WO2023151653A1 - 油凝胶及其制备方法和用途 - Google Patents

油凝胶及其制备方法和用途 Download PDF

Info

Publication number
WO2023151653A1
WO2023151653A1 PCT/CN2023/075433 CN2023075433W WO2023151653A1 WO 2023151653 A1 WO2023151653 A1 WO 2023151653A1 CN 2023075433 W CN2023075433 W CN 2023075433W WO 2023151653 A1 WO2023151653 A1 WO 2023151653A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
protein
oleogel
gel
water
Prior art date
Application number
PCT/CN2023/075433
Other languages
English (en)
French (fr)
Other versions
WO2023151653A9 (zh
Inventor
方素琼
陈文荣
王培建
Original Assignee
仙乐健康科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 仙乐健康科技股份有限公司 filed Critical 仙乐健康科技股份有限公司
Publication of WO2023151653A1 publication Critical patent/WO2023151653A1/zh
Publication of WO2023151653A9 publication Critical patent/WO2023151653A9/zh

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A23L33/12—Fatty acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3526—Organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A61K31/19—Carboxylic acids, e.g. valproic acid
    • A61K31/20—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids
    • A61K31/202—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids having three or more double bonds, e.g. linolenic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/22—Heterocyclic compounds, e.g. ascorbic acid, tocopherol or pyrrolidones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/26—Carbohydrates, e.g. sugar alcohols, amino sugars, nucleic acids, mono-, di- or oligo-saccharides; Derivatives thereof, e.g. polysorbates, sorbitan fatty acid esters or glycyrrhizin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
    • 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
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives 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
    • A61K8/30—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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/65—Collagen; Gelatin; Keratin; 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
    • 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
    • A61K9/0012—Galenical forms characterised by the site of application
    • A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
    • 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
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P11/00—Drugs for disorders of the respiratory system
    • A61P11/06—Antiasthmatics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00—Drugs for skeletal disorders
    • A61P19/02—Drugs for skeletal disorders for joint disorders, e.g. arthritis, arthrosis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00—Drugs for skeletal disorders
    • A61P19/06—Antigout agents, e.g. antihyperuricemic or uricosuric agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P25/00—Drugs for disorders of the nervous system
    • A61P25/28—Drugs for disorders of the nervous system for treating neurodegenerative disorders of the central nervous system, e.g. nootropic agents, cognition enhancers, drugs for treating Alzheimer's disease or other forms of dementia
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P27/00—Drugs for disorders of the senses
    • A61P27/02—Ophthalmic agents
    • A61P27/10—Ophthalmic agents for accommodation disorders, e.g. myopia
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P7/00—Drugs for disorders of the blood or the extracellular fluid
    • A61P7/02—Antithrombotic agents; Anticoagulants; Platelet aggregation inhibitors
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00—Drugs for disorders of the cardiovascular system
    • A61P9/10—Drugs for disorders of the cardiovascular system for treating ischaemic or atherosclerotic diseases, e.g. antianginal drugs, coronary vasodilators, drugs for myocardial infarction, retinopathy, cerebrovascula insufficiency, renal arteriosclerosis
    • 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
    • A61Q19/08—Anti-ageing preparations
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers

