Electrochemical study of 7α,12,20-O-trimethyl-conacytone in acetonitrile

An electrochemical study of the electroreduction in anhydrous acetonitrile of 7α,12,20-O-trimethyl-conacytone, an abietane quinoid diterpene derivative from the natural product 7α-O-methyl-conacytone, showed two reduction signals. At the first reduction step, fast chemical reactions involving the loss of the methoxyl group located at C-7 with simultaneous regeneration of the quinoid moiety were observed. This electrogenerated quinone is reduced again, at the same potential used with the former quinone, resulting in a two-electron peak. These results were obtained by cyclic voltammetry and double-step chronoamperometry experiments. The electrolysis under methylating conditions of 7α-O-methyl-conacytone, at potential values of the second electron transfer, generates as major products, methoxy-hydroquinone, where the methoxy group at C-7 is lost, which is in agreement with the proposed mechanism. Therefore, the second reduction signal was attributed to the reduction of semiquinone intermediates by a mechanism not elucidated.     

Interparticle Potentials in Nonaqueous Silicon Nitride Suspensions

The rheological properties of nonaqueous silicon nitride suspensions are studied. Suspensions were prepared to volume fractions of solids of 0.21, 0.25, 0.29, and 0.33, and dispersed with phosphate ester in a mixture of solvents (methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone). Expanded viscosity curves were obtained by measuring under controlled rate and stress conditions, and the experimental data were fitted to the Cross model that provides the high shear limiting viscosity (η_∞). The evolution of viscosity with volume fraction of solids was fitted to the Krieger-Dougherty equation, to predict the maximum packing fraction (φ_m). The electrostatic pair potential was calculated based on the DLVO theory by evaluating the dielectric constant of the three-component solvent and the Hamaker constant of the Si₃N₄–solvent system. The surface potential was calculated by measuring the elastic modulus through dynamic rheological measurements. The steric potential was also evaluated from the available models. It has been observed that phosphate ester provides a purely steric stabilization at short separation distances (up to 9 nm), while electrostatic forces dominate at larger separation distances.     

Heavy Metals Bioremediation from Polluted Water by Glass-Ceramic Materials

The objective of this research was to study the removal of cadmium and lead from an aqueous solution through a biological treatment. For this purpose a glass-ceramic material was manufactured from industrial and urban wastes. Biofilms of microorganisms found in wastewater were developed on its surface, and continuous tests were conducted in the presence and absence of the biofilm to analyze the glass-ceramic's ability to remove the heavy metals from an aqueous environment. The results suggest that this bioremediation process, developed on an industrial scale, could represent an alternative to the chemical processes currently used.     

Modulation of Aβ42 Aggregation Kinetics and Pathway by Low-Molecular-Weight Inhibitors

The aggregation of amyloid-β 42 (Aβ42) is directly related to the pathogenesis of Alzheimer's disease. Here, we have investigated the early stages of the aggregation process, during which most of the cytotoxic species are formed. Aβ42 aggregation kinetics, characterized by the quantification of Aβ42 monomer consumption, were tracked by real-time solution NMR spectroscopy (RT-NMR) allowing the impact that low-molecular-weight (LMW) inhibitors and modulators exert on the aggregation process to be analysed. Distinct differences in the Aβ42 kinetic profiles were apparent and were further investigated kinetically and structurally by using thioflavin T (ThT) and transmission electron microscopy (TEM), respectively. LMW inhibitors were shown to have a differential impact on early-state aggregation. Insight provided here could direct future therapeutic design based on kinetic profiling of the process of fibril formation.     

Optimal design and operation of a steel plant integrated with a polygeneration system

A process integration approach has been applied to integrate a traditional steelmaking plant with a polygeneration system to increase energy efficiency and suppress carbon dioxide emissions from the system. Using short‐cut models and empirical equations for different units and available technologies for gas separation, methane gasification, and methanol synthesis, a mixed integer nonlinear model is applied to find the optimal design of the polygeneration plant and operational conditions of the system. Due to the complexity of the blast furnace (BF) operation, a surrogate model technique is chosen based on an existing BF model. The results show that from an economic perspective, the pressure swing adsorption process with gas‐phase methanol unit is preferred. The results demonstrate that integration of conventional steelmaking with a polygeneration system could decrease the specific emissions by more than 20 percent. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3659–3670, 2013     

