Preparation and Physical Properties of LLDPE Grafted with Novel Nonionic Surfactants

Copolymers of linear low-density polyethylene (LLDPE) grafted with two novel nonionic surfactants, acrylic glycerol monostearate ester (AGMS) and acrylic polyoxyethylenesorbitan monooleate ester (ATW-EEN80), containing hydrophilic and hydrophobic groups and 1-olefin double bond were prepared by using a plasticorder at 190 degrees C. To evaluate the grafting degree, two different approaches based on H-1-NMR data were proposed, and FTIR calibration was showed to validate these methods. The rheological response of the molten polymers, determined under dynamic shear flow at small-amplitude oscillations, indicated that crosslinking formation of the chains could be decreased with increasing the monomer concentration. Their thermal behavior was studied by DSC and polarization microscope (PLM): The crystallization temperature (T-C) of grafted LLDPE shifted to higher temperature compared with neat LLDPE because the grafted chains acted as nucleating agents. Water and glycerol were used to calculate the surface free energy of grafted LLDPE films.

Effect of surfactants and polyethylene glycol on the activity and stability of a lipase from oilseeds of Pachira aquatica

Lipases from oilseeds have a great potential for commercial exploration as industrial enzymes. Lipases are used mixed with surfactants in cleaning and other formulated products, and accordingly, both components must be compatible with each other. This work presents the results of the effects of anionic, cationic and nonionic surfactants, polyethylene glycol and urea on the activity and stability of a lipase extracted of oilseeds from Pachira aquatica. The enzyme was purified and the spectrophotometric assays were done using p-nitrophenyl acetate (p-NPA) as substrate pH 7.5 and 25 degrees C. The activity was significantly enhanced by the cationic surfactant CTAB. Bile salts increased the lipase activity in the tested concentration range, whereas anionic and nonionic surfactants showed an inhibitory effect. Aqueous solutions of PEG activated the lipase and maximum activation (161%) occurred in PEG 12,000. This effect on lipase that can be due to exposition of some hydrophobic residues located in the vicinity of the active site or aggregation.

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.

The photochemistry of dioxorhenium(V)

The excited-state properties of trans-ReO₂(py)₄⁺ (ReO₂⁺) in acetonitrile solution have been investigated. The excited-state absorption spectrum of ReO₂⁺ is dominated by bleaching of the ground state MLCT and d-d systems. The reduction potential of ReO₂^2+/+* is estimated from emission and electrochemical data to be -0.7 V (SSCE). The ReO₂⁺ excited state efficiently reduces methylviologen and other pyridinium and olefin acceptors. The resulting Re(VI) species oxidizes secondary alcohols and silanes. Acetophenone is the product of sec-phenethyl alcohol oxidation.

The emission properties of ReO₂⁺ in aqueous solutions of anionic and nonionic surfactants have been investigated. The emission and absorption maxima of ReO₂⁺ are dependent on the water content of its environment. Emission lifetimes vary over four orders of magnitude upon shifting from aqueous to nonaqueous environments. The emission lifetime has a large (8.6) isotope effect (k(H₂O)/k(D₂O)) that reflects its sensitivity towards the environment. These properties have been used to develop a model for the interactions of ReO₂⁺ with sodium dodecyl sulfate (SDS). A hydrophobic ReO₂⁺ derivative, ReO₂(3-Ph-py)₄⁺, has been used to probe micelles of nonionic surfactants, and these results are consistent with those obtained with SDS.

The emission properties of ReO₂⁺ in Nafion perfluorosulfonated membranes have been investigated. Absorption and emission spectroscopy indicate that the interior of the membrane is quite polar, similar to ethylene glycol. Two well-resolved emission components show different lifetimes and different isotope effects, indicative of varying degrees of solvent accessibility. These components are taken as evidence for chemically distinct regions in the polymer film, assigned as the interfacial region and the ion cluster region.

The unsubstituted pyridine complex shows monophasic, τ = 1.7 µs, emission decay when bound to calf thymus DNA. Switching to the 3-Ph-py complex yields a biphasic emission decay (τ₁ = 2.4 µs, τ₂ = 10 µs) indicative of an additional, solvent-inaccessible binding mode. Photoinduced electron transfer to methylviologen leads to oxidative cleavage of the DNA as detected by gel electrophoresis. Electrochemical and spectrophotometric techniques used with organic substrates also can be used to monitor the oxidation of DNA. Abstraction of the ribose 4' hydrogen by ReO₂²⁺ is a possible mechanism.

