Nanostructures of Prussian blue supported on activated biochar for the development of a glucose biosensor.

This work emphasizes the utilization of biochar, a renewable material, as an interesting platform for anchoring redox mediators and bioreceptors in the development of economic, environmentally friendly biosensors. In this context, Fe(III) ions were preconcentrated on highly functionalized activated biochar, allowing the stable synthesis of Prussian blue nanostructures with an average size of 58.3 nm. The determination of glucose was carried out by indirectly monitoring the hydrogen peroxide generated through the enzymatic reaction, followed by its subsequent redox reaction with reduced Prussian blue (also known as Prussian white) in a typical electrochemical-chemical mechanism. The EDC/NHS (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-Hydroxysuccinimide) pair was employed for the stable covalent immobilization of the enzyme on biochar. The biosensor demonstrated good enzyme-substrate affinity, as evidenced by the Michaelis-Menten apparent kinetic constant (4.16 mmol L-1), and analytical performance with a wide linear dynamic response range (0.05-5.0 mmol L-1), low limits of detection (0.94 µmol L-1) and quantification (3.13 µmol L-1). Additionally, reliable repeatability, reproducibility, stability, and selectivity were obtained for the detection of glucose in both real and spiked human saliva and blood serum samples.

Platinum Nanoparticles Supported by Carbon Nanotubes: Improvement in electrochemical sensor performance for caffeine determination.

Platinum nanoparticles supported by carbon nanotubes were obtained by a simple chemical route and used for preparation of electrochemical sensor towards caffeine determination. Carbon nanotubes were used before and after an acid treatment, yielding two different materials. Morphological and structural characterization of these materials showed platinum nanoparticles (size around 12 nm) distributed randomly along carbon nanotubes. Modified electrodes were directly prepared through a dispersion of these materials. Voltammetric studies in the presence of caffeine revealed an electrocatalytic effect of platinum oxides, electrochemically produced from the chemical oxidation of the platinum nanoparticles. This behavior was explored in the development a selective method for caffeine determination based on platinum oxide reduction at a lower potential value (+0.45 V vs. Ag/AgCl). Using the best set of experimental conditions, it was shown a linear relationship for the caffeine concentration ranging from 5.0 to 25 µmol L-1 with a sensitivity of 449 nA L µmol-1. Limits of detection and quantification of 0.54 and 1.80 µmol L-1 were calculated, respectively. Recovery values for real samples of caffeine pharmaceutical formulations between 98.6% and 101.0% (n = 3) were obtained using the proposed procedure. Statistical calculations showed good concordance (95% confidence level) between the added and recovery values.

Nanoarchitected graphene/copper oxide nanoparticles/MoS2 ternary thin films as highly efficient electrodes for aqueous sodium-ion batteries.

Sodium-ion batteries (SIBs) operating in aqueous electrolyte are an emerging technology that promises to be safer, cheaper, more sustainable and more efficient than their lithium-based counterparts. One of the great challenges associated with this technology is the development of advanced materials with high specific capacity to be used as electrodes. Herein, we describe an ingenious strategy to prepare unprecedented tri-component nanoarchitected thin films with superior performance when applied as anodes in aqueous SIBs. Taking advantage of the broadness and versatility of the liquid-liquid interfacial route, three transparent nanocomposite films comprising graphene, molybdenum sulphide and copper oxide nanoparticles have been prepared. The samples were characterized using several techniques, and the results demonstrated that depending on the specific experimental strategy, different nanoarchitectures are achieved, resulting in different and improved properties. An astonishing capacity of 1377 mA h g-1 at 0.1 A g-1 and a degree of recovery of 100% were observed for the film in which the interactions among the components were optimized. This is among the highest capacity values reported in the literature and demonstrates the potential of these tri-component materials to be used as anodes in aqueous sodium-ion batteries.

Simultaneous detection of dopamine and ascorbic acid by using a thread-based microfluidic device and multiple pulse amperometry.

