Efficient synthesis of rare sugars from galactose in hot compressed water using eggshells as an environmentally friendly catalyst.

Aqueous galactose solutions containing eggshell was heated at 120 °C to produce calcium supplements containing rare sugars. Galactose was isomerized to rare sugars with improving rare sugar yields compared to those without eggshell. Organic acids were also formed as byproducts during the reaction. These acids were neutralized by dissolving eggshells with increasing the calcium ion concentration in the solution. When eggshell components (calcium carbonate, magnesium carbonate, or calcium phosphate) were used for the treatment, rare sugars were also formed. Especially, addition of magnesium carbonate improved rare sugar yield, but byproduct formation became more pronounced. Eggshells used in the treatment were used for repeated treatments. When eggshells were used three times, rare sugar yield changed only slightly but the selectivity of rare sugars improved significantly. By these processes, we obtained an aqueous solution of rare sugars containing calcium ion at 295 mg/L, which has potential as ingredients for dietary supplements.

Isomerization and epimerization of glucose and galactose in arginine solution and phosphate buffer under subcritical fluid conditions.

Reaction of glucose or galactose was performed in arginine solution or phosphate buffer (pH 7.0) using a batch reactor at 110°C. The yields of products, pH, and absorbances at 280 and 420 nm were measured during the reaction. Fructose, mannose, and allulose were formed from glucose; tagatose, talose, and sorbose were done from galactose. The reaction proceeded more rapidly in arginine solution than in phosphate buffer. In arginine solution, yields of fructose and tagatose were 20% and 16%, respectively, after 30-min reaction; in phosphate buffer, they were 14% and 10%, respectively. However, in both reaction media, the pH drop and increase in absorbances continued even after the yield became almost constant. The absorbance increased particularly in the latter half of the reaction due to formation of browning products. Therefore, to avoid browning, the reaction should be stopped as soon as possible after the yield approaches its maximum value.

Isomerization of galactose to tagatose using arginine as a green catalyst.

This work investigated the isomerization of galactose to tagatose, a low caloric rare sugar, using arginine as a catalyst. Galactose (5 % w/v) and arginine (0.10 mol/mol-galactose) in water were treated at 90-120 °C. The results showed that as the temperature and time increased, galactose was continuously consumed. Rare sugars namely tagatose, talose, and sorbose were formed with the highest yield of 16.8, 2.7, and 3.3 %, respectively at 120 °C, 20 min. High temperature and short time conditions resulted in lower Maillard reaction extent. The arginine concentrations at 0.05, 0.10, and 0.15 mol/mol-galactose resulted in a slight increase in tagatose yield while an increase of the initial galactose concentration from 5 to 20 % resulted in a decrease in tagatose yield, although the tagatose concentration increased. The highest tagatose productivity of 278 g/(L⋅h) was obtained using galactose of 20 % w/v and arginine of 0.10 mol/mol-galactose at 120 °C and 4 min.

Drying Behavior and Curcuminoids Changes in Turmeric Slices during Drying under Simulated Solar Radiation as Influenced by Different Transparent Cover Materials.

Dried turmeric is used as a spice and traditional medicine. The common drying methods for turmeric (Curcuma longa L.) are sun drying and solar drying. In this study, turmeric slices with a thickness of 2 mm were dried at 40, 50, 60, and 70 °C in a laboratory hot-air dryer with a simulated solar radiation applied through transparent polycarbonate cover (UV impermeable) and PMMA cover (UV permeable). Air velocity and relative humidity of drying air were fixed at 1.0 M·s-1 and 25 g H2O kg-1 dry air, respectively. Light significantly increased the sample temperature under both covers. Page was the best model to predict the drying characteristics of turmeric slices. Drying rate correlated with the effective moisture diffusivity, which increased at higher temperature. The hue angle (h°) of turmeric was distinctly lower at 70 °C under both covers. The dried products were of intensive orange color. Curcumin, demethoxycurcumin, and total curcuminoids were affected by the cumulated thermal load (CTL). The lowest curcumin content was found at 40 °C under PMMA (highest CTL). The optimum drying condition was 70 °C under polycarbonate cover due to shorter drying time and better preservation of color and curcuminoids in the dried product.

Osmotic Dehydration, Drying Kinetics, and Quality Attributes of Osmotic Hot Air-Dried Mango as Affected by Initial Frozen Storage.

