Scielo RSS <![CDATA[Journal of the Brazilian Chemical Society]]> http://www.scielo.br/rss.php?pid=0103-505320190004&lang=en vol. 30 num. 4 lang. en <![CDATA[SciELO Logo]]> http://www.scielo.br/img/en/fbpelogp.gif http://www.scielo.br <![CDATA[How Many More Brumadinhos and Marianas Will We be Faced with Yet?]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400681&lng=en&nrm=iso&tlng=en <![CDATA[RM1 Semiempirical Model: Chemistry, Pharmaceutical Research, Molecular Biology and Materials Science]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400683&lng=en&nrm=iso&tlng=en In this review, we show improvements to the semiempirical quantum chemical method RM1 and present a wide range of its applications as reported by researchers of various areas, such as theoretical, organic, physical, analytical, and inorganic chemistry, as well as their interfaces with medicinal chemistry, biology, and materials science. Success of RM1 is seemingly due to its ability to predict structural, energetic, electronic and wave function dependent properties of the investigated systems, coupled with its low computational demand required to perform calculations when compared to ab initio and density functional methods. Moreover, RM1 is widely available in several computational chemistry softwares, such as MOPAC, GAMESS, Amber, Spartan, HyperChem, and AMPAC. This review describes various case studies that perhaps can be of interest to researchers who might need a more solid basis from which to expand the frontier of applicability of RM1 to even more complex problems on larger systems. <![CDATA[Use of Natural Deep Eutectic Solvents for Polymerization and Polymer Reactions]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400717&lng=en&nrm=iso&tlng=en Green chemistry is a key opportunity in chemistry and chemical engineering today because it can potentially preserve the environment and human health. It entails the choice of natural biodegradable raw materials and solvents, environmentally acceptable processes, and minimal use of non-hazardous chemicals. Previously, deep eutectic solvents (DES) have found many applications in organic, analytical, and polymer chemistry. The recent discovery of natural deep eutectic solvents (NADES), where many plant-abundant primary metabolites have been found to change their state from solid to liquid at certain temperatures when mixed in a proper ratio, should accelerate their use as replacements for common organic solvents that exhibit inherent toxicity and high volatility. In this work, we have reviewed the application of NADES as green, sustainable solvents in processes that involve polymerizations and polymer reactions. It is clear that many applications have already been explored. Undoubtedly more progress will be made in the future, and NADES will become more commonly used in polymer-related processes. <![CDATA[New Synthesis Method for a Core-Shell Composite Based on α-Bi<sub>2</sub>O<sub>3</sub> @PPy and its Electrochemical Behavior as Supercapacitor Electrode]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400727&lng=en&nrm=iso&tlng=en New composite based on polypyrrole (PPy) and bismuth oxide (α-Bi2O3) was investigated as supercapacitor electrode. The α-Bi2O3 was obtained by hydrothermal route at 500 ºC for 2 h. Cyclic voltammetry was used to electropolymerize PPy on graphite electrode (GE) or on GE/α-Bi2O3. The X-ray diffraction profile of Bi2O3 revealed the α-Bi2O3 monoclinic structure with space group P21/c.The scanning and transmission electron microscopy images showed that PPy coated α-Bi2O3. Raman spectra showed that PPy inhomogeneously coated α-Bi2O3, but it was still possible to obtain a α-Bi2O3 @PPy core-shell hybrid composite with highly ordered α-Bi2O3 with electronic interaction between the oxide and the polymer chain of the polymer. The GE/α-Bi2O3@PPy composite electrode (type I supercapacitor) displayed a predominantly capacitive profile with low impedance values and good electrochemical stability after 50 charge and discharge cycles. The specific capacitance of α-Bi2O3 @PPy composite was found in the range of 634 to 301 F g-1 to gravimetric current of 3 and 10 A