This study presents a novel approach for the simultaneous detection of ascorbic acid (AA) and dopamine (DA) using an affordable and user-friendly microfluidic device. Microfluidic devices, when combined with electrochemical detectors like screen-printed electrodes (SPEs), offer numerous advantages such as portability, high sample throughput, and low reagent consumption. In this study, a 3D-printed microfluidic device called a µTED was developed, utilizing textile threads as microfluidic channels and an unmodified SPE as the amperometric detector. The method employed multiple pulse amperometry (MPA) with carefully selected potential values (+0.65 V and -0.10 V). The reduction current signals generated by dopamine o-quinone were used to calculate a correction factor for the oxidation signals of ascorbic acid, enabling simultaneous quantification. The developed microfluidic device ensured a stable flow rate of the carrier solution at 1.19 µL s-1, minimizing the consumption of samples and reagents (injection volume of 2.0 µL). Under the optimized experimental conditions, a linear range from 50 to 900 µmol L-1 was achieved for both DA and AA. The obtained sensitivities were 2.24 µA L mmol-1 for AA and 5.09 µA L mmol-1 for DA, with corresponding limits of detection (LOD) of 2.60 µmol L-1 and 1.54 µmol L-1, respectively. To confirm the effectiveness of the proposed method, it was successfully applied to analyze AA and DA in a commercial blood serum sample spiked at three different concentration levels, with a medium recovery rate of 70%. Furthermore, the MPA technique demonstrated its simplicity by enabling the simultaneous determination of AA and DA without the need for prior separation steps or the use of chemically modified electrodes.

Disposable electrochemical platform based on solid-binding peptides and carbon nanomaterials: an alternative device for leishmaniasis detection.

Neglected tropical diseases are those caused by infectious agents or parasites and are considered endemic in low-income populations. These diseases also have unacceptable indicators and low investment in research, drug production, and control. Tropical diseases such as leishmaniasis are some of the main causes of morbidity and mortality around the globe. Electrochemical immunosensors are promising tools for diagnostics against these diseases. One such benefit is the possibility of assisting diagnosis in isolated regions, where laboratory infrastructure is lacking. In this work, different peptides were investigated to detect antibodies against Leishmania in human and canine serum samples. The peptides evaluated (395-KKG and 395-G) have the same recognition site but differ on their solid-binding domains, which ensure affinity to spontaneously bind to either graphene oxide (GO) or graphene quantum dots (GQD). Cyclic voltammetry and differential pulse voltammetry were employed to investigate the electrochemical behavior of each assembly step and the role of each solid-binding domain coupled to its anchoring material. The graphene affinity peptide (395-G) showed better reproducibility and selectivity when coupled to GQD. Under the optimized set of experimental conditions, negative and positive human serum samples responses were distinguished based on a cut-off value of 82.5% at a 95% confidence level. The immunosensor showed selective behavior to antibodies against Mycobacterium leprae and Mycobacterium tuberculosis, which are similar antibodies and potentially sources of false positive tests. Therefore, the use of the graphene affinity peptide as a recognition site achieved outstanding performance for the detection of Leishmania antibodies.

Using low-cost disposable immunosensor based on flexible PET screen-printed electrode modified with carbon black and gold nanoparticles for sensitive detection of SARS-CoV-2.

