Coupling of air-assisted liquid–liquid microextraction method with partial least squares for simultaneous spectrophotometric determination of some preservatives

An air-assisted liquid–liquid microextraction method coupled with a multivariate calibration method, namely partial least squares (PLS), was developed for the extraction and simultaneous determination of benzoic acid (BA) and sorbic acid (SA) via a spectrophotometric approach. In this work, a two-step microextraction method was used. In the first step, analytes were extracted from acidic aqueous solution into octanol, as an organic solvent, and in the second step, the analytes were simultaneously back-extracted into an alkaline aqueous solution. The high absorption signal of octanol was the main reason to perform this back-extraction step. The effects of different parameters on the method efficiency were investigated; the parameters included extraction solvent volume, ionic strength of aqueous solution, pH, number of extraction cycles, and aqueous sample volume. Under optimum conditions, calibration graphs were seen to be linear over the range of 0.1–2.0 µg mL^?1 for the both analytes. Other analytical parameters were obtained as follows: Enrichment factors (EFs) were found to be 14.98 and 13.03, and limits of detection were determined to be 0.03 and 0.04 µg mL^?1 for BA and SA, respectively. As the last step, binary mixtures of the analytes were prepared and simultaneously extracted using the proposed method. Finally, PLS modeling was used for multivariate calibration of spectrophotometric data. It was successfully utilized for the analysis of the target analytes in real samples.     

Nano TiO_2 as a heterogeneous catalyst in an efficient one-pot three-component Mannich synthesis of β-aminocarbonyls

TiO₂ nanoparticles（TiO₂ NPs） worked as an efficient heterogeneous catalyst in a one-pot,three-component,and solvent free Mannich reaction;producing variousβ-aminocarbonyls in good yields,and with good stereoselectivities.The catalyst was easily separated from the reaction mixture and was recycled four times with no significant loss of its catalytic activity.     

UV-prepared salep-based nanoporous hydrogel for controlled release of tetracycline hydrochloride in colon

A highly swelling nanoporous hydrogel (NPH) was synthesized via UV-irradiation graft copolymerization of acrylic acid (AA) onto salep backbone and its application as a carrier matrix for colonic delivery of tetracycline hydrochloride (TH) was investigated. Optimized synthesis of the hydrogel was performed by the classic method. The swelling behavior of optimum hydrogel was measured in different media. The hydrogel formation was confirmed by Fourier transform infrared spectroscopy (FTIR) and thermo-gravimetric analysis (TGA/DTG/DTA). The study of the surface morphology of hydrogels using SEM showed a nanoporous (average pore size: about 350nm) structure for the sample obtained under optimized conditions. The drug delivery results demonstrated that this NPH could successfully deliver a drug to the colon without losing the drug in the stomach, and could be a good candidate as an orally administrated drug delivery system.     

The quantum theory of atoms in positronic molecules: The subsystem variational procedure

This contribution deals with the subsystem variational procedure within the context of the quantum theory of atoms in positronic molecules (QTAIPM). Before introducing the subsystem energy functional termed as joint subsystem energy functional, a novel notation and the combination strategy are disclosed in detail by restating the positronic subsystem hypervirial theorem. They are employed in proposing the proper subsystem energy functional, the validity of which is checked by various criteria. The zero flux surfaces of the joint density distribution are used to define the topological atoms in the positronic molecules, and they are incorporated into the subsystem variational procedure as proper real space boundary conditions. The variational procedure finally yields the flux of the joint current property density that also appears in the positronic subsystem hypervirial theorem. At every stage, the corresponding equations for the purely electronic systems within the context of the quantum theory of atoms in molecules (QTAIM) are presented to clearly reveal the analogy between these two formalisms and to emphasize the importance of combining the property density distributions in the QTAIPM. The presented material demonstrates the internal consistency of the whole framework and discloses the fact that the QTAIM must be regarded as a variant of the QTAIPM. Furthermore, this formalism promises an extended QTAIM, which is hoped to resolve the issue of molecular structure beyond the clamp nuclei approximation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Highly cis‐Diastereoselective Synthesis of Coumarin‐Based 2,3‐Disubstituted Dihydrobenzothiazines by Organocatalysis

An efficient and organocatalyzed asymmetric reaction of phenacyl halides with coumarin‐based dihydrobenzothiazoles was developed to afford cis‐2,3‐disubstituted 3,4‐dihydro‐2H‐benzothiazines. This method provides a one‐step and highly diastereoselective route to a wide variety of coumarin‐based 3,4‐dihydro‐2H‐benzothiazines using the cheap and commercially available Cinchona alkaloid quinine hydrochloride.     