Definitions

  • the invention belongs to the field of functional food, and in particular relates to a functional composition rich in unsaturated fatty acids, which is used as an oral pharmaceutical preparation to improve the physical state of a subject and prevent or treat related diseases or diseases.
  • Unsaturated fatty acid is a kind of fatty acid that constitutes body fat and is an indispensable fatty acid for the human body. Unsaturated fatty acids are divided into monounsaturated fatty acids and polyunsaturated fatty acids according to the number of double bonds.
  • fish oil contains unsaturated fatty acids that combine with cholesterol to form esters, and then degrade into bile acids to be excreted, which can significantly reduce blood cholesterol, triglycerides and increase high-density lipoprotein. , can be used for anti-hyperlipidemia.
  • fish oil also has anti-platelet aggregation, anti-coagulation, and can prevent the occurrence of thrombotic diseases.
  • oil can be divided into small molecule gelling agent and biomacromolecular gelling agent by structuring agent.
  • Small molecule gelling agents usually self-assemble through heating-cooling to form a crystal network structure, and then structure the liquid oil Prepare a grease composition.
  • this type of process needs to be heated above the melting point of the small molecule gelling agent, and the higher operating temperature is likely to cause oxidative rancidity of unsaturated fatty acids.
  • Biomacromolecules, especially proteins are the optimal choice for oil structuring agents due to their high nutritional value and high consumer acceptance.
  • Oil structuring using protein as a structuring agent is usually prepared in an indirect manner, and the main methods include Pickering emulsion template method, foam template method and solvent substitution method.
  • Chinese invention patent application (notification number CN107950684) discloses a method for preparing an oil composition rich in unsaturated fatty acids using Pickering emulsion as a template. The method first prepares gelatin-poly The phenol complex solution is then sheared and homogenized with vegetable oil rich in unsaturated fatty acids to prepare a mixed emulsion, dried and sheared and dried to obtain a solid oil composition. This method needs to go through complex processes such as homogenization, drying, and shearing, and the preparation process is cumbersome.
  • the oil composition finally obtained in this patent contains gelatin, which is not accepted by consumers due to various reasons, and includes antioxidant polyphenols and polysaccharides, which form protein-polyphenol-polysaccharides to adsorb on the oil surface in the form of particles. Further, the method obtains an oil gel by shearing, the viscoelasticity is difficult to control, and the oil content is not high (less than 60%).
  • Chinese invention patent application discloses a porous material prepared from rice bran protein by foam template method for absorbing organic solvents to prepare organic gels, but the gel uses organic solvents, which cannot meet the requirements for oil gel preparation; and The product contains more air, which is not conducive to the protection of grease.
  • Chinese invention patent application discloses a method for continuously preparing oil composition from ethyl cellulose.
  • the method utilizes the property of dissolving ethyl cellulose at high temperature, mixes it with oil in an extruder, and cools the mixture to form an oil composition.
  • the melting zone temperature of the extruder needs to be as high as 100-200° C., and the high-temperature process will accelerate the oxidation of unsaturated fatty acids.
  • the oleogel of the present invention also has the following characteristics: high oil content (higher than 60%), suitable rheological properties (with storage modulus values of 1 ⁇ 10 3 Pa-1 ⁇ 10 5 Pa and with a loss factor of 0.08-0.5) and resistance to High oxidizing property (peroxide value below 2.5mmol/kg).
  • the present invention provides an oleogel comprising 60-90wt% liquid oil, 6-35wt% structuring agent and 4-15wt% water, wherein the liquid oil contains unsaturated fatty acids and the structuring agent is protein The particles are denatured, and the liquid oil is the continuous phase.
  • the liquid oil content is 63-85 wt%; and/or the structuring agent content is 6-25 wt%.
  • the unsaturated fatty acid is one or more of monounsaturated fatty acid and polyunsaturated fatty acid.
  • the monounsaturated fatty acids may include one or more of myristic acid, palmitoleic acid, oleic acid, trans oleic acid, ricinoleic acid, erucic acid, and cetoleic acid.
  • Polyunsaturated fatty acids can to include one or more of omega-3 and omega-6 polyunsaturated fatty acids.
  • the protein is one or more of animal protein and vegetable protein.
  • the animal protein may include one or more of whey protein, casein, collagen, and gelatin.
  • the denatured protein particles are prepared by preparing a protein suspension, denatured by heating, homogenized and dried.
  • the homogenization can be carried out by one or more methods of mechanical stirring homogenization, ultrasonic homogenization, micro-fluidic homogenization, colloid mill homogenization, and ball milling homogenization. Drying can be carried out by one or more methods in vacuum drying, vacuum freeze drying, electric blast drying or spray drying.
  • the protein suspension is a 2-25 wt% whey protein suspension in water.
  • the liquid oil is one or more of olive oil, canola oil, peanut oil, algae oil, fish oil, flaxseed oil, perilla seed oil, chia seed oil, and krill oil.
  • the oleogel may or may not contain antioxidants.
  • the antioxidant may be one or more of oil-soluble antioxidants and water-soluble antioxidants.
  • the oil soluble antioxidants are rosmanol, carnosol, sesamol, vitamin E, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, and tert-butylhydroquinone One or more of them, and the water-soluble antioxidant is one or more of vitamin C, sodium erythorbate, tea polyphenols, gallocatechin gallate, sugars and sugar alcohols; wherein the sugars include Sucrose; sugar alcohols are one or more of xylitol, sorbitol, erythritol and maltitol.
  • the oleogel has one or more of the following characteristics as determined by a rheometer:
  • (1) have a storage modulus value of 1x10 3 Pa-1x10 5 Pa;
  • the present invention provides the application of the oleogel of the present invention in food, health products or cosmetics, or the application of the oleogel of the present invention in the preparation of oral pharmaceutical preparations, wherein the oral pharmaceutical preparations Used for one or more of the following: (1) regulating blood lipids and/or clearing blood clots; (2) preventing Alzheimer's disease, nourishing the brain and/or improving memory; (3) preventing arthritis, relieving gout, asthma, and temporarily relieving Swelling and pain caused by arthritis; (4) improving vision and/or preventing and treating presbyopia; (5) maintaining the retina.
  • the present invention provides an oral pharmaceutical formulation comprising an oleogel of the present invention.
  • the method of the oleogel of the present application comprising:
  • the method further comprises the step of adding an oil-soluble antioxidant, a water-soluble antioxidant, or both to the oil phase, the water phase, or both, respectively.
  • the method does not include the step of heating the liquid oil.
  • the oil gel of the present invention has an oil content higher than 60%, which meets the needs of high oil content products in the prior art.
  • the oil gel of the present invention has solid/semi-solid properties and good rheological properties such as plasticity, spreadability and shear denaturation, and can be widely used in food systems.
  • the oil gel of the present invention has suitable rheological properties (storage modulus values of 1 ⁇ 10 3 Pa-1 ⁇ 10 5 Pa and loss factors of 0.08-0.5).
  • the oil gel of the present invention has higher oxidation resistance (peroxide value below 2.5mmol/kg), and can be stored in an environment easily oxidized for a long time.
  • the preparation process of the oil gel of the present invention is simple, and can be obtained only by homogeneously mixing the components without heating steps.
  • An unsaturated fatty acid-rich oil gel with no layering and uniform appearance was prepared.
  • the process of the invention is capable of rapid continuous and large-scale production, and oil composition products with different viscoelasticities can be prepared by simply controlling the process conditions, so as to meet the application in different foods, health foods, medicines and cosmetics.
  • composition of the present invention has simple components, and no need to add additional stabilizers, avoiding the use of thickeners, emulsifiers and organic reagents.
  • Figure 1 shows a photograph of the appearance of the oil gel.
  • a picture is ++++: transparent, not cloudy;
  • B picture is +++: translucent, basically not cloudy;
  • C picture is ++: basically opaque, slightly turbid;
  • D picture is +: opaque, turbid.
  • the degree of transparency of the oil gel is related to the stability of the product structure, and the more transparent the gel is, the more stable it is.
  • the principle is that the higher the degree of dispersion of the protein network in the oil gel, the smaller the size of the protein aggregates, so the smaller the angle at which light is scattered in the gel, the more transparent the gel.
  • Figure 2 shows a photomicrograph of the stained oleogel.
  • Figure 3 shows the water solubility experiment 1 of the oil gel prepared by different preparation methods.
  • Fig. 4 shows the water solubility experiment 2 of the oil gel prepared by different preparation methods.
  • liquid oil refers to an oil that is in a fluid state, such as an oil that is in a fluid state at room temperature.
  • Liquid oils may include, but are not limited to, olive oil, canola oil, peanut oil, algae oil, fish oil, flaxseed oil, perilla seed oil, chia seed oil, and krill oil.
  • the content of liquid oil is 60-90wt%, such as 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 89wt%.
  • unsaturated fatty acid refers to a straight-chain fatty acid containing more than one double bond, and the carbon chain length is usually 18-22 carbon atoms.
  • Unsaturated fatty acids may include monounsaturated fatty acids and polyunsaturated fatty acids. According to the position and function of the double bond, polyunsaturated fatty acids are divided into omega-6 series and omega-3 series polyunsaturated fatty acids. For example, linoleic acid and arachidonic acid belong to the omega-6 series, and linolenic acid, DHA or EPA belong to the omega-3 series.
  • the unsaturated fatty acids are omega-3 polyunsaturated fatty acids.
  • the amount of unsaturated fatty acids contained in the liquid oil can vary.
  • the content of unsaturated fatty acids can be 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% , 65%, 70%, 75%, 80%, 85%, 90%, or 95% or any range or point value in between.
  • the structuring agent can be protein denatured particles.
  • the protein may be one or more of animal protein and vegetable protein. Examples of animal proteins are whey protein, One or more of casein, collagen and gelatin.
  • the structuring agent is a protein denatured particle.
  • Denatured protein particles can be obtained by preparing protein suspension, denaturing by heating, homogenizing and drying.
  • the homogenization can be performed by one or more methods of mechanical stirring homogenization, ultrasonic homogenization, microfluidic homogenization, colloid mill homogenization, and ball milling homogenization.
  • the drying may be performed by one or more methods of vacuum drying, vacuum freeze drying, electric blast drying or spray drying.
  • the protein suspension is a whey protein suspension, eg 2-25 wt% whey protein aqueous suspension.
  • whey protein denatured granule powder can be prepared by preparing a whey protein suspension with a concentration range of 2-25%, fully dissolving with magnetic stirring, and heating at 75-100°C for 30-100 min to prepare protein denatured granule liquid; and drying after getting.
  • the content of the structuring agent is 6-35wt%, such as 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt% , 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt% %, 33wt% or 34wt% and any range therebetween.
  • continuous phase refers to a substance in which other substances are dispersed in a dispersed system.
  • the continuous phase may be a liquid oil.
  • the oil gel of the present invention may also contain an appropriate amount of water, such as 4-15wt% water, such as 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt% or 14wt% % and any range in between.
  • the weight ratio of structuring agent to water is from 1:3 to 5:1, such as 5:12, 1:2, 7:12, 8:12, 9:12, 10:12, 1:12 1. 20:12, 25:12, 35:12, 40:12.
  • the oil gels of the present invention may or may not contain other ingredients than liquid oils, structuring agents and water.
  • the oleogel of the present invention contains no other ingredients.
  • Other ingredients may include, but are not limited to, antioxidants, gums, stabilizers, thickeners or emulsifiers.
  • Antioxidants may include one or more of oil-soluble antioxidants and water-soluble antioxidants.
  • Oil-soluble antioxidants may include one or more of rosmanol, carnosol, sesamol, vitamin E, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate and tert-butylhydroquinone
  • the water-soluble antioxidant may include one or more of vitamin C, sodium erythorbate, tea polyphenols, gallocatechin gallate, sugars and sugar alcohols.
  • the sugar is sucrose.
  • the sugar alcohols are one or more of xylitol, sorbitol, erythritol and maltitol.
  • peroxide value represents an indicator of the degree of oxidation of oils and fatty acids, usually the content of active oxygen in 1 kg of a sample, expressed in millimoles of peroxides, and is used to illustrate whether the sample is Has been oxidized and deteriorated.
  • the peroxide value is the maximum allowable food oxidation limit set in the food standard, beyond this value, the food is unqualified. If the peroxide value exceeds the standard, it means that the food has deteriorated, and the deteriorated food may have adverse effects on the human body.
  • the peroxide value can be determined by titration and colorimetry, for example as mentioned in the Chinese Food Quality Standard GB/T 5009.37-2003 Hygienic Standard Analysis Method for Edible Oil.
  • the peroxide value/(mmol/kg) should be less than 7.5 (as stipulated in the grain industry standard LS/T 3243-2015 of the People's Republic of China); for vegetable crude edible vegetable oil, the peroxide value/(g/100g ) should be less than 0.25 (as stipulated in the national food safety standard vegetable oil GB2716-2018); for edible hydrogenated oil, peroxide value/(g/100g) should be less than 0.1, for margarine, shortening, cocoa butter substitute, non-dairy cream, For powdered fats and oils, the peroxide value/(g/100g) should be less than 0.13 (as stipulated in the national food safety standard GB15196-2015 for edible oils and fat
  • the peroxide value/(g/100g) should be less than 0.25 (as specified in the corresponding national food safety standards).
  • Most of the products in the prior art focus on the oleogel-forming properties of the structurant, and seldom concern whether the formed oleogel meets the food standard for peroxide value.
  • the inventor found in long-term research that the oil gel of the present invention can have a lower peroxide value, which meets the national peroxide value for various foods.
