Kinetic Study of Radical Polymerization v. Determination of Reactivity Ratio in Copolymerization of Acrylonitrile and Itaconic Acid by 1H‐NMR

Many reports exist in the literature about the application of ¹H and ¹³C‐NMR techniques to analyze the copolymer structure and composition and also determination of reactivity ratios. In this work, on‐line ¹H‐NMR spectroscopy has been applied to identify reactivity ratios of itaconic acid and acrylonitrile in the solution phase (DMSO as the solvent) and in the presence of AIBN as the radical initiator. All the peaks corresponding to the existing protons were assigned quietly. Therefore, the kinetics of the copolymerization reaction was investigated by studying the variation of integral of two characteristic peaks regarding each monomer. The obtained data were used to find the reactivity ratios of acrylonitrile and itaconic acid by linear least‐squares methods such as Finemann‐Ross, inverted Finemann‐Ross, Mayo‐Lewis, Kelen‐Tudos, extended Kelen‐Tudos and Mao‐Huglin. In addition, a non‐linear least‐square method (Tidwell‐ Mortimer) was used at low conversions. Extended Kelen‐ Tudos and Mao‐Huglin were applied to determine reactivity ratio values at high conversions as well.     

Solid–liquid phase equilibria for binary mixtures of propellant’s stabilizers

Solid–liquid equilibria for three binary mixtures of N-(2-acetoxyethyl)-p-nitroaniline (1) + 2-nitrodiphenylamine (2), N-(2-acetoxyethyl)-p-nitroaniline (1) + ethyl centralite (2) and N-(2-acetoxyethyl)-p-nitroaniline (1) + methyl centralite (2) have been determined experimentally using differential scanning calorimeter (DSC). Simple eutectic behaviours for these systems have been observed. The experimental results have been correlated by means of NRTL and UNIQUAC equations. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.61 to 3.32 K and depend on the particular model used. The best solubility correlation has been obtained with the UNIQUAC model.     

Experimental determination and prediction of (solid + liquid) phase equilibria for binary mixtures of heavy alkanes and fatty acids methyl esters

Solid–liquid equilibria for three binary mixtures of {n-eicosane (1) + methyl palmitate (2)}, {n-tetracosane (1) + methyl stearate (2)} and {n-octacosane (1) + methyl stearate (2)} were measured using differential scanning calorimeter. Simple eutectic behaviours for these systems were observed. The experimental results were correlated by means of the modified UNIFAC (Larsen and Gmehling versions), UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.21 K (for UNIQUAC model) to 1.07 K (for Ideal model) and depend on the particular model used. The best solubility correlation was obtained with UNIQUAC model.     

Synthesis of Novel Organosilicon Compounds Possessing Fully Substituted Imidazole Nucleus Sonocatalyzed by Fe-Cu/ZSM-5 Bimetallic Oxides

An efficient four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles is described by one-step condensation of an aldehyde, benzil, ammonium acetate, and primary aromatic amine with nanostructure Fe-Cu/ZSM-5 bimetallic oxides in water under ultrasonic irradiation. The short reaction time, good yields, environmental friendly procedure, mild reaction conditions, and convenient operation are important advantage of this protocol. The products generated during the study have been utilized as substrates for synthesis of organosilicon-containing imidazoles. Synthesis of tris(triorganosilyl)methylimidazole derivatives were carried out using organolithium reagent (Me₃Si)₃CLi, prepared via metalation of (Me₃Si)₃CH with methyllithium in tetrahydrofuran, in excellent yields.     

Simple and Efficient Procedure for the Friedel–Crafts Acylation of Aromatic Compounds with Carboxylic Acids in the Presence of P2O5/AL2O3 Under Heterogeneous Conditions

An efficient and chemoselective method for the Friedel–Crafts acylation of aromatic compounds using P₂O₅/Al₂O₃ and carboxylic acids. Both aromatic and aliphatic carboxylic acids reacted easily to afford the corresponding aromatic ketones in good yields.     

