Kinetic analysis for the isomerization of glucose,fructose, and mannose in subcritical aqueous ethanol

Fructose, glucose, and mannose were treated with subcritical aqueous ethanol for ethanol concentrations ranging from 0 to 80% (v/v) at 180–200 °C. The aldose–ketose isomerization was more favorable than ketose–aldose isomerization and glucose–mannose epimerization. The isomerization of the monosaccharides was promoted by the addition of ethanol. In particular, mannose was isomerized most easily to fructose in subcritical aqueous ethanol. The apparent equilibrium constants for the isomerizations of mannose to fructose, K_eq,M→F, and glucose to fructose, K_eq,G→F, were independent of ethanol concentration and increased with increasing temperature. Moreover, the K_eq,M→F value was much larger than the K_eq,G→F value. The enthalpies for the isomerization of mannose to fructose, ΔH_M→F, and glucose to fructose, ΔH_G→F, were estimated to be 18 and 24 kJ/mol, respectively, according to van’t Hoff equation. Subcritical aqueous ethanol can be used to produce fructose from glucose and mannose efficiently.     

Kinetic analysis of a tod-lux bacterial reporter for toluene degradation and trichloroethylene cometabolism

Kinetics of toluene and trichloroethylene (TCE) degradation and bioluminescence from the bioreporter Pseudomonas putida B2 and TVA8 were investigated utilizing batch and continuous culture, respectively. Degradation was modeled using a Michaelis-Menten expression for the competition of two substrates for a single enzyme system, and bioluminescence was modeled assuming a luciferase enzyme saturational dependence on toluene as the inducer and growth substrate. During the batch experiments, bioluminescence increased at approximately 90 namp/min for initial toluene concentrations of 10 to 50 mg/L, but more slowly at higher toluene concentrations, suggesting maximum promoter induction at below 10 mg/L and toxic effects above 50 mg/L toluene. TCE degradation did not occur until toluene depletion, presumably due to competition between toluene and TCE for the toluene dioxygenase enzyme. During continuous culture, bioluminescence transiently increased, then gradually decreased in response to increasing step changes in toluene feed concentration. Bioluminescence in the CSTR appeared to be limited by growth substrate and/or inducer.     

Kinetic behavior of liquefaction of Japanese beech in subcritical phenol

Non-catalytic liquefaction of Japanese beech (Fagus crenata) wood in subcritical phenol was investigated using a batch-type reaction vessel. After samples were treated at 160 °C/0.9 MPa–350 °C/4.2 MPa for 3–30 min, they were fractionated into a phenol-soluble portion and phenol-insoluble residues. These residues were then analyzed for their chemical composition. Based on the obtained data, the kinetics for liquefaction was modeled using first-order reaction rate law. Subsequently, the liquefaction rate constants of the major cell wall components including cellulose, hemicellulose, and lignin were determined. The different kinetic mechanisms were found to exist for lignin and cellulose at two different temperature ranges, lower 160–290 °C and higher 310–350 °C, whereas for hemicellulose, it was only liquefied in the lower temperature range. Thus, the liquefaction behaviors of these major cell wall components highlighted hemicellulose to be the most susceptible to liquefaction, followed by lignin and cellulose.     

Decomposition kinetics of maltose in subcritical water

The decomposition process of maltose in subcritical water was studied using a tubular reactor in the temperature range of 180 to 260 degrees C and at 10 MPa. The formation of glucose and 5-hydroxymethyl-2-furaldehyde during the maltose decomposition was also observed. The decomposition rate of maltose was faster at higher temperatures. The rate was approximated by first-order kinetics during the early stage of the decomposition, but was accelerated and deviated from these kinetics at the later stage. The effluent pH decreased as the residence time in the reactor increased and the decrease of pH affected the maltose decomposition rate and glucose formation. Low pH of a feed solution accelerated maltose decomposition. A good correlation was obtained between the pH of the effluent and the rate constant of the first-order kinetics.     

Degradation kinetics of passion fruit pectin in subcritical water

The degradation of passion fruit pectin by subcritical water treatment in a continuous flow-type reactor was investigated in the temperature range of 80?160 °C at a constant pressure of 5 MPa. Changes in the degree of polymerization and reducing end formation were monitored and modeled by applying the Emsley equation and zeroth-order kinetics, respectively. The results showed that both the pectin degradation rate constant and the change in the amount of reducing end were enhanced by temperature, and that the temperature dependence of these parameters obeyed the Arrhenius relationship. The activation energies for pectin degradation and reducing end formation were 62.8 and 86.9 kJ/mol, respectively. The non-linear relationship between the ratio of broken galacturonic acid units to the total galacturonic acid units and the change in the amount of reducing end indicated that pectin cleavage became easier as hydrolysis progressed.     

