Selective Acetylation of Alcohols and Amines with Ethyl Acetate in the Presence of H<Subscript>6</Subscript>[PMo<Subscript>9</Subscript>V<Subscript>3</Subscript>O<Subscript>40</Subscript>] as the Catalyst

Summary. Acetylation of various alcohols and benzyl amine was tested in the presence of H₆[PMo₉V₃O₄₀], a mixed addenda heteropolyacid, in ethyl acetate under reflux condition. Phenols and anilines are not affected under the reaction conditions. Selective transestrification of alcohols can be achieved in the presence of phenol and aniline derivatives using this method.     

Surface modified SPIONs‐Cr(VI) ions‐immobilized organic‐inorganic hybrid as a magnetically recyclable nanocatalyst for rapid synthesis of polyhydroquinolines under solvent‐free conditions at room temperature

In this work, a magnetic hybrid dichromate nanocomposite with triphenylphosphine surface modified superparamagnetic iron oxide nanoparticles (SPIONs) as a recyclable nanocatalyst was designed, prepared and characterized by Fourier transform infrared spectroscopy (FT‐IR) spectra, X‐ray diffraction (XRD) pattern analysis, vibrating sample magnetometer (VSM) curves, X‐ray fluorescence (XRF) analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images and dynamic light scattering (DLS) analysis. Then, it was used in a green and efficient procedure for one‐pot multicomponent synthesis of polyhydroquinoline derivatives by the condensation of aldehydes, dimedone or 1,3‐cyclohexadione, ethyl acetoacetate and ammonium acetate. This protocol includes some new and exceptional advantages such as short reaction times, low catalyst loading, high yields, solvent‐free and room temperature conditions, easy separation and reusability of the catalyst.     

A simple and clean method for multicomponent synthesis of spiro [indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives using SBA-Pr-SO3H as catalyst under solvent-free conditions

Sulfonic acid functionalized SBA-15 (SBA-Pr-SO₃H) as a new nanoporous solid acid catalyst was applied in the green one-pot synthesis of spiro[indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives via three-component reaction of isatins, malononitrile or cyanoacetic esters and barbituric acids under solvent-free conditions. SBA-Pr-SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm, which could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused several times without any loss of activity. The advantages of this methodology are high product yields, being environmentally benign, short reaction times, and easy handling.     

ABC Triblock Copolymer Micelles: Spherical Versus Worm‐Like Micelles Depending on the Preparation Method

Well‐defined ABC triblock copolymers based on two hydrophilic blocks, A and C, and a hydrophobic block B are synthesized and their self‐assembly behavior is investigated. Interestingly, at the same solvent, concentration, pH, and temperature, different shape micelles are observed, spherical and worm‐like micelles, depending on the preparation method. Specifically, spherical micelles are observed with bulk rehydration while both spherical and worm‐like micelles are observed with film rehydration.

     

A condition-based algorithm for solving polyhedral feasibility problems

It is known that Polyhedral Feasibility Problems can be solved via interior-point methods whose real number complexity is polynomial in the dimension of the problem and the logarithm of a condition number of the problem instance. A limitation of these results is that they do not apply to ill-posed instances, for which the condition number is infinite. We propose an algorithm for solving polyhedral feasibility problems in homogeneous form that is applicable to all problem instances, and whose real number complexity is polynomial in the dimension of the problem instance and in the logarithm of an “extended condition number” that is always finite.     

Reversible Supramolecular Surface Attachment of Enzyme–Polymer Conjugates for the Design of Biocatalytic Filtration Membranes

To be used successfully in continuous reactor systems, enzymes must either be retained using filtration membranes or immobilized on a solid component of the reactor. Whereas the first approach requires large amounts of energy, the second approach is limited by the low temporal stability of enzymes under operational conditions. To circumvent these major stumbling blocks, we have developed a strategy that enables the reversible supramolecular immobilization of bioactive enzyme–polymer conjugates at the surface of filtration membranes. The polymer is produced through a reversible addition–fragmentation transfer method; it contains multiple adamantyl moieties that are used to bind the resulting conjugate at the surface of the membrane which has surface‐immobilized cyclodextrin macrocycles. This supramolecular modification is stable under operational conditions and allows for efficient biocatalysis, and can be reversed by competitive host–guest interactions.     

