Paulo A. Raymundo-Pereira

Sol-gel thin-film based mesoporous silica and carbon nanotubes for the determination of dopamine, uric acid and paracetamol in urine

This work describes the preparation, characterization and application of a hybrid material composed of disordered mesoporous silica (SiO2) modified with multiwalled carbon nanotubes (MWCNTs), obtained by the sol-gel process using HF as the catalyst. This hybrid material was characterized by N2 adsorption-desorption isotherms, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission microscopy (HR-TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). This new hybrid material was used for the construction of a thin film on a glassy carbon electrode. The modified electrode using this material was designated SiO2/MWCNT/GCE. The electrocatalytic properties of the electrode toward dopamine, uric acid and paracetamol oxidation were studied by differential pulse voltammetry. Well-defined and separated oxidation peaks were observed in phosphate buffer solution at pH 7.0, in contrast with the ill-defined peaks observed with unmodified glassy carbon electrodes. The electrode had high sensitivity for the determination of dopamine, uric acid and paracetamol, with the limits of detection obtained using statistical methods, at 0.014, 0.068 and 0.098 µmol L(-1), respectively. The electrode presented some important advantages, including enhanced physical rigidity, surface renewability by polishing and high sensitivity, allowing the simultaneous determination of these three analytes in a human urine sample.

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L(-1) of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s(-1). A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9×10(-5) to 1.0×10(-3) mol L(-1), with a detection limit of 6.6×10(-5) mol L(-1) using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations.

Short terms effects of air pollution from biomass burning in mucociliary clearance of Brazilian sugarcane cutters

Nasal mucociliary system is the first line of defense of the upper airways and may be affected acutely by exposure to particulate matter (PM) from biomass burning. Several epidemiologic studies have demonstrated a consistent association between levels of air pollution from biomass burning with increases in hospitalization for respiratory diseases and mortality. To determine the acute effects of exposure to particulate matter from biomass burning in nasal mucociliary transport by saccharin transit time (STT) test, we studied thirty-three non-smokers and twelve light smokers sugarcane cutters in two periods: pre-harvest season and 4 h after harvest at the first day after biomass burning. Lung function, exhaled carbon monoxide (CO), nasal symptoms questionnaire and mucociliary clearance (MC) were assessed. Exhaled CO was increased in smokers compared to non-smokers but did not change significantly after harvest. In contrast, STT was similar between smokers and non-smokers and decreased significantly after harvest in both groups (p < 0.001). Exposure to PM from biomass burning did not influence nasal symptoms. Our results suggest that acute exposure to particulate matter from sugarcane burned affects mucociliary clearance in smokers and non-smokers workers in the absence of symptoms.

A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces

We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals.

Sensitive detection of estriol hormone in creek water using a sensor platform based on carbon black and silver nanoparticles

We report the electrochemical detection of estriol using carbon black nanoballs (CNB) decorated with silver nanoparticles (AgNP) as electrode material. Homogeneous, porous films on glassy carbon electrodes (GCE) were obtained, with diameters of 20 - 25nm for CNB and 5 - 6nm for AgNP. CNB/AgNP electrodes had increased conductivity and electroactive area in comparison with bare GCE and GCE/CNB, according to cyclic voltammetry and electrochemical impedance spectroscopy. The oxidation potential peak was also down shifted by 93mV, compared to the bare GC electrode. Differential pulse voltammetry data were obtained in 0.1molL-1 PBS (pH 7.0) to detect estriol without the purification step, in the linear range between 0.2 and 3.0µmolL-1 with detection and quantification limits of 0.16 and 0.5µmolL-1 (0.04 and 0.16mgL-1), respectively. The sensor was used to detect estriol in a creek water sample with the same performance as in the official methodology based on high performance liquid chromatography.

