Antioxidant microcapsule powder grease prepared by using mannose oligosaccharide as a filler, and preparation method and application thereof

Abstract

The application discloses antioxidant microcapsule powder grease prepared by taking mannose oligosaccharide as a filler, and a preparation method and application thereof, and belongs to the technical field of powder grease preparation. The application takes mannose oligosaccharide or a mixture of mannose oligosaccharide and maltodextrin as a filler, takes sodium caseinate as an emulsifier, and takes edible grease as core material, and then the microcapsule powder grease with high oxidation stability is prepared through high-speed dispersion, high-pressure homogenization and spray drying. The application further improves the stability of the grease, reduces the viscosity of the emulsion, and the provided preparation method can not only delay the oxidation and deterioration of the grease, but also endows the product with the intestinal target delivery function, and expands the application range of the product. Meanwhile, the introduction of the mannose oligosaccharide effectively improves the total solid concentration of the emulsion, and then reduces the subsequent drying cost. The microcapsule powder grease prepared by the application has more functions, higher total solid concentration of the emulsion, and has good application prospect and popularization value.

Description

Technical Field

[0001] This invention belongs to the field of powdered oil preparation technology, and particularly relates to an antioxidant microcapsule powdered oil prepared using mannan oligosaccharide as a filler, its preparation method and application. Background Technology

[0002] Powdered oils are products formed by encapsulating oils with a suitable wall material using emulsification technology, followed by drying. Spray drying is the most common and economical drying method. This form of product transforms liquid oil into a solid powder, facilitating transportation and storage. Compared to unencapsulated oils, powdered oils offer advantages such as improved oxidative stability and enhanced quality. They are currently widely used in formulated milk powders, beverages, seasonings, convenience foods, and functional foods, enabling target substances to function more stably and efficiently within the food system, thereby improving product quality.

[0003] Fillers play a crucial role in the spray-drying process for preparing powdered oils, improving encapsulation efficiency, enhancing drying properties (e.g., reducing wall adhesion and shortening drying time), and increasing product yield and flowability. However, conventional fillers such as maltodextrin (MD) suffer from limitations in functionality and protection of the core material. Mannooligosaccharides (MOS), hydrolyzed from mannan, exhibit significantly lower viscosity in water compared to mannan, and the increased number of hydroxyl groups after hydrolysis further enhances their antioxidant capacity. Furthermore, due to their unique chemical structure, mannooligosaccharides are difficult to break down in the stomach and upper small intestine, thus possessing intestinal-targeted delivery characteristics. This makes them an ideal filler with wide applications in the food and pharmaceutical industries.

[0004] However, no research has yet been found on the application of mannan oligosaccharides or mixtures thereof with maltodextrin as fillers in powdered oils. Summary of the Invention

[0005] Based on the above technical requirements, the purpose of this invention is to provide an antioxidant microcapsule powder oil prepared with mannan oligosaccharide as a filler, its preparation method and application. This invention further improves the oxidative stability of the powder oil by optimizing the preparation method of the microcapsule powder oil. The prepared microcapsule powder oil has intestinal targeted delivery function, which broadens its application and enables it to be more widely used in food and pharmaceuticals.

[0006] To achieve the above-mentioned objectives, the present invention employs the following technical solution:

[0007] This invention provides a method for preparing antioxidant microcapsule powder oil using mannan oligosaccharides as a filler, the method comprising the following steps:

[0008] (1) Using mannan oligosaccharide or a mixture of mannan oligosaccharide and maltodextrin as a filler, the filler, emulsifier and edible oil are mixed to obtain a mixed emulsion;

[0009] (2) The mixed emulsion is dispersed at high speed to obtain a crude emulsion;

[0010] (3) The crude emulsion is homogenized under high pressure to obtain a fine emulsion;

[0011] (4) The fine emulsion is spray-dried to prepare microcapsule powder oil.

[0012] Furthermore, in step (1), the average molecular weight of the mannan oligosaccharide is 300-600 Da, the filler accounts for 15-25% of the mass volume of the mixed emulsion, and a mixture of mannan oligosaccharide and maltodextrin is used as the filler, with the mass ratio of mannan oligosaccharide to maltodextrin being 1:3-3:1.

[0013] Furthermore, in step (1), the emulsifier includes sodium caseinate, and the emulsifier accounts for 2.5 to 7.5% of the mass of the mixed emulsion.

[0014] Furthermore, the edible oil includes tuna oil; the mass ratio of edible oil to filler in the mixed emulsion is 2~4:1~3; and the total solids concentration of the mixed emulsion is 40~65%.

[0015] Furthermore, the conditions for high-speed dispersion include: a rotational speed of 8000~14000 r / min and a dispersion time of 3~9 min.

[0016] Furthermore, the conditions for high-pressure homogenization include: a pressure of 150~500 bar and a homogenization cycle of 1~3 times.

[0017] Furthermore, the spray drying conditions include: an inlet air temperature of 140~180℃, a feed rate of 2~6 mL / min, an atomization pressure of 0.1~0.5 MPa, and an inlet air velocity of 5~9 m / min. 3 / min.