Application of Sulfonic Acid Functionalized SBA‐15 as a New Nanoporous Acid Catalyst in the Green One‐Pot Synthesis of Spirooxindole‐4H‐pyrans

Sulfonic acid functionalized SBA‐15 (SBA‐Pr‐SO₃H) as a new nanoporous solid acid catalyst was applied in the green one‐pot synthesis of spirooxindole‐4H‐pyrans via condensation of isatins, malononitrile or methyl cyanoacetate or ethyl cyanoacetate, and 4‐hydroxycoumarin in water solvent. SBA‐Pr‐SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm that could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused for several times without any loss of activity. The significant merits of present methodology are its simplicity, short reaction time, good yields, and environmentally benign mild reaction condition as water was used as a green solvent.     

preconcentration and determination of amoxicillin and ceftriaxone in hospital sewage using vortex-assisted liquid-phase microextraction based on the solidification of the deep eutectic solvent followed by HPLC–UV

In the present study, a new method for extraction and preconcentration of amoxicillin and ceftriaxone was used in hospitalised sewage samples, called vortex-assisted liquid-phase microextraction based on the solidification of deep eutectic solvent. Samples were analysed by high-performance liquid chromatography–ultraviolet detection after preparation and extraction. In this method, the new deep eutectic solvent is used as the extraction solvent, which is obtained from the combination of 1-decyl-3-methylimidazolium chloride and n-butanoic acid. The important advantages of this novel extraction solvent include material stability, low density and good freezing point near room temperature. Under the optimum conditions, enrichment factors are in the range of 164–172. Repeatability and reproducibility of the method based on seven replicate measurements of 50.0 µg L^?1 of the target analytes in analysed samples were in the range of 2.1–3.5% and 3.8–5.2%, respectively. The limit of detections and linearity are in the range of 0.005–0.10 and 3–600 µg L^?1, respectively. The method was successfully applied for the determination of amoxicillin and ceftriaxone in the real sewage samples. The relative recoveries of sewage samples spiked with amoxicillin and ceftriaxone are 91–107%.     

Solubility behavior,dissolution thermodynamics and solute–solvent intermolecular interactions of a solid antioxidant product in water + isopropanol liquid mixtures from 298.15 to 320.15 K

The solid–liquid equilibria of a poorly water-soluble antioxidant agent namely naringoside were assayed to determine solubility in binary liquid mixtures of water?+?isopropanol (iso-PrOH) between 298.15 K and 320.15 K under atmospheric pressure. The mole fraction solubilities of naringoside in the saturated solution were determined using a combination of static shake-flask and ultraviolet spectrophotometry techniques. The dissolution behavior of naringoside was correlated with three solution models consisting of the van’t Hoff equation, the modified Apelblat equation and the Buchowski-Ksiazczak λH equation. The modified Apelblat equation was more consistent than the two other correlation models. Apparent thermodynamic analysis of naringoside dissolution was also performed at the mean harmonic temperature using the model parameters of the modified Apelblat equation. Furthermore, the Kamlet, Abboud and Taft Linear Solvation Energy Relationship (KAT-LSER) model was applied to analyze the effect of the solute–solvent intermolecular interactions on the solubility of this natural bioactive product.     

Enzyme Shielding in an Enzyme‐thin and Soft Organosilica Layer

The fragile nature of most enzymes is a major hindrance to their use in industrial processes. Herein, we describe a synthetic chemical strategy to produce hybrid organic/inorganic nanobiocatalysts; it exploits the self‐assembly of silane building blocks at the surface of enzymes to grow an organosilica layer, of controlled thickness, that fully shields the enzyme. Remarkably, the enzyme triggers a rearrangement of this organosilica layer into a significantly soft structure. We demonstrate that this change in stiffness correlates with the biocatalytic turnover rate, and that the organosilica layer shields the enzyme in a soft environment with a markedly enhanced resistance to denaturing stresses.