In the present study, a novel magnetic dispersive solid-phase extraction method using molecularly imprinted polymer synthesized through semi-covalent imprinting approach was developed for cholesterol (CHO) determination in milk samples by high-performance liquid chromatography with diode array detector (HPLC-DAD). The adsorbent named Fe3O4/SiO2/MIP (MIP: molecularly imprinted polymers) was prepared through sol-gel polymerization of 3-(triethoxysilyl)propyl isocyanate (ICPTES) covalently bonded to CHO with tetraethoxysilane (TEOS), in the presence of Fe3O4/SiO2 particles. The adsorbent was characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS) and scanning electron microscopy (SEM). The proposed molecularly imprinted polymer-based magnetic dispersive solid-phase extraction method (MIP-MDSPE) was based on vortex-assisted preconcentration of 10.0 mL of CHO solution in chloroform as donor phase using 10.0 mg of Fe3O4/SiO2/MIP during 60 s. After this step, the magnetic particles were collected using a permanent magnet and the vortex-assisted elution was carried with 500 µL of ethanol during 180 s. A wide analytical curve ranging from 38.5 to 25000 µg L-1 (determination coefficient (R2) = 0.998) and low limits of detection (LOD) and quantification (LOQ) 11.5 and 38.5 µg L 1, respectively, were obtained. Milk samples (whole and reduced-fat milk) were subjected to MIP-MDSPE method after saponification reaction followed by CHO extraction with chloroform. Using external calibration, the CHO concentration ranged from 99.2 (reduced-fat milk) to 397.6 mg kg 1 (whole milk) and the accuracy was attested by addition and recovery tests (92 to 97%).

Silicon oxycarbide (SiCO) ceramics obtained from polymer pyrolysis and with varied carbon contents were prepared and evaluated as new electrodic materials for sensing of tert butylhydroquinone (TBHQ) and butylated hydroxyanisole (BHA) antioxidants. Three polymers were synthesized varying molecular architecture and aromatic carbon groups, followed by pyrolysis at 1000 and 1500 °C to obtain SiCO ceramics. Graphitization and crystallization processes were evidenced, in different extent, according to precursor chemistry. SiCO at 1500 °C with intermediary carbon content provided slight improvement in the peak anodic separation of TBHQ and BHA and higher peak current compared with glassy carbon electrode (GCE). Higher acidic sites concentration together with more ordered residual carbon phase produced in situ contributed to great electrochemical performance of SiCO towards phenolic compounds detection. Therefore, the ceramic herein prepared exhibits highly efficient features as a new SiCO composited electrode for simultaneous determination of antioxidant phenolic compounds bearing in mind further analytical applications.

This work deals on the preparation of silicon oxycarbide (SiOC) and silicon boron oxycarbide (SiBOC) ceramics from pyrolysis involving alkoxysilanes with different organic groups. Boron content, organic substituent and annealing time were evaluated on crystallization and composition of resulting ceramics. B-free precursors composed of methyltriethoxysilane (MTES), phenyltriethoxysilane (PTES) and vinyltrimethoxysilane (VTMS) were obtained by the sol-gel method, whilst B-containing precursors were prepared by adding to each alkoxysilane a proper amount of boric acid resulting in B/Si atomic ratios of 0.1 and 0.5. Precursors were pyrolyzed at 1500 ºC for 1 and 3 h to produce respective SiOC and SiBOC ceramics. X-ray diffraction (XRD) patterns revealed enhanced SiC phase crystallization for PTES-derived ceramics, followed by those containing vinyl and methyl groups, which was also confirmed by X-ray photoelectron spectroscopy (XPS) from percentages of SiºC and Si?O bonds. Csp2 and Csp3 amounts varied among ceramics, indicating direct influence of organic substituent on conductive carbon phase development. Boron addition induced the growth of SiC crystallites, having more evident effect in matrices with higher proportions of amorphous fraction and lower residual carbon amounts. Organic group nature, boron content and annealing time played an important role for production and evolution of SiC and C phases into ceramics.