[0018] Furthermore, the mass ratio of mannan oligosaccharide to maltodextrin is 2:1, the mass percentage of sodium caseinate is 5%, the mass ratio of edible oil to filler is 3:2, the total solids concentration is 60%, the high-speed dispersion conditions include: rotation speed 12000 r / min, high-speed dispersion for 7 min, the high-pressure homogenization conditions include: pressure 300 bar, homogenization twice; the spray drying conditions include: setting the inlet air temperature to 150℃, the feed rate to 2 mL / min, and the inlet air velocity to 8 m³ / s.

[0019] The present invention also provides an antioxidant microcapsule powder oil prepared by the aforementioned preparation method.

[0020] Furthermore, the microcapsule powder oil is milky white and has no obvious fishy smell.

[0021] The present invention also provides the application of the aforementioned antioxidant microcapsule powder oil in the preparation of formulations that improve the oxidative properties of oils or enhance intestinal targeted delivery performance.

[0022] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0023] 1. This invention uses mannan oligosaccharides, which have antioxidant properties and intestinal-targeted delivery capabilities, to replace part of the maltodextrin as a filler to prepare powdered oils, thereby improving the stability of the oils and giving the prepared powdered oils certain antioxidant and intestinal-targeted delivery capabilities, thus broadening their application scope in food and pharmaceuticals.

[0024] 2. The oil microcapsule powder prepared by the present invention with mannan oligosaccharide or its combination with maltodextrin as filler has a simple and easy preparation process, readily available materials, and requires no special treatment. Moreover, the addition of mannan oligosaccharide during emulsion preparation can effectively reduce the viscosity of the emulsion, thus significantly increasing the total solids concentration of the emulsion and effectively reducing the subsequent drying cost.

[0025] 3. The mannan oligosaccharide production process involved in this invention is mature and can be produced on a large scale. The processing is simple and does not involve pH adjustment, heating or enzymatic hydrolysis. Existing production lines can meet the processing requirements without the need to replace or add equipment. It can be produced on a large scale to meet the new market demand for powdered oils. Attached Figure Description

[0026] Figure 1 The viscosities of five mannan oligosaccharides with different purities and average molecular weights and maltodextrin at different concentrations were measured, where A was at a concentration of 10%, B at a concentration of 20%, and C at a concentration of 30%.

[0027] Figure 2 DSC curves of five mannooligosaccharides with different purities and average molecular weights and maltodextrin.

[0028] Figure 3 DPPH free radical scavenging rates of five mannooligosaccharides with different purities and average molecular weights and maltodextrin.

[0029] Figure 4 The changes in peroxide value (POV) and malondialdehyde (MDA) content of powdered oils prepared with three kinds of mannan oligosaccharides and maltodextrin as fillers in accelerated oxidation experiments are shown in A, where A represents the change in POV and B represents the change in MDA.

[0030] Figure 5 The effect of the polysaccharide ratio in the filler on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0031] Figure 6 The effect of protein addition on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0032] Figure 7 The effect of fish oil addition on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0033] Figure 8 The effect of total solids concentration on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0034] Figure 9 The effect of high-speed dispersion rotation on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0035] Figure 10 The effect of high-speed dispersion time on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0036] Figure 11 The effects of high-pressure homogenization pressure on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0037] Figure 12 The effects of high-pressure homogenization cycles on the viscosity, particle size, and particle size change rate of tuna oil emulsion, where A represents viscosity change and B represents particle size change.

[0038] Figure 13 Appearance of tuna oil emulsions prepared with different fillers.

[0039] Figure 14 Kinematic viscosity changes of tuna oil emulsions prepared with different fillers during 48 h of storage.

[0040] Figure 15 Shear viscosity variation curves of tuna oil emulsions prepared with different fillers.

[0041] Figure 16 DPPH free radical scavenging rate of tuna oil emulsions prepared with different fillers.

[0042] Figure 17Appearance images of tuna oil powder prepared with different fillers, where A is the appearance image of tuna oil powder prepared in Example 16, B is the appearance image of oil powder corresponding to Comparative Example 1, and C is the appearance image of oil powder corresponding to Comparative Example 2.

[0043] Figure 18 Microstructure diagrams of tuna oil powder prepared with different fillers.

[0044] Figure 19 The changes in POV and MDA of tuna oil powder prepared with different fillers in accelerated oxidation test, where A represents the change in POV and B represents the change in MDA. Detailed Implementation

[0045] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0046] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the experimental materials, reagents, and instruments used in the following examples are all commercially available products.

[0047] The mass-volume percentage mentioned in this invention includes the mass-volume percentage of filler in the mixed emulsion, with the mass unit being g and the volume unit being mL.

[0048] Example 1

[0049] This embodiment provides the performance characteristics of mannooligosaccharides with different molecular weights, specifically including the following:

[0050] This embodiment compares the physicochemical properties of five commercially available mannooligosaccharides (MOS) with maltodextrin (MD). No. 1 is maltodextrin, and Nos. 2-6 are mannooligosaccharides produced by different manufacturers, with a minimum purity of 90% and varying molecular weights. Their purity and molecular weight are shown in Table 1.

[0051] Table 1. Purity and average molecular weight of five mannooligosaccharides

[0052]

[0053] 1. Viscosity determination: A certain amount of mannan oligosaccharide or maltodextrin powder was dissolved in water to form aqueous solutions with mass concentrations of 10%, 20%, and 30%, respectively. The solutions were stirred at room temperature until completely dissolved, and their kinematic viscosity was measured using a Pinwitz viscometer. Different mass concentrations were obtained: 10% ( Figure 1 (A) 20% Figure 1 (B) 30% Figure 1 The viscosity change corresponding to C).