Synthesis of New Iminocoumarins Bearing Parabanic Moieties

The synthesis of novel substituted 3-p-nitro-phenyliminocoumarins and corresponding N-ureaiminocoumarins is described. The condensation of these materials with oxalyl chloride leads to the corresponding N-parabanic iminocoumarins, which have not previously been described, in moderate or good yields and high selectivity. The structures were characterized by Fourier transform infrared, ¹H and ¹³C NMR, and elemental analysis.

Polyol-modified layered double hydroxides with attenuated basicity for a truly reversible capture of CO2

Dendrimers bearing hydroxyl groups supported by layered double hydroxides (CO₃–LDH) with Mg/Al ratio ranging from 1:1 to 5:1 showed improved properties for the reversible capture of carbon dioxide (CO₂). The adsorption capacity of the starting LDH was due to the intrinsic base-like behavior, and was found to depend on the Mg/Al ratio. When contacted with polyol dendrimers in aqueous media, no intercalation took place. This was explained in terms of low exfoliation grade of LDH and hydrophobic character of the dendrimer molecules. The latter rather adsorb on the external surface of the LDH stacks for low dendrimer loadings, or aggregate into organic clusters for higher contents. Analyses through thermal programmed desorption of CO₂ revealed that dendrimer incorporation advantageously attenuates the basicity strength of the starting LDH support, by lowering the desorption temperature. The OH groups of the organic moiety were found to display an amphoteric character, and act as the main adsorption sites. The weak interactions with CO₂ facilitate easier release of the major part of adsorbed CO₂ at temperature not exceeding 80–100 °C. On polyol organo-LDHs, the reversible CO₂ retention was discussed herein in terms of acid–base interactions. This concept allows envisaging the capture of diverse pollutants and other greenhouse gases by modifying the chemical groups on the dendritic moiety.     

Stability and Rheological Properties of Suspended Pulp Particles Containing Orange Juice Stabilized by Gellan Gum

Gellan was used to suspend pulp particles in orange juice. Three groups of samples were prepared with 0%, 20%, and 40% orange juice concentrate and supplemented with gellan at different concentrations. A concentration-dependent increase in the size of gellan aggregates and gellan-protein assemblies was observed. Incorporation of gellan into the beverage with 0% juice concentrate changed the rheological behavior of sample to non-Newtonian shear-thinning fluid and increased its surface tension. When juice concentrate proportion was increased from 0% to 20%, the beverage viscosity increased. The highest gellan concentration resulted in a higher yield stress (σ₀) value and inhibited the pulp sedimentation completely.      

Gas chromatographic determination of some phenolic compounds in fuels and engine oil after simultaneous derivatization and microextraction

In this study, a simultaneous derivatization/air‐assisted liquid–liquid microextraction method has been developed for sample preparation of some phenolic compounds in fuels and engine oil. Analytes are transferred by back liquid–liquid extraction into NaOH solution and then are derivatized with butyl chloroformate and extracted simultaneously into carbon tetrachloride. The extracted derivatized analytes are analyzed using gas chromatography with flame ionization detection. The effect of extracting solvent type, derivatization agent and extraction solvent volumes, ionic strength of the aqueous solution, number of extraction cycles, etc., on the extraction efficiency is investigated. The calibration graphs are linear in the range of 3–10 000 μg/L. Enhancement factors, enrichment factors, and extraction recoveries are in the ranges of 497 to 1471, 571 to 991, and 60 to 109%, respectively. Detection limits are obtained in the range of 0.8 to 2.0 μg/L. Relative standard deviations for the extraction of each selected phenols are in the ranges of 2–4% for intraday (n = 6) and 3–6% (n = 5) for interday precisions for 200 μg/L. This technique is successfully applied for the extraction, preconcentration, and determination of the selected phenols in gasoline, kerosene, gas oil, and engine oil.     

Biomimetic Mussel Adhesive Inspired Anchor to Design ZnO@Poly(3‐Hexylthiophene) Hybrid Core@Corona Nanoparticles

The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.