About the kinetics and mechanism of the reactions of 4-(2-pyridylazo)-resorcinol, with Zn2+, Cu2+ and Zn2++Cu2+ equimolar mixtures, in aqueous solutions

The kinetics and mechanism of the reactions between 4(2pyridylazo)-resorcinol and Zn2+, Cu2+ and Zn2++Cu2+ equimolar mixtures were studied. The reactions were performed in aqueous solution (pH = 8.5, borate buffer) and monitored spectrophotometrically at 500 nm using stopped-flow technique. Spectral and kinetic data indicate that the Zn2++Cu2+ equimolar mixture behaves as an unique species and it can be attributed to the interactions of Zn2+ and of Cu2+ with water molecules in the aqueous solution. A mechanism is proposed and the rate constants are calculated.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

Polarographic study and electrode kinetics of [Zn(II) - antibiotics - cephaloglycin] system vis a vis kinetics of electrode reactions

Electrode kinetics and complex formation of Zn(II) using doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin, chloramphenicol and cephaloglycin were reported at pH = 7.30 ± 0.01 in = 1.0 molL-1 NaClO4 used as supporting electrolyte at 25.0°C. Kinetic parameters viz. transfer coefficient (α), degree of irreversibility (λ) and rate constant (k) were determined. The study showed that 'Transition state' behaves between reactant (O) and product (R) response to applied potential. The stability constants varied from 2.14 to 10.31 showing that these drugs or their complexes could be used against Zn toxicity.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

Raw water use charge reduction for the rural sector in the PCJ Watershed

The deficient environmental preservation on agricultural properties has reflected in great soil losses for erosion and the high rate of sedimentation. Therefore, this work brings the application of software to demonstrate that planters can get benefits by the conservationist practices. The benefits will be obtained from the environment aspect (erosion and sedimentation control), as well as economical aspect (financial incentives). A proposal has been created by the Technical Chamber of Rural Water Use and Conservation (CT-Rural) to estimate the reduction in raw water use charge for the rural water users of the PCJ Watershed - this reduction is being possible since January 2007, at the PCJ Committee. The software develops a simple relationship, so that if the rural conservationist action goes more efficient, such as if the conserved rural area goes larger, then the reduction value will bring better benefits for the rural water users. Within the purposes of this study, there is the idealization of mechanisms that may support specific management matters related to the water users of federal rivers from the rural sector of PCJ Watershed.

Decomposition kinetics of gaseous ozone in peanuts

This study was conducted to evaluate the decomposition kinetics of gaseous ozone in peanut grains. This evaluation was made with 1-kg peanut samples, moisture contents being 7.1 and 10.5% wet basis (w.b.), placed in 3-liter glass containers. The peanut grains were ozonated at the concentration of 450 µg L-1, at 25 and 35 ºC, with gas flow rates of 1.0 and 3.0 L min-1. Time of saturation was determined by quantifying the residual concentration of ozone after the gas passed through the grains to constant mass. The decomposition kinetics of ozone was evaluated after the grain mass was ozone-saturated. For the peanut grains whose moisture content was 7.1% (w.b.), at 25 and 35ºC and with flow rates of 1.0 and 3.0 L min-1, the values obtained for time of saturation of gaseous ozone ranged between 173 and 192 min; the concentration of saturation was approximately 260 µg L-1. For the grains whose moisture content was 10.5% (w.b.), a higher residual concentration of gaseous ozone was obtained at 25 ºC, that of 190 µg L-1. As regards the half-life of ozone, the highest value obtained was equivalent to 7.7 min for grains ozonated at 25 ºC, while for those with moisture content of 10.5% at 35 ºC, half-life was 3.2 min. In the process of ozone decomposition in peanut grains, temperature was concluded to be the key factor. An increase of 10 ºC in the temperature of the grains results in a decrease of at least 43% in the half-life of ozone.

KINETICS OF MASS LOSS OF ARABICA COFFEE DURING ROASTING PROCESS

ABSTRACT Roasting is one of the most complex coffee processing steps due to simultaneous transfers of heat and mass. During this process, beans lose mass because of fast physical and chemical changes that will set color and flavor of the commercial coffee beverage. Therefore, we aimed at assessing the kinetics of mass loss in commercially roasted coffee beans according to heating throughout the processing. For that, we used samples of 350-g Arabica coffee processed grains with water content of 0.1217 kga kg-1, in addition to a continuous roaster with firing gas. The roaster had initial temperatures of 285, 325, 345 and 380 °C, decreasing during the process up to 255, 285, 305 and 335 °C respectively. Mass loss was calculated by the difference between grain weight before and after roasting. We observed a linear variation directly dependent on roaster temperature. For each temperature during the process was obtained a constant mass loss rate, which was reported by the Arrhenius model with r2 above 0.98. In a roaster in non-isothermal conditions, the required activation energy to start the mass loss in a commercial coffee roasting index was 52.27 kJ mol -1.

