Core-Shell Nanocables Decorated with Carbon Spherical Shells and Silver Nanoparticles for Sensing Ethinylestradiol Hormone in Water Sources and Pills.

The selective, rapid detection of low levels of hormones in drinking water and foodstuffs requires materials suitable for inexpensive sensing platforms. We report on core-shell Ag@C nanocables (NCs) decorated with carbon spherical shells (CSSs) and silver nanoparticles (AgNPs) by using a hydrothermal green approach. Sensors were fabricated with homogeneous, porous films on screen-printed electrodes, which comprised a 115 nm silver core covered by a 122 nm thick carbon layer and CSSs with 168 nm in diameter. NCs and CSSs were also decorated with 10-25 nm AgNPs. The NC/CSS/AgNP sensor was used to detect ethinylestradiol using square wave voltammetry in 0.1 M phosphate buffer (pH 7.0) over the 1.0-10.0 µM linear range with a detection limit of 0.76 µM. The sensor was then applied to detect ethinylestradiol in tap water samples and a contraceptive pill with recovery percentages between 93 and 101%. The high performance in terms of sensitivity and selectivity for hormones is attributed to the synergy between the carbon nanomaterials and AgNPs, which not only increased the sensor surface area and provided sites for electron exchange but also imparted an increased surface area.

Sustainable plant-wearable sensors for on-site, rapid decentralized detection of pesticides toward precision agriculture and food safety.

The synergy between eco-friendly biopolymeric films and printed devices leads to the production of plant-wearable sensors for decentralized analysis of pesticides in precision agriculture and food safety. Herein, a simple method for fabrication of flexible, and sustainable sensors printed on cellulose acetate (CA) substrates has been demonstrated to detect carbendazim and paraquat in agricultural, water and food samples. The biodegradable CA substrates were made by casting method while the full electrochemical system of three electrodes was deposited by screen-printing technique (SPE) to produce plant-wearable sensors. Analytical performance was assessed by differential pulse (DPV) and square wave voltammetry (SWV) in a linear concentration range between 0.1 and 1.0 µM with detection limits of 54.9 and 19.8 nM for carbendazim and paraquat, respectively. The flexible and sustainable non-enzymatic plant-wearable sensor can detect carbendazim and paraquat on lettuce and tomato skins, and also water samples with no interference from other pesticides. The plant-wearable sensors had reproducible response being robust and stable against multiple flexions. Due to high sensitivity and selectivity, easy operation and rapid agrochemical detection, the plant-wearable sensors can be used to detect biomarkers in human biofluids and be used in on-site analysis of other hazardous chemical substances.

Optimized paper-based electrochemical sensors treated in acidic media to detect carbendazim on the skin of apple and cabbage.

Wearable sensors such as those made with paper are needed for non-destructive routine analysis of pesticides on plants, fruits, and vegetables. Herein we report on electrochemical sensors made with screen-printed carbon electrodes on kraft and parchment papers to detect the fungicide carbendazim. A systematic optimization was performed to find that electrochemical sensors on kraft paper treated in an acidic medium led to the highest performance, with a detection limit of 0.06 µM for carbendazim. The enhanced sensitivity for this sensor was attributed to the porous nature of kraft paper, which allowed for a large electrode surface area, and to the carboxylic groups formed during electrochemical activation. As a proof-of-concept, the electrochemical sensor attached to the skin of apple and cabbage was used to detect carbendazim with the same performance as the gold standard method, thus demonstrating that the sensor can be used in the farm and on supermarket shelves.

Label-Free Electrochemical Immunosensor Made with Tree-like Gold Dendrites for Monitoring 25-Hydroxyvitamin D3 Metabolite.

Flexible, fully printed immunosensors can meet the requirements of precision nutrition, but this demands optimized molecular architectures to reach the necessary sensitivity. Herein, we report on flexible and label-free immunosensor chips made with tree-like gold dendrites (AuDdrites) electrochemically formed by selective desorption of l-cysteine (L-cys) on (111) gold planes. Electrodeposition was used because it is scalable and cost-effective for a rapid, direct growth of Au hyperbranched dendritic structures. The 25-hydroxyvitamin D3 (25(OH)D3) metabolite was detected within 15 min with a limit of detection (LOD) of 0.03 ng mL-1. This high performance was possible due to the careful optimization of the electroactive layer and working conditions for square wave voltammetry (SWV). Electrocrystallization was manipulated by controlling the deposition potential and the molar ratio between HAuCl4 and L-cys. Metabolite detection was performed on human serum and saliva samples with adequate recovery between 97% and 100%. The immunosensors were stable and reproducible, unresponsive to interference from other molecules in human serum and saliva. They can be extended for use as wearable sensors with their mechanical flexibility and possible customization.