To help meet the global demand for reliable and inexpensive COVID-19 testing and environmental analysis of SARS-CoV-2, the present work reports the development and application of a highly efficient disposable electrochemical immunosensor for the detection of SARS-CoV-2 in clinical and environmental matrices. The sensor developed is composed of a screen-printed electrode (SPE) array which was constructed using conductive carbon ink printed on polyethylene terephthalate (PET) substrate made from disposable soft drink bottles. The recognition site (Spike S1 Antibody (anti-SP Ab)) was covalently immobilized on the working electrode surface, which was effectively modified with carbon black (CB) and gold nanoparticles (AuNPs). The immunosensing material was subjected to a multi-technique characterization analysis using X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) with elemental analysis via energy dispersive spectroscopy (EDS). The electrochemical characterization of the electrode surface and analytical measurements were performed using cyclic voltammetry (CV) and square-wave voltammetry (SWV). The immunosensor was easily applied for the conduct of rapid diagnoses or accurate quantitative environmental analyses by setting the incubation period to 10 min or 120 min. Under optimized conditions, the biosensor presented limits of detection (LODs) of 101 fg mL-1 and 46.2 fg mL-1 for 10 min and 120 min incubation periods, respectively; in addition, the sensor was successfully applied for SARS-CoV-2 detection and quantification in clinical and environmental samples. Considering the costs of all the raw materials required for manufacturing 200 units of the AuNP-CB/PET-SPE immunosensor, the production cost per unit is 0.29 USD.

Gold-binding peptide as a selective layer for electrochemical detection of SARS-CoV-2 antibodies.

Electrochemical immunosensors are excellent alternatives to prepare portable platforms used for rapid and inexpensive diagnostic of infectious diseases such as the recently emerged COVID-19. Incorporating synthetic peptides as selective recognition layers combined with nanomaterials such as gold nanoparticles (AuNPs) can significantly enhance the analytical performance of immunosensors. In the present study, an electrochemical immunosensor based on solid-binding peptide was built and evaluated towards SARS-CoV-2 Anti-S antibodies detection. The peptide used as recognition site has two important portions: one based on the viral receptor binding domain (RBD), capable of recognizing antibodies of the spike protein (Anti-S), and another suitable for interacting with gold nanoparticles. Gold-binding peptide (Pept/AuNP) dispersion was used directly to modify a screen-printed carbon electrode (SPE). The voltammetric behavior of the [Fe(CN)6]3-/4- probe after every construction and detection step was recorded using cyclic voltammetry by assessing the stability of the Pept/AuNP as a recognition layer onto the electrode surface. Differential pulse voltammetry was used as a detection technique, and a linear working range from 75 ng mL-1 to 15 µg mL-1 was established, with 1.059 µA dec-1 of sensitivity and R2 = 0.984. The response selectivity against SARS-CoV-2 Anti-S antibodies was investigated in presence of concomitant species. The immunosensor was used to detect SARS-CoV-2 Anti-spike protein (Anti-S) antibodies in human serum samples, successfully differentiating between negative and positive responses of samples at a 95% confidence level. Therefore, the gold-binding peptide is a promising tool to be applied as a selective layer for antibody detection.

Graphene-Binding Peptide in Fusion with SARS-CoV-2 Antigen for Electrochemical Immunosensor Construction.

The development of immunosensors to detect antibodies or antigens has stood out in the face of traditional methods for diagnosing emerging diseases such as the one caused by the SARS-CoV-2 virus. The present study reports the construction of a simplified electrochemical immunosensor using a graphene-binding peptide applied as a recognition site to detect SARS-CoV-2 antibodies. A screen-printed electrode was used for sensor preparation by adding a solution of peptide and reduced graphene oxide (rGO). The peptide-rGO suspension was characterized by scanning electron microscopy (SEM), Raman spectroscopy, and Fourier transform infrared spectroscopy (FT-IR). The electrochemical characterization (electrochemical impedance spectroscopy-EIS, cyclic voltammetry-CV and differential pulse voltammetry-DPV) was performed on the modified electrode. The immunosensor response is based on the decrease in the faradaic signal of an electrochemical probe resulting from immunocomplex formation. Using the best set of experimental conditions, the analytic curve obtained showed a good linear regression (r2 = 0.913) and a limit of detection (LOD) of 0.77 µg mL-1 for antibody detection. The CV and EIS results proved the efficiency of device assembly. The high selectivity of the platform, which can be attributed to the peptide, was demonstrated by the decrease in the current percentage for samples with antibody against the SARS-CoV-2 S protein and the increase in the other antibodies tested. Additionally, the DPV measurements showed a clearly distinguishable response in assays against human serum samples, with sera with a response above 95% being considered negative, whereas responses below this value were considered positive. The diagnostic platform developed with specific peptides is promising and has the potential for application in the diagnosis of other infections that lead to high antibody titers.