Structural changes in microcrystalline cellulose in subcritical water treatment

Subcritical water is a high potential green chemical for the hydrolysis of cellulose. In this study microcrystalline cellulose was treated in subcritical water to study structural changes of the cellulose residues. The alterations in particle size and appearance were studied by scanning electron microscopy (SEM) and those in the degree of polymerization (DP) and molar mass distributions by gel permeation chromatography (GPC). Further, changes in crystallinity and crystallite dimensions were quantified by wide-angle X-ray scattering and (13)C solid-state NMR. The results showed that the crystallinity remained practically unchanged throughout the treatment, whereas the size of the remaining cellulose crystallites increased. Microcrystalline cellulose underwent significant depolymerization in subcritical water. However, depolymerization leveled off at a relatively high degree of polymerization. The molar mass distributions of the residues showed a bimodal form. We infer that cellulose gets dissolved in subcritical water only after extensive depolymerization.     

Kinetic analysis of the inhibitory effect of trichloroethylene (TCE) on nitrification in cometabolic degradation

In this study, the inhibitory effect of TCE on nitrification process was investigated with an enriched nitrifier culture. TCE was found to be a competitive inhibitor of ammonia oxidation and the inhibition constant (K _I ) was determined as 666–802 μg/l. The TCE affinity for the AMO enzyme was significantly higher than ammonium. The effect of TCE on ammonium utilization was evaluated with linearized plots of Monod equation (e.g., Lineweaver–Burk, Hanes–Woolf and Eadie–Hofstee plots) and non-linear least square regression (NLSR). No significant differences were found among these data evaluation methods in terms of kinetic parameters obtained.     

Kinetic models for enzymic cellulose degradation in aqueous two-phase systems

Cellulose materials can readily be degraded into cellobiose and glucose by hydrolysis of the enzymes cellulase and beta-glucosidase in aqueous media. Product inhibition does, however, retard the reaction rate and reduce productivity. This may be avoided by carrying out the degradation of cellulose in an aqueous two-phase system, which permits the enzymes and the substrate to be partitioned to one phase and the products to be extracted into a second phase. In addition, two-phase systems also allow recycling of the enzymes. Here, three models previously developed for "one-phase" enzymic degradation are compared to data from enzymic degradation in an aqueous two-phase system. The models tested agreed relatively well with batch experiments during a period of 200 h. For one of the models tested, continuous degradation also gave accurate agreement.     

Properties of rice straw extract after subcritical water treatment

Rice straw was separated into four parts: the upper, middle, and lower parts of the stem, and the leaf. They were treated with subcritical water at 140 to 260 °C. The yield, carbohydrate, protein, and phenolic contents were obtained as well as the UV-Vis absorption spectra and the radical scavenging activity of the extracts. The extracts obtained from the stem parts had almost the same characteristics and were different from those of the leaf part. The extracts, prepared at higher temperature, exhibited higher radical scavenging ability. The radical scavenging ability and the phenolic content showed a correlation (R2=0.92), suggesting that the phenolic substances in the extract cause its antioxidant ability.     

Fluorescence and bioluminescence analysis of sequential UV-biological degradation of p-cresol in water.

The photolysis and Penicillium tardum H-2 degradation of p-cresol in water containing humic acids was investigated by fluorescence and bioluminescence methods. Humic acids extracted from peat (the Vasuygan bog, Tomsk region of Russia) induce the phototransformation of p-cresol. The influence of humic acids on the phototransformation of p-cresol under different irradiation conditions was investigated. Comparison of the data on the KrCl* (lambda = 222 nm) and XeCl* (lambda = 308 nm) excilamps light showed that the most effective p-cresol degradation was observed with mercury lamp irradiation in the presence of humic acids.     

Value-added subcritical water hydrolysate from rice bran and soybean meal

New value-added product was derived from agricultural by-products: rice bran and soybean meal by means of subcritical water (SW) hydrolysis. The effect of temperature (200-220 degrees C), reaction time (10-30 min), raw material-to-water weight ratio (1:5 and 2:5), was determined on the yields of protein, total amino acids, and reducing sugars in the soluble products. The suitable hydrolysis time was 30 min and the proper weight ratio of the raw material-to-water was 1:5. The reaction temperature suitable for the production of protein and amino acids was 220 degrees C for raw and deoiled rice bran, 210 degrees C for raw soybean meal, and 200 degrees C for deoiled soybean meal. The products were also found to have antioxidant activity as tested by ABTS(.)(+) scavenging assay. In addition, sensory evaluation of milk added with the hydrolysis product of deoiled rice bran indicated the potential use of the product as a nutritious drink.     

Extraction of defatted rice bran by subcritical water treatment

Defatted rice bran was treated with subcritical water in the temperature range of 180–280 °C for 5 min using 117 mL and 9 mL vessels to produce the extracts. The total sugar and protein contents and radical scavenging activity of the extracts were then estimated for both vessels. The total sugar concentration of ca. 0.3 g/L-extract was the highest for the extracts at 200 °C, and it significantly decreased at the higher temperatures. The protein concentration and radical scavenging activity were higher at the higher temperatures. Extraction was also done at 200 °C and 260 °C for various times using the small vessel. The total sugar concentration decreased with the increasing extraction time, while the protein concentration and radical scavenging activity only slightly depended on the extraction time. The extracts at 200 °C or lower temperatures using the large vessel possessed the emulsifying and emulsion-stabilizing activities. The HPLC analysis of the extract at 260 °C for 5 min using the small vessel indicated that it contained both hydrophilic and hydrophobic substances. The hydrophilic fraction of the extract mainly contained low-molecular-mass substances.     