Enhanced Hydrothermal Resistance of Y‐TZP Ceramics Through Colloidal Processing

Two commercial zirconia powders with 3 mol% of yttria (TZ3YE and TZ3YS, labeled as ZE and ZS, respectively) supplied by Tosoh (Japan) were used for this study. Maximum colloidal stability for ZE was achieved by dispersing the powders in a mixture of water/ethanol of 90:10 (wt/wt) using a sonication probe. The rheological behavior of the suspensions was optimized in terms of solids content ranging from 20 to 33 vol% and sonication time (0–6 min), the best results being obtained after 2 min. ZS samples were prepared to a solids loading of 30 vol% in water dispersing with 2 min‐sonication. Samples obtained by slip casting in plaster molds were used for dynamic sintering studies, and fully dense and nanostructured specimens were obtained at temperatures of 1300°C–1350°C (ZE samples) and 1400°C per 2 h (ZS samples). The Hardness (H) and Young's Modulus (E) properties of the specimens were studied by nanoindentation technique giving 17 and 250 GPa mean values for H and E, respectively. The specimens were then forced to a low‐temperature degradation (LTD) treatment at 130°C for 240 h in steps of 60 h. Raman spectroscopy and nanoindentation results of hydrothermally treated samples showed the absence of transformation from tetragonal to monoclinic phase until 180 h whereas the mechanical properties maintained constant even at the sample surface. After 240 h of LTD, the monoclinic phase was detected on all specimens by Raman peaks centered at 180, 191, and 383 cm^?1. The nanoindentation study revealed an important loss of mechanical features reaching 10 and 175 GPa for H and E, respectively. In the case of the ZS specimens, no monoclinic phase is detected after 240 h of LTD treatment and no decay of E or H is detected. The free defect microstructure reached for the ZS specimen revealed a higher hydrothermal resistance so that it is concluded that the excellent behavior against thermal degradation is possible due to the large uniformity obtained by colloidal processing rather than the particle size of the starting powders.     

Steady‐State and Dynamic Reactor Models for Hydrotreatment of Oil Fractions: A Review

The modeling of catalytic hydrotreatment reactors for petroleum fractions have been classified in several ways, for example steady‐state and dynamic, pseudohomogeneous, and heterogeneous, and so on. Depending on the system to be modeled, operating conditions and type of feedstock, these approaches could exhibit some advantages and disadvantages, wide scopes and limitations. In this review, the discussion about those modeling aspects, already published, is used to develop a generalized reactor model, which can be simplified in order to derive each single model previously reported. Some guides to estimate model parameters are also given.     

Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

A precise data set describing the kinetics of the free radical copolymerization of acrylamide/acrylic acid (AM/AA) in the range of low total monomer concentration as a function of the pH, total monomer concentration, initiator concentration, and comonomer ratio is presented. Strong impact on the reactivity ratios has been identified for the pH and total monomer concentration. Specifically, at constant total monomer concentration of 0.4 mol/l and T=313 K the reactivity ratio of AM increases from 0.54 at pH 1.8 to 3.04 at pH 12. Contrarily, the reactivity ratio of AA decreases from 1.48 to 0.32. The crossover occurs at pH≈4.2. Electrostatic effects due to the variation of the degree of ionization of AA are primarily suggested to influence the kinetics. When the total monomer concentration increases from 0.2 to 0.6 mol/l at constant pH=12, the reactivity ratios of AM and AA decrease from 4.01 to 2.13 and increase from 0.25 to 0.47, respectively. Reduction of electrostatic repulsion between the ionized monomer AA and partially charged growing polymer chain ends due to higher ionic strength at higher total monomer concentration serves as explanation of the effect. The precise data set is the prerequisite for a novel approach to calculate copolymer compositions in case of variable monomer reactivity.     

Comparison between the binding of chlorpheniramine maleate to poly(sodium 4-styrenesulfonate) and the binding to other polyelectrolytes

The interactions of the antihistaminic drug chlorpheniramine maleate (CPM) with the negatively charged polyelectrolytes poly(sodium 4-styrenesulfonate) (PSS) and poly(acrylic acid) (PAA) are studied by the washing method of the diafiltration technique at conditions simulating those of the small intestine such as pH 7.5 and 0.13 M NaCl. The results are compared with those already reported involving other pharmacologically important polyelectrolytes such as alginic acid (ALG), carboxymethylcellulose (CMC), and κ- and ι-carrageenan (κ- and ι-CAR). As in the case of ALG, CMC, and CAR, interactions of CPM with PAA appear to be electrostatic and are cleaved in the presence of 0.13 M NaCl. On the contrary, apart from electrostatic interactions, additional interactions are found with PSS and residual interactions are kept in the presence of 0.13 M NaCl, a fact that may be attributed to π-π interactions and hydrophobic forces. The effect of the addition of 4 M urea, branched poly(ethyleneimine) (BPEI), and poly(vinylpyrrolidone) (PVP) is also studied. The addition of urea 4 M or 0.001 M BPEI produces a decrease on the amounts of counterions bound to PSS at infinite elution, while the addition of PVP does not produce any change on the diafiltration profiles.     

Strength Analysis of Self-Supported Films Produced by Aqueous Electrophoretic Deposition

The goal of this work is to study the feasibility of the characterization of the fracture strength of porous alumina/zirconia thin layers by three-point bending and Weibull analysis. Films have been obtained by electrophoretic deposition on graphite and thermo-gelation of the deposit with carrageenan. On sintering, graphite is burned out and self-supported films are obtained. Strength values are well fitted to a simple two-parameter Weibull distribution. The fracture origins are subcritical growth cracks that originated at the surface irregularities associated with the processing method. A Weibull modulus around 3 is obtained.