Novel approach based on GQD-PHB as anchoring platform for the development of SARS-CoV-2 electrochemical immunosensor.

In the present work, we report an innovative approach for immunosensors construction. The experimental strategy is based on the anchoring of biological material at screen-printed carbon electrode (SPE) modified with electrodeposited Graphene Quantum Dots (GQD) and polyhydroxybutyric acid (PHB). It was used as functional substract basis for the recognition site receptor-binding domain (RBD) from coronavirus spike protein (SARS-CoV-2), for the detection of Anti-S antibodies (AbS). SEM images and EDS spectra suggest an interaction of the protein with GQD-PHB sites at the electrode surface. Differential pulse voltametric (DPV) measurements were performed before and after incubation, in presence of the target, shown a decrease in voltametric signal of an electrochemical probe ([Fe(CN)6]3/4-). Using the optimal experimental conditions, analytical curves were performed in PBS and human serum spiked with AbS showing a slight matrix effect and a relationship between voltametric signal and AbS concentration in the range of 100 ng mL-1 and 10 µg mL-1. The selectivity of the proposed sensor was tested against yellow fever antibodies (YF) and the selective layer on the electrode surface did not interact with these unspecific antibodies. Eight samples of blood serum were analyzed and 87.5% of these total investigated provided adequate results. In addition, the present approach showed better results against traditional EDC/NHS reaction with enhancements in time and the possibility to develop an immunosensor in a single drop, since the proteins can be anchored prior to the electrode modification step.

Electrochemical Biosensor for SARS-CoV-2 cDNA Detection Using AuPs-Modified 3D-Printed Graphene Electrodes.

A low-cost and disposable graphene polylactic (G-PLA) 3D-printed electrode modified with gold particles (AuPs) was explored to detect the cDNA of SARS-CoV-2 and creatinine, a potential biomarker for COVID-19. For that, a simple, non-enzymatic electrochemical sensor, based on a Au-modified G-PLA platform was applied. The AuPs deposited on the electrode were involved in a complexation reaction with creatinine, resulting in a decrease in the analytical response, and thus providing a fast and simple electroanalytical device. Physicochemical characterizations were performed by SEM, EIS, FTIR, and cyclic voltammetry. Square wave voltammetry was employed for the creatinine detection, and the sensor presented a linear response with a detection limit of 0.016 mmol L-1. Finally, a biosensor for the detection of SARS-CoV-2 was developed based on the immobilization of a capture sequence of the viral cDNA upon the Au-modified 3D-printed electrode. The concentration, immobilization time, and hybridization time were evaluated in presence of the DNA target, resulting in a biosensor with rapid and low-cost analysis, capable of sensing the cDNA of the virus with a good limit of detection (0.30 µmol L-1), and high sensitivity (0.583 µA µmol-1 L). Reproducible results were obtained (RSD = 1.14%, n = 3), attesting to the potentiality of 3D-printed platforms for the production of biosensors.

Selective carbonaceous-based (nano)composite sensors for electrochemical determination of paraquat in food samples.

A novel electrochemical sensor based on activated biochar (AB4) and reduced graphene oxide (rGO) was developed and tested for detection of paraquat (PQ) in food samples. Precursor biochar was obtained by the pyrolysis of water hyacinth biomass at 400, 500, and 600 °C, followed by a chemical activation step using HNO3 to increase the amount of oxygenated and nitrogenated groups. The modified electrodes (rGO-AB4) were tested in different experimental conditions, and exhibited good response under the optimized conditions, showing linearity from 0.74 to 9.82 µmol L-1 and a limit of detection and limit of quantification of 0.02 µmolL-1 and 0.07 µmol L-1, respectively. Interfering species such as glyphosate caused insignificant changes in the peak current of paraquat, and the selectivity of the method was tested using blank and spiked samples of coconut water, wastewater, honey, lettuce and lemon. Recovery ranged from 87.70±2.07% to 103.80±3.94%.

