Thermal characterization of hydrotalcite used in the transesterification of soybean oil

Hydrotalcite was synthesised by co-precipitation method, calcined and characterized by XRD, BET, IR and TG/DTA/DTG analyses and tested as solid base catalyst in the transesterification of soybean oil with methanol, achieving a methyl ester content of 99.5%. The thermal decomposition of hydrotalcite calcined occurred in four mass loss steps at 28, 105, 203 and 400 °C. The hydrotalcite was recovered and through a simple evaluation by TG/DTA/DTG techniques it was found that at 500 °C is the temperature, where the organic matter should be eliminated from the catalyst. This study shows the importance of thermal analysis in the evaluation of the recovery temperature of hydrotalcite.     

Active sampling followed by solid-phase microextraction for the determination of pyrethroids in indoor air

A method based on solid-phase enrichment followed by headspace (HS)-solid-phase microextraction (SPME) is optimized to determine pyrethroids in air. By active sampling, pyrethroids present in air are retained in 25 mg of activated florisil and then transferred from the solid sorbent to an SPME fiber in the HS mode. A small volume of solvent is added to the adsorbent to favor this process. The selection of the adsorbent, as well as the optimization of certain parameters affecting the SPME, is performed using an experimental design strategy. Linearity is studied by external calibration in a wide range of concentrations using gas chromatography coupled to three different detection systems: electron capture detection, micro-electron capture detection, and mass spectrometry. An analysis of variance with a lack-of-fit test is run to validate the calibration data. Breakthrough of the adsorbent was studied sampling from 0.5 to 10 m(3) air, demonstrating that 1 m(3) air could be sampled without losses of pyrethroids. Quantitative recoveries are obtained at three concentration levels, with adequate repeatability. Limits of detection of the method are estimated at the sub-ng/m(3) level in most cases, well below the regulatory limits. Finally, several real indoor samples are collected and analyzed by the proposed method. Identification and quantitation of all target analytes present in the room air are possible.     

Ultraviolet B light stimulates interleukin-20 expression by human epithelial keratinocytes

The proinflammatory cytokine interleukin-20 (IL-20) may exert the majority of its activity in the skin. We examined the effect of various treatments including several forms of phototherapy on IL-20 expression using cultured normal human epithelial keratinocytes (NHEK). Broadband UVB light, recombinant (r) IL-1 and rIL-8 increased, while hydrocortisone reduced, NHEK supernatant IL-20 levels. Elevation of NHEK IL-20 mRNA and maximal supernatant IL-20 levels occurred with a UVB light dose (40 mJ cm(-2)) that reduced cell viability by approximately 50%. While this UVB light dose also elevated supernatant IL-1 alpha and IL-8 levels, antibody neutralization studies indicated that neither of these cytokines was directly responsible for this increase in IL-20 expression. However, the elevation in IL-20 levels was fully inhibited by the p38 mitogen-activated protein kinase (MAPK) inhibitor SB-203580, suggesting involvement of this stress signaling pathway in this UVB light response. Photodynamic therapy (PDT) with the photosensitizer lemuteporfin, UVA light, cisplatin, lipopolysaccharide (LPS), tumor necrosis factor-alpha (TNF-alpha) or recombinant interferon-gamma (rIFN-gamma) either had little effect or decreased NHEK supernatant IL-20 levels. Reduced IL-20 levels paralleled the cytotoxic actions of PDT, UVA light or cisplatin and the antiproliferative effect of rIFN-gamma. Neither rIL-20 supplementation nor anti-IL-20 antibody treatments affected cell viability indicating that soluble IL-20 did not affect the short-term survival of UVB light-irradiated NHEK. Stimulation of IL-20 expression in keratinocytes by UVB light suggests that this cytokine might participate in skin responses to this ever-present environmental factor and potentially has a role in UV light-associated dermatoses.     

Anti-biofouling properties of comblike block copolymers with amphiphilic side chains

Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.     

A general strategy for creating "inactive-conformation" abl inhibitors

Kinase inhibitors that bind to the ATP cleft can be broadly classified into two groups: those that bind exclusively to the ATP site with the kinase assuming a conformation otherwise conducive to phosphotransfer (type I), and those that exploit a hydrophobic site immediately adjacent to the ATP pocket made accessible by a conformational rearrangement of the activation loop (type II). To date, all type II inhibitors were discovered by using structure-activity-guided optimization strategies. Here, we describe a general pharmacophore model of type II inhibition that enables a rational "hybrid-design" approach whereby a 3-trifluoromethylbenzamide functionality is appended to four distinct type I scaffolds in order to convert them into their corresponding type II counterparts. We demonstrate that the designed compounds function as type II inhibitors by using biochemical and cellular kinase assays and by cocrystallography with Abl.     

