A green and efficient Pd-free protocol for the Suzuki–Miyaura cross-coupling reaction using Fe3O4@APTMS@Cp2ZrClx(x = 0, 1, 2) MNPs in PEG-400

Research on Chemical Intermediates - In this paper, a new application of the Fe3O4@APTMS@Cp2ZrClx(x = 0, 1, 2) MNPs as a robust and highly efficient Pd-free catalytic system in the environmentally...     

Linear and nonlinear free energy relationships in nucleophilic substitution reaction of 2‐bromo‐5‐nitrothiophene with morpholine

The reaction of 2‐bromo‐5‐nitrothiophene with morpholine was studied as an aromatic nucleophilic substitution reaction in various compositions of methanol with ethyl acetate and aqueous solution of methanol, ethanol, and propane‐2‐ol at 25°C. The second‐order rate coefficients of the reaction were spectrophotometerically determined. It was shown that a mounting trend with the mole fraction of water in aqueous solution of alcohols and a mild decreasing with the mole fraction of ethyl acetate in methanol–ethyl acetate mixtures. Solvent effect investigations based on linear free energy relationship (LFER) confirm that polarity has a major effect, whereas the hydrogen‐bond donor and acceptor abilities of the media have a minor effect on the reaction rate. A nonlinear free energy relationship based on preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents, and nonideal behavior was observed in the trend of rate coefficients, which was consistent with LFER results. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 59–67, 2013     

Conformational Behaviors of 2-Substituted Cyclohexanone Oximes: An AB Initio,Hybrid Dft Study,and NBO Interpretation

Abstract

The impacts of the generalized anomeric effect (GAE) and gauche effect (GE) associated with donor–acceptor electron delocalizations and dipole–dipole interactions on the conformational properties of 2-methoxy- (1), 2-methylthio- (2), 2-methylseleno- (3), 2-fluoro- (4), 2-chloro- (5), and 2-bromocyclohexanone oxime (6) have been studied by means of hybrid density functional theory (B3LYP/6–311+G**) and ab initio molecular orbital (HF/6–311+G**)-based methods and natural bond orbital (NBO) interpretation. Both methods used showed that the above compounds exist predominantly in the axial chair conformation and the axial conformation stability increased from 2-methoxy- (1) to 2-methylselenocyclohexanone oxime (3) and also from 2-fluoro- (4) to 2-bromocyclohexanone oxime (6). The NBO analysis showed that the GAE increases from compound 1 to compound 3 and also from compound 4 to compound 6. GE does not have significant impact on the conformational behaviors of compounds 1–6 and GAE succeeds in accounting qualitatively for the increase of the axial preferences in both series of compounds.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Table S1.

Supporting Information Available. The structures optimized and thermodynamic functions of the axial and equatorial conformations of compounds 1–6. This material is available free of charge via the Internet.     

Numerical investigation of blood flow. Part I: In microvessel bifurcations

In some diseases there is a focal pattern of velocity in regions of bifurcation, and thus the dynamics of bifurcation has been investigated in this work. A computational model of blood flow through branching geometries has been used to investigate the influence of bifurcation on blood flow distribution. The flow analysis applies the time-dependent, three-dimensional, incompressible Navier–Stokes equations for Newtonian fluids. The governing equations of mass and momentum conservation were solved to calculate the pressure and velocity fields. Movement of blood flow from an arteriole to a venule via a capillary has been simulated using the volume of fluid (VOF) method. The proposed simulation method would be a useful tool in understanding the hydrodynamics of blood flow where the interaction between the RBC deformation and blood flow movement is important. Discrete particle simulation has been used to simulate the blood flow in a bifurcation with solid and fluid particles. The fluid particle method allows for modeling the plasma as a particle ensemble, where each particle represents a collective unit of fluid, which is defined by its mass, moment of inertia, and translational and angular momenta. These kinds of simulations open a new way for modeling the dynamics of complex, viscoelastic fluids at the micro-scale, where both liquid and solid phases are treated with discrete particles.     

Quasi Left Factorization Structures as Presheaves

In this article the notion of quasi left factorization structure in a category ${\mathcal{X}}$ is given. It is proved that quasi left factorization structures correspond to subobjects of a predefined object in the category of laxed preordered valued presheaves, $\boldsymbol{L}ax({PrOrd}^{{\boldsymbol{\mathcal{X}}}^{op}})$ . The main result proves this correspondence is one to one when quasi left factorization structures are restricted to the so called QLF-codomains.     

Solid Phase Extraction of Lead(II) by Sorption on Grinded Eucalyptus Stem and Determination with Flame Atomic Absorption Spectrometry

A sensitive and simple solid‐phase preconcentration procedure for the determination of trace amount of lead by flame atomic absorption spectrometry (FAAS) is developed. The method is based on the adsorption of Pb²⁺ on the column of fine grinded eucalyptus stem adsorbent, elution of the column by nitric acid and subsequent determination by FAAS. The effect of different variables such as pH, eluent type, flow rate and interfering ions on the recovery of the analyte was investigated and optimum conditions were established. The adsorption of lead onto fine grinded eucalyptus stem can formally be described by a Langmuir equation with a maximum adsorption capacity of 4.49 mg g^?1. A preconcentration factor of 50 was achieved using the optimum conditions. The calibration graph was linear in the range 10–125 ng mL^?1 of lead in the initial solution with r = 0.9982. The limit of detection based on 3S_b criterion was 4.5 ng mL^?1 and the relative standard deviation for eight replicate measurements of 30 and 80 ng mL^?1 of iron was 3.6 and 2.8%, respectively. The method was successfully applied to the determination of lead added to well, tap and wastewater samples.