WO2020000529A1 - 一种基于浓缩乳蛋白的微胶囊壁材及微胶囊 - Google Patents

一种基于浓缩乳蛋白的微胶囊壁材及微胶囊 Download PDF

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WO2020000529A1
WO2020000529A1 PCT/CN2018/095876 CN2018095876W WO2020000529A1 WO 2020000529 A1 WO2020000529 A1 WO 2020000529A1 CN 2018095876 W CN2018095876 W CN 2018095876W WO 2020000529 A1 WO2020000529 A1 WO 2020000529A1
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microcapsule
mpc
exchange resin
ion exchange
cla
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French (fr)
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周鹏
胡锦华
庄丰辰
李翔
金跃杰
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Jiangnan University
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Jiangnan University
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Publication of WO2020000529A1 publication Critical patent/WO2020000529A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/19—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles lyophilised, i.e. freeze-dried, solutions or dispersions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/98—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin
    • A61K8/981—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin of mammals or bird
    • A61K8/986—Milk; Derivatives thereof, e.g. butter
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5052—Proteins, e.g. albumin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/4105—Methods of emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/80—After-treatment of the mixture
    • B01F23/804—Drying the mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/80—After-treatment of the mixture
    • B01F23/809—Freezing the mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043—Drying and spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J3/00—Working-up of proteins for foodstuffs
    • A23J3/04—Animal proteins
    • A23J3/08—Dairy proteins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/413—Homogenising a raw emulsion or making monodisperse or fine emulsions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/414—Emulsifying characterised by the internal structure of the emulsion
    • B01F23/4143—Microemulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof

Definitions

  • the invention relates to a microcapsule wall material and a microcapsule based on concentrated milk protein, and belongs to the technical field of microcapsule preparation.
  • MPC Milk protein concentrate
  • WPC / WPI whey protein concentrates / isolates
  • SC sodium caseinate
  • Microcapsules were prepared with unsaturated fatty acids as the core material and MPC as the microcapsule wall material. It was found that MPC as the microcapsule wall material can protect unsaturated fatty acids and delay its oxidation during storage. However, it was also found in the research process that although MPC can be used as microcapsule wall materials, and microcapsule products are prepared by spray drying or freeze drying, etc., it is a product produced with traditional milk protein microcapsule high quality wall materials WPC or SC. In comparison, the protective effect of MPC as a wall material on core materials still has major defects.
  • WPC when embedding highly oxidizable polyunsaturated fatty acid conjugated linoleic acid (CLA), WPC can provide 90%.
  • the embedding rate is above 80%, while MPC can only provide an embedding rate of about 80%.
  • the oxidation rate of CLA embedded in MPC will be higher than that of WPC microcapsules, and the oxidation rate of some products will be poor. About 7 times.
  • the present invention provides a microcapsule wall material with high embedding efficiency and good core material protection effect, and a prepared microcapsule product.
  • the invention performs pretreatment on MPC, and uses the pretreated MPC as a microcapsule wall material, wherein the pretreatment is performed by using an ion exchange resin or adding an exogenous reagent to adjust the acid and chelate ions.
  • the first object of the present invention is to provide a microcapsule wall material suitable for preparing microcapsules, which is MPC (milk protein concentrated) after pretreatment; the pretreatment is performed using any one of the following methods Treatment: ion exchange resin, adding external reagents to adjust acidity, chelating ions, etc.
  • MPC milk protein concentrated
  • the mass ratio of the ion exchange resin to the MPC (dry weight) to be treated is 1:30 to 3: 1, and optionally 2: 3 to 4: 3.
  • the conditions for the ion exchange resin treatment are: adding 0.1 to 30 g of ion exchange resin to each 100 g of the protein solution, and stirring for a period of time.
  • the protein concentration in the protein solution is 1% to 15%.
  • the ion exchange resin is added in an amount of 0.1-30 g per 100 g of the protein solution.
  • the ion exchange resin is preferably a strong acid cation exchange resin Amberlite SR1L Na.
  • the stirring in the ion exchange resin treatment is stirring at a rotation speed of 500 to 5000 rpm for 0.5 to 6 hours.
  • the stirring speed in the ion exchange resin treatment is preferably 1200 to 1500 rpm, and the preferred stirring time is 1 to 3 hours.
  • the condition for adding an exogenous agent to adjust the acidity is: adding a food-grade acidifying agent, such as hydrochloric acid, sulfuric acid, acetic acid, or gluconolactone, to the protein solution to reduce the pH of the protein and then ultrafiltration
  • a food-grade acidifying agent such as hydrochloric acid, sulfuric acid, acetic acid, or gluconolactone
  • the process gets pre-treated MPC.
  • the optimized treatment method is to reduce the pH to around 5.6, and the amount of each acid is different according to its own properties.
  • the key point of optimization is not to cause system blockage during the ultrafiltration process.
  • the need for ultrafiltration to obtain pre-treated MPC is the complexity and cost increase of this embodiment compared to ion exchange resin treatment.
  • the conditions for adding an external agent to chelate ions are: adding a food-grade ion chelator to the protein solution, including EDTA, citric acid, malic acid, and tartrate.
  • the optimal treatment method is to add calcium ion chelator. Compared with the implementation method of ion exchange resin treatment, this implementation method has the defect that the MPC solution pretreated by the chelating ion of the exogenous reagent will contain more chelating agents.
  • the pretreatment is performed to a decalcification rate of 45% or more.
  • the second object of the present invention is to provide a microcapsule, which uses pretreated MPC as the microcapsule wall material; the pretreatment is processed using any one of the following methods: ion exchange resin, addition Exogenous reagents adjust acid or chelate ion.
  • the conditions for the ion exchange resin treatment are: adding 0 to 30 g of ion exchange resin to each 100 g of the protein solution, and stirring at a speed of 500 to 5000 rpm for 0.5 to 6 hours to obtain a series of different preliminaries.
  • the preferred ion exchange resin is the strong acid cation exchange resin Amberlite SR1LNa.