  • the oil gel of the present invention can be applied to pastry and bread as a nutritional supplement. When appropriate, it can also be used as a nutritional supplement in the above-mentioned types of products and other types of products.
  • viscoelasticity can be characterized by several parameters, such as storage modulus value (G'), and/or loss factor (tan ⁇ ).
  • viscoelasticity can be characterized by a loss factor (tan ⁇ ) to indicate that the research object exhibits solid properties (elasticity) or liquid properties (viscosity).
  • the desired result is 1 ⁇ 10 3 Pa ⁇ G′ ⁇ 1 ⁇ 10 5 Pa, 0.08 ⁇ tan ⁇ 0.5, and an oil gel with elasticity greater than viscosity is obtained.
  • the loss factor is calculated by loss modulus value (G′′)/storage modulus value (G′), where the storage modulus value (G′) and loss modulus value (G′′) can be obtained by flow Variable meter measurement.
  • the oleogel of the present invention can be prepared by mixing a structuring agent, such as whey protein denatured particles, with liquid oil to form an oil phase suspension, and then adding water.
  • a structuring agent such as whey protein denatured particles
  • whey protein denatured granules a whey protein suspension with a concentration range of 2 to 25% can be prepared, and after being fully dissolved by magnetic stirring, the protein denatured granules can be prepared by heating at 75 to 100°C for 30 to 100 minutes; after drying, the Denatured protein powder.
  • 6-35% whey protein denatured granules can be mixed with liquid oil, such as algae oil rich in Omega-3 polyunsaturated fatty acids, and homogenized to obtain an oil phase suspension of whey protein, and then, can be added to the above suspension Add 4 to 15% of water to the mixture, and then homogeneously obtain the oil gel of the present invention.
  • the method may not include the step of heating the liquid oil.
  • heating may be heating above room temperature for a period of time, for example at 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C °C, 100 °C or higher temperature heating, such as 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes or longer.
  • the oil gel of the present invention can have different effects depending on the type of unsaturated fatty acid contained.
  • the oil gel of the present invention may contain one or more of fish oil, squalene, ethyl polyenoate or evening primrose oil, and have the efficacy of these ingredients.
  • the oil gel of the present invention can be prepared into an oral pharmaceutical preparation for realizing various therapeutic effects.
  • Fish oil is a common animal source of omega-3s, rich in the essential fatty acids DHA and EPA that are beneficial to the body.
  • As a functional oil fish oil can be used in medicines. Its main effects are: regulating blood lipids, clearing thrombus, preventing blood coagulation, preventing cerebral thrombosis, cerebral hemorrhage and stroke; preventing arthritis, relieving gout, asthma, temporarily relieving pain caused by joint swelling and pain caused by inflammation; prevent Alzheimer's disease, nourish the brain, improve memory; improve vision, prevent and treat presbyopia; maintain the retina.
  • it can also be applied to the adjuvant treatment of diseases.
  • the applicable groups include: patients with thrombosis, cerebral hemorrhage or stroke; people with three highs (high blood pressure, high blood fat, high cholesterol); vision loss and presbyopia People who are on the trend; people with symptoms of heart disease and arteriosclerosis; people with arthritis, gout, and asthma; people who need to prevent and treat diabetes complications.
  • Squalene is a natural compound found in shark liver oil, which has various physiological functions such as increasing the activity of superoxide dismutase (SOD) in the body, enhancing the body's immunity, improving sexual function, anti-aging, anti-fatigue, and anti-tumor Function.
  • SOD superoxide dismutase
  • squalene is the only drug that has been confirmed to have anti-tumor effects and is widely used in cancer patients.
  • squalene The main functions of squalene are: hepatoprotective effect, promoting liver cell regeneration and protecting liver cells, thereby improving liver function; anti-fatigue and enhancing the body's disease resistance, improving human immune function; protecting the function of adrenal glands, improving stress ability; anti-tumor, especially when used after cancer resection surgery or radiotherapy and chemotherapy, the effect is remarkable, and its biggest feature is to prevent cancer from metastasizing to the lung; increase the role of white blood cells.
  • the application of squalene includes improving the immune system; regulating people's acid-base balance (alkaline products); used as an antioxidant, which can effectively improve skin color and relieve skin diseases such as psoriasis and dermatitis; help treat heart disease, high blood pressure, low blood pressure, sugar Diabetes disease, stomach disease, kidney disease, conjunctivitis, empyema, gynecological diseases, rheumatoid arthritis; it helps people who eat a lot of greasy food to restore the normal level of blood cholesterol; it is a fitness tonic.
  • Ethyl polyenoate is a product of ethyl esterification of polyunsaturated fatty acids obtained by refining and esterifying fish oil extracted from marine fish.
  • the main components are ethyl eicosapentaenoate and ethyl docosahexaenoate, both of which contain more unsaturated bonds. It is a light yellow to yellow clear oily liquid with a slight fishy smell. It has the effect of lowering serum triglyceride and total cholesterol, and is used for hyperlipidemia.
  • evening primrose oil The main components of evening primrose oil are: r-linolenic acid, magnesium, zinc, copper, vitamin C, E, B6, B5. It can be blended with base oils and essential oils. It has multiple therapeutic and whitening functions. It can be taken orally in capsules to treat cardiovascular diseases, premenstrual syndrome, and menopausal syndrome. It can be used in aromatherapy to reconcile lotions and creams. Eczema, psoriasis, help wound healing, nail development, solve hair problems, generally 10% dosage.
  • Step 1 Prepare a whey protein suspension with a concentration range of 2-25%. After fully dissolving by magnetic stirring, heat at 75-100°C for 30-100 minutes to prepare denatured protein granule liquid; obtain denatured protein granule powder after drying;
  • Step 2 Mix 6-35% whey protein denatured granules with algae oil rich in Omega-3 polyunsaturated fatty acids, and homogenize to obtain an oil phase suspension of whey protein;
  • Step 3 adding 4-15% of water to the suspension, and then homogenizing to obtain an oil gel rich in Omega-3 polyunsaturated fatty acids with an oil content as high as 60-90%.
  • Test procedure The rheological properties of the oil-gel were analyzed by small-amplitude oscillatory shear analysis.
  • the oil gel was placed on the sample stage of the rheometer (HAAKE MARS 60), and the sawtooth plate (P35TI/SE) was selected for testing.
  • the gap between the sample stage and the parallel plate is 1 mm.
  • the sample is subjected to strain scanning at 25° C., and the storage modulus (G′), loss modulus (G′′) and loss factor (tan ⁇ ) are recorded to characterize the rheological properties of the oil composition.
  • the storage modulus (G') reflects the elasticity of the composition.
  • Viscoelasticity can be characterized by a loss factor (tan ⁇ ) to indicate that the object of study exhibits solid properties (elasticity) or liquid properties (viscosity).
  • tan ⁇ loss factor
  • the prepared sample was crushed and fully mixed, then placed in a jar, 2 to 3 times the sample volume of petroleum ether was added, shaken, fully mixed, and left to stand for leaching for more than 12 hours. Filter through a funnel equipped with anhydrous sodium sulfate, take the filtrate, and evaporate petroleum ether to dryness with a rotary evaporator in a water bath below 40°C under reduced pressure, and the residue is the sample to be tested.
  • the sample determination should be avoided in direct sunlight. Weigh 2g to 3g of the sample (accurate to 0.001g), place it in a 250mL iodine flask, add 30mL of chloroform-glacial acetic acid mixture, shake gently to dissolve the sample completely. Accurately add 1.00mL saturated potassium iodide solution, stopper the bottle cap tightly, shake gently for 0.5min, and place in the dark for 3min.
  • X peroxide value, unit is millimole per kilogram (mmol/kg);
  • V the volume of sodium thiosulfate standard solution consumed by the sample, in milliliters (mL);
  • V0 the volume of sodium thiosulfate standard solution consumed by the blank test, in milliliters (mL);
  • the calculation result is expressed as the arithmetic mean of two independent measurement results obtained under repeatability conditions, and the result retains two significant figures.
  • the antioxidant capacity of the oil composition is characterized by the peroxide value; the lower the peroxide value, the better the antioxidant capacity.
  • Figure A is ++++ means: transparent, not turbid
  • Picture B is +++ means: translucent, basically not turbid
  • C picture is ++ means: basically opaque, slightly turbid;
  • D picture is + means: opaque, turbid.
  • Embodiment 1 Structural characterization of oil composition
  • Figure 2 shows the results of the formation of an osmotic network of protein particles in an oily composition.
  • the black part is oil
  • the protein has fluorescence absorption after staining, and it appears as a green bright spot under the laser confocal microscope.
  • the protein particles showing green fluorescence are connected and aggregated into chains, and this structure can make liquid oil coagulate into a semi-solid/solid oil composition, that is, oil gel.
  • the specially structured oleogel can effectively block oxygen and slow down the oxidative rancidity of oils and fats rich in Omega-3 polyunsaturated fatty acids, as shown below.
  • the algae oil is the continuous phase
  • the protein particles are the dispersed phase.
  • the solid/semi-solid oil composition can be prepared by heating mono- and distearic acid glyceride and cooling and crystallizing. Since the heating process will accelerate the oxidative rancidity of the oil rich in Omega-3 polyunsaturated fatty acids, the peroxide value is 5.2 mmol/kg by oxidative determination. On the contrary, the preparation process of the oil gel of the present application does not require a heating step, which avoids the oil oxidation caused by the heating process.
  • Unformed refers to that the prepared composition is liquid or obviously fluid suspension oil, which cannot be condensed into solid or semi-solid.
  • the oil gel can be prepared when the protein denatured particle content is 6-35%, and the oil gel cannot be formed when the protein denatured particle content is less than 6% or greater than 35%.
  • the prepared oil gel has better oxidation resistance, the peroxide value is lower than 2.5mmol/kg, and is suitable for being used as food.
  • the inventors have found that protein denatured particles have an effect on the appearance of the oleogel. When the content of denatured protein particles was 10.8%, the appearance of the oil gel was transparent and not cloudy. When the content of denatured protein particles was further increased, the appearance of the oil gel gradually became cloudy.
  • Embodiment 3 the investigation of different algae oil addition amount
  • the rheological properties and peroxide value of the oleogel were evaluated for the content of algae oil in the formulation of the oleogel. Choose a combination with a lower peroxide value, protein denatured particles: purified water ratio of 20:12 to determine the amount of algae oil added. Specifically, the quality of protein denatured particles and water (20g and 12g respectively) was controlled, the quality of algae oil (in g) was changed, and the rheological properties and peroxide value were measured by the method described above. The results are shown in Table 3.
  • the oil composition can be prepared when the algae oil content is 60-90%, and the prepared oil gel has better oxidation resistance. As the algal oil content increased, the oleogel became more transparent. When the ratio of protein denatured particles:purified water is 20:12, the content of algae oil is as high as 89%.
  • Embodiment 4 the investigation of different water additions
  • the oil composition can be prepared when the water content is 4-15%, and the prepared oil gel Has good oxidation resistance. Surprisingly, the inventors noticed that the water content has an effect on the appearance of the oleogel. When the water content was 4.3%, the oil gel was translucent and basically not cloudy; when the water content increased to 15.1%, the oil gel had a tendency to become more cloudy, basically opaque and cloudy.
  • linseed oil and fish oil can also be used to prepare oil compositions by the same method, and the prepared oil gel has better oxidation resistance.
  • Embodiment 6 the investigation of adding antioxidant
  • the oil gel of the present application has better oxidation resistance than control 1 (only algae oil) and control 2 (comprising algae oil and monoglyceride). After adding antioxidants, the antioxidant capacity of the oil gel is improved, but even without adding antioxidants, the oil gel of the present invention also achieves the same order of magnitude of peroxide value, and can be directly used as food.
  • Example 7 The difference in properties between the krill oil oleogel with the oil phase as the continuous phase and the krill oil emulsion gel with the water phase as the continuous phase
  • the krill oil emulsion gel is prepared as follows: 1. Prepare 300 g of 8% whey protein solution; 2. Add 200 g of krill oil to the water phase under high shear at 18,000 rpm, and keep the rotational speed for 5 minutes to form a uniform gel. krill oil emulsion; 3. Heating at 85°C for 30 minutes, and then placing it under ice water to cool, the krill oil emulsion gel can be formed.
  • krill oil gel (tube A) and emulsion gel (tube B) are similar in appearance
  • krill oil gel is insoluble in water and suspended on water.
  • Emulsion gels can be redissolved in water to form emulsions.
  • the continuous phase of oil gels is oil
  • the continuous phase of emulsion gels is water.
  • the fat-soluble pigments are used for dyeing, the oil gel can be dyed, while the emulsion gel is an oil-in-water system, and the fat-soluble pigments cannot penetrate into it, so they cannot be dyed, which has obvious differences.
  • casein, collagen, gelatin, zein and mung bean protein can also be used to prepare oil compositions by the same method, and the prepared oil gel has better antioxidant properties.
  • various proteins such as casein, collagen, gelatin, zein, and mung bean protein may be used instead of whey protein.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Birds (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Rheumatology (AREA)
  • Nutrition Science (AREA)
  • Emergency Medicine (AREA)
  • Pain & Pain Management (AREA)
  • Polymers & Plastics (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Neurosurgery (AREA)
  • Neurology (AREA)
  • Pulmonology (AREA)
  • Biomedical Technology (AREA)
  • Food Science & Technology (AREA)
  • Hematology (AREA)
  • Urology & Nephrology (AREA)
  • Vascular Medicine (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Microbiology (AREA)
  • Hospice & Palliative Care (AREA)
  • Diabetes (AREA)
  • Ophthalmology & Optometry (AREA)
  • Psychiatry (AREA)
  • Mycology (AREA)