g-1, respectively. <![CDATA[Human Hair as Adsorbent of Palladium(II) in Solution: A Precursor of Well-Dispersed Size-Controlled Pd Nanoparticles]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400736&lng=en&nrm=iso&tlng=en This work describes, for the first time, the preparation of palladium nanoparticles supported in thermally-treated human hair. Human hair showed to be an efficient adsorbent of Pd2+ in aqueous media, reaching nearly 100% of adsorption from a 100 ppm solution. The thermal treatment of hair containing Pd2+ at 200 ºC under nitrogen atmosphere led to the formation of an N, S-containing material presenting 0.5 wt.% of palladium. The material was extensively characterized by elemental analysis (CHN and inductively coupled plasma optical emission spectroscopy (ICP OES)), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and Raman spectroscopies, and by thermogravimetry (TG), thermogravimetry coupled to mass spectrometry (TG-MS), scanning electron miscroscopy (SEM), transmission electron microscopy (TEM) and dispersive X-ray spectroscopy (EDS) analyses. It was possible to observe that the surface structure of hair was preserved during thermal treatment, presenting palladium nanoparticles with particle sizes of approximately 4 nm. This material was used as heterogeneous catalyst in a preliminary application in nitrobenzene reduction to aniline in aqueous medium using sodium borohydride. <![CDATA[Cr<sup>3+</sup> Doped Al<sub>2</sub>O<sub>3</sub> Obtained by Non-Hydrolytic Sol-Gel Methodology]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400744&lng=en&nrm=iso&tlng=en This paper reports the synthesis and characterization of Cr3+-doped alumina by the sol-gel non-hydrolytic methodology. The resulting sample was treated at different temperatures. X-ray diffraction revealed that the ruby phase emerged in the sample treated at 1100 ºC, which was later confirmed by absorption bands correspondent to Cr3+ ions allowed transitions at 4A2 → 4T1, 4T2, and forbidden at 4A2 → 2T1, 2E, observed by diffuse reflectance UV-Vis. The luminescence spectroscopy showed the intensity band at 694 nm in red region, characterized of the Cr3+ ion. The peaks at 702 and 705 nm correspond to N1 and N2 lines, respectively, which arose from the second and fourth nearest-neighbor exchange-coupled pairs of chromium(III) ion, respectively, ascribed to high chromium(III) concentration. The Cr3+ cluster formation was observed in electron paramagnetic resonance signal as discussed in this work. Nuclear magnetic resonance evidenced that the 27 Al symmetry changed in the samples treated between 900 and 1100 ºC. <![CDATA[Insights on Structuration of Peroxotungstic Acid in Aqueous Media]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400752&lng=en&nrm=iso&tlng=en Recent studies on tungsten oxide preparation are mainly motivated by its applications in smart windows, energy harvesting and, recently, in cancer therapy. Peroxotungstic acid (PTA) is an important precursor to obtain tungsten oxide in an environmentally-friendly way, through the colloidal synthesis in aqueous media. Despite giving chemically pure products, PTA originates oxides with various morphologies depending on the experimental conditions, a subject open to discussion. PTA, in the presence of sodium dodecyl sulfate (SDS) as architecture-directing agent, was investigated in ethanol/water medium by small angle X-ray scattering (SAXS), fluorescence, surface tension and conductivity measurements; the morphology of tungsten oxide obtained from the precursor systems was also characterized by scanning electron microscopy (SEM). PTA/SDS/ethanol/water systems show a two-level organization in which small micelles are aggregated as fractal structures. There is an inverse correlation between gyration radius of the fractal structures of the PTA/SDS systems and particle size of the tungsten oxide films. The interaction of PTA with SDS is observed by reducing the Gibbs energy of micellization; also, it is evidenced that the supressive effect of PTA on pyrene emission is overrided in presence of SDS. <![CDATA[Dispersive Solid Phase Extraction Headspace Sampling in Gas