nanomaterials with specific functions such as hydrophilic character, chemical and thermal stability, conductivity, biocompatibility, and catalytic activity, as well as the development of new hybrid nanostructures and multifunctional nanocomposites.

Asunto(s)

RESUMEN

Background and purpose: Diclofenac (DCF) is a non-steroidal anti-inflammatory drug possessing analgesic and antipyretic properties. It is used for the treatment of rheumatoid arthritis pain, osteoarthritis, and acute muscle pain conditions and can be administrated orally, topically or intravenously. Because of its widespread use, hydrophilicity, stability and poor degradation (bioaccumulation in the food chain), DCF is an emerging chemical contaminant that can cause adverse effects in the ecosystems. Taking into account the consumption of DCF in pharmaceutical formulations and its negative impact on the environment, the development of new sensitive, selective, cheap, fast, and online capable analytical devices is needed for on-site applications. Experimental approach: This brief review attempts to cover the recent developments related to the use of nanomaterials as catalysts for electrochemical determination of DCF in pharmaceutical formulations, biological fluids and environmental samples. Key results: The article aims to prove how electrochemical sensors represent reliable alternatives to conventional methods for DCF analysis. Conclusion: The manuscript highlights the progress in the development of electrochemical sensors for DCF detection. We have analyzed numerous recent papers (mainly since 2019) on sensors developed for the quantitative determination of DCF, indicating the limit of detection, linear range, stability, reproducibility, and analytical applications. Current challenges related to the sensor design and future perspectives are outlined.

RESUMEN

3D-printing technology has revolutionized electrochemical applications by enabling rapid prototyping of various devices with high precision, even in highly complex structures. However, a significant challenge remains in developing less costly and more sustainable analytical approaches and methods aimed at mitigating the negative environmental impacts of chemical analysis procedures. In this study, we propose a solution to these challenges by creating a simple and versatile electrochemical system that combines 3D-printing technology with recyclable disposable materials, such as graphite from an exhausted battery and a stainless-steel screw. Our results demonstrate a novel strategy for developing electrodes and other laboratory-made devices that align with the principles of sustainability and green chemistry. Furthermore, we provide evidence of the effectiveness of the proposed system in an analytical application involving the simultaneous determination of tert-butylhydroquinone, acetaminophen, and levofloxacin using the voltammetric technique in lake and groundwater samples. The results indicate sufficient accuracy, with recovery values ranging from 91 to 110%. Additionally, we utilized the Analytical GREEnness calculator as a metric system to evaluate the environmental friendliness of the proposed electroanalytical protocol. The final score confirms a favorable level of sustainability, reaffirming the eco-friendly nature of our approach.

RESUMEN

The construction of materials with rapid electron transfer is considered an effective method for enhancing electrochemical activity in electroanalysis. It has been widely demonstrated that valence changes in transition metal ions can promote electron transfer and thus increase electrochemical activity. Recently, valence-variable transition metal oxides (TMOs) have shown popular application in electrochemical analysis by using their abundant valence state changes to accelerate electron transfer during electrochemical detection. In this review, we summarize recent research advances in valence changes of TMOs and their application in electrochemical analysis. This includes the definition and mechanism of valence change, the association of valence changes with electronic structure, and their applications in electrochemical detection, along with the use of density functional theory (DFT) to simulate the process of electron transfer during valence changes. Finally, the challenges and opportunities for developing and applying valence changes in electrochemical analysis are also identified.

RESUMEN

The growth of liquid biopsy, i. e., the possibility of obtaining health information by analysing circulating species (nucleic acids, cells, proteins, and vesicles) in peripheric biofluids, is pushing the field of sensors and biosensors beyond the limit to provide decentralised solutions for nonspecialists. In particular, among all the circulating species that can be adopted in managing cancer evolution, both for diagnostic and prognostic applications, microRNAs have been highly studied and detected. The development of electrochemical devices is particularly relevant for liquid biopsy purposes, and the screen-printed electrodes (SPEs) represent one of the building blocks for producing novel portable devices. In this work, we have taken miR-2115-3p as model target (it is related to lung cancer), and we have developed a biosensor by exploiting the use of a complementary DNA probe modified with methylene blue as redox mediator. In particular, the chosen sensing architecture was applied to serum measurements of the selected miRNA, obtaining a detection limit within the low nanomolar range; in addition, various platforms were interrogated, namely commercial and hand-made SPEs, with the aim of providing the reader with some insights about the optimal platform to be used by considering both the cost and the analytical performance.