Abstract

一种油凝胶及其制备方法和用途。该油凝胶包含60-90wt％液体油、6-35wt％结构化剂和4-15wt％水，其中液体油包含不饱和脂肪酸，且结构化剂是蛋白变性颗粒。该油凝胶作为富含不饱和脂肪酸的抗氧化可食用油脂组合物，无需添加额外的稳定剂，避免增稠剂、乳化剂及有机试剂的使用，且具有抗氧化性，有益于产品的长期存放。该油凝胶可以用作口服药物制剂，实现多种治疗效用。

Description

油凝胶及其制备方法和用途 技术领域
本发明属于功能食品领域，具体地涉及富含不饱和脂肪酸的功能性组合物，用作口服药物制剂，以改善受试者的身体状态、预防或治疗相关的疾病或病症。
背景技术
不饱和脂肪酸是构成体内脂肪的一种脂肪酸，是人体不可缺少的脂肪酸。不饱和脂肪酸根据双键个数的不同，分为单不饱和脂肪酸和多不饱和脂肪酸两种。鱼油作为不饱和脂肪酸的常见动物来源，含有的不饱和脂肪酸通过与胆固醇结合成酯、进而降解为胆酸排出体外，具有显著的降低血中胆固醇、甘油三酯及升高高密度脂蛋白的作用，可用于抗高血脂。此外，鱼油还具有抗血小板聚集、抗凝血、能预防血栓性疾病的发生等作用。
然而，不饱和脂肪酸的氧化一直是备受关注的重要方向，尤其是在油脂工业、药品及食品行业等方面，都大量涉及到不饱和脂肪酸的氧化问题。现有技术中对于不饱和脂肪酸的氧化往往涉及到抗氧化剂的使用。但出于生产成本和健康目的，本领域中尝试了多种方法来避免抗氧化剂的使用。在这些方法中，使用结构化剂处理不饱和脂肪酸以形成油凝胶成为选项之一。
根据分子量大小的不同，油脂可用结构化剂分为小分子凝胶剂和生物大分子凝胶剂。小分子凝胶剂(单，双硬脂酸甘油酸酯、蜡、卵磷脂、脂肪酸及其衍生物等)通常是通过加热-冷却的方式自组装形成晶体网络结构，进而对液体油进行结构化制备油脂组合物。然而，该类工艺需要加热温度至小分子凝胶剂的熔点以上，较高的操作温度易造成不饱和脂肪酸的氧化酸败。生物大分子，尤其是蛋白质，由于其高营养价值和高消费者接受度，成为油脂结构化剂的最优选择。由于亲水性蛋白质不溶解于油脂，这限制了蛋白质在油脂结构化领域的直接应用。采用蛋白作为结构化剂的油脂结构化通常是采用间接的方式进行制备，主要方法包括Pickering乳液模板法、泡沫模板法和溶剂替代法。
中国发明专利申请(公告号CN107950684)公开了一种以Pickering乳液为模板制备富含不饱和脂肪酸的油脂组合物的方法。该方法先制备明胶-多 酚复合物溶液，然后与富含不饱和脂肪酸的植物油剪切均质制备混合乳液，干燥处理并剪切干燥后样品得到固体油脂组合物。该方法需经过均质、干燥、剪切等复杂工序，制备工艺繁琐。该专利最终得到的油脂组合物包含明胶，其由于各种原因而不被消费者所接受，并且包括抗氧化剂多酚以及多糖，形成蛋白-多酚-多糖以颗粒形式吸附在油脂表面。进一步，该方法通过剪切得到油凝胶，粘弹性难以控制，且含油量不高(小于60％)。
中国发明专利申请(公开号CN112063002A)公开了一种米糠蛋白通过泡沫模板法制备多孔材料用于吸附有机溶剂制备有机凝胶，但该凝胶采用有机溶剂，不能满足油凝胶制备的要求；且产品中含有较多空气，不利于油脂的保护。
中国发明专利申请(公开号CN105228461A)公开了一种乙基纤维素连续化制备油脂组合物的方法。该方法利用乙基纤维素高温下溶解的性质，将其与油脂在挤压机中混合，混合物冷却形成油脂组合物。但该方法中挤压机的熔融区温度需高达100～200℃，高温工艺会加速不饱和脂肪酸的氧化。
本领域中仍然需要优化结构化剂以改善现有油凝胶的缺点。
发明内容
针对现有的油凝胶中存在的问题，即含油量低，流变性较差且难以控制，处理过程中由于加热等因素所致的不饱和脂肪酸的氧化，发明人提供了一种新的油凝胶。该油凝胶的制备工艺简单，不包括使不饱和脂肪酸氧化的加热步骤。本发明油凝胶还具备以下特点：含油量高(高于60％)，合适的流变性(具有1x103Pa-1x105Pa的储能模量值和具有0.08-0.5的损耗因子)以及抗氧化性高(2.5mmol/kg以下的过氧化值)。
在一方面，本发明提供了一种油凝胶，其包含60-90wt％液体油、6-35wt％结构化剂和4-15wt％水，其中液体油包含不饱和脂肪酸，结构化剂是蛋白变性颗粒，且液体油为连续相。
在一个实施方案中，液体油含量为63-85wt％；和/或结构化剂含量为6-25wt％。
在一个实施方案中，不饱和脂肪酸是单不饱和脂肪酸和多不饱和脂肪酸中的一种或多种。单不饱和脂肪酸可以包括肉豆蔻油酸、棕榈油酸、油酸、反式油酸、蓖麻油酸、芥酸和鲸蜡烯酸中的一种或多种。多不饱和脂肪酸可 以包括omega-3和omega-6多不饱和脂肪酸中的一种或多种。
在一个实施方案中，蛋白质是动物蛋白和植物蛋白中的一种或多种。动物蛋白可以包括乳清蛋白、酪蛋白、胶原蛋白和明胶中的一种或多种。
在一个实施方案中，蛋白变性颗粒是通过配制蛋白悬浮液，加热变性，均质并且干燥得到。均质可以是通过机械搅拌均质、超声均质、微射流均质、胶体磨均质、球磨均质中的一种或多种方式进行的。干燥可以是通过真空干燥、真空冷冻干燥、电热鼓风干燥或喷雾干燥中的一种或多种方式进行的。
在一个实施方案中，蛋白悬浮液为2-25wt％的乳清蛋白水悬浮液。
在一个实施方案中，液体油是橄榄油、芥花籽油、花生油、藻油、鱼油、亚麻籽油、紫苏籽油、奇亚籽油和磷虾油中的一种或多种。
在一个实施方案中，油凝胶包含或不包含抗氧化剂。抗氧化剂可以是油溶性抗氧化剂和水溶性抗氧化剂中的一种或多种。
在一个实施方案中，油溶性抗氧化剂为迷迭香酚、鼠尾草酚、芝麻酚、维生素E、丁基羟基茴香醚、二丁羟基甲苯、没食子酸丙酯和叔丁基对苯二酚中的一种或多种，并且水溶性抗氧化剂为维生素C、异抗坏血酸钠、茶多酚、没食子儿茶素没食子酸酯、糖类和糖醇类的一种或多种；其中糖类包括蔗糖；糖醇类为木糖醇、山梨糖醇、赤藓糖醇和麦芽糖醇中的一种或多种。
在一个实施方案中，根据流变仪测定，油凝胶具有以下特征中的一项或多项：
(1)具有1x103Pa-1x105Pa的储能模量值；
(2)具有0.08-0.5的损耗因子。
在另一个方面，本发明提供了本发明的油凝胶在食品、保健品或化妆品中的应用，或者本发明的油凝胶在制备用于口服药物制剂中的应用，其中所述口服药物制剂用于以下一项或多项：(1)调节血脂和/或清理血栓；(2)预防老年痴呆症、营养大脑和/或改善记忆；(3)预防关节炎、缓解痛风、哮喘，暂时缓解由关节炎引起的肿痛；(4)改善视力和/或防治老花眼；(5)维护视网膜。
在另一个方面，本发明提供了口服药物制剂，其包含本发明的油凝胶。
在另一个方面，提供了本申请的油凝胶的方法，其包括：
(1)将结构化剂加入液体油中，混合以得到结构化剂的油相悬浮液；以及
(2)将水加入结构化剂的油相悬浮液，均质后得到油凝胶。
在一个实施方案中，方法还包括在油相、水相或这两者中分别添加油溶性抗氧化剂、水溶性抗氧化剂或这两者的步骤。
在一个实施方案中，方法不包括对液体油加热的步骤。
本发明的优点包括：
1.本发明的油凝胶具有高于60％的含油量，满足现有技术中高含油量产品的需要。本发明的油凝胶具有固态/半固态的性状和良好的可塑性、涂抹性和剪切变性等流变特性，可广泛应用于食品体系中。
2.本发明的油凝胶具有适合的流变性(1x103Pa-1x105Pa的储能模量值和0.08-0.5的损耗因子)。
3.本发明的油凝胶具有较高的抗氧化性(2.5mmol/kg以下的过氧化值)，可以贮存于容易氧化的环境中较长时间。
4.本发明的油凝胶的制备工艺简单，仅通过均质混合各组分即可获得，无需加热步骤。制备得到不分层、外观均一的富含不饱和脂肪酸的油凝胶。本发明工艺能够进行快速连续化、规模化生产，可通过简单控制过程条件制备粘弹性不同的油脂组合物产品，满足在不同食品、保健食品、医药和化妆品中的应用。
5.本发明组合物组分简单，可以无需添加额外的稳定剂，避免增稠剂、乳化剂及有机试剂的使用。
附图说明
图1显示了油凝胶的外观照片。A图为++++：透明，不浑浊；B图为+++：半透明，基本不浑浊；C图为++：基本不透明，微浑浊；D图为+：不透明，浑浊。加号越多，油凝胶的外观越有利。油凝胶透明程度与产品结构稳定性有关，越透明表示凝胶越稳定。原理是油凝胶中蛋白质网络的分散程度越高，蛋白聚集体的尺寸就越小，这样光在凝胶中发生散射的角度越小，凝胶也就越透明。
图2显示了染色的油凝胶的显微照片。
图3显示了不同制备方法的油凝胶的水溶性实验一。
图4显示了不同制备方法的油凝胶的水溶性实验二。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对发明权利要求的限制。本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都被视为包括在本发明内。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。虽然相信本领域普通技术人员充分了解以下术语，但仍陈述以下定义以有助于说明本发明所公开的主题。
如本文所使用，术语“包含”与“包括”、“含有”或“特征在于”同义，并且是包括端点在内或是开放式的，并且不排除额外的未叙述的要素或方法步骤。“包含”是权利要求语言中使用的技术术语，意思指存在所述要素，但也可以增加其它要素并且仍形成在所述权利要求范围内的构造或方法。
如本文所使用，“液体油”是指呈流质状态的油，例如在室内温度呈流质状态的油。液体油可以包括但不限于橄榄油、芥花籽油、花生油、藻油、鱼油、亚麻籽油、紫苏籽油、奇亚籽油和磷虾油。在本文中，按照油凝胶的重量计，液体油的含量是60-90wt％，例如65wt％、70wt％、75wt％、80wt％、85wt％、89wt％。
如本文所使用，“不饱和脂肪酸”指含有1个以上双键的直链脂肪酸，碳链长度通常为18-22个碳原子。不饱和脂肪酸可以包括单不饱和脂肪酸和多不饱和脂肪酸。根据双键的位置及功能又将多不饱和脂肪酸分为omega-6系列和omega-3系列多不饱和脂肪酸。例如，亚油酸和花生四烯酸属于omega-6系列，并且亚麻酸、DHA或EPA属于omega-3系列。优选地，不饱和脂肪酸是omega-3多不饱和脂肪酸。液体油中包含的不饱和脂肪酸的含量可以存在变化。例如，不饱和脂肪酸的含量可以为1％、2％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％、90％或95％或它们之间的任何范围或点值。