Chromatography-Mass Spectrometric Analysis of Volatiles: Application to Separation of Polycyclic Aromatic Hydrocarbons]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400764&lng=en&nrm=iso&tlng=en For the first time, dispersive solid phase extraction combined with headspace sampling was introduced and applied to separation and pre-concentration of polycyclic aromatic hydrocarbons (PAHs) as representative of volatile and semi-volatile compounds, from aqueous solutions and sediments using multiwall carbon nanotubes (MWCNTs). After adsorption, PAHs were desorbed thermally from the surface of MWCNTs using a gas chromatography mass spectrometry (GC-MS) CombiPAL headspace device or a homemade thermal desorption system. Pre-concentration was maximized through optimization of solution pH, sorbent amount, and extraction time as well as desorption time and temperature of PAHs. The calibration curves were linear in the range 0.005-30 ng mL-1 for 13 PAHs at optimum conditions, with the coefficients of determination (R2) above 0.992, and detection limit in the range of 0.0021 to 0.0045 ng mL-1. Reproducibility for all PAHs was between 1.6 and 4.2%. Method recoveries were in the range of 94.0-102% for threeReferences spiked levels (1, 10, 20 ng mL-1). The methodology is even better if the selective or specific magnetic sorbent is used. <![CDATA[Deracemization of <em>sec</em>-Alcohols through Sequential Application of <em>C. albicans</em> and Ketoreductases]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400772&lng=en&nrm=iso&tlng=en A biocatalytic cascade process was developed using immobilized cells of the wild type yeast Candida albicans CCT 0776 in calcium alginate beads and a commercially available ketoreductase. The aim was to promote deracemization by stereoinversion of (±)-1-arylethanols in high substrate concentration (above 100 mmol L-1) to prepare the (R)-enantiomers of the alcohols (90-99%), with a high enantiomeric excess (83-99%) after 2 to 19 h. The (R)-1-(3-methoxyphenyl)ethanol, with 70% yield and 91% ee, obtained after 5 h was used to prepare (S)-1-(3-methoxyphenyl)-ethylamine with 60% yield and 91% ee after two steps, a key intermediate in the synthesis of (S)-rivastigmine. <![CDATA[Use of FTIR-ATR Spectroscopy Combined with Multivariate Analysis as a Screening Tool to Identify Adulterants in Raw Milk]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400780&lng=en&nrm=iso&tlng=en The objective of this study was to use Fourier transform infrared (FTIR) spectroscopy combined with multivariate analysis to identify adulterations in raw milk and in samples from producers. Five levels of concentration of sodium bicarbonate, sodium hydroxide, hydrogen peroxide, starch, sucrose and urea were used. A total of 620 samples previously adulterated, frozen and lyophilized were analyzed in FTIR-attenuated total reflection (ATR) equipment and 15 peaks of the spectra were obtained. With the multiple linear regression method for samples adulterated with sodium bicarbonate, sucrose and urea, a coefficient greater than 75% was obtained, and with artificial neural networks all adulterated samples obtained a percentage of correctness greater than 76.6%, making it possible to identify adulterants from 0.1%. Of the 249 samples of producers analyzed, 2.4% were adulterated. With the use of FTIR allied to the multivariate analysis as a screening method, it was possible to obtain a satisfactory classification for the adulterated samples in this study. <![CDATA[Black Carbon Associated to PM<sub>1.0</sub> and PM<sub>2.5</sub>: Mass Variation due to Combustion of Biodiesel/Diesel Blends (B5, B6, B7 and B8)]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400786&lng=en&nrm=iso&tlng=en The present study aims to quantify black carbon (BC), particulate matter (PM1.0 and PM2.5, particles with diameter ≤ 1.0 and 2.5 µm, respectively) levels and their variability during the combustion of biodiesel/diesel blends used in heavy-duty vehicles. The samplings were conducted in the years 2014, 2016 and 2017 inside a semi closed bus station, a direct source of emission from engines burning blends of B5 to B8 biodiesel/diesel. Diesel