Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Using Fluid Bed Granulation to Improve the Dissolution of Poorly Water-Soluble Drugs

In this study, fluid bed granulation was applied to improve the dissolution of nimodipine and spironolactone, two very poorly water-soluble drugs. Granules were obtained with different amounts of sodium dodecyl sulfate and croscarmellose sodium and then compressed into tablets. The dissolution behavior of the tablets was studied by comparing their dissolution profiles and dissolution efficiency with those obtained from physical mixtures of the drug and excipients subjected to similar conditions. Statistical analysis of the results demonstrated that the fluid bed granulation process improves the dissolution efficiency of both nimodipine and spironolactone tablets. The addition of either the surfactant or the disintegrant employed in the study proved to have a lower impact on this improvement in dissolution than the fluid bed granulation process.

Using fluid bed granulation to improve the dissolution of poorly water-soluble drugs

In this study, fluid bed granulation was applied to improve the dissolution of nimodipine and spironolactone, two very poorly water-soluble drugs. Granules were obtained with different amounts of sodium dodecyl sulfate and croscarmellose sodium and then compressed into tablets. The dissolution behavior of the tablets was studied by comparing their dissolution profiles and dissolution efficiency with those obtained from physical mixtures of the drug and excipients subjected to similar conditions. Statistical analysis of the results demonstrated that the fluid bed granulation process improves the dissolution efficiency of both nimodipine and spironolactone tablets. The addition of either the surfactant or the disintegrant employed in the study proved to have a lower impact on this improvement in dissolution than the fluid bed granulation process.

Seasonal Distribution of Airborne Trace Elements and Water-Soluble Ions in Sao Paulo Megacity, Brazil

This study deals with the seasonal distribution of Al, Ca, Cu, Fe, K, Mg, Na, Pb and Zn and water soluble ions (Cl-, PO43-, NO3-, SO42-, HCOO-, CH3COO-, oxalate, succinate, Na+, NH4+, K+, Mg2+ and Ca2+) found in PM10 samples (particulate matter less than 10 mu m in diameter) Sao Paulo City, Brazil, (April 2003-May 2004). Higher atmospheric levels were found for SO42-, NO3-, Cl- and PO43- while the main organic anions were oxalate and formate. Atmospheric levels for elements were: Fe > Al > Ca > K > Na > Mg > Zn > Cu > Pb. Some sources were predominant for some species: (i) fuel burning and/or biomass burning (NO3-, HCOO-, C2O42-, K+, Mg2+, Ca2+, Fe, Pb, Zn, Al, Ca, K and Mg), (ii) gas-to-particle conversion (SO42- and NH4+) and (iii) sea salt spray (Cl-, Na+ and Na).

Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (Sao Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 mu m), and its concentration in total aerosol ranged from 25 to 1186 ng m(-3). The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 +/- 2.97 mu g m(-3) (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 pm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high concentrations of WSOC (and inorganic ions) suggest an important influence on the formation of cloud condensation nuclei, which is likely to affect cloud formation and precipitation patterns. (C) 2012 Elsevier Ltd. All rights reserved.

Previous illumination of a water soluble chlorine photosensitizer increases its cytotoxicity

Photodithazine (PDZ) is an N-methyl-D-glucosamine derivative of chlorine e6 that is water soluble and has an intense absorption in the range of 650-680 nm. PDZ photobleaching and photoproduct formation were induced by illumination with laser at two wavelengths: 514 nm (ion argon laser) as well as in 630 nm (dye laser). The time constants of PDZ photobleaching were: 18 min for 630 nm irradiation and 50 min for 514 nm irradiation, suggesting that degradation after irradiation with red light is faster than with green light. Photoproducts formation was evidenced by the appearance of a new absorption band at 668 nm with slight broaden of the Soret band, suggesting that there was no break of the macrocycle. The cytotoxicity of the photodegradated PDZ was investigated and showed to be lower in the dark and higher than non irradiated PDZ. These results may have important clinical implications for PDT such as the possibility to use the previously irradiated PDZ just before clinical application in order to get increased efficiency.