Using frozen mango for osmotic hot air drying is still uncommon due to a lack of knowledge on the effect of the freezing process on the final product's quality attributes. This study aimed to investigate the effect of the freezing method (slow and quick freezing) and frozen storage time at -18 °C (0, 1, and 2 months) on mass transfer kinetics during osmotic dehydration, drying kinetics during hot air drying, and final quality attributes of the dried mango. The results indicated that Peleg's model could describe the water loss and solid gain during the osmotic dehydration in a 38° Brix sugar solution. Freezing before osmotic dehydration reduced the water loss rate while increasing the solid uptake content. Frozen mangoes showed slightly higher drying rates at 50 and 60 °C than the fresh ones. Freezing and frozen storage also retarded the browning reaction and polyphenol oxidase activities. The osmotic-dried mango obtained from frozen mangoes showed a chewy and gummy texture, which could be considered a distinctive texture characteristic for dried mango.

Protein composition, chlorophyll, carotenoids, and cyanide content of cassava leaves (Manihot esculenta Crantz) as influenced by cultivar, plant age, and leaf position.

The variation of proximate compositions, amino acids, carotenoids, chlorophyll, and total cyanide contents in cassava leaves was studied to identify the most suitable leaves for human consumption. The cassava leaves from 4 cultivars were analysed at 3 leaf positions as well as at 2 plant ages. The leaves of 'Rayong 5' cultivar from the middle position at 6 months after planting contained the highest crude protein, amino acids, carotenoids, and chlorophyll. The total cyanide content was high and therefore, an effective detoxification method is needed. Protein from the cassava leaves was rich in glutamine, aspartic acid, and leucine, but low in methionine and cysteine. Additionally, cassava leaves were found to be a rich source of carotenoids and chlorophyll. This study provided the evidences that cassava leaves can be an alternative source as protein supplement and for carotenoids and chlorophyll extraction and paves the way to valorise this abundant agricultural by-product.

Astaxanthin stability and color change of krill during subcritical water treatment.

Pacific krill (Euphausia pacifica) contains high amounts of astaxanthin, a carotenoid pigment with strong antioxidative activities. In this study, the effects of subcritical water temperatures (100-180 °C) and times (0-10 min) on color changes (L*, a*, and b*) and astaxanthin degradation in Pacific krill were investigated. In addition, an aqueous solution of pure astaxanthin and that of crude astaxanthin from Pacific krill, both at a concentration of 5 mg/L, were subjected to treatment under subcritical water conditions using a flow-type reactor to compare the degradation of free astaxanthin and astaxanthin fatty acid esters. To compare the results of the different treatment conditions on the properties of astaxanthin, the severity factor (log R0) was calculated, which ranged from 0.38 to 3.52. The extractability of astaxanthin enhanced when the subcritical water treatment was carried out at log R0 values of 2.00-2.44. In contrast, astaxanthin underwent 50% degradation at log R0 > 2.44. The changes in the a* values correlated well with the astaxanthin content in the treated krill, while the b* and L* values might relate to the browning components forming owing to Maillard reaction. The results show that free astaxanthin was less stable than crude astaxanthin under subcritical water treatment.

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.

Direct Treatment of Isada Krill under Subcritical Water Conditions to Produce Seasoning with Shrimp-Like Flavour.

Characterization, sensory evaluation, and astaxanthin stability of isada krill under various subcritical water conditions were investigated to optimize the quality of krill extract and residue for producing food seasoning. Raw krill (82% wet basis moisture content) without additional water was treated in a pressure-resistant vessel for 10 min at a temperature range of 100-240 °C. The yield of water-soluble protein was maximized by treatment at 200 °C and decreased with treatment at higher temperatures. The degradation of large molecules and the concomitant production of small molecules depended on the treatment temperature. Astaxanthin in the krill was unstable at temperatures higher than 140 °C. The odour intensities of krill extract and residue increased with higher treatment temperature; however, the highest intensity of pleasant shrimp-like flavour was obtained by treatment at 140 °C. Subjective preference scores were the highest for extract and residue obtained at 140 °C. Thus, treatment at 140 °C is the most promising method for production of seasoning with shrimp-like flavour from isada krill.

Kinetic analysis for the isomerization of cellobiose to cellobiulose in subcritical aqueous ethanol.

