Sequential anaerobic/aerobic treatment of dye-containing wastewaters: colour and COD removals, and ecotoxicity tests

Colour and COD removals of the azo dyes Congo Red (CR) and Reactive Black 5 (RB5) were individually evaluated in a sequential anaerobic/aerobic treatment system. Additionally, dye toxicity was assessed by using acute ecotoxicity tests with Daphnia magna as the indicator-organism. The anaerobic reactor was operated at approximately 27 °C and with hydraulic retention times of 12 and 24 h. The aerobic reactor was operated in batch mode with a total cycle of 24 h. During anaerobic step, high colour removals were obtained, 96.3% for CR (400 mg/L) and 75% for RB5 (200 mg/L). During the aerobic phase, COD effluent was considerably reduced, with an average removal efficiency of 52% for CR and 85% for RB5, which resulted in an overall COD removal of 88% for both dyes. Ecotoxicity tests with CR revealed that the anaerobic effluent presented a higher toxicity compared with the influent, and an aerobic post-treatment was not efficient in reducing toxicity. However, the results with RB5 showed that both anaerobic and aerobic steps could decrease dye toxicity, especially the aerobic phase, which removed completely the toxicity in D. magna. Therefore, the anaerobic/aerobic treatment is not always effective in detoxifying dye-containing wastewaters, sometimes even increasing dye toxicity.     

Purification and Characterization of a Mannose Recognition Lectin from <Emphasis Type="Italic">Oreochromis niloticus</Emphasis> (Tilapia Fish): Cytokine Production in Mice Splenocytes

The aim of this work was to purify and partially characterize a mannose recognition lectin from Nile tilapia (Oreochromis niloticus) serum, named OniL. OniL was isolated through precipitation with ammonium sulfate and affinity chromatography (Concanavalin A–Sepharose 4B). In addition, we evaluated carbohydrate specificity, sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS–PAGE) profiles, and in vitro immunomodulatory activity on mice splenocyte experimental cultures through cytotoxic assays and cytokine production. The ammonium sulfate fraction F2 showed the highest specific hemagglutinating activity (331) and was applied to affinity matrix. Adsorbed proteins (OniL) were eluted with methyl-α-d-mannopyranoside. OniL, a 17-kDa protein by SDS–PAGE constituted by subunits of 11 and 6.6 kDa, showed highest affinity for methyl-α-d-mannopyranoside and d-mannose. Immunological assays, in vitro, showed that OniL did not show cytotoxicity against splenocytes, induced higher IFN-γ production and lower IL-10 as well as nitrite release. In conclusion, OniL lectin was successfully purified and showed a preferential Th1 response in mice splenocytes.     

A column-switching method for quantification of the enantiomers of omeprazole in native matrices of waste and estuarine water samples

This work reports the use of a two-dimensional liquid chromatography (2D-LC) system for quantification of the enantiomers of omeprazole in distinct native aqueous matrices. An octyl restricted-access media bovine serum albumin column (RAM-BSA C₈) was used in the first dimension, while a polysaccharide-based chiral column was used in the second dimension with either ultraviolet (UV-vis) or ion-trap tandem mass spectrometry (IT-MS/MS) detection. An in-line configuration was employed to assess the exclusion capacity of the RAM-BSA columns to humic substances. The excluded macromolecules had a molecular mass in the order of 18 kDa. Good selectivity, extraction efficiency, accuracy, and precision were achieved employing a very small amount (500 μL or 1.00 mL) of native water sample per injection, with detection limits of 5.00 μg L⁻¹, using UV-vis, and 0.0250 μg L⁻¹, using IT-MS/MS. The total analysis time was only 35 min, with no time spent on sample preparation. The methods were successfully applied to analyze a series of waste and estuarine water samples. The enantiomers were detected in an estuarine water sample collected from the Douro River estuary (Portugal) and in an influent sample from the wastewater treatment plant (WWTP) of São Carlos (Brazil). As far as we are concerned, this is the first report of the occurrence of (+)-omeprazole and (−)-omeprazole in native aqueous matrices.     