A flow-injection preconcentration system using detection by the thermospray flame furnace atomic absorption spectrometry (FIA-TS-FF-AAS) is proposed. Cd2+ are adsorbed on avocado seed activated carbon (ASAC) packed into a cylindrical mini-column and eluted using HCl solutions for the detection system. A 25–1 fractional factorial and Doehlert matrix design were employed to determine the optimum conditions for cadmium preconcentration (pH 7.68, buffer concentration (Tris/Tris-HCl) of 0.023 mol L-1, eluent concentration (HCl) of 2.0 mol L-1, the adsorbent mass of 100.0 mg and preconcentration flow rate of 4.8 mL min-1). The preconcentration method presents linearity within the range of 0.41-15.00 µg L-1, limits of quantification and detection of 0.41 and 0.12 µg L-1, respectively, preconcentration factor of 10.7, consumption of index of 0.93 mL and sample throughput of 26 h-1. The precision assessed as the relative standard deviation (RSD) were found to be 0.48, 0.90 and 2.30% for inter-day precision (n = 2), and 0.30, 0.44 and 2.48% for intra-day precision (n = 6) for respective cadmium concentration of 0.50, 5.00 and 15.00 µg L-1. The proposed method was applied satisfactorily in samples of cigarette (62.84 ± 11.28 µg kg-1), human hair (69.61 ± 2.38 µg kg-1) and water samples [lake (0.65 ± 0.01 µg L-1), tap and mineral].

In this study, hybrid polymeric networks were prepared by hydrosilylation reaction as precursors to silicon oxycarbide (SiOC) glass. The polymeric networks were prepared from poly(methylsiloxane) (PMS) and divinylbenzene (DVB) in the 80:20 and 20:80 (PMS/DVB) compositions, with or without activated charcoal (AC), which was used as additional carbon source. Following, polymeric precursors were pyrolysed at 1000 °C, under Ar atmosphere, resulting in SiOC glasses. The effectiveness of the hydrosilylation reaction was evaluated by infrared spectroscopy. The degradation reactions and activation energy (Ea) obtained during polymer-to-glass conversion were investigated by thermogravimetric analysis applying Ozawa method for the determination of the Ea. In addition, the influence of the matrix composition and the presence of the C in both degradation processes and structure of the final products were reported. SiOC glasses were characterized by X-ray diffraction and Raman and 29Si nuclear magnetic resonance spectroscopies.

No presente estudo, um novo material compósito (SiO2/TiO2/ZnO) foi avaliado para pré-concentração de cobre em amostras de água e alimentos. O sorvente foi caracterizado por microscopia eletrônica de varredura (SEM), infravermelho com transformada de Fourier (FT-IR), análise de dados texturais, fluorescência de raios X por energia dispersiva (EDXRF) e difratometria de raios X (XRD). A pré-concentração em linha e determinação espectrofotométrica na região visível foi baseada na pré-concentração de 20,0 mL de amostra em pH 7,0 através de 50 mg do sorvente, numa vazão de 6,4 mL min-1. Um volume fixo de 0,3 mL de HNO3 0,5 mol L-1 elui os íons cobre que reagem com dietilditiocarbamato (DDTC) 0,3% (m/m) cujo complexo formado (Cu(DDTC)2) é monitorado a 452 nm. A seletividade do sorvente foi examinada avaliando o efeito de íons interferentes. O método proposto forneceu linearidade variando de 20,0 a 230,0 mg L-1 (r = 0,998), fator de pré-concentração de 35,9 e limite de detecção de 5,6 mg L-1. Amostras de água e alimentos foram analisadas com sucesso pelo método proposto e a exatidão foi checada por meio de análises de materiais certificados de referência de proteína e fígado de peixe.

In the present study, a new composite material (SiO2/TiO2/ZnO) for copper preconcentration in water and food samples was evaluated. The sorbent was characterized by scanning electronic microscopy (SEM), Fourier transform infrared spectrophotometry (FT-IR), textural data analyses, energy dispersive X-ray fluorescence (EDXRF) and X-ray diffractometry (XRD). The on-line preconcentration and visible spectrophotometric determination was based on loading 20.0 mL of sample at pH 7.0 through 50 mg of sorbent at a flow rate of 6.4 mL min-1. A fixed volume of 0.3 mL of 0.5 mol L-1 HNO3 elutes copper ions, in which react with 0.3% (m/m) diethyldithiocarbamate (DDTC) whose complex formed (Cu(DDTC)2) is monitored at 452 nm. The selectivity of sorbent has been examined by assessing the effect of interfering ions. The proposed method provided linearity ranging from 20.0 to 230.0 mg L-1 (r = 0.998), preconcentration factor of 35.9 and limit of detection of 5.6 mg L-1. Water and food samples were successfully analyzed by proposed method and the accuracy was checked by analysis of certified reference materials of protein and liver of fish.