engines using B5 and B6 presented a high contribution of BC in PM1.0 fraction representing 95 and 98% in mass, respectively. Results obtained from engines fueled with B7 and B8 diesel blends showed about 47% BC mass contribution in fine PM. The ratio PM1.0/PM2.5 remained relatively constant showing that the fine PM mass did not change significantly. Those measurements are important to follow the behavior of the addition of biodiesel in the diesel fuel as well as to help indicate a fingerprint of BC and PM2.5 concentrations in biodiesel increase. <![CDATA[Zika Virus Activity of the Leaf and Branch Extracts of <em>Tontelea micrantha</em> and Its Hexane Extracts Phytochemical Study]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400793&lng=en&nrm=iso&tlng=en The new triterpene friedelan-1,3,21-trione, the known compounds friedelan-3-one, 3β-friedelinol, 3,4-seco-friedelan-3-oic acid, 28-hydroxyfriedelan-3-one, friedelan-3-oxo-28-al, friedelan-3,21-dione, 30-hydroxyfriedelan-3-one, a mixture of 30-hydroxyfriedelan-3-one/21α-hydroxyfriedelan-3-one, 21β-hydroxyfriedelan-3-one, gutta-percha, squalene, and a mixture of palmitic/stearic/oleic acids were isolated from the hexane extracts of leaves and branches of T. micrantha. Their chemical structures were established by Fourier transform infrared spectroscopy (FTIR), gas chromatography (GC), 1D/2D nuclear magnetic resonance (NMR) and comparison with the literature data. All compounds were described for T. micrantha and the genus Tontelea for the first time. The branch and leaf extracts displayed anti-Zika virus activity at the lowest tested concentration of 15.6 µg mL-1, mainly virucidal effect, and presented no cytotoxicity to Vero cells. Furthermore, the ethyl acetate and methanolic leaf extracts demonstrated the best activities at the concentration of 31.2 and 15.6 µg mL-1 at the viral adsorption and penetration stages, respectively. These results showed that these extracts may be promising candidates for the Zika virus treatment. <![CDATA[Combination of Multi-Energy Calibration (MEC) and Laser-Induced Breakdown Spectroscopy (LIBS) for Dietary Supplements Analysis and Determination of Ca, Mg and K]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400804&lng=en&nrm=iso&tlng=en This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered dietary supplements. Multi-energy calibration (MEC) method was applied to obtain a calibration curve. With MEC, it was possible to observe spectral interferences and select adequate emission lines from LIBS. For Ca and Mg, five lines were selected and for K just two lines among four could be selected (compromising the results). The trueness for dietary supplements ranged from 81 to 103% for Ca and 74 to 106% for Mg. For K, just the samples S3 (95%) and S5 (109%) showed acceptable trueness values. In the case of Ca and K, besides the MEC, the normalization using C as internal standard also improved the figure of merit results. The MEC and normalization processes showed that possible matrix effect and spectral interferences could be avoided, and the results of trueness and precision were satisfactory. <![CDATA[Photochemical Synthesis of Gold Nanoparticles by Irradiation of Gold Chloride with the 2<sup>nd</sup> Harmonic of a Nd:YAG Laser]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400813&lng=en&nrm=iso&tlng=en A synthesis method was developed capable of obtaining pristine gold nanoparticles (AuNPs) using the lowest possible amount of auxiliary compounds. An aqueous solution of HAuCl4.3H2O was irradiated, in the absence of any stabilizing species, with the 532-nm radiation of a Nd:YAG laser. Spherical shaped AuNPs were produced by this method with sizes below 10 nm. The crystalline structures were stable for up to 28 days. A mechanism for this process is also proposed based on the initial cleavage of water molecules by the laser irradiation followed by the formation of hydrogen peroxide that reduces the gold species AuIII. The resulting species of these reactions (H2 and O2) were identified by mass spectrometry. This new method suggests that laser irradiation is a feasible alternative to produce ready-to-use