Three‐Electrode‐Integrated Sensor into a Micropipette Tip

This work describes the construction, characterization, and application of a three‐electrode‐integrated sensor into a micropipette tip. The three electrodes (working, pseudoreference and counter) are positioned at the end of a micropipette tip. The working electrode (graphite composite or gold microfiber) is placed inside the micropipette tip and the pseudo‐reference and counter electrodes outside (diametrically opposed sides). This approach is candidate for portable applications and allows the analysis and studies in low‐volume solutions (ca. 10 µL) which are useful for waste minimization and development of clean analytical methods. In addition, the three‐electrode‐integrated sensor can be easy used as detector in flow injection system through its direct joining at the end of polyethylene tubing of the FIA system.     

A compact miniaturized continuous flow system for the determination of urea content in milk

A multicommutation-based flow system with photometric detection was developed, employing an analytical microsystem constructed with low temperature co-fired ceramics (LTCC) technology, a solid-phase reactor containing particles of Canavalia ensiformis DC (urease source) immobilized with glutaraldehyde, and a mini-photometer coupled directly to the microsystem which monolithically integrates a continuous flow cell. The determination of urea in milk was based on the hydrolysis of urea in the solid-phase reactor and the ammonium ions produced were monitored using the Berthelot reaction. The analytical curve was linear in the urea concentration range from 1.0 × 10⁻⁴ to 5.0 × 10⁻³ mol L⁻¹ with a limit of detection of 8.0 × 10⁻⁶ mol L⁻¹. The relative standard deviation (RSD) for a 2.0 × 10⁻³ mol L⁻¹ urea solution was lower than 0.4% (n = 10) and the sample throughput was 13 h⁻¹. To check the reproducibility of the flow system, calibration curves were obtained with freshly prepared solutions on different days and the RSD obtained was 4.7% (n = 6). Accuracy was assessed by comparing the results of the proposed method with those from the official procedure and the data are in close agreement, at a 95% confidence level.     

Statistical design-principal component analysis optimization of a multiple response procedure using cloud point extraction and simultaneous determination of metals by ICP OES

A procedure has been developed for the simultaneous determination of traces amounts of Cd, Cr, Cu, Mn, Ni and Pb from saline oil-refinery effluents and digested vegetable samples using inductively coupled plasma optical emission spectrometry (ICP OES). The procedure is based on cloud point extraction (CPE) of these metals as 2-(bromo-2-pyridylazo)-5-diethyl-amino-phenol (Br-PADAP) complexes into a micellar phase of octylphenoxypolyethoxyethanol (Triton X-114). Optimization of the procedure was performed by response surface methodology (RSM) using a Doehlert design. Principal components (PC) were used to simplify the multiple response analysis. A response surface for the first PC score is useful in determining the optimum conditions for the Cd, Cr, Cu, Mn and Pb determinations whereas the second PC is highly correlated with the Ni response. Improvement factors of 22, 36, 46, 25, 65 and 39, along with limits of detection (3σ_B) of 0.081, 0.79, 0.38, 0.83, 0.28 and 0.69 μg L⁻¹, and precision expressed as relative standard deviation (%R.S.D., n = 8, 20.0 μg L⁻¹) of 1.5, 2.2, 3.5, 2.6, 2.5 and 2.5 were achieved for Cd, Cr, Cu, Mn, Ni and Pb, respectively. The accuracy was evaluated by spike tests in oil-refinery effluent samples and analysis of a vegetable certified reference material (NIST 1571, orchard leaves). Results found were in agreement with certified values.     

