Tuning the nanostructure of DODAB/nickel tetrasulfonated phthalocyanine bilayers in LbL films

Nanostructured films of dioctadecyldimethylammonium bromide (DODAB) and nickel tetrasulfonated phthalocyanine (NiTsPc) were layer-by-layer (LbL) assembled to achieve a synergistic effect considering the distinct properties of both materials. Prior to LbL growth, the effect of NiTsPc on the structure of DODAB vesicles in aqueous medium was investigated by differential scanning calorimetry (DSC). Therefore, DODAB/NiTsPc LbL films were prepared using NiTsPc at concentrations below and above the limit concentration of vesicle formation according to our DSC experiments. As a result, LbL films with distinct nanostructures were obtained, which were studied at micro and nanoscales by micro-Raman and atomic force microscopy, respectively. A linear growth of the LbL films was observed by ultraviolet-visible absorption spectroscopy. However, the bilayer thickness and the surface morphology of the LbL films were radically affected depending on NiTsPc concentration. The electrostatic interaction between DODAB and NiTsPc was identified via Fourier transform infrared (FTIR) absorption spectroscopy as the main driving force responsible for LbL growth. Because LbL films have been widely applied as transducers in sensing devices, DODAB/NiTsPc LbL films having distinct nanostructures were tested as proof-of-principle in preliminary sensing experiments toward dopamine detection using impedance spectroscopy (e-tongue system). The real capacitance vs. dopamine concentration curves were treated using Principal Component Analysis (PCA) and an equivalent electric circuit, revealing the role played by the LbL film nanostructure and the possibility of building calibration curves. © 2013 Elsevier B.V.

Spectroscopic study and thermal behavior of trivalent lanthanides and yttrium(III) chelates of EDTA using TG-DSC, FTIR, and TG-DSC coupled to FTIR

Solid-state compounds of yttrium and lanthanide chelates of ethylenediaminetetraacetic acid have been synthesized. Simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), theoretical and experimental infrared spectroscopy (FTIR), elemental analysis, complexometry and TG-DSC coupled to FTIR were used to characterize and to study the thermal decomposition of these compounds. The results provided information about the composition, dehydration, thermal stability, thermal decomposition and identification of gaseous products evolved during the thermal decomposition of these compounds. The theoretical and experimental spectroscopic data suggest the possible modes of coordination of the ligand with the lanthanum and terbium metal ions. © 2013 Akadémiai Kiadó, Budapest, Hungary.

Evaluation of the chemical interaction between carbon nanotubes functionalized with TGDDM tetrafunctional resin and hardener DDS

In this work, the chemical interaction between carbon nanotubes (MWCNT) functionalized with acyl chloride (SOCl2) and polymer chain tetrafuncional N,N,N′,N′-tetraglycidyl-4,4′- diaminodiphenylmethane (TGDDM) and hardener 4,4′diaminodiphenyl sulfone (DDS) has been monitored by Fourier transform infrared spectroscopy (FTIR) with a attenuated total reflectance (ATR) coupled. MWCNT were obtained from the pyrolysis of a mixture of camphor and ferrocene into a oven. The functionalization process was done by oxidative treatment in order to incorporate carboxylic group over the walls of MWCNT, before to be used SOCl2. The functionalized carbon nanotubes were evaluated by X-ray photoelectron spectroscopy (XPS), Raman and transmission electron microscopy (TEM). Nanostructured composites were processed by using epoxy resin with MWCNT in varying percentages. In this work it was observed that different percentages of functionalized nanotubes modify the interaction between the composite matrix and curing agent, where can be observed that in specimens with content less than 1 wt% MWCNT the chemical bond occurs preferentially from the opening of the SO double bond of the hardener and when is used MWCNT content higher than 1 wt% there is little chemical interaction with the SO bond of the hardener and most MWCNT binds to amine. © 2013 Elsevier Ltd.

Nanocomposite PAAm/methyl cellulose/montmorillonite hydrogel: Evidence of synergistic effects for the slow release of fertilizers

In this work, we synthesized a novel series of hydrogels composed of polyacrylamide (PAAm), methylcellulose (MC), and calcic montmorillonite (MMt) appropriate for the controlled release of fertilizers, where the components presented a synergistic effect, giving very high fertilizer loading in their structure. The synthesized hydrogel was characterized in relation to morphological, hydrophilic, spectroscopic, structural, thermal, and kinetic properties. After those characterizations, the application potential was verified through sorption and desorption studies of a nitrogenated fertilizer, urea (CO(NH2)2). The swelling degree results showed that the clay loading considerably reduces the water absorption capability; however, the hydrolysis process favored the urea adsorption in the hydrogel nanocomposites, increasing the load content according to the increase of the clay mass. The FTIR spectra indicated that there was incorporation of the clay with the polymeric matrix of the hydrogel and that incorporation increased the water absorption speed (indicated by the kinetic constant k). By an X-ray diffraction technique, good nanodispersion (intercalation) and exfoliation of the clay platelets in the hydrogel matrix were observed. Furthermore, the presence of the montmorillonite in the hydrogel caused the system to liberate the nutrient in a more controlled manner than that with the neat hydrogel in different pH ranges. In conclusion, excellent results were obtained for the controlled desorption of urea, highlighting the hydrolyzed hydrogels containing 50% calcic montmorillonite. This system presented the best desorption results, releasing larger amounts of nutrient and almost 200 times slower than pure urea, i.e., without hydrogel. The total values of nutrients present in the system show that this material is potentially viable for application in agriculture as a nutrient carrier vehicle. © 2013 American Chemical Society.

