Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions

Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar₂NCOCl or R₂NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually S_N1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald–Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO₂), the unsubstituted carbamoyl chloride (H₂NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300–400 °C range. There has been very little study of its reactions.     

In Vitro Activity of Copper(II) Complexes,Loaded or Unloaded into a Nanostructured Lipid System,against Mycobacterium tuberculosis

Tuberculosis (TB) is an infectious disease caused mainly by the bacillus Mycobacterium tuberculosis (Mtb), presenting 9.5 million new cases and 1.5 million deaths in 2014. The aim of this study was to evaluate a nanostructured lipid system (NLS) composed of 10% phase oil (cholesterol), 10% surfactant (soy phosphatidylcholine, sodium oleate), and Eumulgin^® HRE 40 ([castor oil polyoxyl-40-hydrogenated] in a proportion of 3:6:8), and an 80% aqueous phase (phosphate buffer pH = 7.4) as a tactic to enhance the in vitro anti-Mtb activity of the copper(II) complexes [CuCl₂(INH)₂]·H₂O (1), [Cu(NCS)₂(INH)₂]·5H₂O (2) and [Cu(NCO)₂(INH)₂]·4H₂O (3). The Cu(II) complex-loaded NLS displayed sizes ranging from 169.5 ± 0.7095 to 211.1 ± 0.8963 nm, polydispersity index (PDI) varying from 0.135 ± 0.0130 to 0.236 ± 0.00100, and zeta potential ranging from −0.00690 ± 0.0896 to −8.43 ± 1.63 mV. Rheological analysis showed that the formulations behave as non-Newtonian fluids of the pseudoplastic and viscoelastic type. Antimycobacterial activities of the free complexes and NLS-loaded complexes against Mtb H₃₇Rv ATCC 27294 were evaluated by the REMA methodology, and the selectivity index (SI) was calculated using the cytotoxicity index (IC₅₀) against Vero (ATCC^® CCL-81), J774A.1 (ATCC^® TIB-67), and MRC-5 (ATCC^® CCL-171) cell lines. The data suggest that the incorporation of the complexes into NLS improved the inhibitory action against Mtb by 52-, 27-, and 4.7-fold and the SI values by 173-, 43-, and 7-fold for the compounds 1, 2 and 3, respectively. The incorporation of the complexes 1, 2 and 3 into the NLS also resulted in a significant decrease of toxicity towards an alternative model (Artemia salina L.). These findings suggest that the NLS may be considered as a platform for incorporation of metallic complexes aimed at the treatment of TB.     

Isothermal crystallization kinetics of poly(lactic acid)/synthetic mica nanocomposites

The isothermal crystallization kinetics of PLA/fluoromica nanocomposites was studied. Three types of synthetic mica at three concentrations (2.5, 5.0, and 7.5 wt % mica) were used and the effect of these micas on the crystallization and thermal properties of PLA was investigated by differential scanning calorimetry (DSC). The Avrami and Hoffman‐Weeks equations were used to describe the isothermal crystallization kinetics and melting behavior. Addition of these micas to the PLA matrix increased the crystallization rate, and this effect depended on the mica type and concentration. While the nonmodified Somasif ME‐100 exerted the smallest effect, the effect observed for the organically modified Somasif MPE was the most pronounced. The lower half‐time of crystallization t_1/2 was around 3 min for the PLA/Somasif MPE nanocomposites containing 7.5 wt % of filler at 90°C, which is about 16 min below that found for neat PLA. The equilibrium melting temperature ( ) of PLA were estimated for these systems, showing an increase in the composites and an increase with increasing loading, except for PLA/Somasif MPE, in which the increase of the mica content decreased about 5°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40322.     

Comparison of vacuum impregnation and soaking techniques for addition of the probiotic Lactobacillus acidophilus to minimally processed melon

This study aimed to evaluate the vacuum impregnation (VI) and soaking methods in the addition of Lactobacillus acidophilusLA‐3 to minimally processed melon (MPM). The melons were washed, sanitised in chlorine solution (200 mg L^?1), peeled and cutted into cubes. Lactobacillus acidophilusLA‐3 (1.4 × 10¹⁰ CFU g^?1) were added to the MPM through both techniques. The L. acidophilusLA‐3 count in MPM was similar to those commonly found in dairy products having probiotic claim, but VI was more efficient than soaking in maintaining the viability (8.61 and 7.98 Log CFU g^?1, respectively). The pH, acidity and soluble solids were not affected by probiotic culture and the incorporation technique; however, the VI affected the firmness of fruit. The MPM was within Brazilian standards for their microbiological characteristics. MPM may be used as a carrier of probiotic bacteria, being one more alternative for individuals who consume probiotic products.     