Quasiperiodic magnonic superlattices with mirror symmetry

We address the spin wave modes propagating in Fibonacci, Thue–Morse, and double period quasiperiodic magnonic superlattices. These structures are made of layers of a metamagnetic material alternating with layers of a nonmagnetic material, presenting mirror symmetry. Our calculations are carried out in the magnetostatic regime for the antiferromagnetic phase. Our model takes into account the presence of an external applied magnetic field, which is perpendicular to the interfaces of the superlattice, as well as the crystalline anisotropic contribution to the inner magnetic field. The magnetostatic bulk and surface modes are obtained by using the transfer matrix technique. The metamagnetic material considered here is FeBr₂, however, our results can be extended to other materials. Our numerical results show the behavior of these modes, for small frequencies of the energy spectra. The results reported here can be experimentally observed by light scattering techniques.     

Dynamic kinetic calculation of castor oil biodiesel

Diesel oil has an important role in the field of urban traffic as well as in the transportation of products. However, the amount of the non-renewable sources is continuously decreasing. This fact and the environmental requirements brought the necessity to search for other, renewable sources. This paper aimed the dynamic kinetic calculation of thermal decomposition of castor oil, methanol biodiesel and ethanol biodiesel using Coats–Redfern, Madhusudanan and Ozawa methods. On the base of the thermogravimetric curves the following thermal stability order could be established: castor oil>ethanol biodiesel>methanol biodiesel. Kinetic data presented coherent results. Methanol biodiesel presented lower activation energy than ethanol biodiesel, suggesting that methanol biodiesel has a better quality for combustion.     

Chromatographic profiles of <Emphasis Type="Italic">Phyllanthus</Emphasis> aqueous extracts samples: a proposition of classification using chemometric models

Taking in consideration the global analysis of complex samples, proposed by the metabolomic approach, the chromatographic fingerprint encompasses an attractive chemical characterization of herbal medicines. Thus, it can be used as a tool in quality control analysis of phytomedicines. The generated multivariate data are better evaluated by chemometric analyses, and they can be modeled by classification methods. “Stone breaker” is a popular Brazilian plant of Phyllanthus genus, used worldwide to treat renal calculus, hepatitis, and many other diseases. In this study, gradient elution at reversed-phase conditions with detection at ultraviolet region were used to obtain chemical profiles (fingerprints) of botanically identified samples of six Phyllanthus species. The obtained chromatograms, at 275 nm, were organized in data matrices, and the time shifts of peaks were adjusted using the Correlation Optimized Warping algorithm. Principal Component Analyses were performed to evaluate similarities among cultivated and uncultivated samples and the discrimination among the species and, after that, the samples were used to compose three classification models using Soft Independent Modeling of Class analogy, K-Nearest Neighbor, and Partial Least Squares for Discriminant Analysis. The ability of classification models were discussed after their successful application for authenticity evaluation of 25 commercial samples of “stone breaker.”     

Mass Spectrometry and X-ray Diffraction Analysis of Two Crystal Types of Dioclea virgata Lectin: An Antinociceptive Protein Candidate to Structure/Function Analysis

The lectin from seeds of Dioclea virgata (DvirL) was purified in a single step affinity chromatography, sequenced by tandem mass spectrometry and submitted to crystallization and biological experiments. DvirL has a molecular mass of 25,412?±?2 Da and the chains β and γ has 12,817 Da?±?2 and 12,612 Da?±?2, respectively. Primary sequence determination was assigned by tandem mass spectrometry and revealed a protein with 237 amino acids and 87% of identify with ConA. The protein crystals were obtained native and complexed with X-Man using vapor-diffusion method at a constant temperature of 293 K. A complete X-ray dataset was collected at 1.8 ? resolution. DvirL crystals were found to be orthorhombic, belonging to the space group I222, with a unit cell parameters a?=?647.5 ?, b?=?86.6 ?, c?=?90.2 ?. Molecular replacement search found a solution with a correlation coefficient of 77.1% and an R(factor) of 44.6%. The present study also demonstrated that D. virgata lectin presents edematogenic and antinociceptive activities in rodents electing this protein as a candidate to structure/function analysis.