  • the preferred amount of the ion exchange resin is 5-12 g per 100 g of the protein solution, the preferred rotation speed is 1200-1500 rpm, and the preferred stirring time is 1 to 3 h.
  • the mass ratio of the ion exchange resin to the MPC (dry weight) to be treated is 1:30 to 3: 1.
  • the microcapsules are liquid (ie, various forms of emulsions) or solid.
  • the emulsion can have many forms, in addition to oil-in-water, water-in-oil, water-in-oil-in-water, oil-in-water-in-oil, water-in-water-in-water, and gelled internal water Phase or external water phase or internal and external water is equal.
  • the solid state may be a microcapsule powder obtained by drying any one of the emulsions described above into a powder.
  • the microcapsules are in a solid form; the microemulsion powder is prepared by spray drying the prepared emulsion immediately, and the inlet temperature of spray drying is 120-160 ° C, and the atomizing gas flow rate and peristalsis are adjusted by adjusting The outlet temperature of the speed control of the pump is unchanged, and the outlet temperature is 60 to 90 ° C.
  • the core material can be various environmentally sensitive active factors (such as vitamins, unsaturated fatty acids, probiotics, vaccines, etc.), volatile substances (such as essential oils, etc.), which need to be changed in gaseous or liquid form to solid application forms Substance.
  • environmentally sensitive active factors such as vitamins, unsaturated fatty acids, probiotics, vaccines, etc.
  • volatile substances such as essential oils, etc.
  • the mass ratio of dry protein pretreated milk protein to core material is 50: 1 to 1: 1.
  • the homogeneous pressure is 10 to 50 MPa, and the homogenization is performed 2 to 6 times.
  • the inlet and outlet temperatures of the spray drying are 120-160 ° C and 60-90 ° C, respectively.
  • the third object of the present invention is to provide the application of the microcapsules, which can be applied to the fields of food, medicine, health products, cosmetics, daily chemical industry, etc., including improving the physical and chemical stability of active functional factors, or changing the application thereof. Form that makes it easy to carry or redisperse.
  • the principle of the invention lies in that through the pretreatment, the existence state of the protein in the MPC and the interaction between the protein components are changed, so that it can form a continuous viscoelastic interface film during the preparation of the emulsion, which is formed in a further drying process A denser shell protects the core material.
  • the invention improves the quality of microcapsule products prepared by using MPC as a wall material, improves the physical and chemical stability of the core material, proposes the application direction and field of MPC, makes MPC a competitive milk protein ingredient, and can be used with WPC , SC and other traditional milk protein ingredients to compete.
  • the invention effectively improves its embedding performance and protection performance as a microcapsule wall material, improves the embedding rate of the core material from about 80% to more than 93%, and simultaneously
  • the compactness of the material is optimized to improve the oxidation stability of the core material, delay the degradation of the core material, and better protect its activity.
  • microcapsules of the invention are suitable for protecting active functional factors and applied in the fields of food, medicine, health products, cosmetics, daily chemical industry and the like.
  • Figure 1 Appearance images of MPC solutions with different decalcification rates
  • FIG. 3 Particle size distribution and optical microscope image of milk protein-conjugated linoleic acid (CLA) emulsion
  • FIG. 4 Transmission electron microscope image of milk protein-conjugated linoleic acid (CLA) emulsion, protein magnification: 1-5000 times; 2, 3-50,000 times;
  • FIG. 5 Scanning electron microscope image one of milk protein-conjugated linoleic acid (CLA) microcapsule powder
  • FIG. 6 Scanning electron microscope image of milk protein-conjugated linoleic acid (CLA) microcapsule powder II;
  • the test of the total oil content in the microcapsules mainly refers to the method of Kim et al .: Take 1g of microcapsule powder in a 50mL centrifuge tube, add 8mL of deionized water at 50 ⁇ 5 °C, and mix thoroughly until the sample is completely dispersed. Cool to room temperature in running water. Add 40mL of n-hexane / isopropanol (3: 1, v / v) mixed solvent, mix at room temperature for 20min, and centrifuge (1500g, 10min). After collecting the upper organic phase, extract the lower aqueous phase again by the same method .
  • Microcapsule yield (%) total oil content / addition amount of conjugated linoleic acid in the formula ⁇ 100%
  • Microcapsule embedding rate (%) 100%-surface oil content / total oil content ⁇ 100%
  • the oxidative stability of microcapsules is mainly through: (1) the primary oxidation product-Peroxide Value (POV); (2) the representative oxidized volatile component of omega-6 unsaturated fatty acids-hexanal content (3) The retention rate of conjugated linoleic acid was evaluated.
  • POV primary oxidation product-Peroxide Value
  • the present invention mainly refers to Smet and GB / T5009.37-2003 to test the peroxide value of CLA in microcapsule powder.
  • the specific operation is as follows:
  • V1 total volume of sample dilution in milliliters (mL);
  • V2 sampling volume during measurement, the unit is milliliter (mL);
  • the headspace heating conditions were 70 ° C and constant temperature for 30min.
  • the chromatographic column was a Rtx-Wax capillary column (30m ⁇ 0.25mm, ID).
  • the carrier gas is high-purity nitrogen, and the heating program is: After constant temperature of 40 ° C for 8 minutes, the temperature is increased to 230 ° C at a rate of 10K / min, and the constant temperature is 7 minutes.
  • the injector and detector temperatures were 180 ° C and 250 ° C, respectively. Test different concentrations of hexanal standard solutions, make a calibration curve to clarify the linear range, and calculate the hexanal content in microencapsulated CLA according to the peak area size, expressed as mg / 100gCLA.
  • the method of Christie et al. was used to extract and methylate the non-esterified conjugated linoleic acid in the microcapsules.
  • the specific operation is as follows: First, take 0.1g of microcapsule powder in 2mL deionized water and mix well. After that, 8 mL of a chloroform-methanol mixed solution (2: 1, v / v) was added, vortexed for 30 s, and centrifuged (12000 g, 20 min).
  • the GC2010PLUS gas chromatography was used to measure the content of conjugated linoleic acid.
