Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

ENTEROTOXIN PRODUCTION IN STRAINS OF CAMPYLOBACTER-JEJUNI, ISOLATED FROM SWINE DIARRHEA

One hundred and twenty-six strains of Campylobacter jejuni isolated from swine with diarrhea were examined for the production of enteroxin, by culture filtrate inoculation into ileal loops in several animal species.Four (3,1 %) of the strains tested produced fluid in ligated ileal loop of albino rabbit, 19 (15 %) in rat and 14(11, 1 %) in swine. By the test of intragastric inoculation in suckling mouse, none of the strains revealed capacity to produce enterotoxin, although two strains were considered suspicious. Twelve (54,5 %) of the strains that induced ileal fluid in rat and swine produced cytotoxic effect in monkey kidney cells (Vero), affecting up to 60 % of the monolayer. However, no alteration was observed in hamster kidney cells (BHK).

Thermal behaviour of intercalated 8-hydroxyquinoline (oxine) in montmorillonite clay

The composite montmorillonite-8-hydroxyquinoline (Swy-1-8-HQ) was prepared by two different processes and studied by using thermogravimetric analysis (TG/DTG and DSC), as well as helpful techniques as fluorescence in the UV-visible region and X-ray diffraction. The composites developed fluorescent appearance, however with quantum poor efficiency and they exhibited distinct TG and DSC thermal behavior. The fluorescence data of spectra associated to the TG/DT curves allowed to suggest that the 8-HQ was present in the composites in two different circumstances: 1 - intercalated in the interlayer spaces (Swy-1-8-HQ2), rigidly associated to the Substrate feasible as a monolayer with the aromatic rings parallel to the silica layer; and/or, 2 - adsorbed on the Surface (Swy-1-8-HQ1), either as a bilayer formation or tilting of the molecules to the silicate layer sheet. All results confirmed above are in agreement with X-ray diffraction patterns, once the interlayer space increases when 8-HQ is incorporated. The experimental results confirm the formation of the composites in agreement with the method used in the preparation.

Thermal analysis and electrochemical study of Hg reactions on Pt-30% Ir alloy electrode

Thermogravimetry (TG), cyclic voltammetry (CV) and other analytical techniques were used to study the reactions of mercury with Pt-30% Ir alloy. The results allowed to suggest that an electrodeposited mercury film interacts with the substrate and when subjected to heat or electrochemical removal at least four mass loss steps or five peaks appeared during the mercury desorption process. The first two steps were attributed to Hg(0) removal probably from the bulk and from the adsorbed monolayer which wets the electrode surface. These two processes are responsible for peaks D and F in the cyclic voltammograms. The last two peaks (G, H) in CV were ascribed to the intermetallic compound decomposition. In TG curves, the last two steps were attributed to the PtHg4 (third step), and PtHg2 decomposition followed by Hg removal from the subsurface. The PtHg2 was formed by an eutectoide reaction: PtHg -> PtHg2+Hg(Pt-Ir). The Hg diffused to the subsurface was not detectable by cyclic voltammetry.

Dipole moments in Langmuir monolayers from aromatic carboxylic acids

The three-layer capacitor model proposed by Demchak and Fort [J. Colloid Interface Sci. 46 (1974) 191] is employed to relate measured surface potentials of Langmuir monolayers from a series of polyphenyl carboxylic acids to molecular dipole moments calculated using semiempirical quantum methods. The effective dielectric constant at the air/monolayer interface is 3.0 +/- 0.6, very close to that estimated for aliphatic compounds. Good agreement between theory and experiment is obtained by adopting a dielectric constant of 6.4 for the monolayer/water interface and a contribution from the water reorientation of -0.064 +/- 0.006 D, which shows that the parameters in the DF model are essentially the same as for aliphatic amphiphiles, such as esters, acids, alcohols and ethers. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Using an effective surface charge to explain surface potentials of Langmuir monolayers from dialkyldimethylammonium halides with the Gouy-Chapman theory

The use of an effective surface charge density has allowed the Gouy-Chapman (CC) theory to explain surface potential isotherms of Langmuir monolayers of dioctadecyldimethylammonium bromide (DODAB). The effective surface charge density of DODAB monolayer increases with the electronegativity of the counterions in the subphase. The pressure-area isotherms indicate a very condensed monolayer for DODAB spread on an I--containing subphase, which exhibits the lowest surface charge density, whereas the monolayer on a F-containing subphase is extremely expanded owing to the high surface charge density or electrostatic repulsion between headgroups. (C) 2001 Published by Elsevier B.V. B.V.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Sorption isotherms of alligator's meat (Caiman crocodilus yacare)

