Selective Monophosphorylation of Aliphatic Diamines

This article describes an improved method to synthesize phosphoramidic acid aminoalkyl esters from diamines by the adaptation of industrial patents. Four mono-phosphorylated products having amino sites were obtained in good a yield. Such compounds have potential coordination properties with transition metals and also potential biological activity.     

Interplay of colloidal stability of cellulose nanocrystals and their dispersibility in cellulose acetate butyrate matrix

Cellulose nanocrystals (CNC) prepared from eucalyptus cellulose CNCs were modified by the reaction with methyl adipoyl chloride, CNCm, or with a mixture of acetic and sulfuric acid, CNCa. The CNC were either dispersed at 0.1 wt% in the pure solvents ethyl acetate (EA), tetrahydrofuran (THF) and dimethylformamide (DMF) or in cellulose acetate butyrate (CAB) solutions prepared in these solvents at 0.9 wt%. The colloidal behavior of these dispersions was systematically investigated using a phase separation analyzer LUMiReader^®. The mechanical properties and morphological features of the films resulting from the mixtures of CAB and CNC were determined by dynamic mechanical analysis, optical microscopy and atomic force microscopy, respectively. Regardless the functional group attached to the surface of CNC, the best colloidal stability was observed for dispersions prepared in CAB/DMF solution. Higher degree of substitution of modified CNCs favored the colloidal stability in EA and THF. Composite films prepared from CAB/DMF solutions were more homogeneous and presented better mechanical performance than those prepared in CAB/EA or CAB/THF. The mechanical performance of composites and neat CAB prepared from DMF was CAB/CNCs > CAB/CNCm > CAB/CNCa > CAB, indicating that the modification weakens the percolation process, which is mediated by H bonding.     

Firefly as a novel swarm intelligence variable selection method in spectroscopy

A critical step in multivariate calibration is wavelength selection, which is used to build models with better prediction performance when applied to spectral data. Up to now, many feature selection techniques have been developed. Among all different types of feature selection techniques, those based on swarm intelligence optimization methodologies are more interesting since they are usually simulated based on animal and insect life behavior to, e.g., find the shortest path between a food source and their nests. This decision is made by a crowd, leading to a more robust model with less falling in local minima during the optimization cycle.     

Average dynamics of a driven set of globally coupled excitable units

We investigate the behavior of the order parameter describing the collective dynamics of a large set of driven, globally coupled excitable units. We derive conditions on the parameters of the system that allow to bound the degree of synchrony of its solutions. We describe a regime where time dependent nonsynchronous dynamics occurs and, yet, the average activity displays low dimensional, temporally complex behavior.     

Optical Characterization in Annatto and Commercial Colorific

Nowadays, the synthetic dyes (as erythrosine, ponceau and tartrazina) and natural colourants (as annatto, paprika, curcuma and anthocyanin) are indispensable in the food, pharmaceutical and cosmetics applications. However, the use of natural colourant has been considered safer for human consumption then synthetic dye. For practical applications of the coloring, optical properties are important for the understanding of the characteristics of them. In this work, we presented the absorption and fluorescence spectroscopic characterizations of annatto extracts obtained from the seeds of the tropical shrub Bixa orellana L. solutions and commercial colourant. The measurements were performed in annatto extracts with acetone and chloroform in different concentrations range (3.5-52.5) μg/mL. The main carotenoids detected in annatto seeds is bixin. The numerical calculus of the absorbance spectra for cis- and trans-bixin conformation is presented. In addition, for commercial colourant, the measurements were performed for six different brands and five lots each one. Modifications in the shape of the colorific fluorescence spectra were observed and it can be an indicative of differences in the industrial methods applied for obtaining annatto pigments powders and/or the possibility of the presence of other impurities added in the commercial powders.     

Pulsed voltammetric/amperometric detection of polycyclic aromatic sulfur heterocycles (PASHs) at the gold disc electrode for studies in petroleum asphalts

This work describes the voltammetric and amperometric behavior of a high number of PASHs (sulfides, thiophenes, benzothiophenes, dibenzothiophenes, indenothiophenes, naphtothiophenes, thienothiophenes, phenanthrothiophenes, and acenaphtothiophenes) at gold disc electrodes aiming at their identification and determination in petroleum asphalts. The adsorption/redox processes expected for sulfur compounds at gold electrodes could be observed in all the studied PASHs in DMSO and hydromethanolic medium. Differential pulse (DP) voltammetry in non-aqueous solutions (0.1 mol L⁻¹ NaClO₄ in DMSO) was approached for determining non-volatile PASHs in asphalts submitted to different aging processes. It was found herein that the DP voltammetric monitoring of PASH oxidation at + 0.7 V (vs. Ag/AgCl/LiCl 3 mol L⁻¹) for virgin/aged asphalts can be used for the comparative study of asphalts based on the consumption of PASHs. Additionally, pulsed amperometric detection (PAD) in hydroalcoholic solution (10 mmol L⁻¹ acetate buffer in 65% methanol) coupled with a chromatographic separation was approached for determining volatile PASHs in asphalts submitted to thermal decomposition processes. A detection cycle of 2 s involving oxidative (0.4 s at + 0.4 V) and reductive (1.2 s at − 1.0 V) cleaning pulses after a detection pulse of − 0.8 V (0.4 s) applied successively to the gold electrode (vs. Pd/PdO) was found to be optimal for regenerating the gold surface during successive chromatographic runs of PASHs. Thus, reversed-phase liquid chromatography (LC)–coupled PAD was found useful to separate a complex mixture of PASHs. The optimized PAD and LC separation was further applied to investigate the presence of electroactive PASHs as volatile compounds in asphalt fumes generated at 260 °C.

     

Synthesis of Dibromo-Vinyl Chalcogenides

β-Bromovinyl chalcogenides were conveniently prepared in good yields by reacting alkynyl chalcogenides with bromine or by addition of organochalcogenyl bromide to bromoacetylenes in the presence of zinc bromide.     

Attractiveness of Brownian queues in tandem

Consider a sequence of n bi-infinite and stationary Brownian queues in tandem. Assume that the arrival process entering the first queue is a zero mean ergodic process. We prove that the departure process from the n-th queue converges in distribution to a Brownian motion as n goes to infinity. In particular this implies that the Brownian motion is an attractive invariant measure for the Brownian queueing operator. Our proof exploits the relationship between Brownian queues in tandem and the last-passage Brownian percolation model, developing a coupling technique in the second setting. The result is also interpreted in the related context of Brownian particles acting under one-sided reflection.