Effect of a stirring process in an isothermal titration microcalorimeter

In this paper, it is analysed the way in which the thermodynamic results obtained in an isothermal titration microcalorimeter, with continuous injection of a liquid and a variable mass are affected. Two aspects are presented, the first one refers to a variation in the baseline that takes place when the liquid mass is increased in the laboratory cell, this variation is due to the change in the thermal coupling between the stirrer and its contact with the thermostat. The second aspect is the analysis of the effect of the stirring process and the injection velocity on the homogenization of the remaining mixture in the laboratory cell.

The aim of the study of these two previous aspects is to increase the accuracy of the thermodynamic measures carried out. The variation of the baseline affects in a percentage from 1 to 2% of the total energy developed. It is also shown the necessity of a stirring process according to the injection velocity in order to obtain a homogeneous mixture at every instant. This fact allows to carry out a deconvolution of the calorimetric signal and to obtain directly the power developed in the mixture process in terms of the amount of mixed substance [Meas. Sci. Technol. 1 (1990) pp. 1285–1290; J. Thermal Analysis 41 (1994) pp. 1385–1392].     

Contribution of air pollution to the fouling of heat exchangers in cooling water circuits

In an open recirculating system with a cooling tower, there are favorable conditions for the development of corrosion and fouling problems. These problems arise from the operating conditions and constant contamination of cooling water. A deep analysis of the system should provide the solutions for those problems. In the Sociedade Portuguesa de Oxigénio, SA, plant, a phosphate-based cooling water treatment ensures low corrosion rates. However, the fouling of heat exchange surfaces is promoted by the cooling water contamination. This contamination may result from the makeup water or from the air scrubbed in the tower. The fouling lowers the process efficiency and makes shutdowns for cleaning necessary. The air pollution produced by a neighboring plant is the main cause for fouling. To solve this problem, a decision was made to invest in equipment for makeup water treatment and reduce the stagnation conditions in the heat exchangers. It was also decided to hold negotiations to persuade the polluting company to reduce the particle emission to the atmosphere.     

Novel polyurethanes from xylan and TDI: Preparation and characterization

Xylan is a hemicellulose, which is found abundantly in nature. In this work, a novel polyurethane was developed involving xylan and tolylene-2,4-diisocyanate (TDI). Polymer synthesis was achieved through conventional heat or microwave-assisted reaction in dimethyl sulfoxide. Because xylan has multiple OH groups on each polymer chain, the TDI/xylan molar ratio had to be adjusted to produce a soluble polymeric product. The reaction products were characterized by ¹³C NMR, FTIR, thermogravimetric analysis, and differential scanning calorimetry. The xylan polyurethane was shown to exhibit improved thermal stability over xylan.     

Computational assessment of synthetic procedures

Synthetic chemistry is hard because some reasonable looking molecules cannot be made, because there are errors in the chemical literature, because it is easy to miss reaction possibilities and because even the shape of molecules is very difficult to determine. We propose an approach to the computational analysis of reactions that tries to circumvent these difficulties, by restricting the analysis to simple rules for reactivity that can generate a large number of competing pathways. This huge ensemble is filtered using computational methods to pick out the most likely pathways, and to suggest possible products.     

Quintom Potentials from Quantum Cosmology Using the FRW Cosmological Model

We construct the quintom potential of dark energy models in the framework of spatially flat Friedmann–Robertson Walker universe in the inflationary epoch, using the Bohm like approach, known as amplitude-real-phase. We find some potentials for which the wave function of the universe is found analytically and we have obtained the classical trajectories in the inflation era.     

Quantum Bianchi Type IX Cosmology in K-Essence Theory

We use one of the simplest forms of the K-essence theory and apply it to the anisotropic Bianchi type IX cosmological model, with a barotropic perfect fluid modeling the usual matter content. We show that the most important contribution of the scalar field occurs during a stiff matter phase. Also, we present a canonical quantization procedure of the theory which can be simplified by reinterpreting the scalar field as an exotic part of the total matter content. The solutions to the Wheeler-DeWitt equation were found using the Bohmian formulation Bohm (Phys. Rev. 85(2):166, 1952) of quantum mechanics, employing the amplitude-real-phase approach Moncrief and Ryan (Phys. Rev. D 44:2375, 1991), where the ansatz for the wave function is of the form Ψ(? ^μ )=χ(?)W(? ^μ ) \(e^{- S(\ell ^{\mu })},\) , where S is the superpotential function, which plays an important role in solving the Hamilton-Jacobi equation.     

Flow microcalorimetry and thermokinetics of liquid mixtures

The identification of the calorimetric curves corresponding to liquid mixtures for different injection flows, given by a flow microcalorimeter, permits to classify in a kinetic way the studied mixtures. For this purpose, it is determined the establishment time constant of the mixture (τ_mix) that allows us to estimate the length occupied by the dissipation (through the parameter λ_mix) and thus to justify the sensitivity variation obtained in different chemical calibrations.     

Oxalyl‐CoA Decarboxylase Enables Nucleophilic One‐Carbon Extension of Aldehydes to Chiral α‐Hydroxy Acids

The synthesis of complex molecules from simple, renewable carbon units is the goal of a sustainable economy. Here we explored the biocatalytic potential of the thiamine‐diphosphate‐dependent (ThDP) oxalyl‐CoA decarboxylase (OXC)/2‐hydroxyacyl‐CoA lyase (HACL) superfamily that naturally catalyzes the shortening of acyl‐CoA thioester substrates through the release of the C₁‐unit formyl‐CoA. We show that the OXC/HACL superfamily contains promiscuous members that can be reversed to perform nucleophilic C₁‐extensions of various aldehydes to yield the corresponding 2‐hydroxyacyl‐CoA thioesters. We improved the catalytic properties of Methylorubrum extorquens OXC by rational enzyme engineering and combined it with two newly described enzymes—a specific oxalyl‐CoA synthetase and a 2‐hydroxyacyl‐CoA thioesterase. This enzymatic cascade enabled continuous conversion of oxalate and aromatic aldehydes into valuable (S)‐α‐hydroxy acids with enantiomeric excess up to 99 %.     

The ROBIA program for predicting organic reactivity

A program to predict organic reactions, ROBIA, has been developed. It achieves reaction prediction on the basis of coded rules and molecular modeling calculations, generating possible transition states, intermediates, and products given the starting material and reaction conditions. The program generates all possible reaction pathways, on the basis of the selected transformations within its database, and evaluates them selecting the most feasible ones. The program has been successfully tested against several examples.