Sorption isotherms were determined for salted alligator's meat at four different temperatures (10degreesC, 15degreesC, 25degreesC and 35degreesC), using a standard gravimetric method. The goodness of fit of five sorption models to experimental data was determined. Five models, namely the GAB, the BET, the Halsey, the Henderson and the Hailwood and Horrobin, were evaluated to determine the best fit for the experimental data. The GAB was the best fitted model for the data of salted alligator's meat with an average error less than 10% for temperature of 10degreesC and less than 5% for the others temperatures. The coefficients of determination (r(2)) were 0.99 for all temperatures considered. The monolayer values decreased as temperature increased. The other four models were not appropriated to fit the data because of the high error values, although the r(2) were also similar to the GAB model. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausis-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Tin oxide nanoparticle formation using a surface modifying agent

This work presents results concerning the preparation of redispersible tin oxide nanoparticles achieved by using Tiron molecule ((OH)(2)C(6)H(2) (SO(3)Na)(2)) as surface modifying agent. The adsorption isotherm measurements show that an amount of 10 wt.% of Tiron is need to recover the SnO(2) nanoparticles surface with a monolayer. These nanoparticles can be easily redispersed in tetramethyl ammonium hydroxide at pH greater than or equal to11 until a powder concentration of 12 vol.% of tin. Under these conditions, hydrodynamic particle size is about 7 nm and increases until 52 nm at pH 6 due to the aggregation phenomenon. The time evolution of the viscoelastic properties indicates that the suspensions at pH 12.5, containing 12 vol.% tin oxide and 10 wt.% of surface modifier are kinetically stable. After thermal treatment at different temperature the powder characterisation evidences that the presence of Tiron monolayer at the nanoparticles surface increases the thermal stability of the porous texture and prevent the micropore size growth. This set of results contributes to satisfy the demand for more controlled synthesis of nanoparticles with high thermal stability as required for fabrication of ultrafiltration ceramic membranes. (C) 2004 Elsevier Ltd. All rights reserved.

Magnetophotoluminescence study of GaAs/AlGaAs coupled double quantum wells with bimodal heterointerface roughness

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

DNA hybridization mechanism in an interfacial environment: What hides beneath first order k (s(-1)) kinetic constant?

The scientific question addressed in this work is: what hides beneath first order kinetic constant k (s(-1)) measured for hybridization of a DNA target on a biosensor surface. Kinetics hybridization curves were established with a 27 MHz quartz microbalance (9 MHz, third harmonic) biosensor, constituted of a 20-base probe monolayer deposited on a gold covered quartz surface. Kinetics analysis, by a known two-step adsorption-hybridization mechanism, is well appropriate to fit properly hybridization kinetics curves, for complementary 20-base to 40-base targets over two concentration decades. It was found that the K-1 (M-1) adsorption constant, relevant to the first step, concerns an equilibrium between non hybridized targets and hybridized pre-complex and increases with DNA target length. It was established that k(2) (s(-1)), relevant to irreversible formation of a stable duplex, varies in an opposite way to K-1 with DNA target length. (C) 2012 Published by Elsevier B.V.

The lipid composition of a cell membrane modulates the interaction of an antiparasitic peptide at the air-water interface

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Contribution to the study of the reaction of mercury with platinum and a platinum-iridium alloy

Thermogravimetry (TG) and other analysis techniques have been used to study the reaction of mercury with Pt and a PtIr alloy. The results suggested that, when heated, the electrodeposited Hg film reacts with Pt or with PtIr to form products of different stabilities, indicated by at least three weight loss steps. In the first step, between room temperature and 170°C, only the bulk Hg is removed. From this temperature to about 280°C the mass loss can be attributed to the desorption of a monolayer of mecury. The last step, from 280 to ≈600°C, can be ascribed to the removal of Hg from a solid solution with Pt and PtIr alloy. © 1995.

Adsorption of silanes bearing nitrogenated Lewis bases on SiO 2/Si (100) model surfaces

The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N- propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with on-spot MALDI-TOF MS detection. © 2005 Elsevier Inc. All rights reserved.

Evaluation of serum- and animal protein-free media for the production of infectious bronchitis virus (M41) strain in a continuous cell line

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)