三孢布拉氏霉发酵产β-胡萝卜素的研究

本论文研究了利用三孢布拉氏霉(Blakeslea trispora)发酵产β-胡萝卜素的培养条件。主要包括：发酵培养基的确定，发酵条件的优化。还考察了发酵菌丝体中β-胡萝卜素的提取方法及薄层层析等。 首先研究了培养基成分对三孢布拉氏霉发酵产β-胡萝卜素的影响。确立了玉米淀粉作为碳源，黄豆粉（热榨）作为氮源，棉籽油作为植物油的发酵培养基配方，其成分为：玉米淀粉 3％，黄豆粉（热榨） 2％，棉籽油 3％，KH2PO4 0.2%，MgSO4·7H2O 0.2%，维生素B1 0.002％，pH值6.0。 其次，通过比较不同的发酵影响因子，分别得到最适的条件：如三孢布拉氏霉正负菌接种比例为1.3：0.7，培养基pH值为7.0（灭菌后），发酵促进因子为Triton X-100。并采用正交试验法，确定其最佳发酵条件为正负菌接种比例1.3/0.7，发酵培养基pH为7.0，在培养基中添加表面活性基Triton X-100 0.08％。使该菌株产β-胡萝卜素的量达到0.73g/L，较初始发酵条件提高了3.3倍。 研究中还找到一个简便有效的对β-胡萝卜素的提取方法，选用盐酸-热处理法进行细胞破壁，并选用沸程为60～90℃的石油醚进行萃取。 用三孢布拉霉菌丝体内类胡萝卜索的石油醚提取液点样于硅胶G板，以丙酮：石油醚（5：95）为展开剂能将β-胡萝卜素与其它类胡萝卜索分离。该方法简便快速，并有一定实用价值。 The fermentative conditions of β-carotene by Blakeslea trispora have been investigated. These conditions include fermentation medium, the optimization of some fermentation factor. The extracting methods and the TLC of carotenoids were also researched. Firstly, the effects of composition of fermentation medium on the yield of β-carotene were studied. the results showed that the best fermentation medium was corn starch 3％，soybean power 2％，cottonseed oil 3％，KH2PO4 0.2%，MgSO4·7H2O 0.2%，vitamin B1 0.002％，pH value 6.0. Secondly, through compared some factors, such as different proportion of plus and minus strains, pH value, nonionic surfactants, respective best values have been obtained. The best proportion of plus and minus strains is 1.3:0.7, pH value of fermentation medium (sterilized) is 7.0, fermentation accelerant which acts as surfactants is Triton x-100. Farther on, the fermentative conditions were optimized through orthogonal experiment, the optimization showed that proportion of plus and minus strains is 1.3:0.7，pH value is 7.0, content of Triton x-100 is 0.08％. And the yield of β-carotene reached 0.73g/L, which was up to 3.3 times through the fermentation. In the extracting study, it has showed hydrochloric acid-heat treatment is a simple, convenient and effective extracting methods is which was used to destroy the cell wall, and the extracting organic solvent is petroleum ether whose boiling range is 60~90 ℃. In the TLC experiments, extracting contents in the petroleum ether were spotted in the silicagel plate, and the mixed liquor of acetone and petroleum ether (5：95) is developping agent, which can distinguish β-carotene from other carotenoids. It is a simple and quick technique.

Selective hydrogenation of citral catalyzed with palladium nanoparticles in CO2-in-water emulsion

CO2-in-Water (C/W) emulsion was formed by using a nonionic surfactant of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) (P123), and palladium nanoparticles were synthesized in situ in the present work. The catalytic performance of Pd nanoparticles in the C/W emulsion has been discussed for a selective hydrogenation of citral. Much higher activity with a turnover frequency (TOF) of 6313 h(-1) has been obtained in this unique C/W emulsion compared to that in the W/C microemulsion (TOF, 23 h(-1)), since the reaction was taking place not only in the surfactant shell but also on the inner surface of the CO2 core in the C/W emulsion. Moreover, citronellal was obtained with a higher selectivity for that it was extracted to a supercritical carbon dioxide (scCO(2)) phase as formed and thus its further hydrogenation was prohibited. The Pd nanoparticles could be recycled several times and still retain the same selectivity, but it showed a little aggregation leading to a slight decrease in conversion.

