Development of an electrochemical sensor based on ternary oxide SiO2/Al2O3/SnO2 modified with carbon black for direct determination of clothianidin in environmental and food samples.

This study presents the development of an electrochemical sensor, denoted as GCE/CB/SiAlSn, based on the modification of a glassy carbon electrode surface with the ternary oxide SiO2/Al2O3/SnO2 associated with carbon black, for direct determination of the neonicotinoid pesticide clothianidin in different matrices, such as environmental and food samples. Morphological characterization by the scanning electron microscopy technique, electroanalytical analyses using the cyclic voltammetry technique and differential pulse voltammetry are presented which demonstrated that the developed electrochemical platform presents high sensitivity in the electroanalytical clothianidin determination. The linear range studied was from 2.99 × 10-7 to 6.04 × 10-5 mol L-1, with an LOD of 2.47 nmol L-1. This high sensitivity was explained using the synergistic relationship between carbon black and ternary oxide that maximized the electroactive surface area of the GCE/CB/SiAlSn sensor. Interferent studies were performed that showed high selectivity of the sensor to the pesticide in the presence of Ca2+, K+, Na+, and Mg2+ and carbendazim, glyphosate, imidacloprid and thiamethoxam pesticides. The sensor was applied to real samples of tap water and apple juice obtaining recoveries from 91.0% to 103.0%.

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 new analytical method for preconcentration/speciation of inorganic antimony in bottled mineral water using FIA-HG AAS system and SiO2/Al2O3/SnO2 ternary oxide.

In the present paper, a new analytical preconcentration/speciation method for antimony species determination in bottled mineral water samples using the SiO2/Al2O3/SnO2 adsorbent was developed. The method is based on selective adsorption of Sb(III) ions by SiO2/Al2O3/SnO2 under a wide pH range (2.5-7.5). Total antimony was determined with previous sample treatment using 0.1% (w/v) l-cysteine and the concentration of Sb(V) species was determined by the difference between total and Sb(III). The proposed method provided an analytical curve ranging from 0.50 to 5.00 µg L-1 (r = 0.999), limit of detection (LD) of 0.17 µg L-1 and preconcentration factor (PF) of 136-fold. The method exhibited tolerance to different metal ions and the accuracy was attested from addition and recovery tests (95.2-106.0%) in bottled mineral water samples using 2.0% (w/v) l-cysteine, as well as by analysis of certified material. Only Sb(III) species were determined in mineral water (0.54-1.04 µg L-1).

Silica nanoparticles doped with anthraquinone for lung cancer phototherapy.

In the present study, SiO2 nanoparticles functionalized with 3-(2-aminoethylamino)propyl group (SiNP-AAP) were used, for the first time, to covalently bond rose bengal (SiNP-AAP-RB) or 9,10-anthraquinone-2-carboxylic acid (SiNP-AAP-OCAq). The functionalized SiNP were characterized by: Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM); elemental analysis (CHN) for determination of the dye concentration; FTIR and UV-vis diffuse reflectance (DR-UV-vis) and a surface area study (BET). The functionalized SiNPs were applied in photodynamic therapy (PDT) against lung cancer cell lines. The evaluated cytotoxicity revealed 20-30% cell survival after 15min of PDT for both materials but the OCAq concentration was half of the RB nanomaterial. The phototoxicity was mainly related to oxidative stress generated in the cellular environment by singlet oxygen and by hydrogen abstraction as confirmed by the laser flash photolysis technique. The unprecedented results indicate that SiNP-AAP-OCAq is a possible system for promoting cell apoptosis by both type I and type II mechanisms.

Cellulose microfiber functionalized with N,N'-bis (2-aminoethyl)-1,2-ethanediamine as a solid sorbent for the fast preconcentration of Cd(II) in flow system analysis.

The present paper describes the synthesis of a new chemically modified cellulose microfiber through oxidation with sodium periodate and functionalization with N,N'-bis (2-aminoethyl)-1,2-ethanediamine for the fast and selective preconcentration of Cd(II) ions in flow system analysis. The new sorbent was characterized by FTIR, SEM, and surface area values. The uptake behavior of Cd(II) ions onto this sorbent was evaluated from kinetic data, pseudo-first-order and pseudo-second-order models, as well as from Langmuir, Freundlich and Langmuir-Freundlich adsorption isotherms. The maximum sorption capacity of 4.59 mg g(-1) was estimated by the Langmuir-Freundlich model with fast kinetics for the sorption of Cd(II) described by the pseudo-second-order kinetic model. After characterization, the sorbent was packed in a mini-column, and a fast flow injection preconcentration system for Cd(II) determination by FAAS was developed. The best Cd(II) preconcentration condition, obtained by means of factorial design and response surface methodology, was achieved at pH 9.36 and a flow rate of 10 mL min(-1) followed by elution with 1.0 mol L(-1) nitric acid. By using 78 s preconcentration time, fast and highly sensitive determination of Cd(II) ions could be achieved with a limit of quantification of 0.20 µg L(-1), preconcentration factor of 26, consumption index of 0.5 mL, concentration efficiency of 20 min(-1), and sample throughput of 39 h(-1). The repeatability for 10 replicate determinations was found to be 7.8 and 2.5% for Cd(II) ion concentrations of 5.0 and 100.0 µg L(-1), respectively. The new sorbent efficiency for the interference-free preconcentration of Cd(II) ions was assessed by analysis of tap, mineral and lake waters, as well as synthetic seawater and normal saline waters. Furthermore, complex samples, such as biological samples, could be analysed by the proposed method in accordance with the accuracy attested by analysis of certified reference materials, TORT-2 (lobster hepatopancreas), and DOLT-4 (dogfish liver).