Low-cost bacterial nanocellulose-based interdigitated biosensor to detect the p53 cancer biomarker.

Low-cost sensors to detect cancer biomarkers with high sensitivity and selectivity are essential for early diagnosis. Herein, an immunosensor was developed to detect the cancer biomarker p53 antigen in MCF7 lysates using electrical impedance spectroscopy. Interdigitated electrodes were screen printed on bacterial nanocellulose substrates, then coated with a matrix of layer-by-layer films of chitosan and chondroitin sulfate onto which a layer of anti-p53 antibodies was adsorbed. The immunosensing performance was optimized with a 3-bilayer matrix, with detection of p53 in MCF7 cell lysates at concentrations between 0.01 and 1000 Ucell. mL-1, and detection limit of 0.16 Ucell mL-1. The effective buildup of the immunosensor on bacterial nanocellulose was confirmed with polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and surface energy analysis. In spite of the high sensitivity, full selectivity with distinction of the p53-containing cell lysates and possible interferents required treating the data with a supervised machine learning approach based on decision trees. This allowed the creation of a multidimensional calibration space with 11 dimensions (frequencies used to generate decision tree rules), with which the classification of the p53-containing samples can be explained.

Wearable sensors made with solution-blow spinning poly(lactic acid) for non-enzymatic pesticide detection in agriculture and food safety.

On-site monitoring the presence of pesticides on crops and food samples is essential for precision and post-harvest agriculture, which demands nondestructive analytical methods for rapid, low-cost detection that is not achievable with gold standard methods. The synergy between eco-friendly substrates and printed devices may lead to wearable sensors for decentralized analysis of pesticides in precision agriculture. In this paper we report on a wearable non-enzymatic electrochemical sensor capable of detecting carbamate and bipyridinium pesticides on the surface of agricultural and food samples. The low-cost devices (

A sandwich-type electrochemical immunosensor based on Au-rGO composite for CA15-3 tumor marker detection.

A sensitive detection of carbohydrate antigen 15-3 (CA15-3) levels may allow for early diagnosis and monitoring the treatment of breast cancer, but this can only be made in routine clinical practice if low-cost immunosensors are available. In this work, we developed a sandwich-type electrochemical immunosensor capable of rapid detection of CA15-3 with an ultra-low limit of detection (LOD) of 0.08 fg mL-1 within a wide linear concentration range from 0.1 fg mL-1 to 1 µg mL-1. The immunosensor had a matrix of a layer-by-layer film of Au nanoparticles and reduced graphene oxide (Au-rGO) co-electrodeposited on screen-printed carbon electrodes (SPCE). The high sensitivity was achieved by using secondary antibodies (Ab2) labeled with horseradish peroxidase (HRP) in the presence of hydrogen peroxide (H2O2) as signal amplifiers, and hydroquinone (HQ) was used as an electron mediator. The immunosensor was selective for CA15-3 in human serum and artificial saliva samples, robust, and stable to permit storage at 4 °C for more than 30 days. With its high performance, the immunosensor may be incorporated into future point-of-care (POC) devices to determine CA15-3 in distinct biological fluids, including in blood and saliva samples.

Flexible and integrated dual carbon sensor for multiplexed detection of nonylphenol and paroxetine in tap water samples.