[0054] from Figure 1 As can be seen, sample 3 maintains a low viscosity at low, medium, and high concentrations. Furthermore, as the sample concentration increases, the viscosity of the MD solution is significantly higher than that of the other five mannooligosaccharide samples.

[0055] 2. Determination of solubility: Approximately 0.5 g (m1) of powder was dispersed in deionized water and magnetically stirred for 20 min. The residue (m2) was then collected by filtration, heated to constant weight at 105°C, and weighed. The solubility of the powder in water was then calculated according to the formula, as shown in Table 2.

[0056]

[0057] Table 2. Solubility of five mannooligosaccharide samples and maltodextrin in water

[0058]

[0059] Table 2 shows that samples No. 2 and No. 6 have the best solubility in water, and both are better than maltodextrin, laying the foundation for the subsequent preparation of powdered oils with good solubility.

[0060] 3. Determination of glass transition temperature (Tg): Weigh 3-6 mg of powder into an aluminum crucible, use nitrogen as a protective gas, set the heating rate to 10 °C / min, and measure its DSC curve in the range of 25 °C to 300 °C to analyze the glass transition temperature. Figure 2 DSC curves for 6 powders, based on Figure 2 The glass transition temperature (Tg) was obtained, as shown in Table 3.

[0061] Table 3 Glass transition temperatures (Tg) of five mannooligosaccharide samples and maltodextrin

[0062]

[0063] Table 3 shows that the glass transition temperature of sample 2 is closest to that of maltodextrin. An excessively high glass transition temperature can lead to poor film-forming properties of the wall material and increased drying energy consumption.

[0064] 4. Determination of DPPH free radical scavenging rate: A certain amount of mannan oligosaccharide and maltodextrin powder were placed in a test tube to form a 10% solution. The solution was stirred at room temperature until completely dissolved in water. 0.5 mL of the solution was placed in a test tube, and 2.4 mL of 0.1 mmol / L DPPH solution and 1.1 mL of deionized water were added to the test tube respectively. After mixing thoroughly, the solution was stored in the dark for 30 min. The absorbance was measured at 517 nm using a UV spectrophotometer. The free radical scavenging rate is shown below. Figure 3 As shown.

[0065] from Figure 3 It can be seen that the DPPH free radicals of mannan oligosaccharides are higher than those of maltodextrin, and sample No. 2 has the best DPPH free radical scavenging effect.

[0066] In summary, mannan oligosaccharide samples No. 2, 3, and 6 were selected as fillers to prepare tuna oil powder for further screening.

[0067] Example 2

[0068] This embodiment provides a method for preparing powdered oils using mannan oligosaccharides and maltodextrin as fillers, specifically including the following:

[0069] Mannooligosaccharides No. 2, 5, and 6, and maltodextrin were used as fillers for wall materials, respectively; sodium caseinate was used as an emulsifier, with a filler-to-emulsifier mass ratio of 9:1. Tuna oil was then added at a core-to-wall ratio (i.e., tuna oil to filler mass ratio) of 2:3. The theoretical oil content of the final powdered oil was 40%, and the total solids concentration was 40%, resulting in a mixed emulsion. This mixed emulsion was dispersed at 12000 r / min for 5 min using a high-speed disperser to obtain a crude tuna oil emulsion. The crude tuna oil emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to obtain a fine emulsion, which was then spray-dried. The inlet air temperature was set to 160 °C, the air velocity to 5 m³ / min, and the feed rate to 3 mL / min for spray drying.

[0070] Figure 4 This shows the changes in peroxide value (POV) and malondialdehyde (MDA) content of powdered oils prepared with different fillers during accelerated oxidation tests. Figure 4 In sample A, it is clearly observed that the POV value of manno-oligosaccharide sample No. 2 reached its peak value the longest, and the peak value was much lower than that of maltodextrin and the other two manno-oligosaccharide samples. Figure 4 In sample B, the MDA value varied with the POV value, and sample 2 maintained a relatively low MDA value compared to the other samples. This further indicates that mannooligosaccharides with an average molecular weight of 300-600 are more suitable as fillers for preparing powdered oils.

[0071] Therefore, sample No. 2 of mannooligosaccharide was selected as a filler for further research.

[0072] Example 3

[0073] Based on the determination of the average molecular weight range of mannan oligosaccharides in Example 2, this example further investigates the effect of the mass ratio of mannan oligosaccharides to maltodextrin on the viscosity and particle size of tuna oil fine emulsions.

[0074] Mannooligosaccharides and maltodextrin were used as wall materials, with mass ratios of mannooligosaccharides to maltodextrin set at 3:1, 2:1, 1:1, 1:2, and 1:3, respectively. These were then mixed with sodium caseinate, followed by tuna oil, and thoroughly mixed to obtain a mixed emulsion. The mass percentage of filler in the mixed emulsion was 17.5% (w / v), and the mass percentage of sodium caseinate was 2.5% (wt%). Tuna oil was added at a core-to-wall ratio of 2:3 to achieve a theoretical oil loading of 40%. The above mixed emulsion was dispersed at 12000 r / min for 5 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity was obtained (…). Figure 5 As shown in Figure A), particle size ( Figure 5 (as shown in B) and the 24-hour particle size change rate ( Figure 5 (As shown in B).

