Kinetic study of controlled release of flavor compounds from spray-dried encapsulated yeast powder using dynamic vapor sorption-gas chromatography.

The release profile of d-limonene and ethyl hexanoate was investigated using a dynamic vapor sorption (DVS) system coupled with gas chromatography. The flavors were encapsulated by spray drying using Saccharomyces cerevisiae cells from which ß-glucan had been partially extracted. Relative humidity (RH) was stepped from 20% to 50, 60, 70, and 80% at 30, 40, 50, and 60ºC. The maximum release flux for d-limonene and ethyl hexanoate was around 12 and 28 mg/s∙m2∙g-powder at 80% RH and 60ºC incubation. The Weibull distribution function was well fitted with the experimental data to analyze release kinetics. The release mechanism parameter was greater than 1.0, which indicates a controlled release with initial induction time. The activation energy for ethyl hexanoate (6 kJ/mol) was lower than d-limonene (41 kJ/mol) at 80% RH, which indicates higher affinition of ethyl hexanoate to migrate from the lipid bilayer membrane towards the water phase.

Release behavior of allyl sulfide from cyclodextrin inclusion complex of allyl sulfide under different storage conditions.

The stability of allyl sulfide, an organosulfur compound present in garlic oil, in its α-, ß-, and γ-cyclodextrin inclusion complexes was investigated under various storage conditions. The complexes of cyclodextrins and allyl sulfide were prepared by spray drying. The storage temperature, relative humidity, and initial moisture content of the inclusion complex had different effects on the release rate of allyl sulfide. Allyl sulfide in α-cyclodextrin complexes had a lower release rate than in ß- and γ-cyclodextrin complexes at 100 °C and at 50 °C under 6, 40, 54, and 73% relative humidity. The initial moisture content affected only the release rate of allyl sulfide from α-cyclodextrin complexes. The release behavior of allyl sulfide can be correlated with the first-order release rate equation with a normal Gaussian distribution of free energy of activation of release rate constant. The results indicated α-cyclodextrin is a suitable material for controlled release of allyl sulfide.

Encapsulation of lemongrass oil with cyclodextrins by spray drying and its controlled release characteristics.

Inclusion of the two isomers of citral (E-citral and Z-citral), components of lemongrass oil, was investigated within the confines of various cyclodextrin (α-CD, ß-CD and γ-CD) host molecules. Aqueous complex formation constants for E-citral with α-CD, ß-CD and γ-CD were determined to be 123, 185, and 204 L/mol, respectively, whereas Z-citral exhibited stronger affinities (157, 206, and 253 L/mol, respectively). The binding trend γ-CD > ß-CD > α-CD is a reflection of the more favorable geometrical accommodation of the citral isomers with increasing cavity size. Encapsulation of lemongrass oil within CDs was undertaken through shaking citral:CD (1:1, 1.5:1, and 2:1 molar ratio) mixtures followed by spray drying. Maximum citral retention occurred at a 1:1 molar ratio with ß-CD and α-CD demonstrating the highest levels of total E-citral and Z-citral retention, respectively. Furthermore, the ß-CD complex demonstrated the slowest release rate of all inclusion complex powders.

Effect of different dextrose equivalents of maltodextrin on oxidation stability in encapsulated fish oil by spray drying.

Encapsulating fish oil by spray drying with an adequate wall material was investigated to determine if stable powders containing emulsified fish-oil-droplets can be formed. In particular, the dextrose equivalent (DE) of maltodextrin (MD) affects the powder structure, surface-oil ratio, and oxidative stability of fish oil. The carrier solution was prepared using MD with different DEs (DE = 11, 19, and 25) and sodium caseinate as the wall material and the emulsifier, respectively. The percentage of microcapsules having a vacuole was 73, 39, and 38% for MD with DE = 11, 19, and 25, respectively. Peroxide values (PVs) were measured for the microcapsules incubated at 60 °C. The microcapsules prepared with MD of DE = 25 and 19 had lower PVs than those prepared with MD of DE = 11. The difference in PV can be ascribed to the difference in the surface-oil ratio of the spray-dried microcapsules.

Effect of oil droplet size on the oxidative stability of spray-dried flaxseed oil powders.

The effect of the size of oil droplets on the oxidative stability of flaxseed oil in spray-dried powders was investigated. Maltodextrin with a dextrose equivalent of 25 was used as a wall material, and sodium caseinate and transglutaminase-polymerized sodium caseinate were used as emulsifiers. The oxidative stability of flaxseed oil encapsulated in the spray-dried powders was evaluated using lipid oxidation and conductometric determination tests at 105 °C. The powders containing larger oil droplets exhibited higher surface oil content after spray drying, and higher peroxide value and conductivity after storage at 105 °C. Removal of the surface oil from the powders by washing with hexane significantly decreased the conductivity. The results indicated that the surface oil of the spray-dried flaxseed oil powders affected the oxidation stability.

