Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Water flux,DSC, and cytotoxicity characterization of membranes of cellulose acetate produced from sugar cane bagasse,using PEG 600

Summary In this article, cellulose acetate produced through the homogeneous acetylation of sugar cane bagasse cellulose was used to produce membranes, using poly(ethyleneglycol) 600 (PEG 600) as an admixture. The membranes were characterized using water flux measurements (Payne’s cup), differential scanning calorimetry (DSC) and neutral red uptake (cytotoxicity). The results showed that PEG 600 acts as a crystallinity inductor and/or pore former in the cellulose acetate matrix. The induction of crystallinity is important for this system since it had not been reported on the literature yet. The results also demonstrated that the studied membranes present a nontoxic behavior.     

Degradation of cellulosic and hemicellulosic substrates using a chelator‐mediated Fenton reaction

The involvement of catechol and hydroxamate chelators, along with hydrogen peroxide and Fe³⁺, in the degradation of cellulosic and hemicellulosic substrates was examined with the purpose of improving our current knowledge of the non‐enzymatic mechanisms involved in wood biodegradation by fungi. It could be demonstrated that a catechol chelator‐mediated Fenton reaction not only clearly degraded hemicellulosic substrates but also significantly accelerated and increased the effectiveness of degradation reactions. On the other hand, when a hydroxamate chelator‐mediated Fenton reaction was used, an inhibitory effect was observed. When cellulosic substrates underwent a chelator‐mediated Fenton reaction, no significant difference in degradation was observed between catechol and hydroxamate chelator‐mediated reactions. However, a catechol‐mediated reaction did accelerate the degradation of cellulosic substrates at the beginning of reactions. In addition, it was observed that with a chelator‐mediated Fenton reaction, oxidation of cellulose proceeds depolymerization. Copyright © 2005 Society of Chemical Industry     

Composition and thermal properties of Rhea oil and its fractions

The rhea (Rhea americana) is a large running bird of the ratite family, native to South America. Oil extracted from rhea fat tissue is used in cosmetic manufacture. Here, the thermal behaviour and the fatty acid and triacylglycerol composition of Uruguayan rhea oil are studied. The results are compared with those obtained from two commercial samples of emu oil. The fatty acid profiles of emu and rhea oils are similar. Small variations are reflected in the non‐identical thermal behaviour of the oils. The solid content of both oils is fairly similar at room temperature. Thus, emu oil and rhea oil may replace one another in certain formulations, without resulting in important changes in physicochemical behaviour. The semisolid rhea oil was fractionated in two successive stages: an olein was obtained at 15 °C, which was refractionated at 10 °C. The thermogram of the olein obtained by cooling at 15 °C does not have the peak found at 34 °C in the thermogram of the original oil and is a softer product than the original oil. A further stage of fractionation of this olein produced a new liquid phase of slightly different thermal behaviour from that of the original olein. This product has a solid fat index around 7% at 15 °C and has melted completely at 20 °C. This second olein has more appropriate physical characteristics than those of the olein obtained from the first fractionation when used in liquid cosmetic formulations.     

Compatibility of polysaccharide/maleic copolymer blends. IV. Thermal behavior of hydroxypropyl cellulose‐containing blends

The compatibility of the hydroxypropyl cellulose (HPC) with maleic acid–vinyl acetate copolymer in the solid state was studied by thermogravimetry, thermo‐optical analysis, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and optical microscopy. It was established that physical interactions are prevalent in blends with a high content of HPC, whereas chemical interactions predominate in blends with a medium and low content of HPC. By increasing the temperature, the thermochemical reactions are favored. Thermal properties are dependent on the mixing ratio of the components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2585–2597, 2003     