AuNPs, for drug delivery, diagnostics or bio-imaging. <![CDATA[Optimization of Atmospheric Pressure Photoionization for the Crude Oil Analysis Using Ultra-High Resolution Mass Spectrometry]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400819&lng=en&nrm=iso&tlng=en Design of experiments (DOE) applied to mass spectrometry (MS), mainly focusing on the optimization of ionization techniques, has been applied to optimize experiments in order to provide the highest amount of information with the lowest number of experiments. However, DOE has not been used in petroleomics. For the first time, we applied DOE to optimize the main parameters associated with the crude oil analysis in a petroleomics approach. For the ionization technique, atmospheric pressure photoionization (APPI) has been selected and data were acquired in a high resolution (400,000 at m/z 400) and high mass accuracy (&lt; 1 ppm) Fourier transform ion cyclotron resonance (FT-ICR) MS. Full and fractional two-level factorial designs were applied for the APPI(±) FT-ICR MS data set from two different crude oil samples with distinct physical and chemical characteristics. The standard ionization parameters that affect the MS responses of the crude oil analysis were optimized for both APPI(+)-MS and APPI(–)-MS. Such ionization parameters were then successfully applied to a crude oil and its saturated, aromatics, resin and asphaltene fractions, all with superior features of merit. Thus, the optimized APPI(±)-MS parameters should serve as reference and can be used as a guide for new studies in petroleomics. <![CDATA[Integrative Analysis Based on HPLC-DAD-MS/MS and NMR of <em>Bertholletia excelsa</em> Bark Biomass Residues:Determination of Ellagic Acid Derivatives]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400830&lng=en&nrm=iso&tlng=en Bertholletia excelsa Bonpl. (Lecythidaceae) is a South American tree worldwide known for providing the Brazil nuts. In the Amazon Region, B. excelsa is found in monocultures, integrating agroforestries and providing raw materials for food and timber industries. Through the application of an integrative analysis based on high-performance liquid chromatography coupled with diode array detector and tandem mass spectrometry (HPLC-DAD-MS/MS) and nuclear magnetic resonance (NMR) techniques, the present study showed that B. excelsa bark biomass residues contain large quantities of ellagic acid (EA) and its derivatives. Qualitatively, five compounds were characterized for the first time in this species. Quantitations were carried out to determine the total amount of these compounds in outer and inner bark tissues. A total of 4.96 and 44.09 g of EA derivatives per kg of dry residues was determined for the outer and inner barks, respectively. Among the EA derivatives, eschweilenol C, ellagic acid and valoneic acid dilactone were the main compounds. These results pointed B. excelsa barks as a valuable biomass residue with potential to be source of health-promoting compounds. Therefore, a potential raw material as source of valuable bioactive phenolic compounds is described herein. <![CDATA[Development and Validation of UHPLC-MS/MS for Simultaneous Determination of Scutellarin and Salicylic Acid in Rat Plasma: Application to Herb-Drug Pharmacokinetic Interaction Study]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400837&lng=en&nrm=iso&tlng=en Dengzhanxixin injection (DI) product has been clinically proven to be effective for treating cardio-cerebrovascular disease. Furthermore, herb-drug interactions between the DI product and drugs that are commonly co-administered, such as aspirin, must be explored to ensure safe clinical use. A reliable ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated for simultaneous determination of scutellarin and salicylic acid (SA) in rat plasma. The proposed method has been successfully applied to pharmacokinetic studies on analytes in rats afteri.g. administration of aspirin alone, i.v. administration of DI alone or a combination of both (i.g .: 10 mg kg-1 aspirin,i.v .: 4 mL kg-1 DI). Both SA and scutellarin exhibited a two-compartment model pharmacokinetic profile. Aspirin did