Use of slag/sugar cane bagasse ash (SCBA) blends in the production of alkali-activated materials

Blast furnace slag (BFS)/sugar cane bagasse ash (SCBA) blends were assessed for the production of alkali-activated pastes and mortars. SCBA was collected from a lagoon in which wastes from a sugar cane industry were poured. After previous dry and grinding processes, SCBA was chemically characterized: it had a large percentage of organic matter (ca. 25%). Solutions of sodium hydroxide and sodium silicate were used as activating reagents. Different BFS/SCBA mixtures were studied, replacing part of the BFS by SCBA from 0 to 40% by weight. The mechanical strength of mortar was measured, obtaining values about 60 MPa of compressive strength for BFS/SCBA systems after 270 days of curing at 20 °C. Also, microstructural properties were assessed by means of SEM, TGA, XRD, pH, electrical conductivity, FTIR spectroscopy and MIP. Results showed a good stability of matrices developed by means of alkali-activation. It was demonstrated that sugar cane bagasse ash is an interesting source for preparing alkali-activated binders. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Synthesis, thermal behavior and spectroscopic study of trivalentlanthanide and yttrium(III) α-hydroxyisobutyrates, in solid state

Thermal and spectroscopic studies on solid trivalent lanthanides and yttrium(III) α-hydroxyisobutyrates, Ln(C4H7O 3)3·nH2O were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), elemental analysis, X-ray diffractometry, complexometry, experimental and theoretical infrared spectroscopy and TG-DSC coupled to FTIR. The dehydration of lanthanum to neodymium and terbium to thulium and yttrium compounds occurs in a single step while for samarium, europium and gadolinium ones it occurs in three consecutives steps. Ytterbium and lutetium compounds were obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occursin two consecutives steps, except lanthanum (five steps) and cerium (single step), with formation of the respective oxides CeO2, Pr6O 11, Tb4O7 and Ln2O3 (Ln = La, Nd to Lu and Y), as final residue. The resultsalso provided information concerning the composition, thermal behavior, crystallinity and gaseous products evolved during the thermal decomposition. The theoretical and experimental spectroscopic data suggested the possible modes of coordination of the ligand with the lanthanides.© 2013 Elsevier B.V.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

Enhanced bulk and superficial hydrophobicities of starch-based bionanocomposites by addition of clay

In this work, thermoplastic starch (TPS)-clay bionanocomposites were obtained by an innovative methodology using a combination of methodologies commonly used in the composites and nanocomposites preparations. The main objectives or novelties were to confirm efficiency of the processing methodology by field emission gun scanning electron microscopy and investigate the effect of clay content on the spectroscopic, bulk and surface hydrophilic/hydrophobic properties of these bionanocomposites. Raman and FTIR spectroscopies confirmed the changes in the spectroscopic properties of the TPS bionanocomposites with the addition of the clay materials. Water absorption and contact angle measurements were also used to analyze the effect of the clay content on the hydrophilic properties of the TPS bionanocomposites. The results also showed that the addition of the cloisite-Na+ clay increased the bulk and surface hydrophobicities of the TPS matrix, which may increase its industrial application, particularly in manufacturing of food containers. © 2013 Elsevier B.V.

Flexible magnetic membranes based on bacterial cellulose and its evaluation as electromagnetic interference shielding material

Flexible magnetic membranes with high proportion of magnetite were successfully prepared by previous impregnation of the never dried bacterial cellulose pellicles with ferric chloride followed by reduction with sodium bisulfite and alkaline treatment for magnetite precipitation. Membranes were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating magnetometer, field emission scanning electron microscopy (FEG-SEM) and impedance spectroscopy. Microwave properties of these membranes were investigated in the X-band (8.2 to 12.4 GHz). FEG-SEM micrographs show an effective coverage of the BC nanofibers by Fe 3O4 nanoparticles. Membranes with up to 75% in weight of particles have been prepared after 60 min of reaction. Magnetite nanoparticles in the form of aggregates well adhered to the BC fibers were observed by SEM. The average crystal sizes of the magnetic particles were in the range of 10 ± 1 to 13 ± 1 nm (estimated by XRD). The magnetic particles in the BC pellicles presented superparamagnetic behavior with a saturation magnetization in the range of 60 emu g- 1 and coercive force around 15 Oe. These magnetic pellicles also displayed high electrical permittivity and a potential application as microwave absorber materials. © 2013 Elsevier B.V.

Synthesis, structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

Estudo do desenovelamento da papaína via espectroscopias de fluorecência e correlação bidimensional no infravermelho

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Otimização das condições de síntese de amostras cerâmicas do composto Y'Ba IND. 2''Cu IND. 3''O IND. 7'-δ através do Método Pechini

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Hipomineralização molar incisivo em escolares de Botelhos, Minas Gerais, Brasil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese de perovskitas nanométricas com estrutura 'PB IND.1-x''M IND.X''TI''O IND.3'(M='BA', 'CA' e 'SR')

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Novas estratégias no estudo da eletro-oxidação de etanol: nanocatalisadores multimetálisos e análises dos produtos de reação

Pós-graduação em Química - IQ