Digestibility and nutritional value of crude oil from three amaranth species

Oils from a selection ofAmaranthus caudatus, A. hypochondriacus andA. cruentus were extracted with hexane. The crude oils were analyzed for acid value, saponification and iodine number, and were included in basal casein diets for rat studies at 5 and 10% levels to replace equal amounts of refined cottonseed oil. The oils fromA. cruentus andA. hypochondriacus were similar in the oil properties studied and different fromA. caudatus. At either 5 or 10% food intake levels, weight gain and PER were not statistically different from values reported for cottonseed oil. True digestibility of amaranth oil was lower than that of cottonseed oil.A. cruentus oil gave the lowest digestibility. Oil levels induced statistical differences in food intake and digestibility. Oils fromA. caudatus, A. hypochondriacus and cottonseed induced similar serum cholesterol levels, while oil fromA. cruentus gave statistically higher values. Hemoglobin, hematocrit and serum proteins were similar among all groups. Microscopic analysis of the organs of the rats revealed some changes that were also found in cottonseed oil-fed rats. It was concluded that crude amaranth oil has lower digestibility than cottonseed oil, but that it is not responsible for growth-depressing effects when the seed is fed raw as compared to processed materials.     

Effect of low‐temperature plasma and chitosan treatment on wool dyeing with Acid Red 27

This study examines in detail the influence of low‐temperature plasma and biopolymer chitosan treatments on wool dyeability. Wool knitted fabrics were treated and characterized by whiteness and shrink‐resistance measurements. Surface modification was assessed by contact‐angle measurements of human hair fibers, which were used as a model to study the wetting properties of the treated wool knitted fabrics. The dyeing behavior was assessed from the diffusion mechanism point of view. The dyeing kinetics were measured at two different pHs (4.2 and 6.5) and three different temperatures (60, 85, and 100°C) to gain information about the contribution of the surface modification treatment to the dyeing mechanism. The exhaustion and reflectance data were compared, and the apparent diffusion coefficients were calculated. On the basis of the obtained results, a model for the dyeing mechanism of the chitosan treated wool was proposed. When treated with chitosan, the polymer sheath spread on the surface of the fibers acted as a predominant dyeing site in very short dyeing times, thus interacting with the dye and in later stages imparting the dye to the wool fiber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2204–2214, 2005     

Optimal Operating Conditions For Lab-Scale Ozonation Reactors

A method for the assessment of the optimal operating conditions for a mechanically stirred gas–liquid reactor is presented. The method exploits both fluid dynamic and chemical information. First, the behavior of the specific stirring power as a function of the stirrer speed allows singling out the dispersion region, in which the most efficient gas–liquid mass transfer is achieved. Inside this region, the analysis of experimental data obtained when considering a chemical system reacting at moderate Hatta numbers (i.e., Ha < about 2) allows determination of the rate constants and the fluid dynamic parameters (i.e., the mass transfer coefficient in the absence of chemical reaction and the characteristic diffusion time).     

Modelling the effects of human papillomavirus in cervical cells

Worldwide, cervical cancer is the second most common cancer in women, after breast cancer. The prevalence of this malignant disease is estimated at 1.4 million cases worldwide, causing about 290,000 deaths and 500,000 new cases per year, of which 80% correspond to women living in developing countries. In this work we propose a family of ordered models for basal cells of the cervix corresponding to different stages ranging from normal cells to the formation of precancerous lesions. We analyse the first member of the family analytically and for the second member we developed a non-standard numerical method in order to extract some biological information.     

Reduction of sulphur in PbSPbCl2NaCl melts

The reduction of dissolved sulphur and the soluble species formed during the electrolysis of PbS dissolved in the PbCl₂NaCl eutectic has been studied chronopotentiometrically. The pre-lead reduction process reported earlier[1] can now be assigned to a subsulphide species that is generated electrochemically. At higher PbS concentrations (eg 10^?3 mol cm^?3), elemental sulphur introduces a new reduction wave in addition to the subsulphide. The saturation solubility of sulphur is approximately proportional to the square of the PbS concentration. It has been estimated to be 2.3× 10^?4 mol S cm^?3 at 430°C for a melt containing 2.4× 10^?3 mol PbS cm^?3 in the PbCl₂-NaCl eutectic.