not change the concentration-time course for scutellarin, but DI decreased the peak plasma concentration and the area under the SA curve. This study indicates that co-administration of aspirin and DI can cause an apparent herb-drug pharmacokinetic interaction in rats. <![CDATA[New Composites CP@AC Based on Lanthanide Succinates]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400845&lng=en&nrm=iso&tlng=en Composites derived from coordination polymers have been gathering great attention due to their singular properties and applications, especially catalysis and adsorption. In this work, seven new composites based on activated carbon (AC) and lanthanide-succinates (LnSuc; Ln = Pr, Nd, Sm, Gd, Dy, Er and Tm, and Suc = succinate) 3D-coordination polymers were obtained using hydrothermal reactions. Coordination polymers in LnSuc@AC composites (Ln = Pr, Nd, Sm, Gd) crystallize in monoclinic system and C2/c space group. However, the LnSuc in composites with Dy, Er and Tm have different crystal structures, due to the influence of the carbon matrix in the reaction. The systems were also characterized by Fourier transform infrared (FTIR) and thermogravimetric (TGA) analysis, and the results are in agreement with the X-ray powder diffraction (XRPD) data. The scanning electron microscopy (SEM) images confirm the crystallization of the compounds inside the pores of the carbon material. Photophysical properties of the NdSuc@AC and DySuc@AC were also investigated. <![CDATA[Comparative Study on Catalytic Dehydration of Glycerol with Alcohols]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400851&lng=en&nrm=iso&tlng=en A comparative study of glycerol dehydration with alcohols (methanol, ethanol, tert-butyl alcohol) over ion exchange resin Amberlyst-35 was performed. The effect of catalyst amounts (1-15 wt.% to glycerol), reaction temperature (50-100 ºC), reaction time (5-10 h), and the molar ratio of alcohols to glycerol (3:1-8:1) were carried out in 50 mL stainless steel autoclave. During the process of glycerol dehydration with alcohols, when the catalyst amount (wt.% to glycerol) is over 10%, it was observed that neither glycerol conversion nor product selectivities are changed significantly. The optimum molar ratios of glycerol to methanol, ethanol and tert-butyl alcohol were 1:6, 1:4, and 1:6, respectively. The appropriate reaction temperature and reaction time were 80 ºC and 8 h at which the selectivities of di-alkyl glycerol ethers and tri-alkyl glycerol ether arrive to the highest. However, the main product was mono-alkyl glycerol ether (MAGE) in glycerol dehydration with tert-butyl alcohol due to steric hindrance influence. If MAGE is considered as the target product, the glycerol dehydration with tert-butyl alcohol could be a good choice. Additionally, the glycerol dehydration with ethanol could be a better route converting biomass material into vehicle fuel in view of its desired yields of higher ethers. <![CDATA[A Novel Colorimetric Immunoassay of Ultrasensitive Alpha-Fetoprotein Sensing in Magnetic Bead-Based Mimic Enzyme-Chromogenic Substrate System]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400859&lng=en&nrm=iso&tlng=en This work described a simple and feasible colorimetric immunoassay. Using hemin (a horseradish peroxidase (HRP) mimic enzyme) and the mimic enzyme-chromogenic substrate system, it can qualitatively and quantitatively detect a-fetoprotein (AFP) at an ultralow concentration. The glucose oxidase (GOx) catalyzed oxidation of glucose leads to the formation of gluconic acid and hydrogen peroxide (H2O2). The latter can oxidize 4-aminoatipyrine (4-AAP) to chromogenic products, and the reaction was catalyzed by hemin. With the increase of H2O2, the absorbance increased, and the color of the solution changed from colorless to pink. On the basis of the system, monitored by recording the color or absorbance (λ = 505 nm), a new immunoassay protocol with GOx-labeled anti-AFP detection antibody was designed. A wide linear dependence was obtained in the range from 0.075 to 280 ng mL-1 with a low detection limit (LOD) of 0.0247 ng mL-1 (S/N = 3). <![CDATA[Investigation on