[0075] from Figure 5 The results show that when the mass ratio of mannan oligosaccharide to maltodextrin is 2:1, the particle size and particle size change rate are relatively low, indicating good stability and low viscosity, which is more conducive to subsequent spray drying.

[0076] Example 4

[0077] This embodiment demonstrates the effect of different mass concentrations of sodium caseinate on the viscosity and particle size of tuna oil fine emulsions.

[0078] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mass-volume percentage of the wall material (filler) in the mixed emulsion was maintained at 20% (w / v). The mass percentages of sodium caseinate were set to 2.5%, 5%, 7.5%, 10%, and 12.5% ​​(wt%). Tuna oil was added at a core-to-wall ratio of 2:3 to achieve a theoretical oil loading of 40%. The above mixed emulsion was dispersed at 12000 r / min for 5 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity ( ) was obtained. Figure 6 As shown in Figure A), particle size ( Figure 6 (as shown in B) and the 24-hour particle size change rate ( Figure 6 (As shown in B).

[0079] The stability of an emulsion is closely related to the concentration of the emulsifier; both excessively high and low emulsifier concentrations are detrimental to emulsion stability. For example... Figure 6As shown, the emulsion viscosity increases significantly with the increase of sodium caseinate concentration. When the mass concentration of sodium caseinate is 5%, the particle size and particle size change rate are low, indicating good stability and low viscosity, which is more conducive to subsequent spray drying.

[0080] Example 5

[0081] This embodiment demonstrates the effect of different oil loadings in the emulsion on the viscosity and particle size of tuna oil fine emulsions.

[0082] Mannooligosaccharides and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharides to maltodextrin of 2:1. These were mixed with sodium caseinate, and then tuna oil was added and thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-volume percentage of 20% (w / v) and a sodium caseinate mass percentage of 5% (wt%). Tuna oil was added at core-to-wall ratios (i.e., the mass ratio of tuna oil to wall material) of 3:7, 2:3, 1:1, 3:2, and 7:3 to achieve theoretical oil loadings of 30%, 40%, 50%, 60%, and 70%, respectively. The above mixed emulsion was dispersed at 12000 r / min for 5 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity ( ) was obtained. Figure 7 As shown in Figure A), particle size ( Figure 7 (as shown in B) and the 24-hour particle size change rate ( Figure 7 (As shown in B).

[0083] from Figure 7 It can be seen that as the theoretical oil loading increases, the emulsion viscosity increases, and when the theoretical oil loading is 60%, the particle size and particle size change rate are low, indicating that the stability is good under this condition.

[0084] Example 6

[0085] This embodiment provides the effect of different oil loadings in the mixed emulsion on the viscosity and particle size of the prepared tuna oil fine emulsion.

[0086] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mass percentage of sodium caseinate in the mixed emulsion was 5% (wt%), and the mass-volume percentage of the wall material in the mixed emulsion was maintained at 20% (w / v). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve total solids concentrations of 40%, 50%, 60%, 70%, and 80%, respectively, while maintaining the proportions of each component. The above mixed emulsion was dispersed at 12000 r / min for 5 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity ( ) was obtained. Figure 8 As shown in Figure A), particle size ( Figure 8 (as shown in B) and the 24-hour particle size change rate ( Figure 8 (As shown in B).

[0087] from Figure 8 The results show that the emulsion viscosity increases with increasing total solids concentration, and begins to surge when the total solids concentration reaches 80%. At total solids concentrations of 50% and 60%, the particle size is relatively small, and the particle size change rate is the lowest, indicating the best emulsion stability. To improve the efficiency of subsequent spray drying, a total solids concentration of 60% was selected for subsequent experiments.

[0088] Example 7

[0089] This embodiment demonstrates the effect of different high-speed dispersion rotation speeds on the viscosity and particle size of the prepared tuna oil microemulsion.

[0090] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-to-volume percentage of 24% (w / v) and a sodium caseinate mass-to-volume percentage of 5% (wt%). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60% and a total solids concentration of 60%. The above mixed emulsion was dispersed at high speeds of 8000, 10000, 12000, 14000, and 16000 r / min for 5 min to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity ( ) was obtained. Figure 9 As shown in Figure A), particle size ( Figure 9 (as shown in B) and the 24-hour particle size change rate ( Figure 9 (As shown in B).

[0091] from Figure 9It can be seen that when the high-speed disperser speed is 12000 r / min, the emulsion system is relatively stable, with low particle size and particle size change rate, and low viscosity, which is more conducive to subsequent spray drying.

[0092] Example 8

[0093] This embodiment demonstrates the effect of different high-speed dispersion times on the viscosity and particle size of the prepared tuna oil microemulsion.

[0094] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-volume percentage of 24% (w / v) and a sodium caseinate mass percentage of 5% (wt%). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60%. The above mixed emulsion was dispersed at 12000 r / min for 1 min, 3 min, 5 min, 7 min, and 9 min respectively to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 600 bar using a high-pressure homogenizer to prepare a fine emulsion. The viscosity ( ) was obtained. Figure 10 (A) Particle size ( Figure 10 (B) and 24 h particle size change rate ( Figure 10 (B)

[0095] from Figure 10 The results show that when the high-speed dispersion time is 7 min and 9 min, the particle size and particle size change rate are relatively low, indicating good stability and low viscosity, which is more conducive to subsequent spray drying. The high-speed dispersion time of 7 min requires less time and consumes less energy, so this time was used for subsequent experiments.