Label-free aptasensor for p24-HIV protein detection based on graphene quantum dots as an electrochemical signal amplifier.

Human immunodeficiency virus (HIV) is still considered a pandemic, and the detection of p24-HIV protein has an important role in the early diagnosis of HIV in adults and newborns. The accessibility of these trials depends on the price and execution difficulty of the method, which can be reduced using electrochemical methods by using enzymeless approaches, disposable and accurate devices. In this work, graphene quantum dots were acquired by a simple synthesis and employed as an electrochemical signal amplifier and support for the aptamer immobilization through a feasible and stable modification of disposable screen-printed electrodes. The device has been easily assembled and used to detect p24-HIV protein without the interference of similar proteins or sample matrix. Using the best set of experimental conditions, a linear correlation between analytical signal and log of p24-HIV concentration from 0.93 ng mL-1 to 93 µg mL-1 and a limit of detection of 51.7 pg mL-1 were observed. The developed device was applied to p24 determination in spiked human serum and provided distinct levels of signal for positive and negative samples, successfully identifying real samples with the target protein. This sensor is a step towards the development of point-of-care devices and the popularization of electrochemical methods for trials and diagnostics of relevant diseases.

3D-printed electrode as a new platform for electrochemical immunosensors for virus detection.

Simple, low-cost, and sensitive new platforms for electrochemical immunosensors for virus detection have been attracted attention due to the recent pandemic caused by a new type of coronavirus (SARS-CoV-2). In the present work, we report for the first time the construction of an immunosensor using a commercial 3D conductive filament of carbon black and polylactic acid (PLA) to detect Hantavirus Araucaria nucleoprotein (Np) as a proof-of-concept. The recognition biomolecule was anchored directly at the filament surface by using N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N-Hydroxysuccinimide (EDC/NHS). Conductive and non-conductive composites of PLA were characterized using thermal gravimetric analysis (TGA), revealing around 30% w/w of carbon in the filament. Morphological features of composites were obtained from SEM and TEM measurements. FTIR measurement revealed that crosslinking agents were covalently bonded at the filament surface. Electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used for the evaluation of each step involved in the construction of the proposed immunosensor. The results showed the potentiality of the device for the quantitative detection of Hantavirus Araucaria nucleoprotein (Np) from 30 µg mL-1 to 240 µg mL-1 with a limit of detection of 22 µg mL-1. Also, the proposed immunosensor was applied with success for virus detection in 100x diluted human serum samples. Therefore, the PLA conductive filament with carbon black is a simple and excellent platform for immunosensing, which offers naturally carboxylic groups able to anchor covalently biomolecules.

Electrochemical sensor based on biochar and reduced graphene oxide nanocomposite for carbendazim determination.

For the first time, a nanocomposite based on biochar and reduced graphene oxide (rGO) was employed to construct a modified carbon paste electrode and applied for the determination of carbendazim (CBZ). Biochar was obtained by through pyrolysis of Eichhornia crassipes biomass, also known how "Aguapé" at 400 °C. The modified electrode with our nanocomposite proposal shows to be able to preconcentrate CBZ and presented the highest analytical response in comparison to the unmodified electrode and by the electrodes prepared with the proposed materials separately. Using differential pulse voltammetry (DPV) under optimized conditions, the sensor showed a linear dynamic response (LDR) from 30 to 900 nmol L-1, a limit of detection (LOD) of 2.3 nmol L-1 and limit of quantification (LOQ) of 7.7 nmol L-1. No significant influence of inorganic ions or organic compounds on sensor response was verified, considering the recovery evaluation data. The proposed sensor was successfully applied for the determination of CBZ in spiked whole orange juice, lettuce leaves, drinking water, and wastewater samples. Good recovery values were found using the ex-situ methodology, showing excellent analytical performance of the electrochemical sensor based on biochar and rGO nanocomposite.