Ruthenium(II) Bipyridine/Ag<sup>III</sup> Complexes Chemiluminescence System and Its Application for Sensitive Norfloxacin and Ofloxacin Detection]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400867&lng=en&nrm=iso&tlng=en The reaction mechanism of AgIII complex ([Ag(HIO6)2]5–) with ruthenium(II) bipyridine (Ru(bpy)32+) in acid medium was investigated. A novel flow injection chemiluminescence (CL) analysis method was developed for the detection of norfloxacin (NFLX) and ofloxacin (OFLX) in commercial drug, milk and human urine samples based on AgIII-ruthenium(II) bipyridine in acidic solution. Under optimal conditions, CL intensities were proportional to drug concentrations in the range of 1.6 × 10-9 to 8 × 10-6 g mL-1 for NFLX and 1.0 × 10-9 to 4 × 10-6 g mL-1 for OFLX. The detection limit was 1.0 × 10-9 g mL-1 for NFLX and 0.8 × 10-9 g mL-1 for OFLX. On the basis of the CL, UV and fluorescence spectra, possible reaction mechanisms were proposed. <![CDATA[Application of a Novel Ion-Imprinted Polymer to the Separation of Traces of Cd<sup>II</sup> Ions in Natural Water: Optimization by Box-Behnken Design]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400873&lng=en&nrm=iso&tlng=en This study describes the preparation of a novel ion-imprinted polymer (IIP) to apply pre-concentration of cadmium ions in water samples of the Pontal Bay in Ilhéus, Brazil. First, cadmium ion was complexed with 2-(2-thiazolylazo)-p-cresol (TAC). Subsequently, there was the polymerization using ethylene glycol dimethacrylate and methacrylic acid monomers along with the radical azobisisobutyronitrile initiator. The mold ions were removed using 2:1 (v v-1) nitric acid. The thermal stability of the polymer was evaluated by thermogravimetry and the characterization was performed by Fourier transform infrared spectroscopy. The maximum adsorption capacity for IIP (qmax = 84.75 mg g-1) could be described by the Langmuir isotherm. The variables: sample flow rate, pH and eluent (nitric acid) were optimized using Box-Behnken design with determination by flame atomic absorption spectrometry (FAAS). The enrichment factor, as well as the limits of detection and quantification (LOQ), were found to be 44, 0.14 and 0.46 µg L-1, respectively. Selectivity was evaluated by using solutions containing CdII, CuII, NiII, PbII, CoII, SO42-, and Cl- ions. The concentration of cadmium ions in the samples varied between &lt; LOQ to 1.25 µg L-1. <![CDATA[Zinc Ferrite Nanoparticles via Coprecipitation Modified Method: Glycerol as Structure Directing and Stabilizing Agent]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532019000400882&lng=en&nrm=iso&tlng=en Coprecipitation is one of the most practical methods used to synthesize ferrite nanoparticles. Fine characteristics of these materials can be improved by means of a series of modifications in the synthesis method. In this paper we present a study of influence of glycerol as structure directing and stabilizing agent in the synthesis of zinc ferrite nanoparticle, exploring its chelating capacity and oxidation. The studied materials include two series of zinc ferrite samples and its precursors obtained with or without glycerol throughout different stages during the synthesis process. The structural and morphological characteristics were evaluated by means of different techniques such as X-ray diffraction, Fourier transformed infrared spectroscopy, scanning and transmission electron microscopy and thermal analysis. The oxidation of glycerol was determined by high-performance liquid chromatograph. The obtained results demonstrate that zinc ferrite crystals synthesized in the presence of glycerol are initially bigger than those synthesized in absence of it, but according to the oxidation process they tend to decrease giving rise to intermediate phases. Interestingly, these samples grow back during more advanced stages and become structurally better organized, compared to the series of samples produced in absence of glycerol. These results indicate that glycerol is capable to modify the synthesis route of zinc ferrite nanoparticles via coprecipitation, acting directly over the size and morphology of the crystals.