  • the column was a DB-WAX capillary column (60m ⁇ 0.32mm, ID).
  • the carrier gas was high-purity nitrogen.
  • the column heating program was: 160 ° C for 3 minutes. The temperature was raised to 220 ° C at a rate of 2 ° C / min, and the temperature was kept constant at 220 ° C for 20 minutes.
  • the content of conjugated linoleic acid in storage samples was determined by the peak area ratio, and the retention rate of conjugated linoleic acid during storage was calculated.
  • Example 1 Preparation of conjugated linoleic acid spray-dried microcapsule powder
  • CLA Conjugated linoleic acid
  • the prepared emulsion was immediately spray-dried.
  • the spray-dried inlet temperature was 160 ° C.
  • the outlet temperature was controlled by adjusting the flow of the atomizing gas and the speed of the peristaltic pump, and the outlet temperature was 80 ° C.
  • the atomizing gas flow rate and the peristaltic pump flow rate are approximately 414 L / h and 13.3 mL / min, respectively.
  • the freshly prepared microcapsules were collected in a waterproof aluminum foil bag and stored in an ultra-low temperature refrigerator at -70 ° C. The samples were equilibrated in a silica gel dryer for 2 hours before use.
  • the treated MPC showed the solution appearance ( Figure 1) and particle size distribution display ( Figure 2). Removal of calcium ions from the MPC solution will cause dissociation of colloidal calcium phosphate in the casein micelles, and changes in the colloidal calcium phosphate as the micellar framework will definitely cause changes in the structure of the casein micelles.
  • Figure 1 shows that when the decalcification rate increases from 0% to 28.0%, the MPC solution changes from milky white to light yellow; when the decalcification rate continues to increase to 59.2%, the MPC wall material solution is relatively clear and transparent. Slightly yellow.
  • the initial photo of the protein solution showed that the higher the decalcification rate, the less the micellar structure in MPC.
  • the change in the appearance turbidity of the decalcified MPC solution preliminarily explained the dissociation of the micelle structure in the solution.
  • the size and distribution of the particle size in the decalcified MPC solution were tested, as shown in Figure 2.
  • the particle size distribution of the protein in the MPC solution is mainly concentrated between 80-450nm.
  • the particle size distribution diagram of the decalcified MPC wall material solution appears at about 45nm. A new small peak was shown, indicating that the micelles in MPC were dissociated on a small scale at this time, and some casein micelle fragments were generated.
  • the volume proportion of small peaks in the particle size distribution diagram of the decalcified MPC solution becomes larger and larger, indicating that the micelles are further dissociated.
  • the particle size distribution of the MPC solution is mainly located at 20-100 nm, that is, most of the micelles have been dissociated.
  • Milk protein-CLA microcapsules undergo oxidation during storage. Specifically, when the microencapsulated CLA contacts the air inside the microcapsules and the air between the powders, the unsaturated fatty acid chains will interact with oxygen.
  • the primary oxidation product, hydroperoxide is formed first, and an increase in peroxide value (POV value) can be observed at this time. After a period of time, the hydroperoxide is further decomposed and converted into volatile secondary oxidation products, such as aldehydes, ketones, and acids, which cause abnormal flavor of the product.
  • CLA as a series of omega-6 polyunsaturated fatty acids, has a higher hexanal content in the secondary oxidation products.
  • the hexanal content is often used to indicate the degree of secondary oxidation of CLA.
  • the POV value of CLA in the WPI + SC group first increased, then decreased, and then increased; the POV value at day 14 was the highest at 27 meq / kg.
  • the POV value of the CLA in the WPC group did not change much during the entire storage process, and was always within 20 meq / kg.
  • the POV value of CLA increased first and then decreased.
  • the POV value of the 7th day reached 146.1 ⁇ 9.0 meq / kg, and stabilized at about 80 meq / kg after 30 days.
  • the microcapsules prepared by the treated MPC have improved the oxidation stability of CLA.
  • the initial POV values of the CLA in the corresponding microcapsules were 18.2 ⁇ 3.5 and 16.0 ⁇ 3.4meq / kg, respectively, which were lower than the initial POV values of the MPC group.
  • these two groups of CLA oxidized faster during storage.
  • the POV values after 7 days were as high as 102.0 ⁇ 1.7 and 92.2 ⁇ 0.9 meq / kg, which were higher than those of the MPC group. After 30 days, POV decreased to 50.9 ⁇ 4.0 and 28.9 ⁇ 1.5meq / kg, respectively.
  • the POV value of CLA in the 45.2% decalcification group was always lower than the POV value of the control group during storage.
  • the POV value of CLA in the 59.2% decalcification rate group remained at a relatively low level (about 40 meq / kg) throughout the 30 days of storage.
  • the hexanal content of CLA in microcapsules during storage was also tested. From the change of hexanal value (Figure 8), the initial hexanal content in the WPC and WPI + SC groups were 9.9 ⁇ 0.1 and 13.3 ⁇ 0.1 mg / kg, respectively; it increased with the increase of storage time, and it was stored until the 30th day. The hexanal content in the WPC and WPI + SC groups increased to 25.1 ⁇ 0.7 and 57.7 ⁇ 0.4 mg / kg, respectively.
  • the hexanal content in the MPC group at day 45 was 295.4 ⁇ 20.4 mg / kg, which was much higher than the CLA hexanal content in the WPC and WPI + SC groups.
  • the microcapsules prepared by the treated MPC have improved the oxidation stability of CLA.
  • the hexanal content in the decalcification rate of 14.0 and 28.0% groups was higher than that of the 0% decalcification rate samples, which increased and then decreased with the increase of storage time. This may be due to the further decomposition of hexanal in the later storage period, or it may be due to the volatilization from the microcapsules to the air during storage, but it was not collected during the sampling process.
  • the hexanal content in the decalcification rates of 45.2 and 59.2% was increasing with time. Overall, during most of the storage period, the CLA microcapsules prepared by MPC with different decalcification rates were sorted according to the quality of hexanal content: 28.0% > 14.0% > 0% > 45.2 > 59.2 %.
