Kinetics and mechanism of myristic acid and isopropyl alcohol esterification reaction with homogeneous and heterogeneous catalysts

The reaction of myristic acid (MA) and isopropyl alcohol (IPA) was carried out by using both homogeneous and heterogeneous catalysts. For a homogeneously catalyzed system, the experimental data have been interpreted with a second order, using the power‐law kinetic model, and a good agreement between the experimental data and the model has been obtained. In this approach, it was assumed that a protonated carboxylic acid is a possible reaction intermediate. After a mathematical model was proposed, reaction rate constants were computed by the Polymath* program. For a heterogeneously catalyzed system, interestingly, no pore diffusion limitation was detected. The influences of initial molar ratios, catalyst loading and type, temperature, and water amount in the feed have been examined, as well as the effects of catalyst size for heterogeneous catalyst systems. Among used catalysts, p‐toluene sulfonic acid (p‐TSA) gave highest reaction rates. Kinetic parameters such as activation energy and frequency factor were determined from model fitting. Experimental K values were found to be 0.54 and 1.49 at 60°C and 80°C, respectively. Furthermore, activation energy and frequency factor at forward were calculated as 54.2 kJ mol^?1 and 1828 L mol^?1 s^?1, respectively. © 2008 Wiley Periodicals, Inc. 40: 136–144, 2008     

N‐[Bis(2,4,6‐tri­methyl­phenoxy)­phos­phinoyl]‐P,P,P‐tris(2,4,6‐tri­methyl­phenoxy)phosphazene

The title compound, C₄₅H₅₅NO₆P₂, consists of an acyclic P=N—P(O) monophosphazene chain and five bulky 2,4,6‐tri­methyl­phenoxy side groups which predominantly determine the molecular shape. Although the P—N single [1.586 (3) Å] and P=N double [1.517 (3) Å] bonds are significantly different from each other, both are substantially shorter than the ideal P—N single bond. The P—N—P angle [146.0 (2)°] corresponds to the upper limit reported for acyclic phosphazene derivatives in the literature.     

A parallel gas-kinetic Bhatnagar–Gross–Krook method for the solution of viscous flows on two-dimensional hybrid grids

In this study, a parallel implementation of gas-kinetic Bhatnagar–Gross–Krook method on two-dimensional hybrid grids is presented. Boundary layer regions in wall bounded viscous flows are discretised with quadrilateral grid cells stretched in the direction normal to the solid surface while the rest of the flow domain is discretised by triangular cells. The parallel solution algorithm on hybrid grids is based on the domain decomposition using METIS, a graph partitioning software. The flow solutions obtained in parallel significantly improve the computation time, a significant deficiency of gas-kinetic methods. Several validation test cases presented show the accuracy and robustness of the method developed.     

Intermediates for the synthesis of tetracyclic indole alkaloids. Synthesis of 4-aminotetrahydrocarbazole derivatives

An efficient method for the synthesis of 4-aminotetrahydrocarbazole derivatives from 2,3-dihydrospiro-[1H-carbazole-1,2′-(1,3)-dithiolan]-4-(9H)-one 1 is described. The structure of compound 6 has been confirmed by X-ray structure analysis.     

Immobilization of immunoglobulin G in a highly oriented manner on a protein-A terminated multilayer system

In this study, we have fabricated a multilayer system consisting of 3-glycidoxypropyldimethylmethoxysilane (GPDS), poly(dimethylsiloxane) bis 3-aminopropyl terminated (PDMS) and protein-A on a silicon wafer surface for oriented immobilization of immunoglobilin G (IgG). The multilayer system with a different component in each layer was characterized by ellipsometry, contact-angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) and fluorescence microscopy. The epoxy-terminated monolayer was formed by the chemisorption of GPDS molecules on the hydroxylated silicon surface. The PDMS film about 4.5 nm thick was produced on the GPDS-monolayer by the chemical reaction between the amine groups at the end of PDMS chain and the epoxy groups of GPDS molecules. By introducing the PDMS chains, the hydrophilic character of GPDS-monolayer decreased. Study of the time dependence of polymer grafting showed that the chemisorption of GPDS is fast, whereas at least 16 h is needed to generate the homogeneous PDMS layer. For immobilization of IgG molecules in a highly oriented manner, protein-A molecules were first chemically bound to an ultrathin (∼4.5 nm) PDMS reactive polymer layer and later used to capture IgG. It was shown that the existence of protein-A in the multilayer system has a strong influence on the binding properties of IgG not only in the efficiency of binding, but also in its specificity. In conclusion, the multilayer system with protein-A has the potential to be further developed into an efficient immunoassay protein chip.     

Macroporous Poly(Acrylamide) Hydrogels: Swelling and Shrinking Behaviors

Macroporous poly(acrylamide) hydrogels have been synthesized by using poly(ethylene glycol) (PEG) with three different molecular weights as the pore‐forming agent. Scanning electron microscope graphs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights of PEG during the polymerization reaction. The swelling ratios of the PEG‐modified hydrogels were much higher than those for the same type of hydrogel prepared via conventional method. However, the swelling/deswelling ratios of the PEG‐modified hydrogels were affected slightly by the change in the amount of the PEG. Scanning electron microscopy experiments, together with swelling ratio studies, reveal that the PEG‐modified hydrogels are characterized by an open structure with more pores and higher swelling ratio, but lower mechanical strength, compared the conventional hydrogel. PAAm has potential applications in controlled release of macromolecular active agents.     

Approximation by modified Szász-Durrmeyer operators

The main goal of this paper is to introduce Durrmeyer modifications for the generalized Szász–Mirakyan operators defined in (Aral et al., in Results Math 65:441–452, 2014). The construction of the new operators is based on a function \(\rho \) which is continuously differentiable \(\infty \) times on \( \left[ 0,\infty \right) ,\) such that \(\rho \left( 0\right) =0\) and \( \inf _{x\in \left[ 0,\infty \right) }\rho ^{\prime }\left( x\right) \ge 1.\) Involving the weighted modulus of continuity constructed using the function \( \rho \), approximation properties of the operators are explored: uniform convergence over unbounded intervals is established and a quantitative Voronovskaya theorem is given. Moreover, we obtain direct approximation properties of the operators in terms of the moduli of smoothness. Our results show that the new operators are sensitive to the rate of convergence to f,  depending on the selection of \(\rho .\) For the particular case \(\rho \left( x\right) =x\), the previous results for classical Szász-Durrmeyer operators are captured.     

Synthesis and crystal structures of two hetarylazo indole disperse dyes

Two new heterocyclic monoazo disperse dyes were prepared by diazotizing 2-amino-5-methylthiazole and ethyl-1-(2-aminothiazol-4-yl)acetate and coupling with 1,2-dimethyl-indole. Characterization of the dyes was carried out by using UV–vis, FTIR, ¹H-NMR and MS spectroscopic techniques. The structures of the dyes have been determined by single-crystal X-ray diffraction method. The maximum absorption peaks (λ_max) in the ultraviolet and visible (UV–vis) spectra of the hetarylazoindole dyes have been determined by using the density-functional (DFT method) and time-dependent density-functional (TD-DFT method) theories. Excellent agreement was found between the calculated and experimental λ_max values.