如本文所使用，“结构化剂”在本文中是指通过分子之间的强相互作用引起的高分子网络凝聚油脂的成分。结构化剂可以是蛋白变性颗粒。蛋白质可以是动物蛋白和植物蛋白中的一种或多种。例如，动物蛋白是乳清蛋白、 酪蛋白、胶原蛋白和明胶中的一种或多种。优选地，结构化剂是蛋白变性颗粒。蛋白变性颗粒可以是通过配制蛋白悬浮液，加热变性，均质并且干燥得到。在一个实施方案中，均质可以是通过机械搅拌均质、超声均质、微射流均质、胶体磨均质、球磨均质中的一种或多种方式进行的。在一个实施方案中，干燥可以是通过真空干燥、真空冷冻干燥、电热鼓风干燥或喷雾干燥中的一种或多种方式进行的。优选地，蛋白悬浮液是乳清蛋白悬浮液，例如2～25wt％的乳清蛋白水悬浮液。例如，乳清蛋白变性颗粒粉可以通过配制浓度范围为2～25％的乳清蛋白悬浮液，磁力搅拌充分溶解后，75～100℃下加热30～100min，制备蛋白变性颗粒液；并且在干燥后得到。在本文中，按照油凝胶的重量计，结构化剂的含量为6-35wt％，例如7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％、21wt％、22wt％、23wt％、24wt％、25wt％、26wt％、27wt％、28wt％、29wt％、30wt％、31wt％、32wt％、33wt％或34wt％以及其间的任何范围。
如本文所使用，“连续相”指分散体系中分散其他物质的物质。在本文的油凝胶中，连续相可以是液体油。
本发明的油凝胶还可以包含适量的水，例如4-15wt％的水，例如5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％或14wt％以及其间的任何范围。在一个实施方案中，结构化剂与水的重量比为1:3-5:1，例如5:12、1:2、7:12、8:12、9:12、10:12、1:1、20:12、25:12、35:12、40:12。
本发明的油凝胶可以包含或不包含液体油、结构化剂和水以外的其它成分。优选地，本发明的油凝胶不包含其它成分。其它成分可以包括但不限于抗氧化剂、胶凝胶、稳定剂、增稠剂或乳化剂。抗氧化剂可以包括油溶性抗氧化剂和水溶性抗氧化剂中的一种或多种。油溶性抗氧化剂可以包括迷迭香酚、鼠尾草酚、芝麻酚、维生素E、丁基羟基茴香醚、二丁羟基甲苯、没食子酸丙酯和叔丁基对苯二酚中的一种或多种，并且水溶性抗氧化剂可以包括维生素C、异抗坏血酸钠、茶多酚、没食子儿茶素没食子酸酯、糖类和糖醇类的一种或多种。优选地，糖类为蔗糖。优选地，糖醇类为木糖醇、山梨糖醇、赤藓糖醇和麦芽糖醇中的一种或多种。
如本文所使用，“过氧化值”表示油脂和脂肪酸等被氧化程度的一种指标，通常是1千克样品中的活性氧含量，以过氧化物的毫摩尔数表示，用于说明样品是否因已被氧化而变质。一般来说，过氧化值越高其酸败程度越高。 过氧化值是食品标准中设定的允许食品氧化的最高限值，超过该值，食品则不合格。如过氧化值超标则说明食品已经变质，而变质的食品可能会对人体产生不良影响。过氧化值可以通过滴定法和比色法来测定，例如如中国食品质量标准GB/T 5009.37-2003食用油卫生标准分析方法中提到的。不同油凝胶的过氧化值标准存在不同。例如，对于DHA藻油，过氧化值/(mmol/kg)应当小于7.5(如中华人民共和国粮食行业标准LS/T 3243-2015规定)；对于植物原油食用植物油，过氧化值/(g/100g)应当小于0.25(如食品安全国家标准植物油GB2716-2018规定)；对于食用氢化油，过氧化值/(g/100g)应当小于0.1，对于人造奶油，起酥油，代可可脂，植脂奶油，粉末油脂等，过氧化值/(g/100g)应当小于0.13(如食品安全国家标准食用油脂制品GB15196-2015规定)。对于糕点与面包，饼干，方便面，速冻调理制品，过氧化值/(g/100g)应当小于0.25(如相应的食品安全国家标准中规定)。现有技术的产品大多关注于结构化剂的油凝胶成型特性，很少关于形成的油凝胶是否满足过氧化值的食品标准。发明人在长期的研究中发现，本发明的油凝胶可以具备较低的过氧化值，满足国家对各类食品的过氧化值。例如，本发明的油凝胶可以作为营养补充剂应用于糕点与面包。在适当时，也可以作为营养补充剂应用于上述各类以及其它种类的产品中。
在本文中，粘弹性是可以通过多个参数来表征，例如储能模量值(G′)，和/或损耗因子(tanδ)。优选地，粘弹性可以通过损耗因子(tanδ)来表征，以表明研究对象呈现固体性质(弹性)或液体性质(粘性)。对于完全弹性材料，tanδ值为0；0<tanδ<1时，研究对象表现出的弹性大于粘性；tanδ＝1时，研究对象处于临界应变下，可以用来衡量延展性；tanδ>1时，研究对象显示出比弹性更多的粘性行为。在本文中，期望的结果是1x103Pa≤G′≤1x105Pa，0.08≤tanδ≤0.5，得到弹性大于粘性的油凝胶。在本文中，损耗因子以损耗模量值(G″)/储能模量值(G′)来计算，其中储能模量值(G′)和损耗模量值(G″)可以通过流变仪测定。
产品的制备方法
本发明的油凝胶可以通过混合结构化剂，例如乳清蛋白变性颗粒与液体油均质形成油相悬浮液，然后添加水来制备。对于乳清蛋白变性颗粒，可以配制浓度范围为2～25％的乳清蛋白悬浮液，磁力搅拌充分溶解后，75～100℃下加热30～100min，即可制备蛋白变性颗粒液；干燥后得到蛋白变性颗粒粉。 可以将6～35％的乳清蛋白变性颗粒与液体油，例如富含Omega-3多不饱和脂肪酸的藻油混合，均质得到乳清蛋白的油相悬浮液，然后，可以在上述悬浮液中加入4～15％的水，然后均质获得本发明的油凝胶。方法可以不包括对液体油加热的步骤。在本文中，加热可以是高于室温加热一段时间，例如于40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃或更高温度加热，例如30分钟、35分钟、40分钟、45分钟、50分钟、55分钟或60分钟或更长时间。
产品的效用
本发明的油凝胶根据所含不饱和脂肪酸的类型可以具备不同的效果。例如，本发明的油凝胶可以包含鱼油、角鲨烯、多烯酸乙酯或月见草油中的一种或多种，并且具备这些成分的功效。本发明的油凝胶可以制备成口服药物制剂，用于实现多种治疗效用。
鱼油是ω-3的常见动物来源，富含对人体有益的必需脂肪酸DHA和EPA。鱼油作为一种功能性油脂，可应用于药品，其主要作用功效有：调节血脂，清理血栓，防止血液凝固，预防脑血栓、脑溢血及中风；预防关节炎、缓解痛风、哮喘，暂时缓解由关节炎引起的肿痛；预防老年痴呆症、营养大脑、改善记忆；改善视力、防治老花眼；维护视网膜。除此之外，还可应用于疾病的辅助治疗，其适用的人群有：有血栓，脑溢血或中风等患病者；三高(高血压、高血脂、高胆固醇)人群；视力衰退有老花趋势者；有心脏病、动脉硬化症状的人群；有关节炎、痛风、哮喘的人群；需防治糖尿病合并症的患者。
角鲨烯是从鲨鱼的肝油中发现的一种天然化合物，具有提高体内超氧化物歧化酶(SOD)活性、增强机体免疫能力、改善性功能、抗衰老、抗疲劳、抗肿瘤等多种生理功能。在海洋鱼油类产品中，角鲨烯是唯一确认有防治肿瘤作用，并被广泛用于肿瘤病人的药物。角鲨烯的主要功效有：保肝作用，促进肝细胞再生并保护肝细胞，从而改善肝脏功能；抗疲劳和增强机体的抗病能力，提高人体免疫功能；保护肾上腺皮的功能，提高应激能力；抗肿瘤，尤其在癌切除外科手术后或采用放化疗时使用，效果显著，其最大的特点是防止癌症向肺部转移；升高白细胞的作用。角鲨烯的应用包括改善免疫系统；调节人的酸碱平衡值(碱性产品)；用作抗氧化剂，可有效改善皮肤色泽，缓解牛皮癣和皮炎这类皮肤疾患；有助于治疗心脏病，高血压，低血压，糖 尿病，胃病，肾病，结膜炎，脓胸，妇女病，类风湿性关节炎；有助于吃大量油腻食品的人士恢复血液中胆固醇的正常水平；是一种健身滋补品。
多烯酸乙酯是自海洋鱼类提取的鱼油经精制、酯化而得的多不饱和脂肪酸乙酯化的产品。主要成分为二十碳五烯酸乙酯和二十二碳六烯酸乙酯，二者含不饱和键较多。为微黄色至黄色的澄清油状液体，略有鱼腥味。具有降低血清甘油三酯和总胆固醇的作用，用于高脂血症。
月见草油的主要成分有：r-亚麻油酸，镁，锌，铜、维生素C、E、B6、B5。可以调合基础油和精油的油脂，具有多项治疗、美白功能，制成胶囊内服可以治疗心血管疾病，经前症候群，更年期综合症，用在芳香疗法中，可以调和乳液、乳霜，改善湿疹，牛皮癣，帮助伤口愈合，指甲发育，解决头发问题，一般是10％的剂量使用。
以下将参考实施例对本申请进行进一步的详细解释。然而，本领域技术人员应理解，这些实施例仅为了说明的目的提供，而不是意图限制本申请。
实施例
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限定本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。除非另外指明，所列出的所有量均基于总重的重量百分比描述。本申请不应解释为受限于所述的具体实施例。
1.制备方法
步骤1：配制浓度范围为2～25％的乳清蛋白悬浮液，磁力搅拌充分溶解后，75～100℃下加热30～100min，即可制备蛋白变性颗粒液；干燥后得到蛋白变性颗粒粉；
步骤2：将6～35％的乳清蛋白变性颗粒与富含Omega-3多不饱和脂肪酸的藻油混合，均质得到乳清蛋白的油相悬浮液；
步骤3：向上述悬浮液中加入4～15％的水，然后均质获得含油量高达60～90％的富含Omega-3多不饱和脂肪酸的油凝胶。
2.测试方法
①流变性质
采用的仪器：流变仪
测试步骤：采用小振幅振荡剪切分析对油凝胶的流变学性质进行分析。将油凝胶置于流变仪(HAAKE MARS 60)样品台，选用锯齿板(P35TI/SE)进行测试。样品台与平行板的间隙为1mm。首先在25℃下对样品进行应变扫描，记录储能模量值(G′)，损耗模量(G″)和损耗因子(tanδ)，用于表征油脂组合物的流变性质。