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.

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.

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.

Interdependent Oxidation of Eicosapentaenoic Acid and Docosahexaenoic Acid in Isada Krill Oil Encapsulated with Maltodextrin by Spray-drying.

The major polyunsaturated fatty acids in krill oil extracted from Euphausia pacifica, known as Isada on the Sanriku coast, are eicosapentaenoic acid (EPA) and docosahexaenoic (DHA) acid. A kinetic model was proposed to explain the relationship between the fractions of unoxidized EPA (Y E) and unoxidized DHA (Y D) in the oil spray-dried with maltodextrin and stored at 25, 50, and 70℃. The relationship between Y E and Y D during storage was independent of the temperature and could be expressed using the proposed model. This indicated that the oxidation of EPA and DHA in krill oil was interdependent.

Kinetic study of thermally stimulated dissociation of inclusion complex of 1-methylcyclopropene with alpha-cyclodextrin by thermal analysis.

The thermally stimulated dissociation of the inclusion complex of 1-methylcyclopropene (1-MCP) with alpha-cyclodextrin (alpha-CD) in solid state was studied by means of thermogravimetry (TG) and differential scanning calorimetry (DSC). The mass loss of 1-MCP/alpha-CD inclusion complex occurs in four separated phases with the thermal dissociation of the inclusion complex and release of 1-MCP taking place in the second phase between 90 and 230 degrees C. The kinetic parameters of the dissociation reaction (the apparent activation energy of dissociation, E(D), the reaction order of thermal dissociation, n, and the pre-exponential factor, k0) were evaluated. The dissociation reaction was satisfactorily described by the unimolecular decay law, where the reaction order, n = 1. The effect of the molar ratio of 1-MCP to alpha-CD (inclusion ratio) in the inclusion complex on the temperature dependence of the dissociation reaction was also studied. The E(D) decreased with increasing inclusion ratio indicating higher complex stability at lower inclusion ratios. The extrapolation of the E(D) of the inclusion complexes with different inclusion ratios to 1 mol 1-MCP/mol alpha-CD yielded the "true" E(D) of 20.9 +/- 2.8 and 18.1 +/- 0.2 kJ/mol for TG and DSC, respectively. The "true" ln k(0TG) and the "true" ln k(0DSC) were also determined by extrapolation, yielding values of +4.5 +/- 1.0 and -0.3 +/- 0.3, respectively.

Improvement of antifungal activity of 10-undecyn-1-ol by inclusion complexation with cyclodextrin derivatives.

The inclusion complexation behavior between 10-undecyn-1-ol and cyclodextrin (CD) derivatives, namely, randomly methylated beta-CD (RM-beta-CD) and hydroxypropyl-beta-CD (HP-beta-CD), was studied in terms of solubility improvement, apparent stability constant, and the inclusion ratios of the resultant inclusion complexes. The aqueous solubility of 10-undecyn-1-ol was greatly improved through complexation with the CD derivatives. RM-beta-CD is comparatively more efficient in solubilizing 10-undecyn-1-ol with an apparent stability constant outstripping that of HP-beta-CD by about an order of magnitude. Comparative in vitro evaluations of the growth inhibition effects of inclusion complex solutions toward Rosellinia necatrix, a phytopathogenic fungus, were performed. In comparison with the positive control, appreciable improvements of the antifungal activity of 10-undecyn-1-ol through the addition of CD derivatives were observed visually. The improvement was evaluated in terms of area covered by the mycelia of Rosellinia necatrix and their growth rate. RM-beta-CD was proven to be more effective compared to HP-beta-CD with regard to the reduction of both fungal mycelium-covered area and growth rate constant, presumably owing to greater solubility enhancement by RM-beta-CD and thus the bioavailability of 10-undecyn-1-ol. Inclusion complexation of 10-undecyn-1-ol with CD derivatives suggests a potential means for production of an environmentally friendly 10-undecyn-1-ol-based fungicide to counteract R. necatrix.

Stability and release behavior of encapsulated flavor from spray-dried Saccharomyces cerevisiae and maltodextrin powder.

Yeast cells (Saccharomyces cerevisiae), from which ß-glucans have been partially extracted, were used to encapsulate flavor inside the lipid bilayer membrane as natural encapsulant. The focus of this study was to investigate the release and stability of flavors (d-limonene and ethyl hexanoate) encapsulated in yeast cells and maltodextrin (MD) (DE = 19) by spray drying. The release behavior of encapsulated flavors from yeast cells was measured at 40, 60, 80, and 105 °C with different moisture content (0, 50, 100, and 200% of powder). Water affected flavor release from the yeast cells. The release rate constants were correlated using Gaussian distribution of the activation energy of the release rate constants. The release of d-limonene from the spray-dried MD powder showed a different trend than that of yeast cells at various temperatures. The activation energies of the release rate constant for ethyl hexanoate and d-limonene from yeast were 55 and 49 kJ/mol, respectively, under a wet condition. The formation rates of limonene oxide and carvone were slower in yeast than that of MD powder at 30 °C after 2 months.