Study on the structural and electrocatalytic properties of Ba2+- and Eu3+-doped silica xerogels as sensory platforms

This work reports on the sol–gel synthesis of barium- and europium-doped silica xerogel and its use as an electrocatalytic sensor. Barium was chosen to assist the network framing and europium to provide electronic properties, including the Eu2+/Eu3+ redox process. The results from different molecular and structural techniques indicated that this xerogel is a composite material that combines a non-crystalline polymeric silica network with a high level of agglomeration and a low degree of reticulation formed by the hydrolysis and condensation of TEOS and M–O bonds (M = Ba2+ and/or Eu3+), whereas the oxygen atoms belong to the xerogel phase. The electrochemical behavior of the silica xerogel:Ba2+,Eu3+ with different amounts of Eu3+ under several different conditions was investigated. The electrochemical sensing platform showed a well-defined redox coupling with a formal potential of 0.06 V, assigned to europium redox sites in silicate. Electrocatalytic activity was observed with an increasing anodic peak current to the isoniazid oxidation, indicating that the electrochemical sensing platform designed here was successfully achieved.

A nanostructured label-free platform based on an ultrathin film for ultrasensitive detection of a secosteroid hormone

We report the electrocatalytic activity of perovskite-type LaNiO3-nanoxide (LN-NO) on secosteroid hormone oxidation in alkaline solution. LN-NO was synthesized by the Pechini method and calcined at 973 K for 2 h under air atmosphere. Subsequently, the LN-NO material was studied by high-resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD) and electrochemical techniques such as cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS). The Rietveld refinement by the XRD pattern indicated the presence only the LN-NO. Optimized electrocatalytic activity was achieved using the LN-NO architecture, on a label-free platform, and nanostructures with sizes ranging between 50 and 100 nm were well distributed throughout the nanoxide. The detection of the secosteroid was performed at a low potential (0.46 V vs. Ag/AgCl) in a range between 0 and 2.6 × 10−5 mol L−1, with a detection limit of 8.3 × 10−7 mol L−1, which is considerably competitive with similar devices. The application of the LN-NO nanostructured label-free platform as a voltammetric sensor showed a good sensitivity of 17.75 A M−1. Finally, the use of LN-NO as a low-cost alternative to carbon nanomaterials (nanotubes and graphene) has the potential to be an excellent approach to sensor development.

Electrochemical biosensor made with tyrosinase immobilized in a matrix of nanodiamonds and potato starch for detecting phenolic compounds

The envisaged ubiquitous sensing and biosensing for varied applications has motivated materials development toward low cost, biocompatible platforms. In this paper, we demonstrate that carbon nanodiamonds (NDs) can be combined with potato starch (PS) and be deposited on a glassy carbon electrode (GCE) in the form of a homogeneous, rough film, with electroanalytical performance tuned by varying the relative ND-PS concentration. As a proof of concept, the ND/PS film served as matrix to immobilize tyrosinase (Tyr) and the resulting Tyr-ND-PS/GCE biosensor was suitable to detect catechol using differential pulse voltammetry with detection limit of 3.9 × 10-7 mol L-1 in the range between 5.0 × 10-6 and 7.4 × 10-4 mol L-1. Catechol could also be detected in river and tap water samples. This high sensitivity, competitive with biosensors made with more sophisticated procedures and materials in the literature, is attributed to the large surface area and conductivity imparted by the small NDs (<5 nm). In addition, the ND-PS matrix may have its use extended to immobilize other enzymes and biomolecules, thus representing a potential biocompatible platform for ubiquitous biosensing.

Use of zein microspheres to anchor carbon black and hemoglobin in electrochemical biosensors to detect hydrogen peroxide in cosmetic products, food and biological fluids

Hemoglobin-containing electrochemical biosensors are useful for detecting hydrogen peroxide through oxidation of the iron ion, but high efficiency can only be reached with appropriate immobilization strategies for hemoglobin. In this work, we combined zein from corn seed with carbon black to immobilize hemoglobin, as proof of concept, and form an electroactive film that could determine hydrogen peroxide within the concentration range from 4.9 × 10-6 to 3.9 × 10-4 mo L-1, and limit of detection of 4.0 × 10-6 mol L-1, using differential pulse voltammetry. The biosensor could also detect hydrogen peroxide in commercial samples of oxygenated water, synthetic serum (physiological and glycoside) and milk. The high performance is ascribed to the large surface area and conductive nature of the porous film that had carbon black and hemoglobin anchored on zein microspheres, according to scanning and transmission electron microscopies. It is significant that a protein from renewable sources (zein) combined with a low-cost carbon material (carbon black) serves as matrix for immobilization of biomolecules.