An electrochemical sensor-based carbon black associated with a modified mixed oxide (SiO2/TiO2/Sb2O5) for direct determination of thiamethoxam in raw honey and water samples.

The study aimed to develop an electrochemical sensor based on glassy carbon, mixed oxide (SiO2/TiO2/Sb2O5), and carbon black. The material was synthesized, characterized, and used to determine thiamethoxam in raw honey and water. The morphologic structure and electrochemical performance of the sensor was characterized by scanning electron microscopy and cyclic voltammetry. Differential pulse voltammetry with a concentration of 0.1 mol L-1 of Britton-Robinson buffer at pH 7.0 allowed the generation of a method to determine thiamethoxam in a linear range of 0.25 to 100.5 µmol L-1 and with a limit of detection of 0.012 µmol L-1. The system efficiently quantified traces of thiamethoxam in raw honey and tap water samples. The modified sensor did not present interferences of K+, Na+, Ca2+, Mg2+, glyphosate, imidacloprid, and carbendazim. In addition, the device showed good recovery values for thiamethoxam when applied directly to honey and water samples without any treatment, presenting an electrochemical sensor to monitor real-time hazardous substances in environmental and food matrices.

Study of the characteristics and properties of the SiO2/TiO2/Nb2O5 material obtained by the sol-gel process.

The SiO2/TiO2/Nb2O5 material was set by the sol-gel method and was characterized by several techniques through thermogravimetric, spectroscopic, and textural analyzes. For the two synthesized materials, the specific surface area was 350.0 and 494.0 m2 g-1 (SiTiNb-A and SiTiNb-B, respectively). An enhance of the crystalline order with the temperature increase of the thermal treatment was observed. Through X-ray Photoelectron Spectroscopy analysis, the binding energy values for the Ti 2p and Nb 3d levels showed the insertion of Ti and Nb atoms in the silica matrix. The Electron Dispersive Spectroscopy analyses also confirmed the high dispersion of the metals presented on the materials surface. The Thermogravimetric Analysis showed weight loss for the of 37.6% (SiTiNb-A) and 29.7% (SiTiNb-B). The presence of the crystalline phases TiO2-anatase and monoclinic-Nb2O5 in the materials was confirmed through the data obtained by association of powder X-ray Diffraction and FT-Raman. Values obtained from optical band-gap aimed the dependence of the oxides concentration and the calcination temperature. Finally, the pyridine adsorption studies have indicated the presence of Lewis and Brønsted acid sites.

Development of a portable electroanalytical method using nickel modified screen-printed carbon electrode for ethinylestradiol determination in organic fertilizers.

Urine and struvite are organic fertilizers that have all nutritional requirements for the growth of a plant. However, these fertilizers may contain some emerging organic contaminants, such as ethinylestradiol, which is one of the most common hormones found in aquatic environments and can cause several changes in living organisms. Thus, the present study developed a fast, sensitive, inexpensive, and portable method for determining ethinylestradiol in urine and struvite, using square wave voltammetry (SWV) and screen-printed carbon electrodes modified with electrodeposited nickel film (SPCE-Ni). The electrodeposition of the nickel film on the screen-printed electrode was performed by cyclic voltammetry and optimized using complete factorial design 23 and central composite design. The parameters optimized for SPCE-Ni were: number of cycles (1000); scan rate (5 V s-1) and Ni2+ concentration (9.4 mmol L-1). The operational parameters of the SWV for ethinylestradiol analysis were also optimized by experimental designs and obtained the following optimal values: step potential (10 mV), modulation amplitude (40 mV), and frequency (20 Hz). The method used 0.1 mol L-1 BR buffer (pH 8.0) as support electrolyte and presented a limit of detection of 0.052 µmol L-1 (R2 = 0.996). Ethinylestradiol recovery test in struvite, human urine, synthetic urine, and pharmaceutical tablets ranged from 93.9% to 107.5%, indicating that there is no matrix effect. Furthermore, an interference test was performed with several drugs did not show any significant changes in the ethinylestradiol analytical signal, guaranteeing a greater precision of the method. These results reinforce the possibility of applying the proposed method in loco with a practical and fast way, without the need to use significant amounts of sample.

Synthesis of New Thiosemicarbazones and Semicarbazones Containing the 1,2,3-1H-triazole-isatin Scaffold: Trypanocidal, Cytotoxicity, Electrochemical Assays, and Molecular Docking.