  • the POV value and the hexanal content can only indirectly reflect the degree of CLA oxidation, and cannot directly indicate the change of the CLA content in the microcapsule powder during storage.
  • the two major isomers of CLA in the MPC and WPI + SC groups (c9, t11 and t10, c12) ) Content was selected for point testing (days 0, 14, 45), and compared with the isomer content in fresh CLA purchased, and expressed as a retention rate (%) (Figure 9).
  • the improvement of CLA retention rate of the microcapsules prepared by the treated MPC was also confirmed.
  • the retention rates of CLA on day 0 in the decalcification rates of 14.0, 28.0, and 59.2% were 91.1%, 95.3%, and 98.6%, respectively.
  • the overall trend is that the higher the decalcification rate, the higher the CLA retention rate in fresh microcapsule samples. This may be related to the speed of microcapsule shell formation during spray drying.
  • the higher the degree of decalcification the smaller the number of casein micelles in the MPC solution corresponding to the wall material, the faster the water evaporation and the formation of the microcapsule shell layer during the spray drying process, and the denser the shell layer.
  • the decalcification rates of the 14.0, 28.0, and 59.2% groups of microcapsules after storage for 7 days decreased to 64.0%, 56.5%, and 84.4%, respectively.

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Abstract

本发明公开了一种基于浓缩乳蛋白的微胶囊壁材及微胶囊，属于微胶囊制备技术领域。本发明通过对浓缩乳蛋白进行阳离子交换处理，然后使用处理后的浓缩乳蛋白作为壁材制备液状或者固状微胶囊。制备得到的微胶囊储藏时物理和化学稳定性都较好，适用于保护活性功能因子应用于食品、药品、保健品、化妆品、日用化工等领域。

Description

一种基于浓缩乳蛋白的微胶囊壁材及微胶囊 技术领域
本发明涉及一种基于浓缩乳蛋白的微胶囊壁材及微胶囊，属于微胶囊制备技术领域。
背景技术
浓缩乳蛋白(milk protein concentrates，MPC)是通过超滤去除脱脂乳中大部分乳糖所制得的一种高蛋白乳粉，具有较好的功能特性和营养价值。就原料自身而言，MPC有极大的应用优势。相比于传统的乳蛋白配料，如乳清浓缩/分离蛋白(whey protein concentrates/isolates，WPC/WPI)和酪蛋白酸钠(sodium caseinate，SC)，MPC的制备工艺更加简单，可基本实现连续化不间断生产，生产成本较低，生产方式也更绿色环保。但由于膜过滤技术的限制，MPC的出现和发展起步较晚，目前其应用研究还十分有限。
在前期的研究过程中，本发明人团队探究了MPC在微胶囊领域应用的可能性。以不饱和脂肪酸为芯材、利用MPC作为微胶囊壁材制备了微胶囊，发现MPC作为微胶囊壁材可以保护不饱和脂肪酸，延缓其在储藏过程中氧化。但是，在研究过程中也发现，虽然MPC可以作为微胶囊壁材应用，经由喷雾干燥或者冷冻干燥等工艺手段制备微胶囊产品，但是与传统的乳蛋白微胶囊优质壁材WPC或者SC生产的产品相比，MPC作为壁材对芯材的保护效果仍存在较大的缺陷，比如在包埋极易氧化的多不饱和脂肪酸共轭亚油酸(conjugated linoleic acid,CLA)时，WPC可以提供90％以上的包埋率，而MPC只能提供80％左右的包埋率；在高温加速储藏实验中，被MPC包埋CLA的氧化速度也会高于WPC微胶囊，部分产品的氧化速度会差7倍左右。这些数据都表明虽然MPC可以用来制备微胶囊产品，但是对芯材的包埋率需要进一步提高，对芯材的物理化学稳定性的保护和改善效果也需要进一步提高，才能成为有市场竞争力的产品。
发明内容
为了解决上述问题，本发明提供了一种包埋效率高、芯材保护效果好的微胶囊壁材，以及制备得到的微胶囊产品。本发明对MPC进行预处理，与预处理后的MPC作为微胶囊壁材，其中预处理是使用离子交换树脂或者添加外源试剂调酸、螯合离子等进行处理。
