Kinetic study of depolymerization of polyurethanes: A experimental and computational insight for chemical recycling

This work reports experimental and computational studies of polyurethanes depolymerization from industrial waste through a reaction with potassium hydroxide. A computational study was performed to identify the chemical reaction mechanism, which is more difficult to determine experimentally. Kinetic and thermodynamic parameters of activation process were also obtained by theoretical calculations. An experimental procedure led to products identified by ¹³C solid-state NMR analysis, which agree to the computational study. A small variation of less than 5% in the activation energy values found between the data obtained through theoretical calculations and experimental methods suggests that the described computational procedure is enough to describe the process in a satisfactory manner.     

Autoacceleration and Cyclization Effects on Styrene/Divinylbenzene Copolymerization

Copolymerizations of styrene with divinylbenzene (DVB) are carried out at low monomer concentrations in order to evaluate the incidence of cyclization reactions. The pendant double bond concentration in the synthesized polymers is measured using Fourier transform infrared spectroscopy. Reactions are carried out at monomer concentrations of 6% and 2% (v/v), DVB concentration in the range 15–80 wt% and temperatures in the range 60–90 °C. A previously developed model is used to interpret the results and analyze the cyclization effects. The predictions of the model accounting for cyclization reactions present a better agreement to the experimental data in comparison to predictions without cyclizations. Autoacceleration effects are observed for cases with higher DVB concentrations, in which the formation of highly entangled structures may have occurred. The model provides an estimate of 0.05 for the crosslink parameter (C _P) and 130 s^?1 for the rate constant of cyclization for the smallest sequence (three units) at 90 °C.

     

Disposable Pencil Graphite Electrode for Ciprofloxacin Determination in Pharmaceutical Formulations by Square Wave Voltammetry

In this work, a new electrochemical sensor based on pencil graphite with interesting features, such as low cost (US$ 0.01 per electrode), ease manufacture, and portability was developed. The sensor showed an adequate manufacturing reproducibility with RSD <5.3 %. Under this electrochemical platform, ciprofloxacin underwent an irreversible oxidation process at 1.03 V, characterized by the diffusion of electroactive species. A simple method by square wave voltammetry (SWV) has been optimized for the determination of ciprofloxacin in pharmaceutical formulations using a pencil graphite electrode (PGE). The method showed satisfactory analytical performance, with a wide linear range (12 to 55 μmol L⁻¹), low detection limit (5.6 μmol L⁻¹), adequate precision (RSD <3.2 %), and accuracy with an average recovery of (102±15)%. Samples of pharmaceutical formulations were evaluated, obtaining levels of ciprofloxacin close to those established by the manufacturers. In addition, the samples were analyzed by liquid chromatography and there was no significant difference between the methods at the 95 % confidence level. In this sense, the method developed proved to be reliable and promising for the quality control of pharmaceutical formulations.     

Experimental and Theoretical Investigation of Sodiated Multimers of Steroid Epimers with Ion Mobility-Mass Spectrometry

Ion mobility-mass spectrometry (IM-MS) has recently seen increased use in the analysis of small molecules, especially in the field of metabolomics, for increased breadth of information and improved separation of isomers. In this study, steroid epimers androsterone and trans-androsterone were analyzed with IM-MS to investigate differences in their relative mobilities. Although sodiated monomers exhibited very similar collision cross-sections (CCS), baseline separation was observed for the sodiated dimer species (R_S = 1.81), with measured CCS of 242.6 and 256.3 Ų, respectively. Theoretical modeling was performed to determine the most energetically stable structures of solution-phase and gas-phase monomer and dimer structures. It was revealed that these epimers differ in their preferred dimer binding mode in solution phase: androsterone adopts a R=O – Na⁺ – OH—R′ configuration, whereas trans-androsterone adopts a R=O – Na⁺ – O=R′ configuration. This difference contributes to a significant structural variation, and subsequent CCS calculations based on these structures relaxed in the gas phase were in agreement with experimentally measured values (ΔCCS ~ 5%). Additionally, these calculations accurately predicted the relative difference in mobility between the epimers. This study illustrates the power of combining experimental and theoretical results to better elucidate gas-phase structures.

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Antifungal Activity of Salicylanilides and Their Esters with 4-(Trifluoromethyl)benzoic Acid

Searching for novel antimicrobial agents still represents a current topic in medicinal chemistry. In this study, the synthesis and analytical data of eighteen salicylanilide esters with 4-(trifluoromethyl)benzoic acid are presented. They were assayed in vitro as potential antimycotic agents against eight fungal strains, along with their parent salicylanilides. The antifungal activity of the presented derivatives was not uniform and moulds showed a higher susceptibility with minimum inhibitory concentrations (MIC) 3 0.49 μmol/L than yeasts (MIC 3 1.95 μmol/L). However, it was not possible to evaluate a range of 4-(trifluoromethyl)benzoates due to their low solubility. In general, the most active salicylanilide was N-(4-bromophenyl)-4-chloro-2-hydroxybenzamide and among esters, the corresponding 2-(4-bromophenylcarbamoyl)-5-chlorophenyl 4-(trifluoromethyl) benzoate exhibited the lowest MIC of 0.49 μmol/L. However, the esterification of salicylanilides by 4-(trifluoromethyl)benzoic acid did not result unequivocally in a higher antifungal potency.     

Ultrastructural characterization of the spermatozoa of Aethalion reticulatum Linnaeus 1767 (Hemiptera: Auchenorrhyncha: Aethalionidae)

The Hemiptera order is currently divided into four suborders. Among them the Auchenorrhyncha suborder is considered to be paraphyletic. Morphology of insect spermatozoa has provided promising characteristics that can be used for phylogenetic inference. In this study, Aethalion reticulatum (Aethalionidae) spermatozoa were examined by light and electron microscopy. The head of the spermatozoa is composed of an acrosome and a nucleus. The nucleus is linear and filled with compact chromatin but has electron-lucid spaces. The centriole adjunct initiates parallel to the nucleus and terminates in the region anterior to the mitochondrial derivatives. Flagella consist of an axoneme, two mitochondrial derivatives and two accessory bodies and the axoneme has the typical 9 + 9 + 2 microtubule pattern. The mitochondrial derivatives are symmetric. The accessory bodies are long and are shaped like a half moon when viewed from a cross-section. The presence of accessory bodies differs from other species of Cicadomorpha previously studied. Spermatozoa morphology of other Auchenorrhyncha families can reveal synapomorphies and contribute to systematics of the suborder.     

Vietoris–Rips Complexes of Planar Point Sets

Fix a finite set of points in Euclidean n-space \mathbbEⁿ\mathbb{E}^{n} , thought of as a point-cloud sampling of a certain domain D ì \mathbbEⁿD\subset\mathbb{E}^{n} . The Vietoris–Rips complex is a combinatorial simplicial complex based on proximity of neighbors that serves as an easily-computed but high-dimensional approximation to the homotopy type of D. There is a natural “shadow” projection map from the Vietoris–Rips complex to \mathbbEⁿ\mathbb{E}^{n} that has as its image a more accurate n-dimensional approximation to the homotopy type of D.     

Algorithmic and structural aspects of the P 3-Radon number

The generalization of classical results about convex sets in ? ⁿ to abstract convexity spaces, defined by sets of paths in graphs, leads to many challenging structural and algorithmic problems. Here we study the Radon number for the P ₃-convexity on graphs. P ₃-convexity has been proposed in connection with rumour and disease spreading processes in networks and the Radon number allows generalizations of Radon’s classical convexity result. We establish hardness results and describe efficient algorithms for trees.