Kinetics of hydrolysis of fructooligosaccharides in mineral-buffered aqueous solutions: influence of pH and temperature

High-performance anion exchange chromatography coupled with a pulsed amperometric detection system (HPAEC-PAD) was used to evaluate the extent of chemical hydrolysis of three fructooligosaccharides (FOS) including 1-kestose (beta-D-Fru-(2-->1)(2)-alpha-D-glucopyranoside, GF2), nystose (beta-D-Fru-(2-->1)(3)-alpha-D-glucopyranoside, GF3), and fructofuranosylnystose (beta-D-Fru-(2-->1)(4)-alpha-D-glucopyranoside, GF4). A kinetic study was carried out at 80, 90, 100, 110, and 120 degrees C in aqueous solutions buffered at pH values of 4.0, 7.0, and 9.0. Under each experimental condition, the determination of the respective amounts of reactants and hydrolysis products showed that FOS hydrolysis obeyed pseudo-first-order kinetics as the extent of hydrolysis, which decreased at increasing pH values, increased with temperature. The three oligomers were found to be degraded mainly under acidic conditions, and at the highest temperature value (120 degrees C), a quick and complete acid degradation of each FOS was observed. Using the Arrhenius equation, rate constants, half-life values, and activation energies were calculated and compared with those obtained from sucrose under the same experimental conditions. It appeared that the hydrolysis of FOS took place much more easily at acidic pH than at neutral or basic pH values.     

Kinetics and mechanism of cymoxanil degradation in buffer solutions

The kinetics and mechanism(s) of the hydrolytic degradation of a compound are needed to evaluate a compound's abiotic degradation in the environment. In this paper, the hydrolysis of cymoxanil [2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino) acetamide] was investigated in dark sterile aqueous solutions under a variety of pH conditions (pH 2.8-9.2) and temperatures (15-50 degrees C). Hydrolysis of cymoxanil was described by first-order kinetics, which was dependent on pH and temperature. Cymoxanil degraded rapidly at pH 9 (half-life = 31 min) and relatively slowly at pH 2.8 (half-life = 722 days). The effect of temperature on the rate of cymoxanil degradation was characterized using the Arrhenius equation with an estimated energy of activation of 117.1 kJ mol(-)(1). An increase in temperature of 10 degrees C resulted in a decrease in half-life by a factor of approximately 5. Three competing degradation pathways are proposed for the hydrolysis of cymoxanil, with two of the pathways accounting for approximately 90% of cymoxanil degradation. These two pathways involved either initial cyclization to 1-ethyldihydro-6-imino-2,3,5(3H)-pyrimidinetrione-5-(O-methyloxime) (1, Figure 1) or direct cleavage of the C-1 amide bond to form cyano(methoxyimino) acetic acid (7). The third pathway of degradation involved initial cyclization to 3-ethyl-4-(methoxyimino)-2,5-dioxo-4-imidazolidinecarbonitrile (8), which rapidly degrades into 1-ethyl-5-(methoxyimino)-2,4-imidazoline-2,4-dione (9). All three pathways eventually lead to the formation of the polar metabolite oxalic acid.     

Degradation of flumorph in soils, aqueous buffer solutions, and natural waters

Flumorph is an oomycete fungicide that is now used extensively in China. A residue analysis method for the determination of flumorph in environmental samples was developed with solid-phase extraction (SPE) for sample preparation and high-performance liquid chromatographic (HPLC) for separation. An environmental fate study was performed concerning the degradation of flumorph in soils, aqueous buffer solutions, and natural waters under laboratory-controlled conditions. The degradation of flumorph in three Chinese soil samples followed a first-order kinetics, with half-lives all longer than 100 days. No degradation of flumorph occurred in aqueous buffer solutions having different pH values or in natural waters with different physical and chemical properties. The data generated from this study could be helpful for risk assessment studies of the pesticide in the environment.     