Multiplex detection of emerging pollutants is essential to improve quality control of water treatment plants, which requires portable systems capable of real-time monitoring. In this paper we describe a flexible, dual electrochemical sensing device that detects nonylphenol and paroxetine in tap water samples. The platform contains two voltammetric sensors, with different working electrodes that were either pretreated or functionalized. Each working electrode was judiciously tailored to cover the concentration range of interest for nonylphenol and paroxetine, and square wave voltammetry was used for detection. An electrochemical pretreatment with sulfuric acid on the printed electrode enabled a selective detection of nonylphenol in 1.0-10 × 10-6 mol L-1 range with a limit of detection of 8.0 × 10-7 mol L-1. Paroxetine was detected in the same range with a limit of detection of 6.7 × 10-7 mol L-1 using the printed electrode coated with a layer of carbon spherical shells. Simultaneous detection of the two analytes was achieved in tap water samples within 1 min, with no fouling and no interference effects. The long-term monitoring capability of the dual sensor was demonstrated in phosphate buffer for 45 days. This performance is statistically equivalent to that of high-performance liquid chromatography (HPLC) for water analysis. The dual-sensor platform is generic and may be extended to other water pollutants and clinical biomarkers in real-time monitoring of the environment and health conditions. Silver pseudo-reference electrodes for paroxetine (REP) and nonylphenol (REN), working electrodes for paroxetine (WP) and nonylphenol (WN), and auxiliary electrode (AE). USP refers to the University of Sao Paulo. "Red" is reduced form and "Oxi" is oxidized form of analytes.

Biomimetic electrochemical sensors: New horizons and challenges in biosensing applications.

The urge to meet the ever-growing needs of sensing technology has spurred research to look for new alternatives to traditional analytical methods. In this scenario, the glucometer is the flagship of commercial electrochemical sensing platforms, combining selectivity, reliability and portability. However, other types of enzyme-based biosensors seldom achieve the market, in spite of the large and increasing number of publications. The reasons behind their commercial limitations concern enzyme denaturation, and the high costs associated with procedures for their extraction and purification. In this sense, biomimetic materials that seek to imitate the desired properties of natural enzymes and biological systems have come out as an appealing path for robust and sensitive electrochemical biosensors. We herein portray the historical background of these biomimicking materials, covering from their beginnings until the most impactful applications in the field of electrochemical sensing platforms. Throughout the discussion, we present and critically appraise the major benefits and the most significant drawbacks offered by the bioinspired systems categorized as Nanozymes, Synzymes, Molecularly Imprinted Polymers (MIPs), Nanochannels, and Metal Complexes. Innovative strategies of fabrication and challenging applications are further reviewed and evaluated. In the end, we ponder over the prospects of this emerging field, assessing the most critical issues that shall be faced in the coming decade.

Electrocatalytic Oxidation of Methanol, Ethanol, and Glycerol on Ni(OH)2 Nanoparticles Encapsulated with Poly[Ni(salen)] Film.

This study describes a systematic investigation of the electrocatalytic activity of poly[Ni(salen)] films, as catalysts for the electro-oxidation of Cn alcohols (Cn = methanol, ethanol, and glycerol) in alkaline medium. The [Ni(salen)] complex was electropolymerized on a glassy carbon surface and electrochemically activated in NaOH solution by cyclic voltammetry. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy results indicate that during the activation step the polymeric film hydrolyzes, leading to the formation of ß-Ni(OH)2 spherical nanoparticles, with an average size of 2.4 ± 0.5 nm, encapsulated with the poly[Ni(salen)] film. Electrochemical results obtained together with the in situ Fourier transform infrared spectroscopy confirm that the electro-oxidation of methanol, ethanol, and glycerol occurs by involving a cycling oxidation of ß-Ni(OH)2 with the formation of ß-NiOOH species, followed by the charge transfer to the alcohols, which regenerates ß-Ni(OH)2. Analyses of the oxidation products at low potentials indicate that the major product obtained during the oxidation of methanol and glycerol is the formate, while the oxidation of ethanol leads to the formation of acetate. On the other hand, at high potentials (E = 0.6 V), there is evidence that the oxidation of Cn alcohols leads to carbonate ions as an important product.

Adsorption according to the Langmuir-Freundlich model is the detection mechanism of the antigen p53 for early diagnosis of cancer.

Biosensors for early detection of cancer biomarkers normally depend on specific interactions between such biomarkers and immobilized biomolecules in the sensing units. Though these interactions are expected to yield specific, irreversible adsorption, the underlying mechanism appears not to have been studied in detail. In this paper, we show that adsorption explained with the Langmuir-Freundlich model is responsible for detection of the antigen p53 associated with various types of cancers. Irreversible adsorption was proven between anti-p53 antibodies immobilized on the biosensors and the antigen p53, with the adequacy of the Langmuir-Freundlich model being confirmed with three independent experimental methods, viz. polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS), nanogravimetry using a quartz crystal microbalance and electrochemical impedance spectroscopy. The method based on this irreversible adsorption was sufficiently sensitive (limit of detection of 1.4 pg mL(-1)) for early diagnosis of Hodgkin lymphoma, pancreatic and colon carcinomas, and bladder, ovarian and lung cancers, and could distinguish between MCF7 cells containing the antigen p53 from Saos-2 cells that do not contain it.