The isomerization of cellobiose to cellobiulose, and other degradation reactions of cellobiose were investigated in subcritical aqueous ethanol with concentrations of ethanol ranging from 0 to 60% (w/w) and at temperatures ranging from 170 to 200 °C. The maximum yield of cellobiulose (ca. 40%) was obtained from the treatment of cellobiose in 60% (w/w) aqueous ethanol at 190 °C. Glucose and fructose were also detected as byproducts. The concentration-time integral method was employed to analyze the rate constants for the isomerization and degradation processes. The rate constant of cellobiose isomerization to cellobiulose was greater than those of the degradation reactions under all experimental conditions, and it increased significantly with treatment temperature and ethanol concentration. However, the use of higher temperatures and ethanol concentrations was restricted due to decomposition of the saccharides and the low solubility of cellobiose, respectively. The effect of initial feed concentration (0.5-5.5% w/w) was also studied. The maximum productivity of cellobiulose, 54.1 kg/(h m(3)-reactor), was accomplished at a feed concentration of 5.5% (w/w) in 20% (w/w) subcritical aqueous ethanol.

Using severity factor as a parameter to optimize krill treatment under subcritical water conditions.

The aim of this study was to optimize the conditions for subcritical water treatment of krill, as expressed with a single parameter: the severity factor (log R0). Raw krill was treated under subcritical water conditions at various log R0 values (1.54-3.75) by varying the treatment temperatures (120-180 °C) and times (0-10 min) in two different sizes of batch-type vessel (10 and 117 mL). The log R0 value could efficiently describe changes in various properties of the obtained liquid extracts and solid residues. The most desirable shrimp-like flavor intensity and highest sensory preference were obtained for log R0 values of 2.75-3.01. The results also proved that severity factor can be used as a single parameter to control subcritical water treatment conditions in differently sized batch-type vessels to produce shrimp-like flavor extract and residue from krill.

Antioxidative Properties of Stearoyl Ascorbate in a Food Matrix System.

Stearoyl ascorbate or 6-O-stearoyl l-ascorbate is a lipophilic derivative of l-ascorbic acid and is commercially used in foods as a fat-soluble antioxidant and surfactant to overcome the disadvantages of using l-ascorbic acid. The objective of this research is to evaluate the antioxidative ability of stearoyl ascorbate, in the presence of wheat starch or gluten as a matrix, by measuring the unoxidized methyl linoleate available in the mixture of them after oxidation under accelerated conditions compared to that when using ascorbic acid. We observed that stearoyl ascorbate and ascorbic acid exhibited mutually adjacent antioxidative ability against oxidation of the methyl linoleate at a molar ratio of 0.0001 in presence of either wheat starch or gluten. In addition, the oxidation process in the mixture containing either stearoyl ascorbate or ascorbic acid was significantly slower than that in the mixture without stearoyl ascorbate or ascorbic acid. Moreover, by altering the initiation and propagation periods of the oxidation process, the mixture containing the stearoyl ascorbate and gluten as the matrix exhibited conspicuously slower oxidation than the mixture containing either the wheat starch or stearoyl ascorbate alone. However, increase in the ratio of stearoyl ascorbate to methyl linoleate to 0.001 or higher resulted in adverse effects due to acceleration of the oxidation process.

Decomposition Kinetics of Glucose and Fructose in Subcritical Water Containing Sodium Chloride.

The kinetics of the decomposition and isomerization of glucose and fructose in pure water and water containing sodium chloride (1-20 % w/w) under subcritical conditions at 180-220 °C was investigated. The addition of sodium chloride in subcritical water accelerated the decrease of glucose, and the rate was expressed by the Weibull equation. Although the isomerization of glucose to fructose was observed in parallel with decomposition, the yield of fructose was lower at higher sodium chloride concentrations. Mannose was also formed from glucose with very low yield. It was seen that fructose decomposed much faster than glucose, in pure and salty subcritical water. The decomposition of fructose obeyed first-order kinetics in the initial stages of the reaction and could be expressed by the autocatalytic model in the later stages. The formation of glucose and mannose from fructose was not observed under any of the conditions investigated.

Degradation of caffeic acid in subcritical water and online HPLC-DPPH assay of degradation products.

Caffeic acid was subjected to degradation under subcritical water conditions within 160-240 °C and at a constant pressure of 5 MPa in a continuous tubular reactor. Caffeic acid degraded quickly at these temperatures; the main products identified by liquid chromatography-diode array detection/mass spectrometry were hydroxytyrosol, protocatechuic aldehyde, and 4-vinylcatechol. The reaction rates for the degradation of caffeic acid and the formation of products were evaluated. Online high-performance liquid chromatography/2,2-diphenyl-1-picryhydrazyl assay was used to determine the antioxidant activity of each product in the solution. It was found that the overall antioxidant activity of the treated solution did not change during the degradation process. This study showed a potential of formation of antioxidants from natural phenolic compounds under these subcritical water conditions, and this may lead to a discovering of novel antioxidants compounds during the extraction by this technique.

Antioxidant characteristics of extracts from cereal residues by their subcritical water treatment.

