Thermal characterization of mangaba-based films

The purpose of this study was to evaluate the physical–chemical properties of starch (SF), mangaba (MF), and mangaba/starch-based films (MSF), using differential thermal analysis, thermogravimetry/derivative thermogravimetry, infrared spectroscopy, mechanical profile, and scanning electron microscopy. The films were prepared by casting process using sucrose and propyleneglycol as plasticizers. The thermal profiles of MF and MSF were similar and showed increased thermal stability. The mechanical properties of MF and MSF presented decreases of tensile strength and elastic modulus when compared with SF. The MSF showed the best thermal and mechanical characteristics.     

An unusual partial occupancy of labile chloride and aqua ligands in cocrystallized isomers of a nickel(II) complex bearing a tripodal N4‐donor ligand

A novel Ni²⁺ complex with the N₄‐donor tripodal ligand bis[(1‐methyl‐1H‐imidazol‐2‐yl)methyl][2‐(pyridin‐2‐yl)ethyl]amine (L), namely, aqua{bis[(1‐methyl‐1H‐imidazol‐2‐yl‐κN³)methyl][2‐(pyridin‐2‐yl‐κN)ethyl]amine‐κN}chloridonickel(II) perchlorate, [NiCl(C₁₇H₂₂N₆)(H₂O)]ClO₄ or [NiCl(H₂O)(L)Cl]ClO₄ ( 1 ), was synthesized and characterized by spectroscopic and spectrometric methods. The crystal structure of 1 reveals an interesting and unusual cocrystallization of isomeric complexes, which are crystallographically disordered with partial occupancy of the labile cis aqua and chloride ligands. The Ni²⁺ centre exhibits a distorted octahedral environment, with similar bond lengths for the two Ni—N(imidazole) bonds. The bond length increases for Ni—N(pyridine) and Ni—N(amine), which is in agreement with literature examples. The bond lengths of the disordered labile sites are also in the expected range and the Ni—Cl and Ni—O bond lengths are comparable with similar compounds. The electronic, redox and solution stability behaviour of 1 were also evaluated, and the data obtained suggest the maintenance of structural integrity, with no sign of demetalation or decomposition under the studied conditions.     

Two‐Photon STED Spectral Determination for a New V‐Shaped Organic Fluorescent Probe with Efficient Two‐Photon Absorption

Two‐photon stimulated emission depletion (STED) cross sections were determined over a broad spectral range for a novel two‐photon absorbing organic molecule, representing the first such report. The synthesis, comprehensive linear photophysical, two‐photon absorption (2PA), and stimulated emission properties of a new fluorene‐based compound, (E)‐2‐{3‐[2‐(7‐(diphenylamino)‐9,9‐diethyl‐9H‐fluoren‐2‐yl)vinyl]‐5‐methyl‐4‐oxocyclohexa‐2,5‐dienylidene} malononitrile ( 1 ), are presented. Linear spectral parameters, including excitation anisotropy and fluorescence lifetimes, were obtained over a broad range of organic solvents at room temperature. The degenerate two‐photon absorption (2PA) spectrum of 1 was determined with a combination of the direct open‐aperture Z‐scan and relative two‐photon‐induced fluorescence methods using 1 kHz femtosecond excitation. The maximum value of the 2PA cross section ～1700 GM was observed in the main, long wavelength, one‐photon absorption band. One‐ and two‐photon stimulated emission spectra of 1 were obtained over a broad spectral range using a femtosecond pump–probe technique, resulting in relatively high two‐photon stimulated emission depletion cross sections (～1200 GM). A potential application of 1 in bioimaging was demonstrated through one‐ and two‐photon fluorescence microscopy images of HCT 116 cells incubated with micelle‐encapsulated dye.     

Analysis of synthetic 19-norsteroids trenbolone, tetrahydrogestrinone and gestrinone by gas chromatography-mass spectrometry

Tetrahydrogestrinone, gestrinone and trenbolone are synthetic 19-norsteroids with androgenic properties sharing a labile conjugated ketotrienyl motif. Their LC-MS analyses tend to overcome classical derivatization problems, a shortcoming to the use of GC-MS. Therefore, alternative derivatization procedures were evaluated. The procedure with methoxylamine: pyridine followed by TMSImid: MSTFA gave the best results. This is attributed to the stability of the MO-TMS derivatives hindering the formation of artifacts and tautomerism. A full method is presented including SPE, hydrolysis and liquid-liquid extraction. It was possible to confirm the analytes below 2 ng/mL in urine, being the method robust and cost effective also for screening proposes.     

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni²⁺ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni²⁺ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni²⁺ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)₂ complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 × 10⁻⁹ to 1.0 × 10⁻⁶ mol L⁻¹ with detection limit of 2.0 × 10⁻⁹ mol L⁻¹. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 μmol L⁻¹ Ni²⁺ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni²⁺ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni²⁺ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step.     

Extended squaraine dyes with large two-photon absorption cross-sections

Extended bis(donor)-substituted squaraine chromophores exhibit very high two-photon cross-sections (as high as 33 000 GM) in the near-IR; these can be attributed to the combination of large transition dipoles with small detuning energies. The modulus of the third-order nonlinear optical susceptibility at 1.3 mum has been found to be 7.0 x 10-11 esu for one of these chromophores.     

Continuous biotreatment of copper-concentrated solutions by biosorption with Sargassum sp.

Seaweed Sargassum sp. biomass proved to be useful for the recovery of ionic copper from highly concentrated solutions simulating effluents from semiconductor production. In the case of solutions containing copper in the form of chloride, sulfate, and nitrate salts, the best pH for the recovery of copper was 4.5. It was observed that copper biosorption from copper nitrate solutions was higher than the recovery of copper from copper chloride or copper sulfate solutions. The continuous system used was constituted of four column reactors filled with the biomass of Sargassum sp. and showed high operational stability. The biomass of Sargassum sp. in the reactors was gradually saturated from the bottom to the top of each column reactor. The biomass of Sargassum sp. in the first column saturated first, followed by a gradual saturation of the remaining columns owing to preconcentration performed by the biomass in the first column. The biomass of Sargassum in the bioreactors completely biosorbed the ionic copper contained in 63 L of copper sulfate solution, 72 L of copper chloride solution, and 72 L of copper nitrate solution, all the solutions containing copper at 500 mg/L. Effluents produced after biosorption presented copper concentrations < 0.5 mg/L.