CN109180808A - A kind of fish scale collagen and its preparation method and application - Google Patents

A kind of fish scale collagen and its preparation method and application Download PDF

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Publication number
CN109180808A
CN109180808A CN201811162213.9A CN201811162213A CN109180808A CN 109180808 A CN109180808 A CN 109180808A CN 201811162213 A CN201811162213 A CN 201811162213A CN 109180808 A CN109180808 A CN 109180808A
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fish scale
collagen
scale collagen
water
preparation
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CN201811162213.9A
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CN109180808B (en
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陈西广
张瀛
于健
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Qingdao Blue Kangdian Marine Biotechnology Co Ltd
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Qingdao Blue Kangdian Marine Biotechnology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K14/00Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/78Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin, cold insoluble globulin [CIG]
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/275Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of animal origin, e.g. chitin
    • A23L29/281Proteins, e.g. gelatin or collagen
    • A23L29/284Gelatin; Collagen
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17Amino acids, peptides or proteins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/65Collagen; Gelatin; Keratin; Derivatives or degradation products thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

Abstract

The invention discloses a kind of fish scale collagens and its preparation method and application, belong to the technical field of collagen.The present invention is the following steps are included: 1) freeze thawing treatment: taking fish scale, cleans, drain, seals freeze thawing, thaw;2) milk of lime is added, is uniformly mixed, stewing process, washing;3) it is soaked in aqueous solutions of organic acids, stewing process, washs;4) 100~125 DEG C of steam treatment is used, hot water, which is incubated for, to be extracted, and is extracted 1~3 time, is collected liquid and is merged, filters, and concentration obtains fish scale collagen.Fish scale of the invention uses freeze thawing treatment, does not need strong acid or highly basic impregnates, without enzymatic hydrolysis, process flow is short, easy to operate, convenient for control, period is short, high production efficiency, it is easy to accomplish industrialization, the collagen in fish scale can effectively be extracted, not fatty, carbohydrate content is lower, maintains the original strand of collagen, hydrogel or solid matter are obtained, the application of fish scale collagen is expanded.