Innovative crystal transformation of dihydrate trehalose to anhydrous trehalose using ethanol.

The crystal transformation of dihydrate trehalose to anhydrous trehalose was investigated using ethanol and a new type of crystal particle with porous structure could be obtained. The specific surface area of the anhydrous crystal transformed at 50 degrees C was 3.3 m(2)/g, with a median pore diameter of 0.21 microm, and void volume of 0.22 mL/g. The crystal transformation was monitored by measuring the crystal moisture content. The crystal transformation rates could be correlated with the Avrami equation, using the mechanism parameter n=11.5, suggesting that the change of surface area occurred during crystal transformation from dehydrate to anhydrous trehalose. The apparent activation energy of the crystal transformation was 132 kJ/mol.

Kinetics of molecular encapsulation of 1-methylcyclopropene into alpha-cyclodextrin.

1-methylcyclopropene (1-MCP), an ethylene inhibiting regulator, is commercially available in the form of an inclusion complex with alpha-cyclodextrin (alpha-CD). In this study, molecular encapsulation of gaseous 1-MCP into aqueous alpha-CD was investigated in a closed, agitated vessel with a flat gas-liquid interface. Molecular encapsulation of gaseous 1-MCP by alpha-CD is a simultaneous two-step reaction which involves the aqueous dissolution of gaseous 1-MCP and the encapsulation of the dissolved molecules by alpha-CD. The kinetics and mechanism of molecular encapsulation were analyzed based on the depletion rate of 1-MCP in the headspace of the vessel. The encapsulation rates could be explained quantitatively by the gas absorption theory with a pseudo-first-order reaction between 1-MCP and alpha-CD. The negative value of the calculated apparent activation energy of encapsulation (-24.4 kJ/mol) implied the significant effect of exothermic aqueous dissolution of 1-MCP. An encapsulation temperature of 15 degrees C was optimal; at this temperature, the highest 1-MCP yield and best inclusion ratio of inclusion complex were obtained. Changes in the X-ray diffraction pattern suggested that the crystal lattice structure of alpha-CD was altered upon inclusion of 1-MCP.

Controlled release of 1-methylcyclopropene from its functionalised electrospun fibres under constant and linearly ramped humidity.

The methodology to electrospin polystyrene (PS) fibres functionalised with the inclusion complex between 1-methylcyclopropene (1-MCP) and α-cyclodextrin (α-CD) has been developed successfully. Due to limited availability, α-CD crystals instead of 1-MCP/α-CD complex were suspended in the electrospinning (ES) solutions to investigate the ES process. The ES solutions were characterised in terms of viscosity, conductivity and surface tension. Meanwhile, the fibres were subjected to scanning electron microscopy. The average fibre diameter was proportional to approximately one-sixth power of the capillary number of the ES solution. Viscosity, which was a function of PS concentration and α-CD loading, was the main property that dictated the spin ability of the ES solutions. ES fibres with 1.5-4.4 µm in diameter were produced with 12.5-20.0% (w/w) PS in ES solution and an equal amount of the inclusion complex for PS. In the case of the ES solutions of 20 wt% PS loaded with the inclusion complex from 0 to 100% (w/w) to PS, all the ES solutions were electrospinnable with the average diameter ranging from 3.8 to 4.6 µm. X-ray diffractometry indicated that the α-CD crystals were homogeneously suspended on the fibre mats. Confocal laser scanning microscopy showed that the crystals were suspended on the fibre mats while being coated with a layer of PS. The complex-functionalised fibre was formed from the ES solution of 20% PS and 50% (w/w) inclusion complex with the ES. The release characteristics of 1-methylcyclopropene (1-MCP) from the functionalised fibre and the inclusion complex were investigated real time under linearly ramping humidity conditions at constant temperatures with a home-built humidity regulating system coupled with gas chromatography. The irregular release profiles were successfully modelled and the activation energies of release for the functionalised fibre and inclusion complex were about 128 and 69 kJ/mol, respectively..

Effect of water activity on the release characteristics and oxidative stability of D-limonene encapsulated by spray drying.