本发明的第一个目的是提供一种适用于制备微胶囊的微胶囊壁材，为预处理后的MPC(浓缩乳蛋白，milk protein concentrates)；所述预处理是使用以下任意一种方法进行处理：离子交换树脂、添加外源试剂调酸、螯合离子等。
在一种实施方式中，离子交换树脂与待处理的MPC(干重)的质量比是1∶30～3∶1，可选地为2:3～4:3。
在一种实施方式中，所述离子交换树脂处理的条件是：每100g蛋白溶液中分别加入离子交换树脂0.1～30g，搅拌处理一段时间。
在一种实施方式中，所述蛋白溶液中蛋白浓度为1％～15％。
在一种实施方式中，所述离子交换树脂的加入量为每100g蛋白溶液加入0.1～30g。
在一种实施方式中，所述离子交换树脂优选为强酸型阳离子交换树脂Amberlite SR1L Na。
在一种实施方式中，所述离子交换树脂处理中的搅拌，是在500～5000rpm的转速下搅拌0.5～6h。
在一种实施方式中，所述离子交换树脂处理中的搅拌，优选的转速为1200～1500rpm，优选的搅拌时间为1～3h。
在一种实施方式中，所述添加外源试剂调酸的条件是：在蛋白溶液中加入食品级酸化剂，比如盐酸、硫酸、醋酸或者葡萄糖内酯等，降低蛋白的pH，再经过超滤工艺得到预处理MPC。其中优化的处理方式是将pH降低至5.6附近，每种酸根据自身性质使用量不同，优化的关键点是不能造成超滤过程中易造成系统的堵塞。需要经过超滤才能得到预处理MPC是该实施方式相比于离子交换树脂处理的工艺复杂处和成本增加点。
在一种实施方式中，所述添加外源试剂螯合离子的条件是：在蛋白溶液中加入食品级离子螯合剂，包括EDTA、柠檬酸、苹果酸和酒石酸盐等。其中优化的处理方式是添加钙离子螯合剂。相比于离子交换树脂处理的实施方法，该实施方法存在的缺陷是经由外源试剂螯合离子预处理后的MPC溶液中会含有较多的螯合剂。
在一种实施方式中，所述预处理是处理到脱钙率45％以上。
本发明的第二个目的是提供一种微胶囊，所述微胶囊是以预处理后的MPC作为微胶囊壁材；所述预处理是使用以下任意一种方法进行处理：离子交换树脂、添加外源试剂调酸或螯合离子等。
在一种实施方式中，所述离子交换树脂处理的条件是：在每100g蛋白溶液中分别加入离子交换树脂0～30g，于500～5000rpm的转速下搅拌0.5～6h，得到一系列不同的预处理MPC蛋白溶液。其中优选的离子交换树脂为强酸型阳离子交换树脂Amberlite SR1L Na，其优选的加入量为每100g蛋白溶液加入5～12g，优选的转速为1200～1500rpm，优选的搅拌时间为1～3h。
在一种实施方式中，离子交换树脂与待处理的MPC(干重)的质量比是1∶30～3∶1。
在一种实施方式中，所述微胶囊为液状(即各种形式的乳状液)或者固状。
在一种实施方式中，所述乳状液可以有很多形式，除了水包油，还有油包水、水包油包水、油包水包油、水包水包水及凝胶化内水相或者外水相或者内外水相等。
在一种实施方式中，所述固状，可以是上述任意一种乳状液干燥成粉末之后得到的微胶囊粉末。
在一种实施方式中，所述微胶囊的制备具体是：准确将预处理后的MPC溶液或者其喷干粉末配制得到一定浓度的蛋白溶液于10～50MPa下均质3次后，按芯材∶壁材＝1∶50～1∶1(w/w)的比例加入芯材，搅拌均匀后，利用高速剪切分散机分散2min。再在10～50MPa的压力下将混合液均质2～6次，得到均匀的乳状液；即为液状微胶囊的一种。
在一种实施方式中，所述微胶囊为固状；包括将制备得到的乳状液立即喷干制备得到微胶囊粉末，喷雾干燥的进口温度为120～160℃，通过调节雾化气体流量和蠕动泵的速度控制出口温度不变，出口温度为60～90℃。
所述芯材可以是各类对环境敏感的活性因子(如维生素、不饱和脂肪酸、益生菌、疫苗等)，易挥发的物质(如精油等)，需要改变气态或液态存在形式为固态应用形式的物质等。
在一种实施方式中，干物质预处理的乳蛋白与芯材的质量比为50∶1～1∶1。
在一种实施方式中，均质的压力为10～50MPa，均质2～6次。
在一种实施方式中，喷雾干燥的进出口温度分别为120～160℃、60～90℃。
本发明的第三个目的是提供所述微胶囊的应用，可以是应用于食品、药品、保健品、化妆品、日用化工等领域，包括改善活性功能因子的物理化学稳定性，或者改变其应用形式，使易于携带或再分散。
本发明的原理在于：通过预处理，改变MPC中蛋白的存在状态和蛋白组分之间的相互作用，使其在制备乳状液时能够形成连续的粘弹性界面膜，在进一步的干燥工艺中形成更加致密的壳层，保护芯材。
本发明的有益效果：
本发明提高了MPC作为壁材应用制备微胶囊产品的品质，改善了芯材的物理化学稳定性，提出了MPC的应用方向和领域，使MPC能成为有竞争力的乳蛋白配料，能够与WPC、SC等传统乳蛋白配料进行竞争。
本发明通过对浓缩乳蛋白进行预处理，有效地提高了其作为微胶囊壁材的包埋性能和保护性能，将芯材的包埋率从80％左右提高到了93％以上，同时通过对壁材致密性进行优化，改善了芯材的氧化稳定性，延缓了芯材的劣化，更好的保护其活性。
本发明的微胶囊，适用于保护活性功能因子应用于食品、药品、保健品、化妆品、日用化工等领域。
附图说明
图1不同脱钙率MPC溶液外观图像；
图2不同脱钙率MPC溶液的粒径分布；
图3乳蛋白-共轭亚油酸(CLA)乳状液的粒径分布及光学显微镜图像；
图4乳蛋白-共轭亚油酸(CLA)乳状液的透射电子显微镜图像，蛋白放大倍数：1-5000倍；2、3-50000倍；
图5乳蛋白-共轭亚油酸(CLA)微胶囊粉末的扫描电子显微镜图像一；
图6乳蛋白-共轭亚油酸(CLA)微胶囊粉末的扫描电子显微镜图像二；