Temperature dependent characteristics of intestinal glycyl-L-leucine dipeptidase in boreal zone fish

Three kinds of boreal zone fish were investigated for gastrointestinal glycyl-L-leucine (GL) dipeptide cleaving activity as a function of feeding stage and seasonal changes. The enzyme activity tested in the perch (Perca fluviatilis L.) intestine increased steadily during digestion and rapidly disappeared after completion. The temperature characteristics and the seasonal changes in dipeptide cleaving activity in pike perch (Stizostedion lucioperca L.) and bream (Abramis brama L.) were studied. In summer, the maximal activities in the pike perch and the bream were found at temperatures of 40 and 30 degrees C, respectively. In winter, the temperature of maximal activity in pike perch fell to only 30 degrees C, whereas no changes were observed in bream. The activation energies in bream and pike perch were several times lower in winter than in summer. Seasonal changes in the dipeptide cleaving activity at low temperature relative to that at the temperature of maximal activity were found. At high temperatures, the stability of the enzyme decreases in winter and increases in summer, but in the presence of a substrate the thermal stability of the enzyme increases both in winter and in summer. In our experiments, we found that in these fish, GL dipeptidase was unstable at 0 and -10 degrees C.     

Kinetic modelling of the degradation of the alpha-tocopherol in biodiesel-rape methyl ester

The aim of this work was to study the influence of three major factors (light, atmospheric oxygen, temperature) responsible for the degradation of tocopherols. The evolution of alpha-tocopherol contents was analysed by high-performance liquid chromatography. Taguchi's experimental design was applied to establish a mathematical model of alpha-tocopherols degradation in function of the studied parameters especially in a domain of temperature between 50 degrees C and 150 degrees C. The results show that the major factor is the temperature, especially above 100 degrees C. Light is a negligible factor, meaning that degradation is mainly due to an autoxidation phenomenon. Moreover, only interactions between temperature and atmospheric oxygen have been observed especially above 100 degrees C. The mathematical model was validated for a temperature of 75 degrees C and permits to calculate a predictive speed of degradation in this domain.     

Kinetics and mechanism of the synthesis of a novel protein-based plastic using subcritical water

We investigated the intermolecular mechanism and kinetics of the synthesis of a novel biodegradable protein-based plastic from bovine serum albumin under subcritical water conditions using batch reactors. The reaction mechanism could be viewed as a chain reaction stabilized by the formation of intermolecular disulfide bonds. The kinetic analysis was based on non-steady-state kinetics using a theoretical model developed in one of our previous works. The activation energy and pre-exponential factor were found to be 7.2 kJ/mol and 0.9 s-1, respectively. These low values signify that the reaction is relatively temperature-insensitive with some diffusion limitation.     

Kinetic analysis of the mechanism of insulin degradation by glutathione-insulin transhydrogenase (thiol: protein-disulfide oxidoreductase).

Kinetic studies have been made with glutathione-insulin transhydrogenase, an enzyme which degrades insulin by promoting cleavage of its disulfide bonds via sulfhydryl-disulfide interchange. The degradation of 125I-labeled insulin by enzyme purified from beef pancreas was studied with various thiol-containing compounds as cosubstrates. The apparent Km for insulin was found to be a function of the type and concentration of thiol; values obtained were in the range from 1 to 40 muM. Lineweaver-Burk plots for insulin as varied substrate were linear, whereas those for the thiol substrates were nonlinears: the plots for low molecular weight monothiols (GSH and mercaptoethanol) were parabolic; those for low molecular weight dithiols (dithiothreitol, dihydrolipoic acid, and 2,3-dimercaptopropanol) were apparently linear modified by substrate inhibition; and the plots for protein polythiols (reduced insulin A and B chains and reduced ribonuclease) were parabolic with superposed substrate inhibition. The nonparallel nature of the reciprocal plots for all substrates shows that the enzyme does not follow a ping-pong mechanism. Product inhibition studies were performed with GSH as thiol substrate. Oxidized glutathione was found to be a linear competitive inhibitor vs. both GSH and insulin. The S-sulfonated derivative of insulin A chain was also linearly competitive vs. both substrates. Inhibition by S-sulfonated B chain was competitive vs. insulin; the data eliminated the possibility that this derivative was uncompetitive vs. GSH. Experiments with the cysteic acid derivatives of insulin A and B chains similarly excluded the possibility that these were uncompetitive vs. either substrate. These inhibition studies indicate that the enzyme probably follows a randdom mechanism.