Sensitive determination of carbendazim in orange juice by electrode modified with hybrid material.

This paper describes the application of a glassy carbon electrode modified with a thin film of mesoporous silica/multiwalled carbon nanotubes for voltammetric determination of the fungicide carbendazim (CBZ). The hybrid material, (SiO2/MWCNT), was obtained by a sol-gel process using HF as the catalyst. The amperometric response to CBZ was measured at +0.73 V vs. Ag/AgCl by square wave voltammetry at pH 8.0. SiO2/MWCNT/GCE responded to CBZ in the linear range from 0.2 to 4.0 µmol L(-1). The calculated detection limit was 0.056 µmol L(-1), obtained using statistical methods. The SiO2/MWCNT/GCE sensor presented as the main characteristics high sensitivity, low detection limit and robustness, allowing CBZ determination in untreated real samples. In addition, this strategy afforded remarkable selectivity for CBZ against ascorbic and citric acid which are the main compounds of the orange juice. The excellent sensitivity and selectivity yielded feasible application for CBZ detection in orange juice sample.

Simultaneous determination of epinephrine and dopamine by electrochemical reduction on the hybrid material SiO2/graphene oxide decorated with Ag nanoparticles.

This paper describes the synthesis, characterization and applications of a new hybrid material composed of mesoporous silica (SiO2) modified with graphene oxide (GO), SiO2/GO, obtained by the sol-gel process using HF as the catalyst. The hybrid material, SiO2/GO, was decorated with silver nanoparticles (AgNPs) with a size of less than 20 nanometres, prepared directly on the surface of the material using N,N-dimethylformamide (DMF) as the reducing agent. The resulting material was designated as AgNP/SiO2/GO. The Ag/SiO2/GO material was characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and high-resolution transmission electron microscopy (HR-TEM). A glassy carbon electrode modified with AgNP/SiO2/GO was used in the development of a sensitive electrochemical sensor for the simultaneous determination of epinephrine and dopamine employing electrocatalytic reduction using squarewave voltammetry. Well-defined and separate reduction peaks were observed in PBS buffer at pH 7. No significant interference was seen for primarily biological interferents such as uric acid and ascorbic acid in the detection of dopamine and epinephrine. Our study demonstrated that the resultant AgNP/SiO2/GO-modified electrode is highly sensitive for the simultaneous determination of dopamine and epinephrine, with the limits of detection being 0.26 and 0.27 µmol L(-1), respectively. The AgNP/SiO2/GO-modified electrode is highly selective and can be used to detect dopamine and epinephrine in a human urine sample.

Highly sensitive contactless conductivity microchips based on concentric electrodes for flow analysis.

In this communication, we describe for the first time the integration of concentric electrodes (wrapping around the microchannel) in microchips. The use of such electrodes has been shown to be effective towards improvement of the sensitivity and detectability in pressure-driven flow platforms incorporating C(4)D.

Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes.

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

Computational, electrochemical, and spectroscopic, studies of acetycholinesterase covalently attached to carbon nanotubes.

This manuscript describes results related to the characterization of electrodes modified with a composite of acetylcholinesterase covalently bound to carbon nanotubes (CNT). The characterization was performed by computational methods and complemented by cyclic voltammetry, infrared spectroscopy, and electrochemical impedance spectroscopy. In-silico simulations enabled the identification of the binding site and the calculation of the interaction energy. Besides complementing the computational studies, experimental results obtained by cyclic voltammetry showed that the addition of CNT to the surface of electrodes yielded significant increases in effective area and greatly facilitated the electron transfer reactions. These results are also in agreement with impedance spectroscopy data, which indicated a high apparent rate constant, even after the immobilization of the enzyme. These results lend new information about the physical and chemical properties of biointerfaces at the molecular level, specifically about the mechanism and consequences of the interaction of a model enzyme with CNT.

A new strategy to investigate the toxicity of nanomaterials using Langmuir monolayers as membrane models.