BACKGROUND: Chagas disease, also known as American trypanosomiasis, is classified as one of the 17 most important neglected diseases by the World Health Organization. The only drugs with proven efficacy against Chagas disease are benznidazole and nifurtimox, however both show adverse effects, poor clinical efficacy, and development of resistance. For these reasons, the search for new effective chemical entities is a challenge to research groups and the pharmaceutical industry. OBJECTIVE: Synthesis and evaluation of antitrypanosomal activities of a series of thiosemicarbazones and semicarbazones containing 1,2,3-1H triazole isatin scaffold. METHOD: 5'-(4-alkyl/aryl)-1H-1,2,3-triazole-isatins were prepared by Huisgen 1,3-dipolar cycloaddition and the thiosemicarbazones and semicarbazones were obtained by the 1:1 reactions of the carbonylated derivatives with thiosemicarbazide and semicarbazide hydrochloride, respectively, in methanol, using conventional reflux or microwave heating. The compounds were assayed for in vitro trypanocidal activity against Trypanosoma cruzi, the aetiological agent of Chagas disease. Beyond the thio/semicarbazone derivatives, isatin and triazole synthetic intermediates were also evaluated for comparison. RESULTS: A series of compounds were prepared in good yields. Among the 37 compounds evaluated, 18 were found to be active, in particular thiosemicarbazones containing a non-polar saturated alkyl chain (IC50 = 24.1, 38.6, and 83.2 µM; SI = 11.6, 11.8, and 14.0, respectively). To further elucidate the mechanism of action of these new compounds, the redox behaviour of some active and inactive derivatives was studied by cyclic voltammetry. Molecular docking studies were also performed in two validated protein targets of Trypanosoma cruzi, i.e., cruzipain (CRZ) and phosphodiesterase C (TcrPDEC). CONCLUSION: A class of thio/semicarbazones structurally simple and easily accessible was synthesized. Compounds containing thiosemicarbazone moieties showed the best results in the series, being more active than the corresponding semicarbazones. Our results indicated that the activity of these compounds does not originate from an oxidation-reduction pathway but probably from the interactions with trypanosomal enzymes.

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.

Electrogeneration of hydrogen peroxide applied to the peroxide-mediated oxidation of (R)-limonene in organic media

Horse radish peroxidase (HRP) from Armoracia rusticana catalyses the oxidation of (R)-limonene into the oxidized derivatives carveol and carvone. This study compares the direct addition (DA) of hydrogen peroxide with its continuous electrogeneration (EG) during the enzymatic oxidation of (R)-limonene. Reaction mixtures containing HRP, (R)-limonene as substrate, and hydrogen peroxide, added directly or electrogenerated, in 100 mM sodium-potassium phosphate buffer pH 7.0, at 25ºC were studied. Two electrochemical systems for the hydrogen peroxide electrogeneration were evaluated, both containing as auxiliary electrode (AE) a platinum wire and saturated calomel electrode (SCE) as reference. Reticulated vitreous carbon foam (RVCF) and an electrolytic copper web (CW) were evaluated as working electrodes (WE). Results were compared in terms of hydrogen peroxide electrogeneration, (R)-limonene residual concentration or conversion and product selectivity. Best results in terms of maximum H2O2 concentration (1.2 mM) were obtained using the CW electrode at -620 mV SCE, and continuous aeration. Use of the EG system under optimized conditions, which included the use of acetone (30% v/v) as a cosolvent in a 3 hrs enzymatic reaction, lead to a 45% conversion of (R)-limonene into carveol and carvone (2:1). In comparison to the results obtained with DA, the use of EG also improved the half-life of the enzyme.

Chloroperoxidase mediated oxidation of chlorinated phenols using electrogenerated hydrogen peroxide

Chloroperoxidase (CPO) from Caldariomyces fumago catalyses the oxidation of several chlorinated phenols (CP) commonly found in industrial waste waters in the presence of hydrogen peroxide. This study compares the direct addition of hydrogen peroxide (DA) with its continuous electrogeneration (EG) during the enzymatic oxidation of CP. Reaction mixtures were studied containing chemically modified CPO, hydrogen peroxide and the phenolic substrates: phenol (P), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), in 100 mM sodium-potassium phosphate buffer pH 6.0, at 25ºC. Results were compared in terms of residual phenol concentration (oxidation efficiency), precipitate formation (removal) and residual enzyme activity (stability). With the electrochemical system evaluated at -620 mVSCE, and continuous aeration the maximum H2O2 concentration of 1.2 mM was obtained. Under this conditions and after 4 hrs using EG, no phenol or 4-CP were detected, and 97 percent, 93 percent and 88 percent of 2,4-DCP, 2,4,6-TCP and PCP were degraded, respectively. The use of EG improves enzyme half-life time in comparison to the results obtained by DA.