Kinetics of epsilon antitoxin antibodies in different strategies for active immunization of lambs against enterotoxaemia

Enterotoxaemia, a common disease that affects domestic small ruminants, is mainly caused by the epsilon toxin of Clostridium perfringens type D. The present study tested four distinct immunization protocols to evaluate humoral response in lambs, a progeny of non-vaccinated sheep during gestation. Twenty-four lambs were randomly allocated into four groups according to age (7, 15, 30 and 45 days), receiving the first dose of epsilon toxoid commercial vaccine against clostridiosis with booster after 30 days post vaccination. Indirect ELISA was performed after the first vaccine dose and booster to evaluate the immune response of the lambs. Results showed that for the four protocols tested all lambs presented serum title considered protective (≥0.2UI/ml epsilon antitoxin antibodies) and also showed that the anticipation of primovaccination of lambs against enterotoxaemia conferred serum title considered protective allowing the optimization of mass vaccination of lambs.

The molecular basis of selective permeability of connexins is complex and includes both size and charge

Although gap junction channels are still widely viewed as large, non-specific pores connecting cells, the diversity in the connexin family has led more attention to be focused on their permeability characteristics. We summarize here the current status of these investigations, both published and on-going, that reveal both charge and size selectivity between gap junction channels composed of different connexins. In particular, this review will focus on quantitative approaches that monitor the expression level of the connexins, so that it is clear that differences that are seen can be attributed to channel properties. The degree of selectivity that is observed is modest compared to other channels, but is likely to be significant for biological molecules that are labile within the cell. Of particular relevance to the in vivo function of gap junctions, recent studies are summarized that demonstrate that the connexin phenotype can control the nature of the endogenous traffic between cells, with consequent effects on biological effects of gap junctions such as tumor suppression.

Kinetics of TNF-alpha and IFN-gamma mRNA expression in islets and spleen of NOD mice

Insulin-dependent diabetes mellitus is caused by autoimmune destruction of pancreatic ß cells. Non-obese diabetic (NOD) mice spontaneously develop diabetes similar to the human disease. Cytokines produced by islet-infiltrating mononuclear cells may be directly cytotoxic and can be involved in islet destruction coordinated by CD4+ and CD8+ cells. We utilized a semiquantitative RT-PCR assay to analyze in vitro the mRNA expression of TNF-alpha and IFN-gamma cytokine genes in isolated islets (N = 100) and spleen cells (5 x 10(5) cells) from female NOD mice during the development of diabetes and from female CBA-j mice as a related control strain that does not develop diabetes. Cytokine mRNAs were measured at 2, 4, 8, 14 and 28 weeks of age from the onset of insulitis to the development of overt diabetes. An increase in IFN-gamma expression in islets was observed for females aged 28 weeks (149 ± 29 arbitrary units (AU), P<0.05, Student t-test) with advanced destructive insulitis when compared with CBA-j mice, while TNF-alpha was expressed in both NOD and CBA-j female islets at the same level at all ages studied. In contrast, TNF-alpha in spleen was expressed at higher levels in NOD females at 14 weeks (99 ± 8 AU, P<0.05) and 28 weeks (144 ± 17 AU, P<0.05) of age when compared to CBA-j mice. The data suggest that IFN-gamma and TNF-alpha expression in pancreatic islets of female NOD mice is associated with ß cell destruction and overt diabetes.

Kinetics of cardiac and vascular remodeling by spontaneously hypertensive rats after discontinuation of long-term captopril treatment

Angiotensin-converting enzyme inhibitors reduce blood pressure and attenuate cardiac and vascular remodeling in hypertension. However, the kinetics of remodeling after discontinuation of the long-term use of these drugs are unknown. Our objective was to investigate the temporal changes occurring in blood pressure and vascular structure of spontaneously hypertensive rats (SHR). Captopril treatment was started in the pre-hypertensive state. Rats (4 weeks) were assigned to three groups: SHR-Cap (N = 51) treated with captopril (1 g/L) in drinking water from the 4th to the 14th week; SHR-C (N = 48) untreated SHR; Wistar (N = 47) control rats. Subgroups of animals were studied at 2, 4, and 8 weeks after discontinuation of captopril. Direct blood pressure was recorded in freely moving animals after femoral artery catheterism. The animals were then killed to determine left ventricular hypertrophy (LVH) and the aorta fixed at the same pressure measured in vivo. Captopril prevented hypertension (105 ± 3 vs 136 ± 5 mmHg), LVH (2.17 ± 0.05 vs 2.97 ± 0.14 mg/g body weight) and the increase in cross-sectional area to luminal area ratio of the aorta (0.21 ± 0.01 vs 0.26 ± 0.02 μm²) (SHR-Cap vs SHR-C). However, these parameters increased progressively after discontinuation of captopril (22nd week: 141 ± 2 mmHg, 2.50 ± 0.06 mg/g, 0.27 ± 0.02 μm²). Prevention of the development of hypertension in SHR by using captopril during the prehypertensive period prevents the development of cardiac and vascular remodeling. Recovery of these processes follows the kinetic of hypertension development after discontinuation of captopril.