A contribution to the interpretation of polymer viscoelasticity in DMTA testing

Some ideas relevant to the prevailing viscoelasticity interpretations of dynamic mechanical thermal analysis (DMTA) experiments are presented. The main aspect is the inclusion of kinetic energy and inertia as variables, seeing the relaxing mass constantly increasing during strain, assigning inertial variation and not viscosity to energy dissipation. The equations developed make it possible to obtain the values of important viscoelastic properties, under in any experimental condition, with the data taken from previous experiments.     

Effect of cooling rate on Ti–Cu eutectoid alloy microstructure

Titanium alloys present a combination of properties that makes them suitable materials for various medical applications, and there is special interest in Ti–Cu alloys for the fabrication of dental prostheses. The addition of Cu to Ti lowers the melting point of the alloy, as well as leading to the development of desirable mechanical properties. In this study a eutectoid alloy was prepared and heat treated, then cooled at various cooling rates. The eutectoid structure (α + Ti₂Cu) was observed for all cooling rates used, and evidence of α′ martensite was found for cooling rate higher than 9 °C s^–1. Lower cooling rates resulted in higher modulus values. This was attributed to the volume fraction of the α and Ti₂Cu phases. Higher cooling rates produced structures with lower modulus values and greater hardness, a result attributed mainly to the development of a martensitic structure.     

On The Roles of APIs in the Coordination of Collaborative Software Development

The principle of information hiding has been very influential in software engineering since its inception in 1972. This principle prescribes that software modules hide implementation details from other modules in order to reduce their dependencies. This separation also decreases the dependency among software developers implementing these modules, thus simplifying the required coordination. A common instantiation of this principle widely used in the industry is in the form of application programming interfaces (APIs). While previous studies report on the general use and benefits of APIs, they have glossed over the detailed ways in which APIs facilitate the coordination of work. In order to unveil these mechanisms, we performed a qualitative study on how practitioners use APIs in their daily work. Using ethnographic data from two different software development teams, we identified three roles played by APIs in the coordination of software development projects. These roles are described using three metaphors: APIs as contracts, APIs as boundaries, and APIs as communication mechanisms. As contracts, APIs allow software developers to work in parallel and independently. As a communication mechanism, APIs facilitate communication among software developers by giving them something specific to talk about. At the same time, APIs establish the boundaries between developers, and, accordingly, what should be talked about. This paper also reports on problems the studied teams face when using APIs to coordinate their work. Based on these results, we draw theoretical implications for collaborative software engineering.     

Evaluation of thermodynamic properties using GAB model to describe the desorption process of cocoa beans

The desorption isotherms and thermodynamic properties of cocoa beans were obtained during the drying process of this product. The isotherms were determined by dynamic method for various temperature (25, 35, 45 and 55 °C) and relative humidity (RH) conditions (30, 40, 50, 60, 70 and 80%). Equilibrium moisture content data were correlated by the Guggenheim–Anderson–de Boer (GAB) model, which presented good fit to the data, according to statistical procedures. Equilibrium moisture content ranged from 5.90 to 16.67 d.b.; it increased with an increment in the RH and decreased with increased temperature at a constant RH. Enthalpy values for each model coefficient were encountered, ranging from ?90.05 to 545.96 kJ kg^?1. The integral isosteric heat of desorption and differential entropy increased with decreased equilibrium moisture content, a tendency also found for Gibbs free energy.     

Finite field trigonometric transforms

In this paper, the finite field trigonometric transforms (FFTT) are introduced. The FFTT family includes eight types of cosine transforms and eight types of sine transforms, which are developed from concepts related to the finite field trigonometry. New lemmas are presented and some properties of the FFTT are discussed.     

Pt-Ru-TiO2 photoelectrocatalysts for methanol oxidation

Novel photoelectrocatalysts composed of PtRuTiO₂/C are prepared by the polymeric precursor method and are characterized by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy and cyclic voltammetry. The onset potential for methanol oxidation is similar (0.3 V vs. RHE) for all of the photoelectrocatalyst layers investigated, although the peak current density is dependent on the layer composition. Irradiation of UV light on the photoelectrocatalyst surfaces enhances the chronoamperometric responses up to 18%, which clearly demonstrates a synergistic effect between the photo- and electrocatalysts. The comparison between all the layers prepared indicates that there is an appropriate ratio of metallic nanoparticles and TiO₂ to obtain the best performance of these photoelectroactive layers. These results demonstrate that methanol oxidation is achieved by electro- and photocatalysis using a simple and affordable method. This procedure can be conveniently exploited to enhance the response of direct methanol fuel cell electrodes.