图7储藏过程中微胶囊粉末中CLA的过氧化物值(POV)的变化；
图8储藏过程中微胶囊化CLA的己醛含量变化；
图9储藏过程中微胶囊粉末中CLA保留率的变化。
具体实施方式
指标测定的方法：
1、微胶囊产率及微胶囊效率的测定
微胶囊中总油含量的测试主要参考了Kim等人的方法：取1g微胶囊粉末于50mL离心管中，加入8mL 50±5℃的去离子水，充分混合，直到试样完全分散，放入流动水中冷却至室温。加入40mL正己烷/异丙醇(3∶1，v/v)的混合溶剂，室温下混合20min后离心(1500g，10min)，收集上层有机相后，将下层水相中按同样方法再提取一次。合并有机相于圆底烧瓶中，旋转蒸发掉有机溶剂后，将圆底烧瓶放入45℃的烘箱中直至重量不再改变，利用差值法计算微胶囊中的总油含量。
微胶囊表面含油量的测试：将4g微胶囊粉末加入到60℃的石油醚中，轻微振荡混合10min后，过滤，收集有机相于圆底烧瓶中。将圆底烧瓶置于45℃真空干燥箱中直至重量不再改变，利用差值法计算表面含油量。
微胶囊产率(％)＝总油含量/配方中共轭亚油酸添加量×100％
微胶囊包埋率(％)＝100％－表面油含量/总油含量×100％
2、水分活度
利用LabSwift-aw水分活度仪测试微胶囊粉末的水分活度，仪器在测试前使用a w＝0.11和a w＝0.23的标准液进行校正。取适量微胶囊粉(1g左右)末于测试槽中，仪器自动平衡后读取数值。
3、微胶囊粉末中共轭亚油酸(CLA)的氧化稳定性测试
取5g左右新鲜制备的WPC-CLA、MPC-CLA、WPI+SC-CLA微胶囊粉末装满7.5mL的离心管(未压实，顶部不留空隙)，密封后，用铝箔纸包裹，避光置于35℃的恒温箱中储藏45天。而脱钙MPC-CLA微胶囊粉末在进行储藏实验时，方法稍作改变。取5g左右的粉 末装满7.5mL离心管并压实，除去粉末间的空气，密封避光储藏30天。
微胶囊的氧化稳定性主要通过：(1)氧化初级产物——过氧化物值(Peroxide Value，POV)；(2)ω-6系列不饱和脂肪酸的代表性氧化挥发成分——己醛含量；(3)共轭亚油酸的保留率来进行评价。
4、微胶囊粉末中CLA的过氧化物值(POV)的测试
本发明主要参考了Smet和GB/T5009.37-2003对微胶囊粉末中CLA的过氧化物值进行了测试，具体操作如下：
取0.25g储藏后的粉末于7.5mL离心管中，加入4.75mL的去离子水，混合30min，制备成5％(w/w)的溶液。取2g溶液于15mL离心管中，加入6mL三氯甲烷-甲醇混合溶液(2∶1，v/v)，涡旋振荡30s后，于室温下离心(12000g，20min)。取1mL下层有机相于10mL棕色容量瓶中，加入50μLFeCl2(3.5g/L)，用三氯甲烷-甲醇(7∶3，v/v)定容。向上述溶液中添加50μL的KSCN溶液(300g/L)，放置5min后，于500nm处测量吸光度值。过氧化物值的计算参考国标表示为：
X＝(C-C0)×V1÷(m×V2×55.84×2)    (1)
注:X——试样中过氧化值含量(meq/kg)；
C——由标准曲线上查得试样中铁的质量，单位为μg；
C0——零管铁的质量，单位为μg；
V1——试样稀释总体积，单位为毫升(mL)；
V2——测定时取样体积，单位为毫升(mL)；
M——粉末试样中总油质量，单位为克(g)；
5、微胶囊化CLA的己醛含量测试
利用GC 2010 PLUS气相色谱和Turbo Matrix16顶空进样器对微胶囊化CLA中的己醛含量进行测试，具体操作如下：
取0.5g微胶囊粉末于20mL顶空瓶中，加入3mL去离子水以溶解壁材。顶空加热条件为70℃，恒温30min。色谱柱为Rtx-Wax毛细管柱(30m×0.25mm，ID)。载气为高纯氮气，升温程序为：40℃恒温8min后，以10K/min的速率升温至230℃，并恒温7min。进样器和检测器的温度分别为180℃和250℃。测试不同浓度的己醛标准溶液，做出标曲以明确线性范围，根据峰面积大小计算微胶囊化CLA中的己醛含量，以mg/100gCLA表示。
6、微胶囊化CLA的保留率的测试
本实验采用Christie等人的方法对微胶囊中的非酯化的共轭亚油酸进行提取和甲酯化，具体操作如下：首先，取0.1g的微胶囊粉末于2mL去离子水中，混合均匀后，加入8mL 三氯甲烷-甲醇混合溶液(2∶1，v/v)，漩涡振荡30s，离心(12000g，20min)。用注射器吸取2.5mL离心后下层有机相于试管中，氮气吹干后(37℃，15min)，加入1mLBF3-甲醇溶液反应10min，进行甲酯化。甲酯化完全后，加入2mL正己烷提取水相中的共轭亚油酸甲酯，将提取后的含有共轭亚油酸甲酯的正己烷用5mL×2的去离子水清洗2次，以除去存留的甲醇等物质，无水硫酸钠吸取多余的水分后，待测。
利用GC2010 PLUS气相色谱测试共轭亚油酸含量，色谱柱采用DB-WAX毛细管柱(60m×0.32mm，ID)，载气为高纯氮气，色谱柱升温程序为：160℃下恒温3min后，以2℃/min的速率升温至220℃，并在220℃恒温20min。配置不同浓度的共轭亚油酸甲酯标准溶液，制作标曲。通过峰面积比值确定储藏样品中共轭亚油酸含量，计算储藏过程中共轭亚油酸的保留率。
为了更好的解释本发明，下面结合具体实施例对本发明进行进一步详细解释。
实施例1：制备共轭亚油酸喷雾干燥微胶囊粉末
准确称取120g浓缩牛乳蛋白(MPC485)粉末于880g去离子水中，制备得到12％的蛋白溶液。加入0.02％的NaN 3，搅拌过夜充分水合后，于30MPa的压力下均质3次。每100g蛋白溶液中分别加入0、1.5、3、3.5、8、16g阳离子交换树脂Amberlite SR1L Na，于1500rpm的转速下搅拌2h，得到一系列不同的预处理的MPC蛋白溶液(编号分别为MPC0、MPC1、MPC2、MPC3、MPC4、MPC5，经测定脱钙率分别为0％、14.0％、27.6％、28.0％、45.2％、59.2％)，备用。