Genotoxicity assessment of water soluble fractions of biodiesel and its diesel blends using the Salmonella assay and the in vitro MicroFlow (R) kit (Litron) assay

The designation of biodiesel as an environmental-friendly alternative to diesel oil has improved its commercialization and use. However, most biodiesel environmental safety studies refer to air pollution and so far there have been very few literature data about its impacts upon other biotic systems, e.g. water, and exposed organisms. Spill simulations in water were carried out with neat diesel and biodiesel and their blends aiming at assessing their genotoxic potentials should there be contaminations of water systems. The water soluble fractions (WSF) from the spill simulations were submitted to solid phase extraction with C-18 cartridge and the extracts obtained were evaluated carrying out genotoxic and mutagenic bioassays [the Salmonella assay and the in vitro MicroFlow (R) kit (Litron) assay]. Mutagenic and genotoxic effects were observed, respectively, in the Salmonella/microsome preincubation assay and the in vitro MN test carried out with the biodiesel WSF. This interesting result may be related to the presence of pollutants in biodiesel derived from the raw material source used in its production chain. The data showed that care while using biodiesel should be taken to avoid harmful effects on living organisms in cases of water pollution. (C) 2011 Elsevier Ltd. All rights reserved.

Seasonal distribution of airborne trace elements and water-soluble ions in São Paulo Megacity, Brazil

This study deals with the seasonal distribution of Al, Ca, Cu, Fe, K, Mg, Na, Pb and Zn and water soluble ions (Cl-, PO4(3-), NO3-, SO4(2-), HCOO-, CH3COO-, oxalate, succinate, Na+, NH4+, K+, Mg2+ and Ca2+) found in PM10 samples (particulate matter less than 10 mm in diameter) São Paulo City, Brazil, (April 2003-May 2004). Higher atmospheric levels were found for SO4(2-), NO3-, Cl- and PO4(3-) while the main organic anions were oxalate and formate. Atmospheric levels for elements were: Fe > Al > Ca > K > Na > Mg > Zn > Cu > Pb. Some sources were predominant for some species: (i) fuel burning and/or biomass burning (NO3-, HCOO-, C2O4(2-), K+, Mg2+, Ca2+, Fe, Pb, Zn, Al, Ca, K and Mg), (ii) gas-to-particle conversion (SO4(2-) and NH4+) and (iii) sea salt spray (Cl-, Na+ and Na).

Effect of cellulose physical characteristics, especially the water sorption value, on the efficiency of its hydrolysis catalyzed by free or immobilized cellulase

Cellulase, an enzymatic complex that synergically promotes the degradation of cellulose to glucose and cellobiose, free or adsorbed onto Si/SiO(2) wafers at 60 degrees C has been employed as catalyst in the hydrolysis of microcrystalline cellulose (Avicel), microcrystalline cellulose pre-treated with hot phosphoric acid (CP), cotton cellulose (CC) and eucalyptus cellulose (EC). The physical characteristics such as index of crystallinity (I(C)), degree of polymerization (DP) and water sorption values were determined for all samples. The largest conversion rates of cellulose into the above-mentioned products using free cellulase were observed for samples with the largest water sorption values; conversion rates showed no correlation with either IC or DP of the biopolymer. Cellulose with large water sorption value possesses large pore volumes, hence higher accessibility. The catalytic efficiency of immobilized cellulase could not be correlated with the physical characteristics of cellulose samples. The hydrolysis rates of the same cellulose samples with immobilized cellulase were lower than those by the free enzyme, due to the diffusion barrier (biopolymer chains approaching to the immobilized enzyme) and less effective contact between the enzyme active site and its substrate. Immobilized cellulase, unlike its free counterpart, can be recycled at least six times without loss of catalytic activity, leading to higher overall cellulose conversion. (C) 2011 Elsevier B.V. All rights reserved.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel

In this study, particulate matter (PM) were characterized from a place impacted by heavy-duty vehicles (Bus Station) fuelled with diesel/biodiesel fuel blend (B3) in the city of Londrina, Brazil. Sixteen priority polycyclic aromatic hydrocarbons (PAH) concentrations were analyzed in the samples by their association with atmospheric PM, mass size distributions and major ions (fluorite, chloride, bromide, nitrate, phosphate, sulfate, nitrite, oxalate; fumarate, formate, succinate and acetate; lithium, sodium, potassium, magnesium, calcium and ammonium). Results indicate that major ions represented 21.2% particulate matter mass. Nitrate, sulfate, and ammonium, respectively, presented the highest concentration levels, indicating that biodiesel may also be a significant source for these ions, especially nitrate. Dibenzo[a,h]anthracene and indeno[1,2,3,-cd]pyrene were the main PAH found, and a higher fraction of PAH particles was found in diameters lower than 0.25 mu m in Londrina bus station. The fine and ultrafine particles were dominant among the PM evaluated, suggesting that biodiesel decreases the total PAH emission. However, it does also increase the fraction of fine and ultrafine particles when compared to diesel.

