Synthesis,characterization, X-ray structure and preliminary in vitro antitumor activity of the nitrosyl complex fac-[RuCl3(NO)(dppf)], dppf = 1,1′-bis(diphenylphosphine)ferrocene

The reaction of RuCl₃NO · 2H₂O with stoichiometric amount of dppf, 1,1′-bis(diphenylphosphino)ferrocene, afforded the new neutral nitrosyl complex fac-[RuCl₃(NO)(dppf)] which was characterized by spectroscopical, electrochemical and X-ray crystallography techniques as well as elemental analysis. The ν_NO band in the IR spectrum is at 1860 cm⁻¹ (CH₂Cl₂ solution) and in the cyclic voltammogram an irreversible wave was observed at −1.35 V, both are characteristics of a nitrosonium (NO⁺) character for the coordinated NO. Additionally, preliminary in vitro antitumor activity against the MDA-MB-231 breast tumor cell line was carried out for the new complex. The initial results indicated an important activity for fac-[RuCl₃(NO)(dppf)] (IC₅₀ = 10 ± 3 μM ). The complex has a higher cytotoxicity than the precursor complex RuCl₃NO · 2H₂O, the free dppf ligand as well as the reference metallodrug cisplatin.     

Determination of pyrimethanil and kresoxim-methyl in soils by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A method using headspace solid-phase microextraction (HS-SPME) then gas chromatography–mass spectrometry with selected ion monitoring (GC–MS, SIM) has been developed for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in soil and humic materials. Both fungicides were extracted on to a fused-silica fibre coated with 85 m polyacrylate (PA). Response-surface methodology was used to optimise the experimental conditions. For soil samples the linear dynamic range of application was 0.004–1.000 g g^–1 for pyrimethanil and 0.013–1.000 g g^–1 for kresoxim-methyl. The detection limits were 0.001 g g^–1 and 0.004 g g^–1 for pyrimethanil and kresoxim-methyl, respectively. HP-SPME–GC–MS analysis was highly reproducible—relative standard deviations (RSD) were between 6.7 and 12.2%. The method was validated by analysis of spiked matrix samples and used to investigate the presence of pyrimethanil and kresoxim-methyl above the detection limits in soil and humic materials.     

Successive projections algorithm improving the multivariate simultaneous direct spectrophotometric determination of five phenolic compounds in sea water

This paper proposes an analytical method to determine directly and simultaneously five phenolic compounds (4-nitrophenol, 2-nitrophenol, phenol, 2,4,6-trichlorophenol and 4-chlorophenol) in sea water (Ria de Bahía Blanca, Argentine). The advantages of this method is that only requires spectrophotometric measurements (separation steps and derivatization reagents are avoided) and chemometric modelling (PLS and MLR–SPA).The statistical comparison between PLS — a well established multivariate method — and MLR–SPA — a recently presented chemometric modelling — demonstrated better analytical performance for the later one. This fact is indicative of the potentiality of MLR–SPA for solving complex analytical problems.     

Comparison between experimental and theoretical values of effectiveness factor in cephalosporin C production process with immobilized cells

Cells ofCephalosporium acretnonium ATCC 48272 immobilized in calcium alginate beads were utilized for cephalosporin C production and the results were compared with those obtained with free cells. The experiments were performed with synthetic medium containing glucose and sucrose as carbon and energy sources. Experimental effectiveness factor values were obtained at various cell and dissolved-oxygen concentrations, considering Monod kinetics for the respiration rate, and were compared with the values calculated with zero-order kinetics in spherical bioparticle. The results showed that the assumption of oxygen limitation by diffusion in the bioparticle was correct, and that cephalosporin C production with immobilized cells is perfectly viable, although a slightly lower rate than that obtained in the free cell process was observed.     