Kinetics of abiotic hydrolysis of isoxaflutole: influence of pH and temperature in aqueous mineral buffered solutions

A kinetic study of the chemical hydrolysis of isoxaflutole [5-cyclopropyl-4-(2-methanesulfonyl-4-trifluoromethylbenzoyl)is oxazol e (IFT)], a new herbicide recently developed by Rh?ne-Poulenc Agro, in buffered, sterile aqueous solutions was carried out in the dark at 295, 308, and 323 K and at nine pH values between 1.8 and 10.1. Samples were analyzed by HPLC-UV. The decrease in IFT concentration was accompanied by an increase in the concentration of its diketonitrile derivative (DKN). Obeying pseudo-first-order kinetics, isoxaflutole hydrolysis increased with increasing pH and temperature: for 295 K and pH 9.3 the rate of degradation was 100-fold faster than at pH 3.8. Using the Arrhenius equation, the rate constants K(obsd), activation energies E(a), and entropies DeltaS() were calculated, and plotting log(K(obsd)) against pH showed that the effect of pH varied with temperature. According to DeltaS() values the mechanism of the reaction was found to be different with respect to pH range. The benzoic acid derivative, known as a degradation product of DKN in plants, was not detected in the present study.     

Kinetics of Fe(III) reduction by ascorbic acid in aqueous solutions

The reaction of Fe(III) and ascorbic acid (AA) in food products and digestive tracts affects the efficiency and uptake of these two nutrients. We investigated the kinetics of Fe(III) reduction by AA at pH 5 and 6 in a model system at 25 degrees C. The results indicate that the reduction of Fe(III) by AA is of zero order with respect to AA. The reaction order with respect to Fe(III) cannot be represented by a simple kinetic model at pH 5 or 6. The major stage of the reduction (about 80%, stoichiometrically), however, could be represented by a general equation of -d[Fe(III)]/dt = k[Fe(III)],(1. 811) where k is a rate constant and [Fe(III)] is the total ferric concentration. The rate constant decreased 1 order of magnitude as pH increased from 5 to 6. Aging of Fe(III) solution slows its reduction rate at pH 6 but not at pH 5.     

Kinetics and mechanism of imazosulfuron hydrolysis

Knowledge of the kinetics and pathways of hydrolytic degradation is crucial to the prediction of the fate and transport mechanism of chemicals. This work first describes the kinetics of the chemical hydrolysis of imazosulfuron, a new sulfonylurea herbicide, and evaluates the results to propose a degradation pathway. The hydrolysis of imazosulfuron has been studied in aqueous buffers both within the pH range 1.9-12.3 at ambient temperature (thermostated at 25 +/- 2 degrees C) and at pH 3.6 within the temperature range of 15-55 degrees C. The hydrolysis rate of imazosulfuron was characterized by a first-order kinetics, pH- and temperature-dependent, and accelerated by acidic conditions and higher temperatures. The calculated half-lives at pH 4.5 and 5.9 were 36.5 and 578 days, respectively. At pH 6.6, 7.4, 9.2, and 12.3 no significant change in imazosulfuron concentration was observed after 150 days. Half-lives were much lower at pH <4 (= imazosulfuron pK(a)), at which they ranged from 3.3 to 6.3 days. Moreover, a change in temperature from 15 to 25 degrees C in acidic conditions (pH 3.6) decreased the half-life of imazosulfuron by a factor of approximately 4.0; in any case, a 3-5-fold increase in the rate of hydrolysis was found for each 10 degrees C increase in temperature. In acidic conditions the only hydrolysis products were the two molecules resulting from the cleavage of the sulfonylurea bridge.     

Rheology of zein solutions in aqueous ethanol.

Aqueous ethanol solutions prepared with commercial zein exhibited Newtonian behavior. Temperature, zein concentration, and ratio of water to ethanol affected viscosity of the zein solutions. The influence of temperature on zein solution viscosity was expressed by an Arrhenius-type equation. As zein concentration increased, solution viscosity exponentially increased. Generally speaking, viscosity decreased when the ethanol concentration increased. Parameters were estimated for an Arrhenius-type equation to describe the viscosity as a function of temperature, zein concentration, and ethanol concentration.     

Semi-mechanistic partial buffer approach to modeling pH, the buffer properties, and the distribution of ionic species in complex solutions

In many biological science and food processing applications, it is very important to control or modify pH. However, the complex, unknown composition of biological media and foods often limits the utility of purely theoretical approaches to modeling pH and calculating the distributions of ionizable species. This paper provides general formulas and efficient algorithms for predicting the pH, titration, ionic species concentrations, buffer capacity, and ionic strength of buffer solutions containing both defined and undefined components. A flexible, semi-mechanistic, partial buffering (SMPB) approach is presented that uses local polynomial regression to model the buffering influence of complex or undefined components in a solution, while identified components of known concentration are modeled using expressions based on extensions of the standard acid-base theory. The SMPB method is implemented in a freeware package, (pH)Tools, for use with Matlab. We validated the predictive accuracy of these methods by using strong acid titrations of cucumber slurries to predict the amount of a weak acid required to adjust pH to selected target values.     