对于流变测试，储能模量(G′)值可以评价弹性度量或存储能量；损耗模量(G″)的值可以评价粘度量度或耗散能量。损耗因子tanδ＝G″/G′。
储能模量(G′)反映了组合物的弹性大小。
粘弹性可以通过损耗因子(tanδ)来表征，以表明研究对象呈现固体性质(弹性)或液体性质(粘性)。对于完全弹性材料，tanδ值为0；0<tanδ<1时，研究对象表现出的弹性大于粘度；tanδ＝1时，研究对象处于临界应变下，可以用来衡量延展性；tanδ>1时，研究对象显示出比弹性更多的粘性行为。
②氧化性
采用的仪器：酸式滴定管，碘量瓶，旋转蒸发仪
测试步骤：
(1)取样
将制备得到的样品破碎并充分混匀后置于广口瓶中，加入2～3倍样品体积的石油醚，摇匀，充分混合后静置浸提12h以上。经装有无水硫酸钠的漏斗过滤，取滤液，在低于40℃的水浴中，用旋转蒸发仪减压蒸干石油醚，残留物即为待测试样。
(2)样本测定
应避免在阳光直射下进行试样测定。称取试样2g～3g(精确至0.001g)，置于250mL碘量瓶中，加入30mL三氯甲烷-冰乙酸混合液，轻轻振摇使试样完全溶解。准确加入1.00mL饱和碘化钾溶液，塞紧瓶盖，并轻轻振摇0.5min，在暗处放置3min。取出加100mL水，摇匀后立即用硫代硫酸钠标准溶液(过氧化值估计值在5.91mmol/kg及以下时，用0.002mol/L标准溶液；过氧化值估计值大于5.91mmol/kg g时，用0.01mol/L标准溶液)滴定析出的碘，滴定至淡黄色时，加1mL淀粉指示剂，继续滴定并强烈振摇至溶液蓝色消失为终点。同时进行空白试验。空白试验所消耗0.01mo1/L硫代硫酸钠溶液体积V0不得超过0.1mL。
(3)分析结果的表述
用1kg样品中活性氧的毫摩尔数表示过氧化值时，按公式：X＝(V-V0)x c/(2x m)x 1000计算。
式中：
X：过氧化值，单位为毫摩尔每千克(mmol/kg)；
V：试样消耗的硫代硫酸钠标准溶液体积，单位为毫升(mL)；
V0：空白试验消耗的硫代硫酸钠标准溶液体积，单位为毫升(mL)；
c：硫代硫酸钠标准溶液的浓度，单位为摩尔每升(mol/L)；
m：试样质量，单位为克(g)；
1000：换算系数。
计算结果以重复性条件下获得的两次独立测定结果的算术平均值表示，结果保留两位有效数字。
评价标准：以过氧化值表征油脂组合物的抗氧化能力；过氧化值越低，则抗氧化性越好。
③外观评价
如图1中所示，A图为++++表示：透明，不浑浊；
B图为+++表示：半透明，基本不浑浊；
C图为++表示：基本不透明，微浑浊；
D图为+表示：不透明，浑浊。
实施例1：油脂组合物的结构表征
1.根据表1的配方制备油凝胶。具体地，将18wt％的乳清蛋白蛋白变性颗粒加入70wt％富含Omega-3多不饱和脂肪酸的藻油中，混合0.5～3h得到蛋白的油相悬浮液；然后将12wt％纯化水加入到上述油相悬浮液中，均质3～30min后得到所述富含Omega-3多不饱和脂肪酸的油凝胶。
表1：油凝胶的配方
对油凝胶进行了显微观察(染色方式)以进行结构表征：蛋白颗粒在制 备过程中使用硫磺素T(Th T)荧光染色；使用Leica TCS SP5共聚焦激光扫描显微镜(Leica Microsystems Inc.,Heidelberg,Germany)捕获蛋白质颗粒或网络的成像，激发波长为458nm。
图2中显示了油脂组合物中蛋白颗粒形成渗透网络的结果。根据图2中所示，黑色部分为油脂，而蛋白经染色后具有荧光吸收，在激光共聚焦显微镜下呈现绿色亮点。根据显微图片，显示绿色荧光的蛋白颗粒连结、聚集成链状，该结构可使液体油脂凝结成半固态/固态油脂组合物，即油凝胶。该特殊结构的油凝胶可有效阻隔氧气，减缓富含Omega-3多不饱和脂肪酸的油脂的氧化酸败，如下文所示。根据图2可知，在该油凝胶中，藻油为连续相，而蛋白颗粒为分散相。
2.单，双硬脂酸甘油酸酯结构油脂对比例。
将90wt％藻油与10wt％单，双硬脂酸甘油酯充分混合后，70～100℃下加热30～60min后冷却，即得油脂组合物。
通过加热单，双硬脂酸甘油酯冷却结晶的方式可制得固体/半固体油脂组合物。由于该加热过程会加速富含Omega-3多不饱和脂肪酸的油脂的氧化酸败，通过氧化性测定，过氧化值为5.2mmol/kg。相反，本申请的油凝胶的制备过程不需要加热步骤，避免了加热过程中导致的油脂氧化。
实施例2：不同蛋白变性颗粒添加量的考察
对油凝胶的配方中的乳清蛋白变性颗粒的含量对油凝胶的流变性质和过氧化值进行的评估。具体地，控制藻油和水的质量(分别为70g和12g)，改变蛋白变性颗粒的质量(以g计)，通过上文描述的方法测定流变性质和过氧化值。表2中显示了结果。
表2：不同蛋白变性颗粒添加量对流变性质和过氧化值的影响
不成型：指制备后的组合物呈液状或明显流动的混悬油液，无法凝结成固态或半固态。
根据表2中显示，蛋白变性颗粒为6～35％时能够制备出油凝胶，在蛋白变性颗粒含量小于6％或大于35％时不能形成油凝胶。制备的油凝胶具有更好的抗氧化性，过氧化值低于2.5mmol/kg，适合于用作食品。发明人发现蛋白变性颗粒对油凝胶的外观有影响。当蛋白变性颗粒含量为10.8％时，油凝胶外观透明、不浑浊，当进一步增加蛋白变性颗粒含量时，油凝胶外观变得逐渐浑浊。
在一定范围6～35％内，随着蛋白微颗粒的含量增加，凝胶强度增加；在超过一定范围后，蛋白微颗粒处于过饱和状态，无法较好分散于油脂中，导致蛋白微颗粒析出。当蛋白变性颗粒：纯化水＝3:12或45:12时，不能形成油凝胶。令人惊讶地，随着蛋白变性颗粒:纯化水从3:12增加到25:12时，过氧化值有逐渐降低的趋势，然后从25:12进一步增加到45:12时，过氧化值又会逐渐增加。当蛋白变性颗粒：纯化水为25:12时，油凝胶的过氧化值最低。
实施例3：不同藻油添加量的考察
对油凝胶的配方中的藻油的含量对油凝胶的流变性质和过氧化值进行的评估。选择具有较低过氧化值的组合，蛋白变性颗粒：纯化水为20:12以测定藻油添加量。具体地，控制蛋白变性颗粒和水的质量(分别为20g和12g)，改变藻油的质量(以g计)，通过上文描述的方法测定流变性质和过氧化值。表3中显示了结果。
表3：不同藻油添加量对流变性质和过氧化值的影响
根据表3可知，藻油为60～90％时能够制备出油脂组合物，且制备的油凝胶具有较好的抗氧化性。随着藻油含量的增加，油凝胶变得更加透明。当蛋白变性颗粒:纯化水为20:12时，藻油含量高达89％。
实施例4：不同水添加量的考察
对油凝胶的配方中的水含量对油凝胶的流变性质和过氧化值进行的评估。具体地，控制蛋白变性颗粒和藻油的质量(分别为20g和70g)，改变水的质量(以g计)，通过上文描述的方法测定流变性质和过氧化值。表4中显示了结果。
表4：不同水添加量对流变性质和过氧化值的影响
根据表4可知，水为4～15％时能够制备出油脂组合物，且制备的油凝胶 具有较好的抗氧化性。令人惊讶地，发明人注意到水含量对于油凝胶的外观有影响。当水含量为4.3％时，油凝胶半透明，基本不浑浊；当水含量增加到15.1％时，油凝胶具备变得更加浑浊的趋势，基本不透明且浑浊。
实施例5：不同油脂来源制备的油凝胶考察
还考察了本发明的油凝胶对不同液体油的适用性。具体地，油凝胶的配方如表5中所示，制备方法与以上所述的方法相同，只是添加不同的液体油。
表5：不同油脂来源制备的油凝胶的流变性质和过氧化值
根据表5可知，除藻油外，亚麻籽油和鱼油也能用同样的方法制备出油脂组合物，且制备的油凝胶具有较好的抗氧化性。
实施例6：添加抗氧化剂的考察
还考察了抗氧化剂的添加对本发明的油凝胶的流变性和过氧化值的影响。具体地，油凝胶的配方如表6中所示，制备方法与以上所述的方法相同，只是额外添加抗氧化剂，维生素C(VC)、蔗糖和赤藓糖醇。结果如表6中所示。
表6：抗氧化剂的添加对本发明的油凝胶的流变性和过氧化值的影响
*样品加速稳定考察条件：温度40℃，湿度75％下放置一个月
根据表6可知，本申请的油凝胶比对照1(仅藻油)和对照2(包含藻油和单甘脂)，具有更好的抗氧化性。在添加抗氧化剂后，油凝胶抗氧化能力提高，但是即便不添加抗氧化剂，本发明的油凝胶也实现了相同数量级的过氧化值，可以直接用作食品。
实施例7：以油相为连续相的磷虾油油凝胶与以水相为连续相的磷虾油乳液凝胶的性质区别
A：按照表1中组合物的配比，只是用磷虾油替换藻油，制备磷虾油的油凝胶；
B：采用乳清蛋白为凝胶剂，制备磷虾油的乳液凝胶。具体地，磷虾油乳液凝胶如下制备：1、配制8％的乳清蛋白溶液300g；2、水相在18000rpm下高剪切，加入200g磷虾油，保持该转速剪切5min，形成均一的磷虾油乳液； 3、85℃下加热30min，再放置于冰水下冷却，即可形成磷虾油乳液凝胶。
分别取A和B两种凝胶各0.5g于50mL 60℃的纯化水中，设定500rpm的转速进行充分搅拌10min，观察对比两种凝胶的状态。
由图3和图4可得，磷虾油凝胶(A管)和乳液凝胶(B管)在外观上虽较为相似，但磷虾油凝胶不溶于水，悬浮于水上，磷虾油乳液凝胶能复溶于水，形成乳液从结构分析，油凝胶的连续相为油脂，而乳液凝胶连续相为水。当采用脂溶性色素分别进行染色时，油凝胶可染色，而乳液凝胶为水包油体系，脂溶性色素无法渗透进去，因此不能染色，具有明显区别。
实施例8不同种类蛋白制备的油凝胶的流变性质和过氧化值
还考察了不同蛋白对本发明的油凝胶的适用性。具体地，油凝胶的配方如表7中所示，制备方法与以上所述的方法相同，只是采用不同种类的蛋白。
表7：不同种类蛋白对油凝胶的流变性质和过氧化值的影响
根据表7可知，除乳清蛋白外，酪蛋白、胶原蛋白、明胶、玉米醇溶蛋白和绿豆蛋白也能用同样的方法制备出油脂组合物，且制备的油凝胶具有较好的抗氧化性。在本文中，各种蛋白质诸如酪蛋白、胶原蛋白、明胶、玉米醇溶蛋白和绿豆蛋白可以替换乳清蛋白使用。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述 实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (14)