Carboxymethyl lignin as stabilizing agent in aqueous ceramic suspensions

Identifying new uses for residues of industries that process large quantities of biomass, as in bioethanol production, is essential for a sustainable development with reduced impact on the environment, which is the reason why many efforts have been devoted to find noble uses for lignins. in this study, a lignin obtained from sugarcane bagasse in a bioethanol producing plant was carboxymethylated to yield the water-soluble carboxymethyl lignin (CML), which was then used as stabilizing agent in aqueous alumina (Al2O3) suspensions. CML had a degree of substitution 0.46 +/- 0.01, in relation to the C9 unit of lignin, and behaved as a polyelectrolyte in a large pH range owing to the dissociation of carboxylic groups. The action of CML as stabilizing agent of alumina aqueous suspensions was investigated using viscometry, zeta potential, and photon correlation spectroscopy (PCS) measurements, mainly as a function of pH and time. Overall, the results showed that CML had a good performance as a deflocculating agent, because it led to dispersions with low viscosity and small change in particle size as a function of time. The positive effect from the addition of CML was confirmed in the morphological features of the material obtained from the alumina suspensions after elimination of water, as indicated by scanning electron microscopy. The stabilization of alumina suspensions afforded by CML opens the way for similar applications of modified lignins, whose electrical and structural properties may be tuned for specific uses in various industries, including the ceramic industry. (C) 2011 Elsevier B.V. All rights reserved.

Adding value to the Brazilian sisal: acid hydrolysis of its pulp seeking production of sugars and materials

The present work is inserted into the broad context of the upgrading of lignocellulosic fibers. Sisal was chosen in the present study because more than 50% of the world's sisal is cultivated in Brazil, it has a short life cycle and its fiber has a high cellulose content. Specifically, in the present study, the subject addressed was the hydrolysis of the sisal pulp, using sulfuric acid as the catalyst. To assess the influence of parameters such as the concentration of the sulfuric acid and the temperature during this process, the pulp was hydrolyzed with various concentrations of sulfuric acid (30-50%) at 70 A degrees C and with 30% acid (v/v) at various temperatures (60-100 A degrees C). During hydrolysis, aliquots were withdrawn from the reaction media, and the solid (non-hydrolyzed pulp) was separated from the liquid (liquor) by filtering each aliquot. The sugar composition of the liquor was analyzed by HPLC, and the non-hydrolyzed pulps were characterized by viscometry (average molar mass), and X-ray diffraction (crystallinity). The results support the following conclusions: acid hydrolysis using 30% H2SO4 at 100 A degrees C can produce sisal microcrystalline cellulose and the conditions that led to the largest glucose yield and lowest decomposition rate were 50% H2SO4 at 70 A degrees C. In summary, the study of sisal pulp hydrolysis using concentrated acid showed that certain conditions are suitable for high recovery of xylose and good yield of glucose. Moreover, the unreacted cellulose can be targeted for different applications in bio-based materials. A kinetic study based on the glucose yield was performed for all reaction conditions using the kinetic model proposed by Saeman. The results showed that the model adjusted to all 30-35% H2SO4 reactions but not to greater concentrations of sulfuric acid. The present study is part of an ongoing research program, and the results reported here will be used as a comparison against the results obtained when using treated sisal pulp as the starting material.

Dissolution Enhancement and Characterization of Nimodipine Solid Dispersions with Poloxamer 407 or PEG 6000

The solid dispersion approach is an alternative to increase drug solubility. Many carriers have been studied, but there is few information about poloxamer 407 (P407). Consequently, the objective of this study was to evaluate P407 as a carrier for nimodipine solid dispersions and to compare its solubility and dissolution rates with those from polyethylene glycol (PEG 6000). The solid dispersions were prepared by the hot melting and solvent methods and they were characterized by FTIR, DSC, solubility, and dissolution tests. The results indicated a three-fold increase in solid dispersions solubility in the presence with P407 than those prepared with PEG.

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Objectives. The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. Methods. A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R-p(max)) profile of the model resin. Results. In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and R-p(max) values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an R-p(max) value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity. Significance. Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.