A simple enzymeless approach for Paraoxon determination using imidazole-functionalized carbon nanotubes.

This work describes the application of a glassy carbon electrode (GCE) modified with imidazole functionalized carbon nanotubes (CNT-H-IMZ) for Paraoxon (PX) determination in samples of commercial, fresh and 100% orange juice. Homemade multi-walled CNTs were treated according to the Hummers procedure to oxidize graphite and later chemically functionalized with imidazole groups. Modified electrodes with CNT-H-IMZ presented a high peak current of PX reduction and an electrocatalytic effect in comparison to the other electrodes. This behavior was associated with the synergistic contribution of IMZ and CNT that increases the electrochemical activity of PX. Repeatability and reproducibility studies showed that the relative peak current values did not show significant differences between them, less than 10%, and it was possible to define that the diffusional process is the mechanism that limits the electrode mass transport. After the optimization of parameters inherent to the methodology and the voltammetric technique, the proposed device presented a linear region of 1.0 to 16.0 µM-1 (R2 = 0.99), presenting LOD and LOQ as 120 and 400 nM-1, respectively. The method proposed was successfully applied to PX determination in spiked samples.

Quick electrochemical immunoassay for hantavirus detection based on biochar platform.

This work describes the first method using biochar (BC) as carbonaceous platform for immunoassay application. BC is a highly functionalized material obtained through biomass pyrolysis under controlled conditions. Due to the highly functionalized surface, covalent binding between BC and biomolecules can be performed by EDC/NHS conjugation. The application of the modified electrode was done with Hantavirus, that are etiologic agents mainly transmitted by wild rodents. Among its pathologies Hantavirus Cardiopulmonary Syndrome (HCPS) arises at Americas, caused by Hantavirus Araucária and reaches 40% lethality. The diagnostic is based on the presence of specific hantavirus nucleoprotein (Np), under viremic condition or IgG2b antibodies (Ab), during first symptoms. The results presented a device sensitivity of 5.28 µA dec-1 and a LOD of 0.14 ng mL-1 to the Np detection, ranging from 5.0 ng mL-1 to 1.0 µg mL-1, the Ab detection works as qualitative type sensor above 200 ng mL-1. Both sensors were evaluated its selectivity and serum samples; selectivity against Gumboro disease, VP2 protein, and antibody IgG2a against Yellow fever disease (YF), respectively. So, the devices here proposed are promising tool suitable for both rodent and human hantavirus clinical surveys.

Green method for glucose determination using microfluidic device with a non-enzymatic sensor based on nickel oxyhydroxide supported at activated biochar.

This paper reports the use of nickel ions supported at activated biochar carbon paste electrode (NiAB-CPME) coupled in a microfluidic thread-based electroanalytical device (µTED) for non-enzymatic glucose determination. Biochar was initially prepared from castor oil cake at 400 °C and activated by HNO3 refluxing. Activation process promoted an increase of functional groups, surface area and porosity in comparison to precursor biochar. Activated biochar (AB) has shown an excellent performance to spontaneous preconcentration of Ni(II) ions. In alkaline conditions a stable voltammetric profile associated to Ni(OH)2/NiOOH redox pair was verified and a significant catalytic effect was observed in presence of glucose which was used for its monitoring. Microfluidic device was assembled at a plastic platform printed using 3D printer being easy to construction using low cost materials. Non-enzymatic amperometric glucose sensor coupled in µTED showed a good repeatability of 3.84% for successive injections of glucose (n = 10), a constant flow rate of 1.11 µL s-1 and an analytical frequency of 61 injections per hour. A linear dynamic range (LDR) from 5.0 to 100.0 µmol L-1, limit of detection (LOD) of 0.137 µmol L-1 and limit of quantification (LOQ) 0.457 µmol L-1 glucose were obtained. The proposed device was applied to glucose determination in real biological samples of human saliva and blood serum. Finally, the method was considered a green analytical procedure with Eco-Scale score of 81.