New pi-complexation adsorbents for propane-propylene separation

New adsorbents were prepared and tested for the separation of propane-propylene mixtures by adsorption. The ordered mesoporous material SBA-15 was used as the starting material for silver-ion deposition for pi-complexation with propylene. Two different loadings of silver were evaluated. Adsorption equilibrium and kinetic measurements of propane and propylene in the matrix (pure SBA-15) and the silver-modified adsorbents were performed at 323, 343, and 373 K. In this temperature range, the selectivity of propylene in one of the materials (Ag/SBA-15 = 0.5) is in the range 13-22 because the amount of propane adsorbed is very small, 0.095 mmol/g of propane versus 1.12 mmol/g of propylene at 100 kPa and 343 K. The diffusivity of both hydrocarbons is not seriously affected by the introduction of silver into the mesoporous structure.     

Fenton’s reagent-mediated degradation of residual Kraft black liquor

In this work, the effect of Fento’s reagent on the degradation of residual Kraft black liquor was investigated. The effect of Fenton’s reagent on the black liquor degradation was dependent on the concentration of H₂O₂. At low concentrations (5 and 15 mM) of H₂O₂, Fenton’s reagent caused the degradation of phenolic groups (6.8 and 44.8%, respectively), the reduction of reaction medium pH (18.2%), and the polymerization of black liquor lignin. At a high concentration (60 mM) of H₂O₂, Fenton’s reagent induced an extensive degradation of lignin (95–100%) and discoloration of the black liquor. In the presence of traces of iron, the addition of H₂O₂ alone induced mainly lignin fragmentation. In conclusion, Fenton’s reagent and H₂O₂ alone can degrade residual Kraft black liquor under acidic conditions at room temperature.     

Evaluation of uncertainty sources associated with toxic trace element concentrations in rice

Todays and tomorrows globalized world requires the acceptance of each others capabilities, competence and metrological traceability of measurements to the International System of Units and thus mutual acceptance of quantitative results. Therefore, mutually and publicly recognized standards and certificates are needed at national and international levels. An important step to attain this ambitious goal is to intensify regional metrological collaboration. The exercises of interlaboratorial comparisons are important as part of a system to guaranty the quality of analysis. To estimate the sources of uncertainty associated with the determination of toxic trace element concentrations in rice and to perform an interlaboratorial comparison, a sample containing cadmium, copper, lead and zinc was distributed to four Brazilian laboratories. The laboratories used atomic emission spectroscopy, graphite furnace atomic absorption spectroscopy and flame atomic absorption spectroscopy. The evaluation of the results provided by the laboratories was made by statistical and graphical methods comparing the results of each laboratory to the certified value.     

Effect of surface treatments on the localized corrosion resistance of the AA2198-T8 aluminum lithium alloy welded by FSW process

In this work, the effect of eight types of surface treatments on the corrosion resistance of friction stir welded samples of an AA2198-T8 Al-Cu-Li alloy were tested and compared in an attempt to find suitable alternatives to toxic and carcinogenic hexavalent chromium treatments. All the samples were anodized and subjected to different post-anodizing treatments. The post-anodizing treatments were (1) hydrothermal treatment in Ce (NO₃)₃ 6H₂O solution; (2) hydrothermal treatment in Ce (NO₃)₃ 6H₂O solution with H₂O₂; (3) hydrothermal treatment in boiling water; (4) hexavalent chromium conversion coating; and (5) immersion in BTSE (bis-1,2-(triethoxysilyl) ethane. The corrosion resistance of the treated samples was evaluated by immersion tests in sodium chloride solution (0.1 mol L⁻¹ NaCl) and electrochemical impedance spectroscopy (EIS) of the friction stir weldment. The results showed that among the alternative treatments, the Ce-containing solutions presented the best corrosion resistance, especially when used without peroxide.     

Nanoparticle-based assays in automated flow systems: A review

Nanoparticles (NPs) exhibit a number of distinctive and entrancing properties that explain their ever increasing application in analytical chemistry, mainly as chemosensors, signaling tags, catalysts, analytical signal enhancers, reactive species generators, analyte recognition and scavenging/separation entities.