准确称取不同的蛋白配置成质量浓度为12％的蛋白溶液，具体为分别称取120gWPC(乳清浓缩蛋白)、MPC、WPI+SC(乳清分离蛋白WPI与酪蛋白酸钠SC，这两种蛋白混合比例为1∶4，w/w)以及预处理后的脱钙率分别为0％、14.0％、27.6％、28.0％、45.2％、59.2％的MPC粉末(MPC0、MPC1、MPC2、MPC3、MPC4、MPC5)于去离子水中，制备得到12％的蛋白溶液。分别加入0.02％的NaN 3后，搅拌过夜充分水合，于30MPa下均质3次后，备用。
将蛋白浓度为12％的上述溶液分别作为壁材使用，按芯材∶壁材＝1∶8(w/w)的比例加入共轭亚油酸(CLA)，搅拌均匀后，利用高速剪切分散机分散2min。在30MPa的压力下将混合液均质3次，得到均匀的乳状液。
将制备得到乳状液立即喷干，喷雾干燥的进口温度为160℃，通过调节雾化气体流量和蠕动泵的速度控制出口温度不变，出口温度为80℃。雾化气体流速和蠕动泵流速分别约为 414L/h和13.3mL/min。收集新鲜制备的微胶囊于防水铝箔袋中，置于-70℃的超低温冰箱中保藏，样品使用前置于硅胶干燥器中平衡2h。
经过处理后的MPC呈现的溶液外观(图1)和粒径分布显示(图2)。脱除MPC溶液中的钙离子会使得酪蛋白胶束中的胶体磷酸钙发生解离，而作为胶束骨架的胶体磷酸钙的变化必定会引起酪蛋白胶束结构的改变。使用拍照的方式对不同脱钙程度的MPC溶液的外观特征进行描述。图1显示，当脱钙率从0％增加到28.0％时，MPC溶液的由乳白色变逐渐变成淡黄色；当脱钙率继续升高至59.2％时，MPC壁材溶液相对澄清、透明，呈微黄色。蛋白溶液外观照片初步的表明脱钙率越高，MPC中的胶束结构就越少。脱钙MPC溶液外观浊度的变化初步说明了溶液中胶束结构发生了解离。在此基础上，对脱钙MPC溶液中粒径的大小及分布进行了测试，如图2所示。当脱钙率为0％时，MPC溶液中蛋白的粒径分布主要集中在80～450nm之间，当脱钙率为14.0％时，脱钙MPC壁材溶液的粒径分布图在45nm左右出现了一个新的小峰，说明此时MPC中的胶束发生了小规模的解离，产生了一部分酪蛋白胶束碎片。随脱钙率的进一步上升，脱钙MPC溶液粒径分布图中小峰的体积占比越来越大，表明胶束进一步解离。当脱钙率为59.2％时，MPC溶液的粒径分布主要位于20～100nm，即绝大数的胶束都已经解离。
对不同乳蛋白-共轭亚油酸乳状液的光学显微镜图像和粒径分布、乳状液的透射电子显微镜图像、喷雾干燥所得的微胶囊粉末的扫描电子显微镜图像，以及储藏过程中微胶囊粉末中CLA的过氧化物值(POV)变化、己醛含量变化、CLA保留率变化等等，进行分析，结果如图1至图9所示。
以WPC，WPI+SC(不含胶束结构)的传统乳蛋白壁材作为参照，可知未经处理的MPC微胶囊效率比较低，处理后MPC制备所得的MPC-CLA微胶囊效率提升到与传统壁材可相比拟(表1)。综合乳液的粒径和分布(图3)、乳液的形貌(图4)以及微胶囊粉末的形貌和内部结构(图5、图6)可知，MPC中酪蛋白胶束结构的存在会导致乳状液中油滴粒径增大，对应的微胶囊效率降低，微胶囊中油脂分布不均匀，粉末表面凹陷程度较深，内壁中有较多的裂痕和孔洞。
表1
Figure PCTCN2018095876-appb-000001
Figure PCTCN2018095876-appb-000002
乳蛋白-CLA微胶囊在储藏过程中会发生氧化，具体来说，当微胶囊化的CLA与微胶囊内部空气以及粉末间的空气相接触时，不饱和脂肪酸链就会与氧气相互作用。首先生成初级氧化产物——氢过氧化物，此时可以观察到过氧化物值(POV值)的升高。经过一段时间，氢过氧化物进一步分解，转化生成醛、酮、酸等导致产品风味异常的挥发性二级氧化产物。CLA作为一种ω-6系列的多不饱和脂肪酸，其二级氧化产物中，己醛含量较高，因此常常选用己醛含量来表示CLA的二级氧化程度。从POV值(图7)观察，35℃储藏45天后，WPI+SC组CLA的POV值随储藏时间的增加先上升后下降，再上升；第14天时的POV值最高，为27meq/kg。WPC组中CLA的POV值在整个储藏过程中变化不大，一直处于20meq/kg以内。而MPC组中CLA的POV值呈先上升，后下降的趋势，第7天的POV值达到146.1±9.0meq/kg，30天后稳定在80meq/kg左右。经过处理之后的MPC制备得到的微胶囊对CLA的氧化稳定性得到了改善。当脱钙率为14.0和28.0％时，对应微胶囊中CLA的初始POV值分别为18.2±3.5和16.0±3.4meq/kg，低于MPC组的初始POV值。但这两组CLA在储藏过程中的氧化速度更快，7天后的POV值高达102.0±1.7和92.2±0.9meq/kg，高于MPC组。30天后，POV分别下降至50.9±4.0和28.9±1.5meq/kg。脱钙率45.2％组中CLA的POV值在储藏过程中始终低于对照组的POV值。脱钙率59.2％组中CLA的POV值在储藏的30天内始终处于相对较低水平(大约为40meq/kg)。
