High‐Temperature Na2SO4 Deposit‐Assisted Corrosion of Silicon Carbide – I: Temperature and Time Dependence

Time and temperature dependence of Na₂SO₄‐induced hot corrosion were studied for sintered‐α (Hexoloy) as well as CVD‐SiC at temperatures between 900°C and 1100°C and at times from 0.75 to 96 h. The extent of corrosion was quantified using mass change measurements, removal of corrosion products using sequential water, HCl, and HF dissolution steps followed by ICP‐OES analysis, and by optical profilometry of corroded materials to characterize pitting on the sample surface. In addition, SEM, EDS, and XRD were used to better understand the morphology, distribution, and phase composition of corrosion products. It was found that hot corrosion of Hexoloy was more severe than that of high‐purity CVD‐SiC. Hot corrosion is initially rapid until a continuous silica layer is formed underneath the mixed silicate layer. Once a continuous silica layer was formed the temperature dependence of the corrosion rate was consistent with diffusion of oxygen through the silica layer.     

Molecular Mechanism of Action of 2‐Ferrocenyl‐1,1‐diphenylbut‐1‐ene on HL‐60 Leukemia Cells

The aim of this work was to investigate the mechanism of action of 2‐ferrocenyl‐1,1‐diphenylbut‐1‐ene ( 1 ) on HL‐60 human leukemia cells. While inactive against noncancerous cells, 1 provoked a concentration‐dependent decrease in viable tumor cells, primarily via apoptosis, as evidenced by analysis of cell morphology, activation of caspases 3 and 7, increased DNA fragmentation, and externalization of phosphatidylserine. Necrosis was observed only at the highest tested concentration (4 μM ). Compound 1 interfered with the cell cycle, causing an accumulation of cells in the G₁/G₀ phase. Interaction of 1 with dsDNA and ssDNA was observed by differential pulse voltammetry and confirmed by hyperchromicity in the UV/Vis spectra of dsDNA, with an interaction constant of 2×10⁴ M ^?1. Both the organic analogue 1,1,2‐triphenylbut‐1‐ene ( 2 ) and ferrocene were inactive against cancer and noncancer cell lines and did not react with DNA. These results reinforce the idea that the hybrid strategy of conjugating ferrocene to the structure of tamoxifen derivatives is advantageous in finding new substances with antineoplastic activity.     

The Development of a New Synthesis Process for 3,3′‐Diamino‐4,4′‐azoxyfurazan (DAAF)

Process optimization studies were performed for the preparation of the high explosive 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF). These process studies were pursued to address issues such as problematic waste generation products, particle size, impurities, and manufacturability. This paper describes the original synthesis method and inherent issues. An optimization process was designed to investigate the issues with purity and manufacturability. Particle size effects were addressed by adding a recrystallization step to the synthesis. Ultimately, a complete solution to all observed issues was found with a new synthesis process, which now allows DAAF to be prepared without any impurities, with good particle size and without the need for recrystallization. Importantly, the new synthesis process can be performed in an environmentally friendly manner, with the production of non‐hazardous waste.     

Reactions of low molecular weight highly functionalized maleic anhydride grafted polyethylene with polyetherdiamines

Reaction between low molecular weight highly functionalized maleic anhydride grafted polyethylene and several diamines were carried out using xylene as a reaction media. The influence of varying the amine to maleic anhydride (NH₂/MAH) molar ratio and chain length of diamine on reaction was investigated. It was shown that the reactions of these materials cannot be followed by FTIR measurements alone. In these examples, colorimetric titrations were used to assess residual acid/anhydride content that was not detected by FTIR. The reaction between anhydride and amine was observed to be fast. The degree of reaction and crosslinking in the reactor was observed to depend on the concentration of the reaction mixture and the NH₂/MAH molar ratio. In some cases, a gelatinous insoluble mass was produced in the reactor and this material was not easily processed for further characterization. All soluble reaction products obtained were observed to be thermoplastic and could be melt processed at elevated temperatures. However, further reaction and crosslinking of these materials occurred during processing to produce thermosets, as demonstrated by rheological measurements and sintering experiments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Response surface modeling and optimization of biodiesel production from Cynara cardunculus oil

Cardoon (Cynara cardunculus L.) is a perennial spontaneous thistle grown in Mediterranean countries and well adapted to marginal lands, recently considered as a non‐food energy crop. Their seeds contain 24% of oil (dry basis). In this study, modeling and optimization of the production of fatty acid methyl esters (FAME) from cardoon oil for biodiesel uses was performed at laboratory scale, via response surface methodology, following a central composite rotatable design. FAME were obtained by transesterification of crude cardoon oil with methanol in the presence of a catalyst (sodium methoxide) for 120 min. The temperature ranged from 26 to 94 °C, the amount of sodium methoxide varied between 0.12 and 2.5 wt‐% and the molar ratio methanol/oil from 0.95 : 1 to 11 : 1. The estimated yield of FAME (97%) was obtained after 30 min, at 52 °C, for a molar ratio of 6.4 : 1 and 1.4 wt‐% of catalyst. In laboratory‐scale model validation experiments, 94% of FAME yield was obtained after 30 min of reaction. Transesterification was performed in a 30‐L reactor, under previously optimized conditions: A yield of 88% FAME was obtained after 90 min of reaction time, due to mass transfer limitations. After purification, the biodiesel showed high quality according to DIN EN 14214 standard specifications.     

