Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A strategy for the electro-organic synthesis of new hydrocaffeic acid derivatives

Electrochemical treatment processes can significantly contribute to the protection of the environment through the minimization of waste and toxic materials in effluents. From a pharmaceutical point of view and due to the existing resemblance between the electrochemical and biological reactions, it can be assumed that the oxidation mechanisms on the electrode and in the body share similar principles. In this paper, the application of electrochemical studies in the design of an environmentally friendly method was delineated for the new hydrocaffeic acid (HCA, 3,4-dihydroxy hydrocinnamic acid) derivatives synthesis at carbon electrodes in an undivided cell. In this cell, the EC mechanism reaction was involved, comprising two steps alternatively; (1) electrochemical oxidation and (2) chemical reaction. In particular, the electro-organic reactions of HCA, an important biological molecule, were studied in a water–acetonitrile (90:10 v/v) mixture in the presence of benzenesulfinic acid (3) and p-toluenesulfinic acid (4). The research included the use of a variety of experimental techniques, such as cyclic voltammetry, controlled-potential electrolysis and product spectroscopic identification.     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Impacts of varnishes and impregnation chemicals on combustion properties of oak (Quercus petreae lipsky)

This study was performed to determine the effects of varnishing after impregnation with boron compounds on combustion properties of oak. For this aim, the test samples prepared from oak (Quercus petreae Liebl.) wood were impregnated according to ASTM D 1413‐99 with boric acid (Ba) and borax (Bx) by vacuum technique. After impregnation, surfaces were coated by cellulosic (Cv), synthetic (Sn), polyurethane (Pu), waterborne (Wb), acrylic (Ac), and acid hardening (Ah) varnishes in accordance to ASTM D 3023. Combustion properties of samples after varnishing process were determined, according to ASTM E 160‐50. According to material and process types, combustion temperature was the highest in Bx and Cv, the lowest in Ba and Ac. An important difference was not observed between without flame source combustion (WFSC) and flame source combustion (FSC). According to combustion type, impregnation material and varnish type, combustion temperature was the highest value in WFSC + Bx + acid hardening varnish combination and the lowest in WFSC + Ba + acrylic varnish combination. As a result, the tested varnishes showed an increasing impact but boron compounds showed a decreasing impact on combustion properties of oak. In consequence, for usage areas having a high risk of fire, impregnation of wood material with boron compounds before varnishing will decrease combustion temperature and provide security. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Studies of substrate specificities of lipases from different sources

Although lipases are widely applied in a wide variety of reactions, available information on the factors that are responsible for the substrate specificities of lipases from different sources is scarce. In this paper, nine lipase‐producing microorganism strains were isolated from oil‐containing samples. The properties of these enzymes, including pH optima, temperature optima, thermal stability, and pH stability, vary significantly with the different sources from which these lipases were isolated. The substrate specificities of the nine lipases, including fatty acid and positional specificities, were also studied. The fatty acid specificities of the nine lipases were observably different toward 15 substrates with different carbon chain lengths, different saturation degrees and different side chains. The lipases from S₃ Penicillium citrinum (PCL), MJ₁ Aspergillus niger (ANL), MJ₂ Aspergillus oryzae (AOL), YM Bacillus coughing (BCL), S₉ Geotrichum candidum (GCL), and S₁₁ Candida lypolytica (CLL) showed the strongest specificities to short‐chain esters, and the other lipases showed strong selectivity for medium‐ or long‐chain and branched esters. The positional specificities were examined by analyzing the hydrolytic products of triolein catalyzed by the nine lipases, using TLC. The lipases can be mainly classified into two groups by their specificities for the ester bond at position 2 of triglycerides; one group can selectively hydrolyze the ester bond at position 2 of the triglycerides, the other group cannot. All these nine lipases were divided into four groups by hierarchical clustering analysis on the basis of the results of fatty acid and positional specificities.     

A study of synthesizing benzaldehydes from propenylbenzenes and cinnamic acid derivatives

Propenylbenzenes and cinnamic acid derivatives yield correspondingly substituted benzaldehydes when oxidized by lead-ruthenium pyrochlore oxide in the presence of sodium hydrochlorite as a co-oxidant at pH 11 under heterogeneous conditions. The reaction of terminal and internal aliphatic alkenes under similar conditions affords no aldehydes.     

Effect of Ammonia on the Gas-Phase Hydration of the Common Atmospheric Ion HSO4?

Hydration directly affects the mobility, thermodynamic properties, lifetime and nucleation rates of atmospheric ions. In the present study, the role of ammonia on the formation of hydrogen bonded complexes of the common atmospheric hydrogensulfate (HSO₄⁻) ion with water has been investigated using the Density Functional Theory (DFT). Our findings rule out the stabilizing effect of ammonia on the formation of negatively charged cluster hydrates and show clearly that the conventional (classical) treatment of ionic clusters as presumably more stable compared to neutrals may not be applicable to pre-nucleation clusters. These considerations lead us to conclude that not only quantitative but also qualitative assessment of the relative thermodynamic stability of atmospheric clusters requires a quantum-chemical treatment.     

The effect of aromatics on paraffin mild hydrocracking reactions (WNiPd/CeY–Al2O3)

The conversion of heavy paraffin and aromatics into a high-quality diesel fraction was performed in a microplant using a WNiPd/CeY-alumina catalyst. The effects of aromatics and naphtheno-aromatics on mild hydrocracking of hexadecane were studied at different concentrations. Two catalysts, with and without Pd and thermal treatment, were characterized by FTIR, XPS, and TPD of ammonia and ammonia plus naphthalene to complement previous study about the surface composition. The hydrocracking activity and selectivity were tested using different amounts and types of aromatics. This study demonstrated the presence of two acid strengths that contribute in different ways to paraffin and aromatics isomerization, ring opening, and cracking reactions. The product distribution obtained by mild hydrocracking of n-C₁₆ is between amorphous (SiO₂Al₂O₃) and Y-zeolite type of support. The aromatic adsorption on acid sites reduces the cracking rate and improves the survival of di- and tri-branched paraffin. A model for the path of reaction is discussed to explain the results.