Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical alcohol/water mixtures

This work investigates and compares the reaction performance of soybean oil transesterification under supercritical methanol and ethanol, in a continuous catalyst-free process, as a cleaner alternative to conventional chemically catalyzed process. Reactions were performed in a tubular reactor, at 20 MPa, with oil to alcohol ratio of 1:40, varying the temperature in the range from 250 °C to 350 °C, and at two levels of water concentrations, 0 and 10 wt%. Although both processes proceeded with a relatively high reaction rate, conversion achieved by methanolysis was higher than that obtained by ethanolysis. Water positively affected both process: higher ester content and triacylglycerols depletion occurred when 10 wt% water was used compared with anhydrous conditions. Temperature increase favored the conversion of soybean oil to the corresponding methyl or ethyl esters, although temperatures above 300 °C increased the fatty acid degradation degree, a phenomenon responsible for the low ester contents obtained at the highest temperatures and lowest flow rates studied.     

Microstructure and mechanical properties of AlN films obtained by plasma enhanced chemical vapor deposition

AlN films were prepared with a microwave plasma enhanced chemical vapor deposition reactor working at different process temperatures in order to obtain polycrystalline 〈0001〉 oriented films for piezoelectric applications. The films developed were characterized in terms of microstructure, composition, and mechanical properties. Crystalline development and a single orientation were obtained at high temperatures, where at the same time an increase in mechanical intrinsic stresses was observed. Well crystallized 〈0001〉 films were obtained at temperature as low as 500 °C. Furthermore, the evolution of microstructure with thickness at higher temperatures showed a single 〈0001〉 orientation with progressive increase of the texture as the thickness increased. This fact was related with changes in the observed microstructure along the film z-axis, evaluated by high resolution transmission electronic microscopy and selected area electron diffraction. Although orientation dispersion of these films, evidenced by the rocking curves FWHM, remained relatively high (>9°), they can be regarded as promising for piezoelectric applications. Annealing tests conducted at relatively high temperatures with films deposited at low temperature indicated that thermal effects have only a major effect during the film growth for the temperature values employed.     

Optimal camera placement for accurate reconstruction

Three-dimensional (3D) measurements can be recovered from several views by triangulation. This paper deals with the problem of where to place the cameras in order to obtain a minimal error in the 3D measurements, also called camera network design in photogrammetry. We pose the problem in terms of an optimization design, dividing it into two main components: (1) an analytical part dedicated to the analysis of error propagation from which a criterion is derived, and (2) a global optimization process to minimize this criterion. In this way, the approach consists of an uncertainty analysis applied to the reconstruction process from which a covariance matrix is computed. This matrix represents the uncertainty of the detection from which the criterion is derived. Moreover, the optimization has discontinuities due to the presence of occluding surfaces between the viewpoint and the object point group, which leads to a combinatorial optimization process. These aspects are solved using a multi-cellular genetic algorithm. Experimental results are provided to illustrate the effectiveness and efficiency of the solution.     

Hydrochloric acid leaching of nickel sulfide precipitates

Nickel sulfide precipitates produced by the AMAX Acid Leach Process for oxide nickel ores were leached in hydrochloric acid. The effects of process variables such as temperature, acid concentration, stoichiometric excess of HCl, gas sparging and heat treatment of feed were investigated. The nickel leachability was found to be in the 60–80% range. Chemical and mineralogical examination of the leach residues indicated the presence of NiS₂. This higher nickel sulfide is insoluble in hydrochloric acid, and its presence hinders the leaching of NiS. Several methods are suggested to reduce the sulfur content in order to attain complete dissolution. The thermodynamics and kinetics of nickel sulfide leaching are briefly discussed.     

Biochemical mechanism of the effect of barbital on rifamycin B biosynthesis by Amycolatopsis mediterranei (M18 strain)

It is well known that 5,5-diethylbarbituric acid (barbital) in the culture medium can stimulate the production of rifamycin B by Amycolatopsis mediterranei, particularly in industrial processes. However, the mechanism by which barbital exerts this effect is unknown. Results in this work show that the barbital effect is only evident under low aeration conditions (50-ml microfermentors with 7 ml of medium, 0.08 l/h air flow). Under these conditions, cultures with barbital showed similar CO2 production (in relation to a control without barbital), but higher oxygen uptake indicated that the extra O2 consumed was used in the increased rifamycin biosynthesis. Moreover, using a resting cell system where no antibiotic is produced, it was possible to show that barbital inhibits the respiratory chain, since O2 uptake decreased by 30%. Finally, we present biochemical results that suggest that a cytochrome P450-type monoxygenase, which can use atmospheric oxygen, is induced by barbital in an industrial-type strain of A. mediterranei.     

Dosage individualization of erythropoietin using a profile-dependent support vector regression

The external administration of recombinant human erythropoietin is the chosen treatment for those patients with secondary anemia due to chronic renal failure in periodic hemodialysis. The objective of this paper is to carry out an individualized prediction of the EPO dosage to be administered to those patients. The high cost of this medication, its side-effects and the phenomenon of potential resistance which some individuals suffer all justify the need for a model which is capable of optimizing dosage individualization. A group of 110 patients and several patient factors were used to develop the models. The support vector regressor (SVR) is benchmarked with the classical multilayer perceptron (MLP) and the Autoregressive Conditional Heteroskedasticity (ARCH) model. We introduce a priori knowledge by relaxing or tightening the epsilon-insensitive region and the penalization parameter depending on the time period of the patients' follow-up. The so-called profile-dependent SVR (PD-SVR) improves results of the standard SVR method and the MLP. We perform sensitivity analysis on the MLP and inspect the distribution of the support vectors in the input and feature spaces in order to gain knowledge about the problem.     

Daily solar radiation from NASA-POWER product: assessing its accuracy considering atmospheric transparency

ABSTRACT

Satellite remote sensing in estimating solar energy budget components at the top of the atmosphere (TOA) level and at the terrestrial level plays a very important role in various types of applications. Solar radiation data are especially problematic because of a quite generalized lack of sufficient data in quantity and quality. Satellite images allow solving the problem of continuity or lack of solar radiation data. The objective of this work was to fit daily solar radiation from NASA-POWER (National Aeronautics and Space Administration – Prediction Of Worldwide Energy Resources), considering different intervals of atmospheric transparency index. The accuracy was assessed from the analysis of voluminous data-sets registered by meteorological ground stations, 31 in number, located in whole Spain, during the period from 2000 to 2017. Clearness index (K_T) was calculated to define nine classes of cloud cover conditions. The study reveals that the degree of correlation between the satellite data and observatory data depends upon atmospheric conditions and the correlation accuracy improves for higher values of K_T. The coefficients of determination (R²), considering all K_T values, were between 0.85 and 0.96; particularly for clear days R² = 0.96 and root-mean-square error equal to 1.78 MJ m^?2 d^?1 were obtained. Geographically, the better statistic values were located in the central region of the country. NASA-POWER shows potential to estimate solar radiation and that it is an important information resource for different applications.