Nonenzymatic electrochemical sensor based on imidazole-functionalized graphene oxide for progesterone detection.

The modification of electrode surfaces has been the target of study for many researchers in order to improve the analytical performance of electrochemical sensors. Herein, the use of an imidazole-functionalized graphene oxide (GO-IMZ) as an artificial enzymatic active site for voltammetric determination of progesterone (P4) is described for the first time. The morphology and electrochemical performance of electrode modified with GO-IMZ were characterized by scanning electron microscopy and cyclic voltammetry, respectively. Under optimized conditions, the proposed sensor showed a synergistic effect of the GO sheets and the imidazole groups anchored on its backbone, which promoted a significant enhancement on electrochemical reduction of P4. Figures of merits such as linear dynamic response for P4 concentration ranging from 0.22 to 14.0 µmol L-1, limit of detection of 68 nmol L-1 and limit of quantification and 210 nmol L-1 were found. In addition, presented a higher sensitivity, 426 nA L µmol-1, when compared to the unmodified electrode. Overall, the proposed device showed to be a promising platform for a simple, rapid, and direct analysis of progesterone.

Activated biochar: Preparation, characterization and electroanalytical application in an alternative strategy of nickel determination.

This work reports for the first time the use of chemically activated biochar as electrode modifier for nickel determination. The biochar activation was performed by refluxing with HNO3, which promoted a higher nickel preconcentration compared to unmodified and modified biochar precursor electrodes. Morphological and structural characterization revealed the increase of surface acid groups, surface area and porosity of biochar after activation. Nickel determination was investigated adopting an alternative voltammetric methodology based on monitoring the Ni(II)/Ni(III) redox couple. In the proposed method, it was not necessary to use a complexing agent and the biochar itself was responsible for the analyte preconcentration. A linear response for Ni(II) concentration range from 1.0 to 30 µmol L-1 and a limit of detection of 0.25 µmol L-1 were obtained. The method was successfully applied for Ni(II) determination in spiked samples of bioethanol fuel and discharge water, with recoveries values between 103 and 109%.

Design of a new nanocomposite between bismuth nanoparticles and graphene oxide for development of electrochemical sensors.

This study describes a new route for preparation of a nanocomposite between graphene oxide (GO) and bismuth nanoparticles (BiNPs) and its evaluation as modifier electrode for development of electrochemical sensors. BiNPs were synthesized under ultrasound conditions using Bi(NO3)3 as metal precursor and ascorbic acid (AA) as reducing agent/passivating. Some experimental parameters of BiNPs synthesis such as Bi3+:AA molar ratio and reaction time were conducted aiming the best voltammetric performance of the sensor. Glassy carbon electrodes (GCE) were modified by drop-casting with the BiNPs dispersions and anodic stripping voltammetry measurements were performed and revealed an improvement in the sensitivityfor determination of Cd(II) and Pb(II) compared to an unmodified electrode. The best electrochemical response was obtained for a BiNPs synthesis with Bi3+:AA molar ratio of 1:6 and reaction time of 10min, which yielded Bi metallic nanoparticles with average size of 5.4nm confirmed by XRD and TEM images, respectively. GO was produced by graphite oxidation using potassium permanganate and exfoliated with an ultrasound tip. GO-BiNPs nanocomposite was obtained by a simple mixture of GO and BiNPs dispersions in water and kept under ultrasonic bath for 1h. GCE were modified with a nanocomposite suspension containing 0.3 and 1.5mgmL-1 of GO and BiNPs in water, respectively. Under optimized conditions, the proposed nanocomposite was evaluated on the voltammetric determination of Pb (II) and Cd (II), leading to a linear response range between 0.1 and 1.4µmolL-1 for both cations, with limit of detection of 30 and 27nmolL-1, respectively. These results indicate the great potential of the GO-BiNPs nanocomposite for improving the sensitivity of voltammetric procedures.