Subcritical water treatment of cereal residues including okara, defatted rice bran, desalted soy sauce lees, sake lees, corn kernel hull, and defatted rapeseed was conducted at 260°C for 5 min to obtain the antioxidative extracts. The antioxidative activities of the extracts were evaluated using DPPH radical, peroxyl radical, hydroxyl radical, hypochlorite ion, and peroxynitrite ion. The results show that the extracts from the sake lees, corn kernel hull, and defatted rapeseed had differently the antioxidative activities against all radicals and ions. However, the okara, defatted rice bran and desalted soy sauce lees had no activity against the hypochlorite ion.

Subcritical water extraction of flavoring and phenolic compounds from cinnamon bark (Cinnamomum zeylanicum).

Cinnamon bark (Cinnamomum zeylanicum) powder was treated with subcritical water at 150 and 200°C in a semi-continuous system at a constant flow rate (3 mL/min) and pressure (6 MPa). Major flavoring compounds, i.e., cinnamaldehyde, cinnamic acid, cinnamyl alcohol and coumarin, were extracted at lower recoveries than the extraction using methanol, suggesting that degradation of these components might occur during the subcritical water treatment. Caffeic, ferulic, p-coumaric, protocatechuic and vanillic acids were identified from the subcritical water treatment. Extraction using subcritical water was more effective to obtain these acids than methanol (50% v/v) in both number of components and recovery, especially at 200°C. Subcritical water treatment at 200°C also resulted in a higher total phenolic content and DPPH radical scavenging activity than the methanol extraction. The DPPH radical scavenging activity and total phenolic content linearly correlated but the results suggested that the extraction at 200°C might result in other products that possessed a free radical scavenging activity other than the phenolic compounds.

Degradation kinetics of gamma-oryzanol in antioxidant-stripped rice bran oil during thermal oxidation.

Gamma-oryzanol, a group of phytosterol ferulates found in rice bran, possesses antioxidative activity and other bioactivities. The kinetics of thermal degradation of gamma-oryzanol in stripped rice bran oil (SRBO) were investigated under heating at 132, 160, 192 and 222 degrees C for 480, 140, 60 and 50 h, respectively. Losses of the overall gamma-oryzanol and its components (cycloartenyl ferulate, 24-methylene cycloartanyl ferulate, campesteryl ferulate and beta-sitosteryl ferulate) could be expressed by the first-order kinetics model. The rate constant of thermal degradation of gamma-oryzanol increased with increasing heating temperatures. The temperature dependence of the obtained rate constants was found to obey the Arrhenius equation. Campesteryl ferulate showed slightly more thermally resistant than other components at temperature lower than 160 degrees C. However, the change in the absorbance from 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay as a function of heating time exhibited the same pattern for the SRBO with and without gamma-oryzanol for all studied heating temperatures.

Preparation of finely dispersed O/W emulsion from fatty acid solubilized in subcritical water.

A novel method for preparing a finely dispersed oil-in-water emulsion is proposed. Octanoic acid dissolved in water at a high temperature of 220 or 230 degrees C at 15 MPa was combined with an aqueous solution of a surfactant and then the mixture was cooled. When a nonionic surfactant, decaglycerol monolaurate (ML-750) or polyoxyethylene sorbitan monolaurate (Tween 20), was used, fine emulsions with a median oil droplet diameter of 100 nm or less were successfully prepared at ML-750 and Tween 20 concentrations of 0.083% (w/v) and 0.042%, respectively, or higher. The diameters were much smaller than those of oil droplets prepared by the conventional homogenization method using a rotor/stator homogenizer. However, an anionic surfactant, sodium dodecyl sulfate, was not adequate for the preparation of such fine emulsions by the proposed method. Although the interfacial tensions between octanoic acid and the surfactant solutions were measured at different temperatures, they were not an indication for selecting a surfactant for the successful preparation of the fine emulsion by the proposed method.

Solubility of saturated fatty acids in water at elevated temperatures.

The solubility in water of saturated fatty acids with even carbon numbers from 8 to 18 was measured in the temperature range of 60 to 230 degrees C and at a pressure of 5 or 15 MPa. The pressure had no significant effect on the solubility. The solubility of the fatty acids increased with increasing temperature. At temperatures higher than about 160 degrees C, the logarithm of the solubility in mole fraction was linearly related to the reciprocal of the absolute temperature for each fatty acid, indicating that the water containing solubilized fatty acid molecules formed a regular solution at the higher temperatures. The enthalpy of a solution of the fatty acids in water, which was evaluated from the linear relationship at the given temperatures, increased linearly with the carbon number of the fatty acid.