  1. 一种油凝胶，其包含60-90wt％液体油、6-35wt％结构化剂和4-15wt％水，其中液体油包含不饱和脂肪酸，结构化剂是蛋白变性颗粒，且液体油为连续相。
  2. 根据权利要求1所述的油凝胶，其中液体油含量为63-85wt％；和/或结构化剂含量为6-25wt％。
  3. 根据权利要求1所述的油凝胶，其中不饱和脂肪酸是单不饱和脂肪酸和多不饱和脂肪酸中的一种或多种；单不饱和脂肪酸包括肉豆蔻油酸、棕榈油酸、油酸、反式油酸、蓖麻油酸、芥酸和鲸蜡烯酸中的一种或多种；多不饱和脂肪酸包括omega-3和omega-6多不饱和脂肪酸中的一种或多种。
  4. 根据权利要求1所述的油凝胶，其中蛋白是动物蛋白和植物蛋白中的一种或多种；其中动物蛋白包括乳清蛋白、酪蛋白、胶原蛋白和明胶中的一种或多种。
  5. 根据权利要求1所述的油凝胶，其中蛋白变性颗粒是通过配制蛋白悬浮液，加热变性，均质并且干燥得到；其中均质是通过机械搅拌均质、超声均质、微射流均质、胶体磨均质、球磨均质中的一种或多种方式进行的；其中干燥是通过真空干燥、真空冷冻干燥、电热鼓风干燥或喷雾干燥中的一种或多种方式进行的。
  6. 根据权利要求5所述的油凝胶，其中蛋白悬浮液为2-25wt％的乳清蛋白水悬浮液。
  7. 根据权利要求1所述的油凝胶，其中液体油是橄榄油、芥花籽油、花生油、藻油、鱼油、亚麻籽油、紫苏籽油、奇亚籽油和磷虾油中的一种或多种。
  8. 根据权利要求1所述的油凝胶，其包含或不包含抗氧化剂；其中抗氧化剂是油溶性抗氧化剂和水溶性抗氧化剂中的一种或多种。
  9. 根据权利要求8所述的油凝胶，其中油溶性抗氧化剂为迷迭香酚、鼠尾草酚、芝麻酚、维生素E、丁基羟基茴香醚、二丁羟基甲苯、没食子酸丙酯和叔丁基对苯二酚中的一种或多种，并且水溶性抗氧化剂为维生素C、异抗坏血酸钠、茶多酚、没食子儿茶素没食子酸酯、糖类和糖醇类的一种或多种；其中糖类包括蔗糖；糖醇类为木糖醇、山梨糖醇、赤藓糖醇和麦芽糖醇中的一种或多种。
  10. 根据权利要求1所述的油凝胶，其中根据流变仪测定，油凝胶具有以下特征中的一项或多项：
    (1)具有1x103Pa-1x105Pa的储能模量值；
    (2)具有0.08-0.5的损耗因子。
  11. 根据权利要求1所述的油凝胶在食品、保健品或化妆品中的应用，或者根据权利要求1所述的油凝胶在制备用于口服药物制剂中的应用，其中所述口服药物制剂用于以下一项或多项：(1)调节血脂和/或清理血栓；(2)预防老年痴呆症、营养大脑和/或改善记忆；(3)预防关节炎、缓解痛风、哮喘，暂时缓解由关节炎引起的肿痛；(4)改善视力和/或防治老花眼；和(5)维护视网膜。
  12. 口服药物制剂，其包含根据权利要求1所述的油凝胶。
  13. 制备权利要求1的油凝胶的方法，其包括：
    (1)将结构化剂加入液体油中，混合以得到结构化剂的油相悬浮液；以及
    (2)将水加入结构化剂的油相悬浮液，均质后得到油凝胶。
  14. 根据权利要求13所述的方法，其还包括在油相、水相或这两者中分别添加油溶性抗氧化剂、水溶性抗氧化剂或这两者的步骤；方法不包括对液体油加热的步骤。
PCT/CN2023/075433 2022-02-11 2023-02-10 油凝胶及其制备方法和用途 WO2023151653A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210126905.8 2022-02-11
CN202210126905.8A CN114158733B (zh) 2022-02-11 2022-02-11 油凝胶及其制备方法和用途