Biologically-induced hydrolysis of parathion in soil: Kinetics and modelling

The hydrolysis of the organophosphorus insecticide, parathion (O,O-diethyl O-p-nitrophenyl phosphorothioate) in a silty loam sierozem soil (Gilat, Israel) occurred primarily through microbial action. Parathion (labelled with ¹⁴C in the alkyl chain) was applied at levels of 10–160 μg dry soil^?1 to soil remoistened to 20% and incubated at 25°C for 8 days. Bacterial numbers increased to a maximum 4–5 days after application of parathion and the increase was proportional to the concentration of parathion added. The rate of hydrolysis of parathion per μg applied was independent of the concentration of parathion. A model developed to predict the relationship between parathion concentration, microbial numbers and hydrolysis kinetics was in general agreement with the data experimentally obtained. The course of decomposition of successive additions of parathion, determined experimentally and predicted by the model, was characterized by rapid hydrolysis of parathion and successive increases in bacterial numbers. A portion of the ¹⁴C applied in these experiments was strongly absorbed by the soil and was not used by the soil microorganisms during the incubation period tested.     

Aluminium speciation in aqueous solutions

Water, Air, & Soil Pollution - An analytical scheme for the speciation of monomeric and polymeric forms of Al in aqueous solutions is presented. After monomer isolation by complexation with...     

近临界水中大豆油无催化水解反应动力学研究

为系统研究油脂在近临界水中的水解动力学机理，系统地测定了压力10 MPa下，温度180～240℃范围内大豆油在近临界水中水解反应的动力学数据。试验结果表明，近临界水中大豆油水解反应是一个典型的自催化反应，在无任何外加催化剂的情况下大豆油可以在近临界水中顺利进行水解反应生成脂肪酸和甘油。温度对水解反应影响很大，随温度升高，水解反应速率迅速增大。采用二级自催化反应动力学模型对动力学数据进行了拟合，得到大豆油在近临界水中水解反应的活化能为43.2 kJ/mol。     

Kinetics of acid hydrolysis of water-soluble spruce O-acetyl galactoglucomannans

Water-soluble O-acetyl galactoglucomannan (GGM) is a softwood-derived polysaccharide, which can be extracted on an industrial scale from wood or mechanical pulping waters and now is available in kilogram scale for research and development of value-added products. To develop applications of GGM, information is needed on its stability in acidic conditions. The kinetics of acid hydrolysis of GGM was studied at temperatures up to 90 degrees C in the pH range of 1-3. Molar mass and molar mass distribution were determined using size exclusion chromatography with multiangle laser light scattering and refractive index detection. The molar mass of GGM decreased considerably with treatment time at temperatures above 70 degrees C and pH below 2. The molar mass distribution broadened with hydrolysis time. A first-order kinetic model was found to match the acid hydrolysis. The reaction rate constants at various pH values and temperatures were calculated on the basis of the first-order kinetic model. Furthermore, the activation energy, E, was obtained from the Arrhenius plot. The activation energy E was 150 kJ mol (-1) for acid hydrolysis of spruce GGM. The apparent rate constant during acid hydrolysis increased by a factor of 10 with a decrease in pH by 1 unit, regardless of temperature. In addition, gas chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry were applied to study the released GGM monomers and oligomers.     

Simulated sunlight-induced photodegradations of triasulfuron and cinosulfuron in aqueous solutions

To elucidate the photochemical behavior of two sulfonylureas (cinosulfuron and triasulfuron) for which the chemical formulas are relatively close, their photodegradation was studied in water. All experiments were carried out under laboratory conditions using a xenon arc lamp as the source of radiation to simulate environmental conditions. Polychromatic quantum efficiencies were calculated to determine the photochemical pesticide lifetimes at pH 7, and a comparison with hydrolysis lifetimes has been performed. The results obtained showed clearly that at pH 7, photodegradation becomes a more important pathway than chemical degradation. HPLC-DAD was used to study the kinetics for both sulfonylureas and their photoproducts, whereas HPLC-MS (ESI in positive and negative modes) was used to identify photoproducts. These results suggest that the photodegradation of these two sulfonylureas proceeds via a number of reaction pathways: (1) cleavage of the sulfonylurea bridge; (2) desulfonylation, which can proceed either by a carbon-sulfur cleavage or a nitrogen-sulfur cleavage; (3) O-demethylation of methoxy moieties present on the triazine ring; and (4) O-dealkylation of benzene derivatives. In addition, it was found that the desulfonylation represented the main step and that it was wavelength dependent.     