Este trabalho descreve as alterações estruturais, texturais e morfológicas de cerâmicas porosas derivadas de polímeros e obtidas pela pirólise de compósitos polissiloxano/argila, contendo formador de poros à base de poli(dimetilsiloxano) e acetato de níquel como indutor de nanoestruturas. Os compósitos foram obtidos a partir de molde de aço-inox, seguido por tratamento térmico a 950 °C e 1500 °C (atmosfera inerte). O aumento da temperatura associado com a presença de Ni resultou em cerâmicas mais cristalinas e porosas, além de maior ordenamento da fase de Clivre. As cerâmicas revelaram ampla faixa de tamanho de poros. Em 950 °C, foram gerados poros e ilhas ricas em Ni e C dispersas na superfície de fratura. Entretanto, a 1500 °C, foram obtidos nanofios com alta razão de aspecto constituídos de Si, C e O. Assim, a presença de Ni associada a maior quantidade de poros originou um ambiente apropriado para a nucleação e crescimento de nanofios de SiCO.

This study describes the structural, porosity and morphological changes of porous polymer-derived ceramics obtained by pyrolysis of polysiloxane-clay composites, containing a pore former based on poly(dimethylsiloxane) and nickel acetate as nanostructure inductor. The composites were blended in a steel mold, thermally treated at 950 °C and 1500 °C (inert atmosphere). The increase of the temperature together with the presence of Ni resulted in more crystalline and porous ceramics and a higher ordering process of Cfree phase in the Ni-containing sample. The ceramics revealed a wide pore size distribution, from micro to macropores. At 950 °C the ceramic revealed the presence of pores and Ni- and C-rich islands dispersed on the fracture surface. However, at 1500 °C, nanowires with large aspect ratio, constituted by Si, C and O elements were generated. Thus, the presence of Ni associated to higher pores amount gave rise to an appropriate environment for the nucleation and growth of SiCO nanowires.

In this paper, we describe the synthesis of an ion imprinted polymer (IIP) by homogeneous polymerization and its use in solid-phase to extract and preconcentrate zinc ions. Under optimal conditions (pH 5.0, preconcentration flow rate of 12.0 mL min-1, and eluted with 1.0 mol L-1 HNO3) this procedure allows the determination of zinc with an enrichment factor of 10.2, and with limits of detection and quantification of 1.5 and 5.0 µg L-1, respectively. The accuracy of our results was confirmed by analysis of tap water and certified reference materials: NIST 1570a (Spinach leaves) and NIST 1515 (Apple leaves).

No presente trabalho foi avaliado um novo material como adsorvente, SiO2/Al2O3/Nb2O5 (designado SiAlNb), empregado na determinação e pré-concentração online de Zn2+ por um método espectrofotométrico por injeção em fluxo. O método de pré-concentração é baseado na adsorção de Zn2+ em meio alcalino (pH 9,0) sobre a superfície de SiAlNb. A etapa de eluição é realizada usando solução de HNO3 e é seguida da reação dos íons Zn2+ com 1-(2-piridilazo)-2-naftol (pan) na presença de Tween-80 em solução amoniacal (pH 9,3). O complexo formado, [Zn(pan)2], é posteriormente determinado a 560 nm. O método apresentou faixa linear entre 7,6 e 180,0 µg L-1 (r = 0,9992) e limites de detecção e quantificação de 2,3 e 7,6 µg L-1, respectivamente. De acordo com o modelo linear de Langmuir, a capacidade máxima de adsorção foi de 7,0 mg de Zn2+ por grama de SiAlNb. O método proposto foi aplicado com sucesso na determinação de Zn2+ em amostras de água (lago, mineral e torneira) e material certificado de referência (TORT-2 Lobster Hepatopancreas).

In the present work, a new material, SiO2/Al2O3/Nb2O5 (designated as SiAlNb), was evaluated as an adsorbent in a flow injection spectrophotometric method for online preconcentration and determination of trace amounts of Zn2+ ions. The preconcentration method is based on Zn2+ adsorption onto the surface of SiAlNb in alkaline medium (pH 9.0). The elution step is carried out using HNO3 solution, followed by reaction of the Zn2+ ions with 1-(2-piridylazo)-2-naphtol (pan) in ammoniacal buffer solution (pH 9.3) containing Tween-80. The [Zn(pan)2] complex formed is determined at 560 nm. The method presented a linear range between 7.6 and 180.0 µg L-1 (r = 0.9992) and limits of detection and quantification of 2.3 and 7.6 µg L-1, respectively. According to the Langmuir linear model, the maximum adsorption capacity was found to be 7.0 mg of Zn2+ g-1 of SiAlNb. The proposed method was successfully applied to the Zn2+ determination in water samples (lake, mineral, tap) and certified reference material (TORT-2 Lobster Hepatopancreas).