由于测量取点具有一定偶然性，POV柱状图中的最高点不一定是储藏过程中POV值最大的点，所以POV值只能初步反应微胶囊化CLA的氧化情况。因此，还对储藏过程中微胶囊内CLA的己醛含量进行了测试。从己醛值的变化(图8)观察，WPC与WPI+SC组的初始己醛含量分别为9.9±0.1和13.3±0.1mg/kg；随储藏时间的增加而增加，储藏至第30天时，WPC和WPI+SC组的己醛含量分别增加至25.1±0.7和57.7±0.4mg/kg。MPC组第45天时的己醛含量为295.4±20.4mg/kg，远远高于WPC和WPI+SC组中CLA的己醛含量。经过处理之后的MPC制备得到的微胶囊对CLA的氧化稳定性得到了改善。而脱钙率14.0和28.0％组的己醛含量总体高于脱钙率0％组样品，随储藏时间的增加先上升后下降。这可能是因为储藏后期己醛进一步分解，也可能是因为在储藏过程中从微胶囊中挥发至空气中，而在采样过程中未被收集到。脱钙率45.2和59.2％组的己醛含量随时间的延长一直在增加。总体看来，在储藏的绝大部分时间里，不同脱钙率MPC所制得的CLA微胶囊按所含己醛质量由高到低排序为：28.0％＞14.0％＞0％＞45.2＞59.2％。
POV值和己醛含量只能间接反应CLA的氧化程度，不能直观的表示储藏过程中微胶囊粉末中CLA含量的变化情况。为更加明确胶束结构对乳蛋白-CLA微胶囊的氧化稳定性的影响，对储藏过程中，MPC和WPI+SC组中CLA的两种主要同分异构体(c9,t11和t10,c12)的含量进行了选点测试(第0、14、45天)，将其与购买的新鲜CLA中的同分异构体含量进行对比后，以保留率(％)方式表示(图9)。结果发现，c9,t11和t10,c12这两种CLA的主要异构体的氧化速度相同，含胶束结构的MPC组中CLA含量变化与不含胶束结构的WPI+SC组差别较大。第0天时，MPC组微胶囊中CLA的保留率为90.5％，WPI+SC组中CLA的保留率却为95.2％。35℃储藏30天后，MPC组中CLA的保留率下降至42.0％，而WPI+SC组中CLA的保留率储藏45天后仍高达78.5±1.5％。经过处理之后的MPC制备得到的微胶囊对CLA的保留率改善也得到了证实。脱钙率14.0、28.0和59.2％组中CLA在第0天保留率分别为91.1％、95.3％以及98.6％，总体趋势为脱钙率越高，新鲜微胶囊样品中的CLA保留率就较高，这可能与喷干过程中微胶囊壳层形成的速度有关。脱钙程度越高，对应壁材MPC溶液中的水合能力较强的酪蛋白胶束数目就越少，喷干过程中的水分蒸发及微胶囊壳层的形成也越快，壳层愈致密。从而，雾化液滴内部的CLA与温度较高的干燥空气的接触时间就越短，CLA的损失越少。脱钙率14.0、28.0和59.2％组微胶囊储藏7天后CLA的保留率分别下降至64.0％、56.5％以及84.4％。储藏30天后CLA的保留率分别为52.3％、43.4％以及70.7％。
由此可知，在储藏过程中，具有胶束结构的MPC组微胶囊中CLA的氧化速度和程度要高于不含胶束结构的WPI+SC组。也就是说酪蛋白胶束结构影响了MPC对芯材的保护效果。因此，与传统乳蛋白配料相比，MPC要作为具有市场竞争力的微胶囊壁材得到应用，则其结构和性能都需要进一步改善。经过合适得加工处理之后，我们可以有效地提升MPC作为微胶囊壁材的应用特性，提高其微胶囊效率和对芯材的物理化学稳定性得保护。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (13)

  1. 一种微胶囊，其特征在于，所述微胶囊的壁材为预处理后的浓缩乳蛋白MPC；所述预处理是使用以下任意一种方法进行处理：离子交换树脂、添加外源试剂调酸、螯合离子；当采用离子交换树脂时，离子交换树脂与待处理的MPC(干重)的质量比是1∶30～3∶1；所述预处理是处理到脱钙率45％以上。
  2. 一种微胶囊，其特征在于，所述微胶囊的壁材为预处理后的浓缩乳蛋白MPC；所述预处理是使用以下任意一种方法进行处理：离子交换树脂、添加外源试剂调酸、螯合离子等。
  3. 根据权利要求2所述的微胶囊，其特征在于，离子交换树脂与待处理的MPC(干重)的质量比是1∶30～3∶1。
  4. 根据权利要求2所述的微胶囊，其特征在于，所述离子交换树脂处理的条件是：每100g蛋白溶液中分别加入离子交换树脂0.1～30g，搅拌处理一段时间。
  5. 根据权利要求2所述的微胶囊，其特征在于，所述离子交换树脂为强酸型阳离子交换树脂Amberlite SR1L Na。
  6. 根据权利要求2所述的微胶囊，其特征在于，所述添加外源试剂调酸的条件是：在蛋白溶液中加入食品级酸化剂，降低蛋白的pH，再经过超滤工艺得到预处理MPC。
  7. 根据权利要求2所述的微胶囊，其特征在于，所述添加外源试剂螯合离子的条件是：在蛋白溶液中加入食品级离子螯合剂。
  8. 根据权利要求2所述的微胶囊，其特征在于，所述预处理是处理到脱钙率45％以上。
  9. 根据权利要求2所述的微胶囊，其特征在于，所述所述微胶囊为液状或者固状。
  10. 根据权利要求9所述的微胶囊，其特征在于，所述微胶囊的制备具体包括：准确将预处理后的MPC溶液或者其喷干粉末配制得到一定浓度的蛋白溶液于10～50MPa下均质多次后，按芯材∶壁材＝1∶50～1∶1(w/w)的比例加入芯材，搅拌均匀后，利用高速剪切分散机分散；再在10～50MPa的压力下将混合液均质2～6次，得到均匀的乳状液；即为液状微胶囊的一种。
  11. 根据权利要求9所述的微胶囊，其特征在于，所述微胶囊为固状；包括将权利要求9制备得到的乳状液立即喷干或者冻干制备得到微胶囊粉末；喷雾干燥的工艺条件为：进口温度为120～160℃，通过调节雾化气体流量和蠕动泵的速度控制出口温度不变，出口温度为60～90℃；冷冻干燥的条件为，在液氮或者-80℃的条件下将液态乳状液冻结为固态，经由冷冻干燥仪制备得到冻干的微胶囊粉末。
  12. 根据权利要求2-11任一所述的微胶囊，其特征在于，所述芯材可以是任一对环境敏感的活性因子、易挥发的物质、需要改变气态或液态存在形式为固态应用形式的物质。
  13. 权利要求2-12任一所述微胶囊的应用。
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