[0096] Example 9

[0097] This embodiment demonstrates the effect of different pressure homogenization conditions on the viscosity and particle size of the prepared tuna oil fine emulsion.

[0098] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-to-volume percentage of 24% (w / v) and a sodium caseinate mass-to-volume percentage of 5% (wt%). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60%. The above mixed emulsion was dispersed at 12000 r / min for 7 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice using a high-pressure homogenizer at 150 bar, 300 bar, 450 bar, 600 bar, and 750 bar to prepare a fine emulsion. The viscosity (…) was obtained. Figure 11 (A) Particle size ( Figure 11 (B) and 24 h particle size change rate ( Figure 11 (B)

[0099] Excessive homogenization pressure can reduce the particle size of the emulsion, but this is detrimental to the stability of the emulsion system. Figure 11 It can be seen that when the homogenization pressure is 300 bar, the particle size and particle size change rate are low, indicating good stability and low viscosity, which is more conducive to subsequent spray drying.

[0100] Example 10

[0101] This embodiment demonstrates the effect of homogenization times on the viscosity and particle size of the prepared tuna oil fine emulsion.

[0102] Mannooligosaccharide and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharide to maltodextrin of 2:1. These were then mixed with sodium caseinate, and tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-to-volume percentage of 24% (w / v) and a sodium caseinate mass-to-volume percentage of 5% (wt%). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60%. The above mixed emulsion was dispersed at 12000 r / min for 7 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized at 300 bar for 1, 2, 3, 4, and 5 times to prepare a fine emulsion. The viscosity (…) was obtained. Figure 12 (A) Particle size ( Figure 12 (B) and 24 h particle size change rate ( Figure 12 (B)

[0103] Excessive homogenization can reduce the particle size of the emulsion, but this is detrimental to the stability of the emulsion system. Figure 12 It can be seen that when the homogenization is repeated twice, the particle size and particle size change rate are low, indicating good stability and low viscosity, which is more conducive to subsequent spray drying.

[0104] Example 11

[0105] This embodiment provides the unique advantages of using mannan oligosaccharides as a filler for the prepared tuna oil fine emulsion.

[0106] In this embodiment, mannooligosaccharides, maltodextrin, and a composite filler (mannooligosaccharides:maltodextrin = 2:1) were used as fillers, mixed with sodium caseinate, and then tuna oil was added and thoroughly mixed to obtain a mixed emulsion. The mass-volume percentage of the filler in the mixed emulsion was 24% (w / v), the mass percentage of sodium caseinate was 5% (wt%), and tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60%. The above mixed emulsion was dispersed at 12000 r / min for 7 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 300 bar using a high-pressure homogenizer to prepare a fine emulsion. The appearance of the obtained fine emulsion is as follows. Figure 13 As shown.

[0107] 1. Calculate the change curve of kinematic viscosity of tuna oil fine emulsion during 48 h of storage using a Pints ​​viscometer. Figure 14 ).

[0108] like Figure 14 As shown, the fresh emulsion using maltodextrin as a single filler has a high kinematic viscosity, and its viscosity changes significantly after a period of time. The emulsion using manno-oligosaccharides as a single filler, or with a composite filler of manno-oligosaccharides and maltodextrin, has a much lower viscosity than the emulsion using maltodextrin as a single filler. This phenomenon indicates that manno-oligosaccharides, as a filler, have the effect of reducing emulsion viscosity during the preparation of powdered oils. In the spray drying process, a lower emulsion viscosity is beneficial for accelerating water evaporation, shortening drying time, improving the quality of the finished powdered oil, reducing wall adhesion, and increasing yield. After 48 hours, the kinematic viscosity of the emulsion using manno-oligosaccharides as a filler changes little, indicating that the addition of manno-oligosaccharides results in good physical stability. In actual production, this leads to high feed consistency, small product variability, and eliminates the need for on-the-spot preparation processes, effectively reducing costs.

[0109] 2. The tuna oil microemulsions prepared with the three carriers were placed on the sample stage of an interfacial rheometer. PP50 plates were used, and the plate spacing was set to 0.2 mm. The shear viscosity of the complex was measured (shear rate set to 0.1~100 s⁻¹). -1 The shear viscosity curve of the complex was measured.

[0110] like Figure 15As shown, at low shear rates, the tuna oil emulsion using manno-oligosaccharide-maltodextrin composite filler has a higher viscosity than that using maltodextrin alone, indicating greater stability during storage. However, as the shear rate increases, the tuna oil emulsions using both manno-oligosaccharide-maltodextrin composite filler and single-manno-oligosaccharide filler show lower viscosity, indicating better flowability when pumped into spray drying equipment, which is beneficial for the preparation of powdered oils.

[0111] 3. Take 0.5 mL of each of the three carrier tuna oil fine emulsions into different test tubes. Add 2.4 mL of 0.1 mmol / L DPPH solution and 1.1 mL of deionized water to each test tube, mix well, and store in the dark for 30 min. Measure the absorbance at 517 nm using a UV spectrophotometer. The free radical scavenging rate is as follows: Figure 16 As shown.

[0112] from Figure 16 It can be seen that the DPPH free radical scavenging rate of tuna oil microemulsions with mannooligosaccharide-maltodextrin composite filler and single mannooligosaccharide filler is higher than that of tuna oil microemulsions with single maltodextrin filler.