The stability of encapsulated D-limonene, which was prepared by spray drying, was studied in view of the release characteristics and oxidation stability. Gum arabic, soybean water-soluble polysaccharide, or modified starch, blended with maltodextrin were used as the wall materials. The powders were stored under the conditions of 23-96% relative humidity at 50 degrees C. The release rate and the oxidation rate were closely related to the relative humidity. The relationship was not simple. Initially, the release rate and the oxidation rate increased with increasing water activity, but around the glass transition temperature, the rates decreased sharply to increase again at a further increase of water activity. The results could be explained by a change in the powder structure, where a glass capsule matrix was changed into rubbery state during storage.

Encapsulation of alcohol dehydrogenase in mannitol by spray drying.

The retention of the enzyme activity of alcohol dehydrogenase (ADH) has been studied in various drying processes such as spray drying. The aim of this study is to encapsulate ADH in mannitol, either with or without additive in order to limit the thermal denaturation of the enzyme during the drying process. The retention of ADH activity was investigated at different drying temperatures. When mannitol was used, the encapsulated ADH was found inactive in all the dried powders. This is presumably due to the quick crystallization of mannitol during spray drying that resulted in the impairment of enzyme protection ability in comparison to its amorphous form. Maltodextin (dextrose equivalent = 11) was used to reduce the crystallization of mannitol. The addition of maltodextrin increased ADH activity and drastically changed the powder X-ray diffractogram of the spray-dried powders.

Micelle formation of coenzyme Q10 with dipotassium glycyrrhizate using inclusion complex of coenzyme Q10 with γ-cyclodextrin.

Micelles can be formed from coenzyme Q10 (CoQ10) and dipotassium glycyrrhizate (GZK2) by using an inclusion complex of CoQ10 with γ-cyclodextrin (γ-CD). The mechanism of micelle formation was kinetically investigated. Adding GZK2 to a supersaturated solution of the CoQ10/γ-CD inclusion complex led to a linear increase in the solubility of CoQ10 due to the formation of micelles of CoQ10 when the molar ratio of GZK2/γ-CD increased to ∼1.6, after which the concentration remained constant. The equilibrium constant K for micelle formation was 0.68 (-) and the ratio of GZK2 to CoQ10 was 1. These results suggest that the formation of CoQ10 micelles with GZK2 might proceed via the displacement of CoQ10 by GZK2 in the γ-CD cavity followed by the formation of CoQ10 micelles.

High-oil-load encapsulation of medium-chain triglycerides and D-limonene mixture in modified starch by spray drying.

UNLABELLED: Oil mixtures of medium-chain triglycerides (MCT) and D-limonene in mixing ratios from 10 to 100 wt% were encapsulated in modified starch (wall material) by spray drying to produce oil-rich powders. The oil load (mass ratio of oil mixture to wall material) of the infeed emulsion markedly influenced the properties of the infeed liquid and the characteristics of the resulting powder. The viscosity of the infeed liquid and the particle size of the powder exponentially decreased with increasing oil load, while the emulsion droplet size in the infeed liquid increased. In addition, retention of D-limonene during spray drying also decreased markedly with increasing oil load. Irrespective of the different oil loads and concentrations of the wall material, D-limonene retention was well correlated with the emulsion droplet diameter of the infeed liquid. The encapsulation efficiency of the oil mixture exhibited a maximum value (almost 100%) at an oil load between 0.5 and 1.0, before decreasing at higher oil loads. At an oil load of 2.0, the encapsulation efficiency of D-limonene was reduced to almost zero, while around 40% of the initial MCT was encapsulated in the powder. The increase in oil load also led to increased amounts of surface oil of MCT and D-limonene in the resulting powder due to the increasing emulsion droplet diameter of the infeed liquids. PRACTICAL APPLICATION: This study proposes the microencapsulation of medium-chain triglycerides under high-oil-load conditions by spray drying. The powders prepared by this process provide significant benefits in terms of rapid energy conversion after consumption without accumulation in the body. Important quality factors of the powder products such as the encapsulation efficiency and the amount of surface oil were examined to understand the optimum process conditions for spray drying.

Formation of a new crystalline form of anhydrous ß-maltose by ethanol-mediated crystal transformation.

ß-Maltose monohydrate was transformed into an anhydrous form by ethanol-mediated method under several temperatures with agitation. A new stable anhydrous form of ß-maltose (Mß(s)) was obtained, as substantiated by the X-ray diffraction patterns. Mß(s) obtained by this method presented a fine porous structure, resulting in greater specific surface area compared to those of ß-maltose monohydrate and anhydrous ß-maltose obtained by vacuum drying (Mß(h)). The crystal transformation presumably consisted of two steps: dehydration reaction from the hydrous to amorphous forms and crystal formation from the amorphous forms to the noble anhydrous form. The kinetics of these reactions were determined by thermal analysis using Jander's equation and Arrhenius plots. The overall activation energies of the dehydration reaction and the formation of anhydrous maltose were evaluated to be 100 and 90 kJ/mol, respectively.