Separation of natural colorants from the fermented broth of filamentous fungi using colloidal gas aphrons

There is a worldwide interest in the development of processes for producing colorants from natural sources. Microorganisms provide an alternative source of natural colorants produced by cultivation technology and extracted from the fermented broth. The aim of the present work was to study the recovery of red colorants from the fermented broth of Talaromyces amestolkiae using the technique of colloidal gas aphrons (CGA) comprising surfactant-stabilized microbubbles. Preliminary experiments were performed to evaluate the red colorants’ solubility in different organic solvents, octanol/water partitioning, and their stability in surfactant solutions, namely hexadecyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylenesorbitan monolaurate (Tween 20), which are cationic, anionic and nonionic surfactants, respectively. The first recovery experiments were carried out using CGA generated by these surfactants at different volumetric ratios (VR, 3–18). Subsequently, two different approaches to generate CGA were investigated at VR values of 6 and 12: the first involved the use of CTAB at pH 6.9–10.0, and the second involved the use of Tween 20 using red colorants partially dissolved in ethanol and Tween 20. The characterization results showed that red colorants have a hydrophilic nature. The highest recoveries were obtained with Tween 20 (78%) and CTAB (70%). These results demonstrated that the recovery of the colorants was driven by both electrostatic and hydrophobic interactions. The VR was found to be an important operating parameter and at VR 12 with CTAB (at pH 9) maximum recovery, partitioning coefficient (K = 5.39) and selectivity in relation to protein and sugar (SP = 3.75 and SS = 7.20 respectively) were achieved. Furthermore, with Tween 20, the separation was driven mainly by hydrophobic interactions. Overall CGA show promise for the recovery of red colorants from a fermented broth. Although better results were obtained with CTAB than with Tween 20 the latter may be more suitable for some application due to its lower toxicity.

Multiple stages of detergent-erythrocyte membrane interaction-A spin label study

The various stages of the interaction between the detergent Triton X-100 (TTX-100) and membranes of whole red blood cells (RBC) were investigated in a broad range of detergent concentrations. The interaction was monitored by RBC hemolysis-assessed by release of intracellular hemoglobin (Hb) and inorganic phosphate- and by analysis of EPR spectra of a fatty acid spin probe intercalated in whole RBC suspensions, as well as pellets and supernatants obtained upon centrifugation of detergent-treated cells. Hemolysis finished at ca. 0.9 mM TTX-100. Spectral analysis and calculation of order parameters (S) indicated that a complex sequence of events takes place, and allowed the characterization of various structures formed in the different stages of detergent-membrane interaction. Upon reaching the end of cell lysis, essentially no pellet was detected, the remaining EPR signal being found almost entirely in the supernatants. Calculated order parameters revealed that whole RBC suspensions, pellets, and supernatants possessed a similar degree of molecular packing, which decreased to a small extent up to 2.5 mM detergent. Between 3.2 and 10 mM TTX-100, a steep decrease in S was observed for both whole RBC suspensions and supernatants. Above 10 mM detergent, S decreased in a less pronounced manner and the EPR spectra approached that of pure TTX-100 micelles. The data were interpreted in terms of the following events: at the lower detergent concentrations, an increase in membrane permeability occurs: the end of hemolysis coincides with the lack of pellet upon centrifugation. Up to 2.5 mM TTX-100 the supernatants consist of a (very likely) heterogeneous population of membrane fragments with molecular packing similar to that of whole cells. As the detergent concentration increases, mixed micelles are formed containing lipid and/or protein, approaching the packing found in pure TTX-100 micelles. This analysis is in agreement with the models proposed by Lasch (Biochim. Biophys Acta 1241 (1995) 269-292) and by Le Maire and coworkers (Biochim. Biophys. Acta 1508 (2000) 86-111). (C) 2010 Elsevier B.V. All rights reserved.

Determinação experimental e modelagem termodinâmica do ponto de turbidez de sistemas aquosos com tensoativos nonilfenolpolietoxilados

The nonionic surfactants are composed of substances whose molecules in solution, does not ionize. The solubility of these surfactants in water due to the presence of functional groups that have strong affinity for water. When these surfactants are heated is the formation of two liquid phases, evidenced by the phenomenon of turbidity. This study was aimed to determine the experimental temperature and turbidity nonilfenolpoliethoxyled subsequently perform a thermodynamic modeling, considering the models of Flory-Huggins and the empirical solid-liquid equilibrium (SLE). The method used for determining the turbidity point was the visual method (Inoue et al., 2008). The experimental methodology consisted of preparing synthetic solutions of 0,25%, 0,5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% and 20% by weight of surfactant. The nonionic surfactants used according to their degree of ethoxylation (9.5, 10, 11, 12 and 13). During the experiments the solutions were homogenized and the bath temperature was gradually increased while the turbidity of the solution temperature was checked visually Inoue et al. (2003). These temperature data of turbidity were used to feed the models evaluated and obtain thermodynamic parameters for systems of surfactants nonilfenolpoliethoxyled. Then the models can be used in phase separation processes, facilitating the extraction of organic solvents, therefore serve as quantitative and qualitative parameters. It was observed that the solidliquid equilibrium model (ESL) was best represented the experimental data.