[0113] Example 12

[0114] This embodiment demonstrates the effect of different inlet air temperatures on the surface oil, total oil, and yield of tuna oil powder during spray drying.

[0115] Mannooligosaccharides and maltodextrin were used as wall materials, with a mass ratio of mannooligosaccharides to maltodextrin of 2:1. These were mixed with sodium caseinate, and then tuna oil was added. The mixture was thoroughly mixed to obtain a mixed emulsion. The mixed emulsion maintained a wall material mass-volume percentage of 24% (w / v) and a sodium caseinate mass percentage of 5% (wt%). Tuna oil was added at a core-to-wall ratio of 3:2 to achieve a theoretical oil loading of 60%. The mixed emulsion was dispersed at 12000 r / min for 7 min using a high-speed disperser to prepare a crude tuna oil emulsion. The crude emulsion was then homogenized twice at 300 bar using a high-pressure homogenizer to prepare a fine emulsion. The fine emulsion was then spray-dried to obtain tuna oil powder with mannooligosaccharides and maltodextrin as fillers.

[0116] The spray drying specifically includes: setting the inlet air temperature to 130, 140, 150, 160, and 170°C respectively, the feed rate to 3 mL / min, the physicochemical pressure to 0.1 MPa, and the spray drying process to 5 m... 3 Spray drying was performed at an inlet air velocity of / min, with the remaining processes remaining the same. The table below shows the surface oil, total oil, and yield data of the tuna oil powder prepared in this example.

[0117] Table 4. Effect of inlet air temperature on surface oil, total oil, and yield of tuna oil powder with mannan oligosaccharide as filler.

[0118]

[0119] When the inlet air temperature is 150 °C, the oil content on the powder surface is significantly lower than other levels, at 4.93%, while the oil loading is higher than other levels, at 46.92%, resulting in the highest final yield of 15.99%. Therefore, 150 °C is selected as the optimal inlet air temperature.

[0120] Example 13

[0121] This embodiment demonstrates the effect of different feed rates in spray drying on the surface oil, total oil, and yield of tuna oil powder.

[0122] The main difference between this implementation and Example 12 is that the feed rate in the spray drying is set to 1, 2, 3, 4, and 5 mL / min, respectively, at 150 °C, 0.1 MPa physicochemical pressure, and 5 m 3 Spray drying was performed at an air inlet velocity of / min, with the remaining processes remaining the same. The table below shows the surface oil, total oil, and yield data of the tuna oil powder prepared in this example using mannan oligosaccharides and maltodextrin as fillers.

[0123] Table 5. Effects of feed rate on surface oil, total oil, and yield of tuna oil powder with mannan oligosaccharide as filler.

[0124]

[0125] When the feed rate is 2 mL / min, the oil content on the powder surface is significantly lower than other levels, at 3.86%, while the oil loading is higher than other levels, at 50.97%, resulting in the highest final yield of 26.27%. Therefore, 2 mL / min is selected as the optimal feed rate.

[0126] Example 14

[0127] This embodiment demonstrates the effect of different air inlet velocities on the surface oil, total oil, and yield of tuna oil powder during spray drying.

[0128] The main difference between this implementation and Example 12 is that the inlet air velocity was set to 5, 6, 7, 8, and 9 m³ / min during spray drying, and spray drying was carried out at 150 °C, 0.1 MPa physicochemical pressure, and a feed rate of 2 mL / min. The remaining processes are the same. The table below shows the surface oil, total oil, and yield data of the tuna oil powder with mannan oligosaccharides as a filler prepared in Example 14.

[0129] Table 6. Effect of air inlet velocity on surface oil, total oil, and yield of tuna oil powder with mannan oligosaccharide as filler.

[0130]

[0131] When the air inlet velocity is 8 m³ / min, the powder surface oil content is lower than other levels at 9.44%, and the oil load is higher than other levels at 56.45%, resulting in the highest final yield of 29.83%. Therefore, 8 m³ / min is selected as the optimal air inlet velocity.

[0132] Example 15

[0133] This embodiment demonstrates the effect of different oil loadings on the surface oil, total oil, and yield of tuna oil powder.

[0134] The main difference between this implementation and Example 12 is that the theoretical oil loading is set to 50%, 55%, 60%, 65%, and 70% respectively, while the remaining process parameters, including total solids concentration, filler, and protein ratio, remain unchanged. The prepared fine emulsion was spray-dried at 150 °C, 0.1 MPa physicochemical pressure, 2 mL / min feed rate, and 8 m³ / min air inlet velocity. The table below shows the surface oil, total oil, and yield data of the tuna oil powder with mannan oligosaccharides as filler prepared in Example 15 of this invention.

[0135] Table 7. Effect of oil loading on surface oil, total oil, and yield of tuna oil powder with mannan oligosaccharide as filler.

[0136]

[0137] When the oil loading is 60%, the oil content on the powder surface is lower than other levels, at 4.48%, and the final yield reaches the highest value of 26.27%. In summary, 60% is selected as the optimal oil loading.