The utilization of specific interactions to enhance the mechanical properties of polysiloxane coatings

Moisture-curable polysiloxanes were modified with ionic groups to enable specific interactions between the polysiloxane matrix and silica nanoparticle reinforcement. A trimethoxysilane-functional quaternary ammonium salt (QAS) was used to modify the polysiloxane matrix. A comparison of the mechanical properties of coatings containing QAS modification to analogous coatings without QAS modification showed that QAS modification resulted in a dramatic improvement in mechanical properties of silica nanoparticle-reinforced coatings. QAS modification provided major enhancements in both tensile modulus and toughness. The coatings were characterized using positron annihilation spectroscopy, photo-acoustic FT-IR, differential scanning calorimetry, transmission electron microscope, and atomic force microscopy. The characterization results suggested that the QAS moieties present in the polysiloxane matrix undergo specific interactions with the surface of silica nanoparticles enabling an enhancement in interfacial adhesion between the polymer matrix and the nanoparticles. Most likely, the specific interaction that provided the enhanced mechanical properties was an ion–dipole interaction involving silanol groups present on the surface of the silica nanoparticles. The enhanced modulus and toughness of these polysiloxane materials may enable their application as a fouling-release coating for ship hulls, since current polysiloxane-based fouling release coatings suffer from poor mechanical properties and durability.     

XCMS: processing mass spectrometry data for metabolite profiling using nonlinear peak alignment, matching, and identification

Metabolite profiling in biomarker discovery, enzyme substrate assignment, drug activity/specificity determination, and basic metabolic research requires new data preprocessing approaches to correlate specific metabolites to their biological origin. Here we introduce an LC/MS-based data analysis approach, XCMS, which incorporates novel nonlinear retention time alignment, matched filtration, peak detection, and peak matching. Without using internal standards, the method dynamically identifies hundreds of endogenous metabolites for use as standards, calculating a nonlinear retention time correction profile for each sample. Following retention time correction, the relative metabolite ion intensities are directly compared to identify changes in specific endogenous metabolites, such as potential biomarkers. The software is demonstrated using data sets from a previously reported enzyme knockout study and a large-scale study of plasma samples. XCMS is freely available under an open-source license at http://metlin.scripps.edu/download/.     

pH response of carboxy-terminated colorimetric polydiacetylene vesicles

Carboxy-terminated polydiacetylene vesicles are known to undergo dramatic color transitions in response to exposure to external stimuli such as pH, temperature, and receptor-ligand binding. FTIR spectroscopy was used to identify the breakdown in the interfacial hydrogen-bonding interactions of the carboxylic acid headgroups of polymerized 10,12-tricosadiynoic acid (TRCDA) vesicles in aqueous solution during pH chromic transition. The headgroup structure was monitored as the chromic transition takes place and the dissociation dependence of the pKa was determined. Due to the attenuated acidity of the interfacially confined carboxy groups, which exhibit pKa values in the range 9.5-9.9, it was found that the deprotonation-triggered blue-red chromic transition occurred in the pH range 9.0-10.1 and that the mechanism of the transition required interaction with the surface carboxyl group, which is of importance in the design of a biochromic mechanism using PDA assemblies. Transmission electron microscopy and FTIR spectroscopy revealed that the surface ionization and the pH-induced chromogenic transition was also accompanied by a dramatic vesicle-planar morphological transition alongside subtle changes to the alkyl chain conformation and packing. A two-step mechanism was implicated as causing the chromic transition that first involves surface deprotonation and then specific cation binding, which can aid the design of sensitive surface-ligand chemistry for new PDA structures.     

Comprehensive interpretation of gel electrophoresis data

From temperature analysis of polyacrylamide gel electrophoresis data for rigid-rod DNA analytes, it is proposed that an entropic force term is responsible for the discrepancy between Ogston-Morris-Rodbard-Chrambach model predictions and experimental results. This entropic force originates from reduction of the orientational freedom of anisotropic analytes in small pores of polyacrylamide gels. Time-dependent fluorescence anisotropy decay measurements confirm that, even in the absence of an external field, orientation of anisotropic analytes is restricted in polyacrylamide gels. A new comprehensive model is proposed that takes this effect into consideration. Predictions based on this model are found to compare favorably with experimental data for linear and three-arm asymmetrically branched rigid-rod DNA analytes covering a broad range of molecular aspect ratios and sizes. A new length scale is also proposed for describing the effect of analyte topology on electrophoretic mobility. This length scale reduces to the analyte radius of gyration in the limiting cases of spherically symmetric and linear rigid-rod species. Based on these results, a general approach is proposed for interpreting gel electrophoresis data of charged analytes possessing simple and complex topologies.