Antioxidant activity of anacardic acids

Anacardic acids, 6-pentadec(en)ylsalicylic acids isolated from the cashew Anacardium occidentale L. (Anacardiaceae) nut and apple, were found to possess preventive antioxidant activity while salicylic acid did not show this activity. These anacardic acids prevent generation of superoxide radicals by inhibiting xanthine oxidase (EC 1.1.3.22, Grade IV) without radical-scavenging activity. Notably, the inhibition kinetics of anacardic acids do not follow hyperbolic dependence of enzyme inhibition on inhibitor contents (Michaelis–Menten equation) but follow the Hill equation instead. Anacardic acid (C_15:1) inhibited the soybean lipoxygenase-1 (EC 1.13.11.12, Type 1) catalyzed oxidation of linoleic acid with an IC₅₀ of 6.8 μM. The inhibition is a slow and reversible reaction without residual enzyme activity. The inhibition kinetics indicate that anacardic acid (C_15:1) is a competitive inhibitor and the inhibition constant, K_I, was 2.8 μM. Anacardic acids act as antioxidants in a variety ways, including inhibition of various prooxidant enzymes involved in the production of the reactive oxygen species and chelate divalent metal ions such as Fe²⁺ or Cu²⁺, but do not quench reactive oxygen species. The C₁₅-alkenyl side chain is largely associated with the activity.     

A kinetic study on isothermal crystallization of palm oil by solid fat content measurements

Isothermal crystallization of plam oil was studied by means of differential scanning calorimetry (DSC) as well as by nuclear magnetic resonance spectrometry to monitor its solid fat content (SFC). The temperature of crystallization (Tc) varied from 0 to 30°C, depending on the method used. The plot of %SFC vs. time at 25°C was sigmoidal in shape. However, at lower temperatures, two consecutive curves were clearly visible. Results from DSC experiments showed the following interesting features. At each Tc, the crystals produced were of different compositions. From 0 to 8°C, the thermogram showed three peaks, with the first two peaks (I and II) sharp, and the third (III) rather broad. At elevated temperatures up to 20°C, peak II disappeared totally while peak III tended to shift toward peak I. Above 20°C, both peaks shifted downward to longer times. Peak I continued to be broadened, and then suddenly disappeared at Tc above 24°C. The melting thermograms of the crystals obtained above and below this cut-off point were distinctly different. Kinetic studies on isothermal crystallization based on the data of SFC measurements showed that the data fit well into the Avrami-Erofeev equation with n=3 over the first 70% of the crystallization.     

Kinetic study of the reaction between molybdenum trioxide and gaseous carbon tetrachloride

The kinetics of the chlorination reaction of molybdenum trioxide with gaseous carbon tetrachloride has been studied at temperatures between 713 and 753 K. The effects of temperature, reaction time, residence time and gaseous reactant concentration on conversion were studied throughout the reaction. In all cases, there was an increase in conversion when the above operating variables were increased. The kinetic model proposed is consistent with and correlates the experimental data. In the range studied for the different variables, the step that controls the rate of reaction is the surface chemical reaction. Values of the rate constant and the activation energy were estimated.     

New intramolecular effect observed for polyesters: An anomeric effect

A series of polyesters was prepared to evaluate hydrolytic stability as a function of cyclohexyl dibasic acid content. The three cyclohexyl dibasic acids: 1,2; 1,3; and 1,4 were formulated into polyesters with two glycols. The proportion of cis and trans isomers was evaluated via ¹H NMR. The hydrolytic stability of short chain polyesters was evaluated in an acetone/water mixture which solubilized the polyesters to mimic oligoester behavior within a thermosetting polyester coating environment. The rate of hydrolysis was monitored by acid titration and corroborated by GPC. Surprisingly, 1,2-cylohexyl diacid-based polyesters were robust, and 1,3-cyclohexyl diacid-based polyesters were the most susceptible to hydrolysis. Evidently, a 1,2-anchimeric effect for cyclohexyl dibasic acid polyesters was not an important consideration, while the 1,3-cyclohexyl ester interaction was. Consequently, an anomeric effect was proposed. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

三元催化转化器中的现象分析与研究

在介绍和分析国内外研究现状的基础上，论述了三元催化转化器中的传递现象及化学反应动力学．探讨了三元催化转化器在暖机过程中有害物质的催化转化模型，并建议采用数学模型的方法对催化器在发动机所有工况下的工作过程进行模拟。     

Dissolution kinetics of ulexite in acetic acid solutions

Ulexite is an important boron mineral used for the production of boron compounds. The aims of this study are to examine the dissolution kinetics of ulexite in acetic acid solutions, and to present an alternative process to produce boric acid. In order to investigate the dissolution kinetics of ulexite in acetic acid solutions, the concentration of solution, reaction temperature, solid-to-liquid ratio, and particle size were selected as experimental parameters. It was determined that the dissolution rate of ulexite increased with increasing solution concentration and temperature and decreasing particle size and solid-to-liquid ratio. The activation energy of the process was found to be 55.8 kJ/mol.     

Effect of mineral matter on coal self-heating rate

Adiabatic self-heating tests have been conducted on subbituminous coal cores from the same seam profile, which cover a mineral matter content range of 11.2-71.1%. In all cases the heat release rate does not conform to an Arrhenius kinetic model, but can best be described by a third order polynomial. Assessment of the theoretical heat sink effect of the mineral matter in each of the tests reveals that the coal is less reactive than predicted using a simple energy conservation equation. There is an additional effect of the mineral matter in these cases that cannot be explained by heat sink alone. The disseminated mineral matter in the coal is therefore inhibiting the oxidation reaction due to physicochemical effects.     

Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

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