Extração do corante reactive blue 19 utilizando tensoativo não iônico

The generation of effluent from the finishing process in textile industry is a serious environmental problem and turned into an object of study in several scientific papers. Contamination with dyes and the presences of substances that are toxic to the environment characterize this difficult treatment effluent. Several processes have already been evaluated to remove and even degrade such pollutants are examples: coagulation-flocculation, biological treatment and advanced oxidative processes, but not yet sufficient to enable the recovery of dye or at least of the recovery agent. An alternative to this problem is the cloud point extraction that involves the application of nonionic surfactants at temperatures above the cloud point, making the water a weak solvent to the surfactant, providing the agglomeration of those molecules around the dyes molecules by affinity with the organic phase. After that, the formation of two phases occurred: the diluted one, poor in dye and surfactant, and the other one, coacervate, with higher concentrations of dye and surfactants than the other one. The later use of the coacervate as a dye and surfactant recycle shows the technical and economic viability of this process. In this paper, the cloud point extraction is used to remove the dye Reactive Blue from the water, using nonionic surfactant nonyl phenol with 9,5 etoxilations. The aim is to solubilize the dye molecules in surfactant, varying the concentration and temperature to study its effects. Evaluating the dye concentration in dilute phase after extraction, it is possible to analyze thermodynamic variables, build Langmuir isotherms, determine the behavior of the coacervate volume for a surfactant concentration and temperature, the distribution coefficient and the dye removal efficiency. The concentration of surfactant proved itself to be crucial to the success of the treatment. The results of removal efficiency reached values of 91,38%, 90,69%, 89,58%, 87,22% and 84,18% to temperatures of 65,0, 67,5, 70,0, 72,5 and 75,0°C, respectively, showing that the cloud point extraction is an efficient alternative for the treatment of wastewater containing Reactive Blue

Estudo de uma coluna de absorção recheada para desidratação do gás natural utilizando microemulsão como absorvente

During natural gas processing, water removal is considered as a fundamental step in that combination of hydrocarbons and water favors the formation of hydrates. The gas produced in the Potiguar Basin (Brazil) presents high water content (approximately 15000 ppm) and its dehydration is achieved via absorption and adsorption operations. This process is carried out at the Gas Treatment Unit (GTU) in Guamaré (GMR), in the State of Rio Grande do Norte. However, it is a costly process, which does not provide satisfactory results when water contents as low as 0.5 ppm are required as the exit of the GTU. In view of this, microemulsions research is regarded as an alternative to natural gas dehydration activities. Microemulsions can be used as desiccant fluids because of their unique proprieties, namely solubilization enhancement, reduction in interfacial tensions and large interfacial area between continuous and dispersed phases. These are actually important parameters to ensure the efficiency of an absorption column. In this work, the formulation of the desiccant fluid was determined via phases diagram construction, employing there nonionic surfactants (RDG 60, UNTL L60 and AMD 60) and a nonpolar fluid provided by Petrobras GMR (Brazil) typically comprising low-molecular weight liquid hydrocarbons ( a solvent commonly know as aguarrás ). From the array of phases diagrams built, four representative formulations have been selected for providing better results: 30% RDG 60-70% aguarrás; 15% RDG 60-15% AMD 60-70% aguarrás, 30% UNTL L60-70% aguarrás, 15% UNTL L60-15% AMD 60-70% aguarrás. Since commercial natural gas is already processed, and therefore dehydrated, it was necessary to moister some sample prior to all assays. It was then allowed to cool down to 13ºC and interacted with wet 8-12 mesh 4A molecular sieve, thus enabling the generation of gas samples with water content (approximately 15000 ppm). The determination of the equilibrium curves was performed based on the dynamic method, which stagnated liquid phase and gas phase at a flow rate of 200 mL min-1. The hydrodynamic study was done with the aim of established the pressure drop and dynamic liquid hold-up. This investigation allowed are to set the working flow rates at 840 mL min-1 for the gas phase and 600 mLmin-1 for the liquid phase. The mass transfer study indicated that the system formed by UNTL L60- turpentine-natural gas the highest value of NUT