Measuring acetylene concentrations using a frequency chirped continuous wave diode laser operating in the near infrared

Two frequency chirped continuous wave diode lasers operating in the near infrared (IR) at wavelengths of lambda approximately 1.535 microm and lambda approximately 1.520 microm have been used to measure acetylene concentrations using the P(17) and R(9) rotational lines of the (nu1 + nu3) vibrational combination band. The diode lasers were frequency chirped by applying an electrical current pulse to the laser driver at a repetition rate of greater than 1 kHz. As the laser is operated at high repetition rates, more than 1000 spectra per second can, in principle, be acquired and summed, allowing fast accumulation of data, rapid averaging and consequent improvement of the signal to noise ratio and detection limit. Experiments were performed using a single-pass cell with a path length of 16.4 cm, and also an astigmatic multi-pass absorption cell aligned to give a path length of 56 m. Detection limits corresponding to minimum detectable absorption coefficients, alpha(min), of 5.6 x 10(-5) and 7.8 x 10(-8) cm(-1), respectively, were obtained over a 4 s detection bandwidth. These detection limits would correspond to mixing ratios of 21 parts per million by volume (ppmv) and 59 parts per billion by volume (ppbv) of acetylene at 1 atm in air, with the deleterious effects of pressure broadening accounted for. The single-pass cell was used to perform breakthrough volume (BTV) experiments for the low volume adsorbent traps used to pre-concentrate organic compounds in air, taking advantage of the capability of the system to measure concentrations in real time.     

Difference in precedence effect between children and adults signifies development of sound localization abilities in complex listening tasks

The precedence effect refers to the fact that humans are able to localize sound in reverberant environments, because the auditory system assigns greater weight to the direct sound (lead) than the later-arriving sound (lag). In this study, absolute sound localization was studied for single source stimuli and for dual source lead-lag stimuli in 4-5 year old children and adults. Lead-lag delays ranged from 5-100 ms. Testing was conducted in free field, with pink noise bursts emitted from loudspeakers positioned on a horizontal arc in the frontal field. Listeners indicated how many sounds were heard and the perceived location of the first- and second-heard sounds. Results suggest that at short delays (up to 10 ms), the lead dominates sound localization strongly at both ages, and localization errors are similar to those with single-source stimuli. At longer delays errors can be large, stemming from over-integration of the lead and lag, interchanging of perceived locations of the first-heard and second-heard sounds due to temporal order confusion, and dominance of the lead over the lag. The errors are greater for children than adults. Results are discussed in the context of maturation of auditory and non-auditory factors.     

Laser Control of Zeolite Nucleation

Precursor solutions for the synthesis of zeolites are irradiated by means of a Nd‐YAG laser. These solutions are subsequently submitted to a hydrothermal treatment and the results analyzed by X‐ray diffraction and electron microscopy. Laser irradiation promotes the formation of silica nanoparticles that nucleate into zeolite (silicalite‐1), following a hydrothermal treatment. The average crystal size (in the 0.6–3.6 μm range) of the zeolite exponentially decreases as a function of laser irradiation time. In addition, a longer irradiation time results in a narrower crystal size distribution.     

Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase

A temperature and pressure kinetic study for the CH(3)O(2) + ClO reaction has been performed using the turbulent flow technique with a chemical ionisation mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH(3)O(2) + ClO reaction: k(10)(T) = (1.96(?0.24)(+0.28)) × 10(-11) exp[(-626 ± 35)/T] cm(3) molecule(-1) s(-1) where the uncertainty associated with the rate coefficient is given at the one standard deviation level. Over a range of pressure (100-200 Torr) and temperature (298-223 K) no pressure dependence is observed. The smaller rate coefficients measured at lower temperatures compared with both previous low temperature studies are believed to arise through the reduction of secondary chemistry and greater sensitivity in terms of reactant detection (hence much lower initial concentrations were employed). These new data reduce the effectiveness of ozone loss cycles involving reaction of CH(3)O(2) + ClO in the polar stratosphere by around a factor of 1.5 and restrict the importance of the reaction to the tropical and extra-tropical clean marine environments in the troposphere.