[0138] Example 16

[0139] Based on the process optimization of tuna oil powder provided in Examples 1-15, this example provides the optimal process for tuna oil powder, specifically including the following:

[0140] 1. Mannooligosaccharide and maltodextrin are used as wall materials (fillers). The mass ratio of mannooligosaccharide to maltodextrin is 2:1. They are mixed with sodium caseinate and then tuna oil is added. The mixture is thoroughly mixed to obtain a mixed emulsion. The mass-volume ratio of the wall material in the mixed emulsion is maintained at 24% (w / v), and the mass percentage of sodium caseinate is 5% (wt%). Tuna oil is added at a core-to-wall ratio of 3:2 to make the theoretical oil loading capacity 60%.

[0141] 2. The above mixed emulsion was dispersed at 12000 r / min for 7 min using a high-speed disperser to prepare a crude tuna oil emulsion.

[0142] 3. The crude emulsion is homogenized twice at 300 bar using a high-pressure homogenizer to prepare a fine emulsion. The fine emulsion is then spray-dried. During the spray-drying process, the inlet air temperature is set to 150 °C, the feed rate is 2 mL / min, the physicochemical pressure is 0.1 MPa, and the spray drying time is 8 m. 3 Spray drying is performed at an air intake speed of / s.

[0143] A tuna oil powder with mannan oligosaccharide-maltodextrin as a filler was prepared. It was milky white and had no obvious fishy odor. The powdered oil appeared as follows: Figure 17 As shown in Figure A.

[0144] Example 17

[0145] This embodiment provides two comparative examples and uses the method of Example 16 to prepare powdered oils.

[0146] Comparative Example 1

[0147] The difference between this comparative example and Example 16 is that the filler consists only of maltodextrin, while the raw materials and other preparation steps are the same as in Example 16. A tuna oil powder with maltodextrin as the filler is obtained; it is a milky white powder with a slight fishy odor. The powder appears as follows: Figure 17 As shown in B.

[0148] Comparative Example 2

[0149] The difference between this comparative example and Example 16 is that the filler consists only of mannooligosaccharides, while the raw materials and other preparation steps are the same as in Example 16. A tuna oil powder with mannooligosaccharides as the filler was obtained; it was a milky white powder with no obvious fishy odor. The powdered oil appeared as follows... Figure 17 As shown in C.

[0150] Example 18

[0151] In this embodiment, the microstructure, oil loading, surface oil content, encapsulation efficiency, moisture content, solubility, rehydration, dispersibility, flowability, storage stability (temperature), and cumulative release rate in simulated gastric and intestinal fluids of the tuna oil powder prepared in Examples 16-17 were measured.

[0152] 1. Microstructure of powdered oils

[0153] Figure 18The differences in surface morphology of microcapsules with different fillers were depicted. Powdered oils prepared with single maltodextrin and single mannooligosaccharide as fillers exhibited obvious wrinkles and depressions on the surface. In contrast, powdered oils prepared with a mannooligosaccharide-maltodextrin composite filler showed superior protective effects, with relatively mild surface depressions and wrinkles, and no hollow microcapsules were observed.

[0154] 2. Oil loading capacity, surface content, and yield of powdered greases

[0155] Table 8. Effects of different fillers on oil loading, surface saturation content, and yield of powdered oils

[0156]

[0157] Table 8 lists the oil loading, surface oil content, and yield of the powdered greases. Compared to powdered greases prepared with a single filler, powdered greases prepared with composite fillers exhibited a lower surface oil content, reaching 4.48%. Furthermore, both total oil and yield reached the highest values.

[0158] 3. Flowability of powdered grease

[0159] Table 9. Effects of different fillers on the bulk density, tap density, Karl Fischer index, and angle of repose of powdered grease.

[0160]

[0161] Table 9 lists the measured values ​​of bulk density, tap density, Karl Fischer index, and angle of repose for the powdered greases. Compared to powdered greases prepared with a single filler, powdered greases prepared with composite fillers exhibited a lower Karl Fischer index, reaching a minimum of 29.24%. Furthermore, powdered greases prepared with composite fillers showed a relatively larger angle of repose. The angle of repose for all powdered greases did not exceed 50°, indicating that they all possessed good flowability.

[0162] 4. Effect of accelerated oxidation test on the stability of powdered oils

[0163] Accelerated oxidation experiments were conducted on powdered oils with three different fillers to determine their peroxide value (POV) and malondialdehyde (MDA) content. The microcapsule powdered oil prepared with mannan oligosaccharide-maltodextrin as filler was designated as MOS+MD, the microcapsule powdered oil prepared with mannan oligosaccharide as filler was designated as MOS, and the microcapsule powdered oil prepared with maltodextrin as filler was designated as MD.

[0164] The microcapsule powdered oil, prepared by spray drying, was placed in a 50°C oven in the dark to test its oxidative stability. The changes in peroxide value (POV) and malondialdehyde (MDA) content of the powdered oil were measured at 0, 1, 3, 5, 7, and 9 days. The results are as follows: Figure 19 As shown.

[0165] Depend on Figure 19 As shown in Table A, the peroxide values ​​of the three powdered oils all exhibit a trend of first increasing and then decreasing. Combined with Table 8, Comparative Examples 1-2 have higher surface oil content, leading to rapid accumulation of peroxide value during the accelerated oxidation experiment, resulting in a higher initial peroxide value. Compared to powdered oils prepared using mannan oligosaccharides as a filler, the powdered oils prepared with maltodextrin as the sole filler show a faster rate of peroxide value increase and a higher peak value, indicating that mannan oligosaccharides play a positive role in delaying rancidity and improving oxidative stability of powdered oils.