Nanomaterials such as carbon nanotubes (CNTs) and nanoparticles have received enormous attention in analytical areas for their potential applications as new tools for biotechnology and life sciences. Most of these possible applications involve the use of CNTs and related materials as vehicles for drug delivery and/or gene therapy. In this study, we introduce a methodology to evaluate the interactions between CNTs/dendrimers nanoconjugates and phospholipid biomembrane models, using the Langmuir film balance technique. Our main goal was to elucidate the action of engineered nanomaterials in cell membranes, at the molecular level, using a membrane model system. The penetration of single-walled carbon nanotubes (SWCNTs)/polyamidoamine dendrimer nanocomplexes into dipalmitoylphosphatidylcholine monolayers was pronounced, as revealed by adsorption kinetics and surface pressure measurements. These findings suggest that SWCNTs were able to interact even at high surface pressure values, ∼30 mN/m. Therefore, the results confirm that the presence of the nanomaterial affects the packing of the synthetic membranes. We believe the methodology introduced here may be of great importance for further nanotoxicity studies.

Electrochemical detection of carbamate pesticides in fruit and vegetables with a biosensor based on acetylcholinesterase immobilised on a composite of polyaniline-carbon nanotubes.

A sensitive electrochemical acetylcholinesterase (AChE) biosensor was successfully developed on polyaniline (PANI) and multi-walled carbon nanotubes (MWCNTs) core-shell modified glassy carbon electrode (GC), and used to detect carbamate pesticides in fruit and vegetables (apple, broccoli and cabbage). The pesticide biosensors were applied in the detection of carbaryl and methomyl pesticides in food samples using chronoamperometry (CA). The GC/MWCNT/PANI/AChE biosensor exhibited detection limits of 1.4 and 0.95µmolL(-1), respectively, for carbaryl and methomyl. These detection limits were below the allowable concentrations set by Brazilian regulation standards for the samples in which these pesticides were analysed. Reproducibility and repeatability values of 2.6% and 3.2%, respectively, were obtained in the conventional procedure. The proposed biosensor was successfully applied in the determination of carbamate pesticides in cabbage, broccoli and apple samples without any spiking procedure. The obtained results were in full agreement with those from the HPLC procedure.

Use of hg-electroplated-pt ultramicroelectrode for determining elemental sulphur in naphtha samples.

This paper describes the applicability of a Hg-electroplated-Pt ultramicroelectrode in the quantification of elemental sulphur in naphtha samples by square-wave voltammetry. A reproducible deposition methodology was studied and is reported in this paper. This methodology is innovative and relies on the quality of the mercury stock solution to obtain reproducible surfaces required for the analytical methodology. All analyses were performed using a Hg-electroplated-Pt ultramicroelectrode (Hg-Pt UME) due to the low sensibility of such devices to ohmic drops in resistive solutions. The responses of the peak areas in voltammetric experiments were linear in all of the range studied. The method developed here is accurate and reproducible, with a detection limit of 0.010 mg L(-1) and a good recovery range for both standard solutions of elemental sulphur (85 to 99%) and real naphtha sample (79%). These results attest to the potential for the application of this electroanalytical methodology in determining elemental sulphur in naphtha samples containing mercaptans and disulphides.

SnO(2)-based materials for pesticide degradation.

This study presents the results of the degradation of the pesticide atrazine using electrochemical and photo-assisted electrochemical degradation techniques using SnO(2)-containing electrode of nominal composition electrodes of composition Ti/Ru(X)Sn(1-X)O(2) (where X=0.10, 0.15, 0.20, 0.25 and 0.30). The materials were characterized ex situ and in situ in order to correlate the observed atrazine removal rates with electrode morphology/composition. The results obtained demonstrate the effectiveness of the photo-assisted electrochemical degradation. Using purely electrochemical methods the rate of atrazine removal is almost zero at all the electrodes studied. However, the application of photo-assisted degradation results in almost complete atrazine removal in 1h of electrolysis. The efficiency of atrazine degradation does not seem to be greatly affected by the electrode material or by SnO(2) content, but the overall COD removal is dependent on the SnO(2) content. Overall, the SnO(2)-containing electrodes do not reach the level of COD removal (maximum approximately 21%) seen for the Ti/Ru(0.3)Ti(0.7)O(2) electrode. An interesting correlation between the morphology factor (phi) and chemical oxygen demand removal is observed.