Publications (2)

Publication Number Publication Date
WO2023151653A1 true WO2023151653A1 (zh) 2023-08-17
WO2023151653A9 WO2023151653A9 (zh) 2023-10-19

Family

ID=80489707

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/075433 WO2023151653A1 (zh) 2022-02-11 2023-02-10 油凝胶及其制备方法和用途

Country Status (2)

Country Link
CN (1) CN114158733B (zh)
WO (1) WO2023151653A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114158733B (zh) * 2022-02-11 2022-05-17 仙乐健康科技股份有限公司 油凝胶及其制备方法和用途
CN114917779A (zh) * 2022-04-08 2022-08-19 沈阳师范大学 一种液体植物油基质毛细悬浮液塑性脂肪及其构建方法
CN116268423B (zh) * 2023-02-28 2024-03-22 鲁维制药集团有限公司 活性成分-蛋白质冷凝胶及其制备方法和应用
CN116941771B (zh) * 2023-08-03 2024-05-10 中国海洋大学 一种具有多重功效的南极磷虾油递送体系及其制备和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120308704A1 (en) * 2009-06-02 2012-12-06 Peter Eisner Emulsion or Gel for Producing food Products Including Omega-3 Fatty Acid
WO2016062685A1 (en) * 2014-10-20 2016-04-28 Stichting Top Institute Food And Nutrition Protein-stabilised oleogels
US20160120206A1 (en) * 2013-06-25 2016-05-05 Nestec S.A. Whey protein aggregates particles and use thereof
WO2020242313A1 (en) * 2019-05-29 2020-12-03 Wageningen Universiteit One step procedure for producing a protein oleogel
WO2021231847A1 (en) * 2020-05-15 2021-11-18 Massachusetts Institute Of Technology Oleogel and oleopaste compositions and uses thereof
CN114158733A (zh) * 2022-02-11 2022-03-11 仙乐健康科技股份有限公司 油凝胶及其制备方法和用途
CN114190443A (zh) * 2021-11-17 2022-03-18 华南理工大学 一种蛋白凝胶剂制备油凝胶的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108200969B (zh) * 2016-12-20 2021-08-13 中粮集团有限公司 一种玉米醇溶蛋白含油凝胶及其制备方法
CN113261594B (zh) * 2021-05-12 2022-01-04 华南农业大学 一种米糠蛋白油凝胶及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120308704A1 (en) * 2009-06-02 2012-12-06 Peter Eisner Emulsion or Gel for Producing food Products Including Omega-3 Fatty Acid
US20160120206A1 (en) * 2013-06-25 2016-05-05 Nestec S.A. Whey protein aggregates particles and use thereof
WO2016062685A1 (en) * 2014-10-20 2016-04-28 Stichting Top Institute Food And Nutrition Protein-stabilised oleogels
WO2020242313A1 (en) * 2019-05-29 2020-12-03 Wageningen Universiteit One step procedure for producing a protein oleogel
WO2021231847A1 (en) * 2020-05-15 2021-11-18 Massachusetts Institute Of Technology Oleogel and oleopaste compositions and uses thereof
CN114190443A (zh) * 2021-11-17 2022-03-18 华南理工大学 一种蛋白凝胶剂制备油凝胶的方法
CN114158733A (zh) * 2022-02-11 2022-03-11 仙乐健康科技股份有限公司 油凝胶及其制备方法和用途

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAO, ZHENYU ET AL.: "Advance in Technology of Edible Vegetable Oil-Gelling", CHINA OILS AND FATS, vol. 44, no. 8, 31 December 2019 (2019-12-31), pages 57 - 64, XP055786855 *
HONGJUAN LI; AIRONG QIN; YONGMING ZHANG; HONGMEI YU; YANJUN SUN; HONGBO LI; JINGHUA YU: "Characterisation of a thermally denatured whey protein isolate–butter emulsion/emulsion gel mediated by citric acid and a pre‐emulsification method", INTERNATIONAL JOURNAL OF DAIRY TECHNOLOGY, SOCIETY OF DAIRY TECHNOLOGY, HUNTINGDON,, GB, vol. 74, no. 3, 13 April 2021 (2021-04-13), GB , pages 600 - 605, XP072057319, ISSN: 1364-727X, DOI: 10.1111/1471-0307.12779 *

Also Published As

Publication number Publication date
WO2023151653A9 (zh) 2023-10-19
CN114158733B (zh) 2022-05-17
CN114158733A (zh) 2022-03-11

Similar Documents

Publication Publication Date Title
WO2023151653A1 (zh) 油凝胶及其制备方法和用途
Martín-Illana et al. Bigels as drug delivery systems: From their components to their applications
Ivanov et al. Flaxseed additive application in dairy products production
Liu et al. Wheat gluten based percolating emulsion gels as simple strategy for structuring liquid oil
CN110215416B (zh) 一种山茶油油凝胶乳液及其制备方法
Dong et al. Oleogel-based Pickering emulsions stabilized by ovotransferrin–carboxymethyl chitosan nanoparticles for delivery of curcumin
CN109287770B (zh) 一种富含多酚的固态状茶油及制备方法
CN114304283A (zh) 一种基于油脂凝胶和水凝胶的食品级双凝胶的制备方法
Li et al. Interfacial engineering approaches to improve emulsion performance: Properties of oil droplets coated by mixed, multilayer, or conjugated lactoferrin-hyaluronic acid interfaces
US5151451A (en) Translucent, thixotropic hygel
Yang et al. Effect of the water and oleogelator content on characteristics and stability of BC-loaded oleogel-based emulsion
Fu et al. Effects of psyllium husk powder on the emulsifying stability, rheological properties, microstructure, and oxidative stability of oil-in-water emulsions
Chen et al. Development and characterization of antioxidant-fortified oleogels by encapsulating hydrophilic tea polyphenols
JPS60160840A (ja) 健康食品
Vershkov et al. The effect of preparation temperature and composition on bigel performance as fat replacers
CN103070390B (zh) 纳米脂质载体组合物及其制备方法
Li et al. Novel bigels based on walnut oil oleogel and chitosan hydrogel: Preparation, characterization, and application as food spread
Yan et al. Construction and characterization of egg white protein-gallic acid-xanthan gum-based emulsion and oleogel
JPS5911148A (ja) 蔗糖グリセリドの新規な流動性調剤、それらの製造方法およびそれらの応用
US8921351B2 (en) Liquid crystalline phytosterol-glycerine complex for enhanced bioavailability and water dispersal
Abdelraouf et al. Preparation and characterization nanoemulsion moringa oil by whey protein and application in ice cream as a food model
CN101731355A (zh) 一种含共轭亚油酸甘油三酯的液态奶及其制备方法
TWI339125B (en) Aqueous solution of ascorbic acid and method for producing same
JP4007715B2 (ja) 植物ステロール含有組成物
Dhal et al. Bigels: An Innovative Hybrid of Hydrogels/Oleogels for Food Applications

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23752432

Country of ref document: EP

Kind code of ref document: A1