Asunto(s)

RESUMEN

BACKGROUND: Synthetic cannabinoids (SCs) are a broad class of illicit drugs that are classified according to the chemical structure of the aromatic core that they present (i.e., indole, imidazole, pyrrole) and their detection is still a challenge, despite their widespread diffusion. The identification of a specific class of SC in complex matrices, such as real samples with a rapid, economic analytical device useable directly in the field, is highly desirable, as it can provide immediate and reliable information that eventually addresses more targeted analyses. RESULTS: The present paper proposes a Molecularly Imprinted Polymer (MIP)-based voltammetric sensor for the rapid and selective detection of indazole-type SCs. In this context, a polyacrylate-based MIP was used to functionalize a Pt electrode. The MIP composition was optimized through a Design of Experiments approach, and for the sake of safety, a non-psychotropic compound structurally related to the selected SCs was employed as the template in the MIP formulation. A complete characterization of the electrochemical behavior of the selected SCs was performed, and differential pulse voltammetry (DPV) in acetonitrile/lithium perchlorate 0.1 M was the technique applied for their quantification. LOD around 0.01 mM and linearity up to 0.8 mM were found. Comparison with the non-imprinted (NIP) modified and bare electrodes showed better selectivity and reproducibility of the MIP-based sensor. Recovery tests (in the 70-115 % range) were performed on simulated pills and smoking mixtures to test the reliability of the proposed method. SIGNIFICANCE: The method proposed allows the identification and quantification of indazole-based SCs as a class in complex matrices. Due to the selectivity of the obtained device, no clean-up of the sample before analyses is needed. For the same reason, the interference of cutting substances and natural cannabinoids was negligible.

Asunto(s)

RESUMEN

Liposomes have emerged as a drug delivery system for various chemotherapeutics providing enhanced bioavailability and reduced toxicity. In vitro drug release profiling of liposomal formulations is one of the essential tests for the premarket approval and post market quality control. We developed an automated electroanalytical method for drug release profiling of liposomal doxorubicin formulation. In this electroanalytical method, square wave voltammetry mode was selected to determine the released drug, the only redox-active analyte, by measuring the current at the pulsed potential ranges. Therefore, no separation from liposomal encapsulated doxorubicin is needed. This electroanalytical method provided a continuous drug release measurement for 24 h. The drug release increased as the release media pH and temperature increased. At 37 °C, the drug release increased from 7 % to 40 % when the pH increased from 5.5 to 7.4, In addition, at pH 6.5, as the temperature increased from 37 °C to 52 °C, total drug release increased by more than two-fold. Complete drug release (more than 80 %) was obtained at pH 6.5 and 52 °C in less than 3 h. The brand name and the two generic formulations showed similar drug release profile in all experimental conditions. This method is an alternative to traditional methods which require separation steps such as dialysis or solid phase extraction to quantitate released doxorubicin. This method may be further applied in the in vitro release testing of other liposomal formulations containing redox-active drug substances, e.g., liposomes encapsulating daunorubicin.

Asunto(s)

RESUMEN

The highly toxic arsenite (As(III)) could cause serious cytotoxicity on metabolism, resulting in several diseases. However, it is still a great challenge on the precise sensing of As(III) in complicated conditions, especially in cellular environment. In this work, a nanoporous gold microelectrode (NPG-µE) was fabricated by a simple electrochemical alloying/dealloying method and developed for the electroanalysis of As(III) in the lung cancer cellular (A549 cells) environment. The as-fabricated NPG-µE exhibited the excellent electrochemical performance towards As(III) detection at physiological pH (0.1 M PBS solution, pH 7.4) with a high sensitivity of 5.07 µA ppb-1 cm-2 and a low limit of detection of 0.25 ppb (S/N = 3). The large surface area derived from the nanoporous structure, and the well-dispersed active sites as well as the highly electro-catalytic activity of gold played a critical role on the improved electrochemical behaviors. Furthermore, the effect of the exposure time on electrochemical monitoring As(III) in A549 cellular environment was successfully investigated, revealing the fatal impact of As(III) on cell cycle. This work offered a great trial on investigating of the cytotoxicity of arsenite and their precise detection in complicated cellular environment.

Asunto(s)

RESUMEN

An electrochemical sensor for the detection of uric acid was constructed using cobalt oxide-modified porous carbon@multi-walled carbon nanotube (MWCNTs) composite material for the modification of the electrode. Firstly, ZIF-67 is generated on carbon nanotubes using the surfactant cetylammonium bromide (CTAB) as template. The vesicles generated by CTAB act as nucleation sites for the in situ growth of ZIF-67. Then, cobalt oxide-modified porous carbon was obtained after high-temperature carbonization of ZIF-67, leading to the formation of cobalt oxide-modified porous carbon@MWCNT composite materials. Co-N and Co-O active sites on the composite material can improve the oxidation of uric acid on the electrode surface, leading to enhanced sensitivity and selectivity for uric acid detection. The sensor has a good linear range from 1 to 40 µM for uric acid detection with a detection limit of 0.09 µM. The sensor was utilized for determination of uric acid in actual serum samples.