Determination of pectin methylesterase activity in commercial pectinases and study of the inactivation kinetics through two potentiometric procedures

Pectinases are enzymes that degrade pectic substances and are widely used in juice and fruit beverages to improve the quality of the process. The objective of this study was to determine the optimum pH and temperature of two samples of commercial pectinases and propose an alternative procedure to determine the residual activity comparing the data with those of the traditional procedure. The pectin methylesterase (PME) activity in Pectinex 100 L Plus and Panzyn Clears was determined by potentiometry. The reaction consisted of 5.00 mg.mL-1 apple pectin, 0.100 mol.L-1 NaCl, and 50 µL enzyme to a total volume of 30 mL. The pectin reaction in the presence of PME in all experiments revealed a first order kinetics. The PME in the two enzyme preparations showed higher activity at pH 4.0 to 4.5 and temperature of 45 ºC. From the results of both procedures ΔV NaOH/Δt and ΔpH/Δt, it was concluded that the inactivation of PME occurred at 75 ºC. The results obtained from the ratio ΔpH/Δt showed good correlation with those obtained from the ratio ΔV NaOH/Δt. In the reaction accompanied by the ratio ΔpH/Δt, the release of H3O+ occurred in the real time reaction.

Color degradation kinetics in low-calorie strawberry and guava jellies

The purpose of this study was to follow-up color changes in low-calorie strawberry and guava jellies during storage. To this end, one formulation of each flavor was prepared varying the application of hydrocolloids (pectin and modified starch). The jellies were studied regarding pH, soluble solids, water activity and syneresis. In order to follow-up color changes, the samples remained stored for 180 days in chambers with controlled temperatures of 10 °C (control) and 25 °C (commercial), and color instrumental analyses (L*, a*, and b*) were performed every 30 days. Arrhenius model was applied to reaction speeds (k) at different temperatures, where light strawberry and guava jellies showed greater color changes when stored at 25 °C compared to the samples stored at 10 °C. Activation energy values between 13 and 15 kcal.mol-1 and Q10 values between 2.1 and 2.3 were obtained for light strawberry jelly and light guava jelly, respectively. Therefore, it was concluded that, with respect to color changes, every 10 °C temperature increase reduces light jellies shelf-life by half.

The kinetics of lipase activity and hydrolytic rancidity of raw, parboiled, and extruded rice bran during storage

The main problem related to rice bran use is that it goes rancid right after its production. The objective of the present study was to apply a mathematical model to evaluate the kinetics of the lipase activity and hydrolytic rancidity of the raw rice bran (RRB), extruded rice bran (ERB), and parboiled rice bran (PRB) stored in low density polyethylene bags at room temperature for 180 days. Extrusion and parboiling were efficient in preventing free fatty acid formationin ERB and PRB.Extrusion reduced the velocity constant of lipase activity as compared to that of RRB while parboiling increased it, and both decreased the lipase activity after equilibrium from 150 days. The extrusion and parboiling treatments increased the velocity constants for the liberation of free fatty acids although the equilibrium was reached with reduced production of free fatty acids in relation to the production of raw rice bran after 150 days ofstorage. Extrusion proved the best treatment under the storage temperature conditions of rice bran from cultivar BRS Primavera.

Dehydration of "dedo de moça" pepper: kinetics and phytochemical concentration

Red pepper is rich in vitamin C and other phytochemicals and can be consumed as a dehydrated product. The evaluation of the best drying conditions can ensure a better quality product. This study aimed to investigate the effect of air temperature (55, 65, and 75 ºC) on drying kinetics of red peppers and on vitamin C, total phenolic content, and color of dried pepper as compared to the fresh product. Dehydration was carried out in a forced convection oven. Drying kinetics was determined by periodic weighting until constant weight. The moisture content of the fresh pepper was approximately 86%. The drying curves were fitted to three different models available in the literature. The Page model showed the best fit for this process. Analysis of variance revealed that the air drying temperature significantly influenced (p < 0.05) the quality parameters (vitamin C content, total phenolic content, and color) of the dried pepper as compared to the fresh pepper. After drying, the vitamin C retention increased with reduced air-drying temperature. In general, products dried at lower temperatures exhibited better quality due to reduced losses of bioactive compounds.