Silabenzene through divalent precursors at theoretical levels

Abstract  Based on geometries and relative energies, three different mechanisms are proposed for the rearrangements of five isomers of silacyclohexadienylidenes to silabenzene at B3LYP and MP2 levels: (1) [1,2]-hydrogen migration through a planar transition state, (2) [1,4]-hydrogen migration through a boat transition state, and (3) zip-zap mechanism, comprised of three successive [1,2]-hydrogen migrations. The above results are compared and contrasted to rearrangements of the corresponding cyclohexadienylidenes to benzene. Graphical abstract   Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Perspectives of Microwaves‐Enhanced Heterogeneous Catalytic Gas‐Phase Processes in Flow Systems

The paper discusses the currents status and future perspectives of the utilization of microwaves, as a selective and locally controlled heating method, in heterogeneous catalytic flow reactors. Various factors related to the microwave‐catalyst interaction and the design of microwave‐assisted catalytic reactor systems are analyzed. The analysis clearly shows the superiority of the traveling‐wave systems over the mono‐mode and multi‐mode cavity‐based systems when it comes to the design and application of microwave flow reactors at relevant production scales.     

Beryllium bonding with noble gas atoms

Quantum chemical calculations were carried out to investigate the nature of the bonding between a neutral Be₃ ring and noble gas atom. Electronic structure calculation for these complexes was carried out at different computational levels in association with natural bond orbital, quantum theory of atoms in molecules, electron localization function, symmetry adapted perturbation theory, and molecular electrostatic potential surface analysis of Be₃ complexes. The Be atoms in the Be₃ moiety are chemically bonded to one another, with the Be Be bond dissociation energy being ~125 kJ mol⁻¹. The Be₃ ring interacts with the noble gases through non-covalent interactions. The binding energies of the noble gas atoms with the Be₃ ring increases with increase in their atomic number. The non-covalent interaction index, density overlap region indicator and independent gradient model analyses reveal the presence of non-covalent inter-fragment interactions in the complexes. Energy decomposition analysis reveals that dispersion plays the major role towards stabilizing these systems.     

An Efficient Solvent-free Synthetic Technique of 4,4’-Diaminotriarylmethane Leuco Materials

An efficient, versatile and solvent-free synthetic technique of diaminotriarylmethanes was reached by treating N,N-dimethylaniline with some arylaldehydes over zirconium(IV) oxide chloride (ZrOCl2•8H2O), in which ZrOCl2•8H2O has good activity, easy availability, recovery as well as reusability.     

Effect of Nitric Oxide on Lachnum YMU50 Extracellular Polyphenol Accumulation and Antioxidant Defense System

The effect of sodium nitroprusside (SNP) of different concentrations (0.05, 0.1, 0.2 mM) on biomass and extracellular polyphenol accumulation and antioxidant defense system of Lachnum YMU50 had been studied in this article. Results showed that, when the NO donor was SNP, both 0.05 and 0.1 mM SNP could promote the biomass accumulation of Lachnum YMU50 and activate the phenylalanine ammonia lyase, thus promoting its extracellular polyphenol accumulation and activate and induce its antioxidant defense system by activating the activities of catalase, superoxide dismutase, and ascorbate peroxidase, and 0.1 mM SNP has a stronger effect than 0.05 mM SNP. SNP 0.2 mM was adverse to the accumulation of the biomass and extracellular polyphenol of Lachnum YMU50, decreasing the activities of catalase, superoxide dismutase, and ascorbate peroxidase and increasing the contents of hydrogen peroxide and malondialdehyde, which indicated that 0.2 mM SNP damaged the antioxidant defense system of Lachnum YMU50.