Electromigration of chitosan D-glucosamine and oligomers in dilute aqueous solutions

The electromigration behavior of chitosan D-glucosamine and oligomers with a degree of polymerization from 1 to 6 in dilute aqueous systems containing either NaCl or KCl salt at 0.01, 0.05, and 0.1 M at pH values from 2 to 9 was evaluated. The results showed that the electromigration of the chitosan D-glucosamine and oligomers did not change by changing the type of salt in the running medium and that the pH had a significant effect on the direction of migration under an external electric field. In addition, the increase in the ionic strength of the medium caused a significant decrease on the absolute value of the electrophoretic mobility, and the highest values of the electromobility were observed in water. However, the ionic strength had no significant effect on the electrophoretic mobilities at pH 2 in comparison with the other pH values. The dimer showed the highest electrophoretic mobility in the alkaline zone of the pH. At pH values lower than the pKa of the D-glucosamine, the chitosan D-glucosamine, and oligomers migrated toward the anode, where the amine groups are protonated and carry positive charge. At higher pH values, chitosan D-glucosamine and oligomers migrated toward the anode, even though they did not carry any electric charge. The contribution of the difference in the dielectric constants between the solvent and the solute to this phenomenon was highlighted. It was shown that the glucose moiety contributes to the direction of migration of the chitosan D-glucosamine and oligomers under alkaline conditions and that the difference in the dielectric constant of glucose and the solvent accounts for the direction and the extent of electromobility.     

Photodegradation of triazine herbicides in aqueous solutions and natural waters

The photodegradation of three triazines, atrazine, simazine, and prometryn, in aqueous solutions and natural waters using UV radiation (lambda > 290 nm) has been studied. Experimental results showed that the dark reactions were negligible. The rate of photodecomposition in aqueous solutions depends on the nature of the triazines and follows first-order kinetics. In the case of the use of hydrogen peroxide and UV radiation, a synergistic effect was observed. The number of photodegradation products detected, using FIA/MS and FIA/MS/MS techniques, suggests the existence of various degradation routes resulting in complex and interconnected pathways.     

Bioavailability of an organophosphorus pesticide,fenamiphos, sorbed on an organo clay

Hydrolysis of an insecticide/nematicide, fenamiphos [ethyl-3-methyl-4-(methylthio)phenyl-(1-methylethyl)phosphoramidate], immobilized through sorption by cetyltrimethylammonium-exchanged montmorillonite (CTMA-clay) by a soil bacterium, Brevibacterium sp., was examined. X-ray diffraction analysis, infrared spectra, and a negative electrophoretic mobility strongly indicated that fenamiphos was intercalated within the bacterially inaccessible interlayer spaces of CTMA-clay. The bacterium hydrolyzed, within 24 h, 82% of the fenamiphos sorbed by the CTMA-clay complex. There was a concomitant accumulation of hydrolysis product, fenamiphos phenol, in nearly stoichiometric amounts. During the same period, in abiotic (uninoculated) controls, 4.6% of the sorbed insecticide was released into the aqueous phase as compared to 6.0% of the sorbed fenamiphos in another abiotic control where activated carbon, a sink for desorbed fenamiphos, was present. Thus, within 24 h, the bacterium hydrolyzed 77% more fenamiphos sorbed by organo clay than the amounts desorbed in abiotic controls. Such rapid degradation of an intercalated pesticide by a bacterium has not been reported before. Evidence indicated that extracellular enzymes produced by the bacterium rapidly hydrolyzed the nondesorbable fenamiphos, even when the enzyme itself was sorbed. Fenamiphos strongly sorbed to an organo clay appears to be readily available for exceptionally rapid degradation by the bacterium.     

Kinetics of the surface hydrolysis of raw starch by glucoamylase

The hydrolysis of raw starch catalyzed by glucoamylase has been studied with starch granules of different sizes by use of an amperometric glucose sensor by which the direct and continuous observation of the concentration of glucose can be achieved even in a thick raw starch suspension. The initial rate of the enzymatic hydrolysis in the raw starch suspension increased with increasing concentration of the enzyme to approach a saturation value and was proportional to the amount of substrate. Also, the rate was proportional to the specific surface area of the substrate. The experimental results can be explained well by the rate equations derived from a three-step mechanism, which consists of adsorption of the free enzyme onto the surface of the substrate, reaction of the adsorbed enzyme with the substrate, and liberation of the product.