[0166] Depend on Figure 19 As shown in Figure B, the malondialdehyde (MDA) content of the three powdered oils showed an increasing trend. Due to the secondary metabolites of MDA oxidation, its content was low in the initial stage of the accelerated oxidation experiment, but gradually increased with the accumulation of these metabolites, while the peroxide value began to decrease. The powdered oil using mannan oligosaccharides as a filler had a lower MDA content than the powdered oil using maltodextrin as a filler, and the rate of increase was slower. Figure 19 The results in option A are consistent, indicating that adding mannan oligosaccharides during the preparation of powdered oils has a positive effect on inhibiting the oxidation of powdered oils.

[0167] 5. Release rates of tuna oil powders prepared with different fillers in simulated gastric and intestinal fluids.

[0168] Table 10 Release rates of tuna oil powder prepared with different fillers in simulated gastric and intestinal fluids.

[0169]

[0170] Table 10 shows the release rates of tuna oil powder prepared with different fillers in simulated gastric and intestinal fluids. Tuna oil powder with maltodextrin as a filler showed moderate release in gastric fluid; tuna oil powder with mannan oligosaccharides as a filler was very stable in gastric fluid, but its absorption efficiency was relatively low; tuna oil powder prepared with a composite filler combined the anti-gastric acid properties of mannan oligosaccharides with the high digestibility of maltodextrin, achieving a balance between slow release in the stomach and efficient release in the intestines.

[0171] In summary, the tuna oil powder prepared with mannooligosaccharides as a filler exhibits significantly improved antioxidant properties, effectively delaying oil oxidation. Furthermore, the addition of mannooligosaccharides during powder preparation demonstrated a significant reduction in emulsion viscosity, positively impacting oil quality and spray drying efficiency. Traditional powdered oils suffer from poor antioxidant properties and short shelf life; their high viscosity during emulsion preparation hinders subsequent spray drying, forcing a reduction in solids content or oil loading. Compared to powdered oils using maltodextrin as a filler, the powdered oil with mannooligosaccharides as a filler shows significantly improved viscosity and better oxidative stability. Simultaneously, simulated gastrointestinal fluid accumulation and release rates demonstrate its targeted delivery capability.

[0172] This invention utilizes the antioxidant properties and reluctance to decompose in gastric juices of mannan oligosaccharides to improve the oxidative stability of tuna oil in microencapsulated powder and enhance the targeted delivery of the powdered oil. This method for improving the oxidative stability of tuna oil powder is simple, convenient, and shows promising application prospects in both food and pharmaceutical processing.

[0173] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or make equivalent substitutions for some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.

Claims

1. A method for preparing antioxidant microcapsule powder oils using mannan oligosaccharides as a filler, characterized in that, The method includes the following steps: (1) Using mannan oligosaccharide or a mixture of mannan oligosaccharide and maltodextrin as a filler, the filler, emulsifier and edible oil are mixed to obtain a mixed emulsion; (2) The mixed emulsion is dispersed at high speed to obtain a crude emulsion; (3) The crude emulsion is homogenized under high pressure to obtain a fine emulsion; (4) The fine emulsion is spray-dried to prepare microcapsule powder oil.

2. The method according to claim 1, characterized in that, The average molecular weight of the mannan oligosaccharide in step (1) is 300~600 Da, the mass ratio of the mannan oligosaccharide to maltodextrin is 1:3~3:1, and the filler accounts for 15~25% of the mass volume of the mixed emulsion.

3. The method according to claim 2, characterized in that, In step (1), the emulsifier includes sodium caseinate, and the emulsifier accounts for 2.5 to 7.5% of the mass of the mixed emulsion.

4. The method according to claim 1, characterized in that, The edible oil includes tuna oil; the mass ratio of edible oil to filler in the mixed emulsion is 2~4:1~3; the total solids concentration of the mixed emulsion is 40~65%.

5. The method according to claim 1, characterized in that, The conditions for high-speed dispersion include: a rotation speed of 8000~14000 r / min and a dispersion time of 3~9 min.

6. The method according to claim 1, characterized in that, The conditions for high-pressure homogenization include: a pressure of 150~500 bar and a homogenization frequency of 1~3 times.

7. The method according to claim 1, characterized in that, The spray drying conditions include: inlet air temperature of 140~180℃, feed rate of 2~6 mL / min, atomization pressure of 0.1~0.5 MPa, and inlet air velocity of 5~9 m / min. 3 / min.

8. The method according to any one of claims 1 to 7, characterized in that, The mass ratio of mannan oligosaccharide to maltodextrin is 2:1, the mass percentage of sodium caseinate is 5%, the mass ratio of edible oil to filler is 3:2, the total solids concentration is 60%, the high-speed dispersion conditions include: rotation speed 12000 r / min, high-speed dispersion for 7 min, the high-pressure homogenization conditions include: pressure 300 bar, homogenization twice; the spray drying conditions include: inlet air temperature set at 150℃, feed rate at 2 mL / min, and inlet air velocity at 8 m³ / s.

9. The antioxidant microcapsule powder oil prepared by the method according to any one of claims 1 to 7.

10. The use of the antioxidant microcapsule powder oil according to claim 9 in the preparation of formulations that improve the oxidative properties of oils or enhance intestinal targeted delivery performance.

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