Description

A kind of fish scale collagen and its preparation method and application
Technical field
The invention belongs to the technical field of collagen, particularly relates to a kind of fish scale collagen and preparation method thereof and answer With.
Background technique
Fish scale refers to the shell that fish appearance protects itself and prevents water flow from losing, accounts for the 2~3% of fish body weight, rich in Protein, fat and multivitamin also contain iron, zinc, calcium and a variety of the essential trace elements of the human bodys and colloid, and contain A variety of unsaturated fatty acids can reduce accumulation of the cholesterol on vascular wall, have prevention of arterial hardening, hypertension and heart disease And other effects.Collagen, also referred to as ossein, are a kind of collagen fabrics of filiform, and major physiological function is to do connective group The adhesion substance knitted can make skin firm high resilience, it is present in the positions such as human skin, bone, tendon.Scale collagen egg White, performance of keeping humidity is good, and so that skin is full of, profit is bright and clean, and injury of the prevention sunlight to skin is an important Cosmetic Ingredient, answers extensively For in various nutritional health foods and the cosmetics of super quality.
Currently, occurring much extracting the technology of collagen from fish scale in the prior art, preparation process is generally The step such as pre-treatment (including degreasing, deliming etc.), enzymatic hydrolysis, enzyme deactivation, decoloration, filtering, concentration, degerming and spray drying including fish scale Suddenly.Such as: Chinese patent CN105725109A disclose a kind of fish glue from scale preparation method and prepared fish glue from scale, the preparation Method includes that fish scale is put into soda bath for 1:1.5~3 according to mass ratio to complete the first immersion;Fish after first is impregnated Squama is put into the mixed solution of acid protease and defatting enzyme that mass fraction is 0.1~0.5% after being cleaned with clear water, uses acetic acid After adjusting pH value is 3~4, second is completed at 30~40 DEG C and is impregnated;It is 1 that the fish scale that completion second is impregnated, which is put into mass concentration, Third immersion is carried out in~5% hydrochloric acid solution;It will complete to be put into mass concentration after the fish scale that third is impregnated is cleaned with clear water and be The 4th is carried out in 0.2~0.5% limewash to impregnate;The fish scale that will complete the 4th immersion successively passes through 2~5 acetic acid and washes and 2 After~5 washings, filtered after fish scale and water are successively carried out filtering after the first tanning, the second tanning and third tanning after mistake Filter obtains the first tanning glue, the second tanning glue and third tanning glue;Wherein, the first tanning, the second tanning and third are endured The mass ratio of fish scale and water is respectively 1:1.5~3,1:1.5~4 and 1:2~3 in system, and the first tanning, the second tanning and third are endured The condition of system is respectively 60 DEG C of 2~3h of tanning, 65 DEG C of tannings, 3~4h and 70 DEG C of 3~4h of tanning;Glue, second are boiled by first Heating concentration is carried out after tanning glue and third tanning glue mixing, obtains fish glue from scale.This fish glue from scale during the preparation process, is adopted It is handled with strong acid and strong base, although this strong acid and strong base degreasing deliming effect is very good, strong acid and strong base not only causes ring Border pollution, and the heavy-metal residual of collagen product is also caused, seriously constrain the popularization and application of collagen;In addition, This fish glue from scale during the preparation process, boils the method for glue and long-time enzymatic hydrolysis using long-time heating pressurization also to solve fish scale enzyme The problem of solution, but long-time heating pressurization boils glue and long-time enzymatic hydrolysis and can not be fully solved fish scale and digest incomplete ask Topic causes the problems such as wastage of material, energy consumption are high, recovery rate is low, further limits the development of fish scale collagen.
Summary of the invention
The present invention provides a kind of fish scale collagen and its preparation method and application, solves scale collagen in the prior art The preparation method of albumen has that complex process, properties of product difference and energy consumption are high.
A kind of preparation method of fish scale collagen of the invention, is mainly realized by the following technical programs : the following steps are included: 1) taking fish scale, cleans, drain, freeze thawing is sealed at -4~-20 DEG C, thaw is repeated in close Freeze-up warm thaw operation, repeated several times, the fish scale after obtaining freeze thawing treatment;2) after the resulting freeze thawing treatment of step 1) Fish scale in add milk of lime, the mass ratio of fish scale and milk of lime is 1:1~6, be uniformly mixed, stewing process, coprocessing 1~ 5h, washing, until the pH value of washing water is neutrality;3) the resulting fish scale of step 2) is soaked in aqueous solutions of organic acids, fish scale with The mass ratio of aqueous solutions of organic acids is 1:3~30, and the mass concentration of organic acid is 1~10%, is stirred evenly, stewing process, altogether 0.5~10h, washing are handled, until the pH value of washing water is neutrality;4) the resulting fish scale of step 3) is used to 100~125 DEG C of steaming Vapour processing, processing time are 5~15min, and hot water, which is incubated for, to be extracted, and mass ratio 1:2~30 of fish scale and water, the temperature of water is 70 It~100 DEG C, every 10~20min, uses power for 60~120s of ultrasonication of 150~300W, is incubated for 0.5~2h, Gu Liquid separation, liquid are fish scale collagen, and solid continues hot water and is incubated for extraction, repeats 0~2 time, collect liquid and merge, concentration, Obtain fish scale collagen.
Fish scale of the invention is not limited to perch fish scale, can also be carp fish scale, silver carp fish scale and grass carp scales;Fish scale Using freeze thawing treatment, does not need strong acid or highly basic impregnates, not will cause environmental pollution, the weight of collagen product will not be caused Metal residual;Without enzymatic hydrolysis, process flow is short, easy to operate, and convenient for control, process cycle is short, high production efficiency, less energy consumption, It is at low cost, it is easy to accomplish industrialization;The collagen in fish scale can be effectively extracted, amino acid in polypeptide molecule is reduced Structural damage;Gained fish scale collagen can be hydrogel and be also possible to solid matter, and not fatty, carbohydrate contains It measures lower, maintains the original strand of collagen;Solid matter expands by that can also obtain hydrogel after being added with water to The big application of fish scale collagen.
Embodiment as one preferred in the step 4), after concentration, obtains concentrate, protein in concentrate Mass content is 1.5~15%, is heated to 80~120 DEG C of progress sterilization processings, is sealed, and cooling obtains fish scale collagen water-setting Glue.The present invention generallys use ultrafiltration membrane and is concentrated after being filtered until clear, and after being cooled to room temperature, is placed on low temperature Lower preservation, this low temperature are usually 1~10 DEG C;The resulting fish scale collagen hydrogel gelling temperature of the present invention is high, 1% fish Squama collagen hydrogels placed at 15 DEG C can plastic, improve the concentration of collagen, highest gelling temperature will It increases;With better material gelation, high mechanical strength, there is good viscoplasticity, the cohesion of gel is good, and glue sense is good, With apparent chewable property.
Embodiment as one preferred in the step 4), after concentration, obtains concentrate, protein in concentrate Mass content is 3~15%, and spray drying or freeze-drying, sealing obtain fish scale collagen solid.The present invention can also be direct Fish scale collagen solid i.e. fish scale collagen powder or fish scale collagen block are prepared by drying, and is sealed, Before the use, the concentration before drying is configured to using water, this fish scale collagen solid conservation is convenient, convenient for making With.
Embodiment as one preferred, in the step 1), thaw is carried out in 20~35 DEG C of water. Fish scale sealing freeze thawing is the interaction force destroyed inside flap using the characteristic of ice crystal expansion, and energy consumption is low, operation letter Just, accelerate subsequent processing to the treatment process of the deodorant degreasing deliming of flap, carry out thaw again after sealing freeze thawing, and Continue to repeat to seal freeze thawing and thaw, is destroyed this interaction force inside flap constantly, further decreases It can be consumed, and accelerate subsequent processes;This thaw mode rate is fast, improves production efficiency.
Embodiment as one preferred in the step 1), seals the number of repetition of freeze thawing and thaw operation It is 0~2 time.The interaction that can be sufficiently destroyed by 1~3 continuous sealing freeze thawing and thaw inside flap Power promotes the treatment process of subsequent fish scale.
Embodiment as one preferred, in the step 2), milk of lime be quick lime and water according to mass ratio 1:3~ The mixture that the mixture of 5 compositions either white lime and water are formed according to mass ratio 1:2.5~3.Under the action of milk of lime, Fish scale completes the processing of degreasing deliming, and this milk of lime can be the mixture of quick lime and water composition, be also possible to white lime With the mixture of water composition, quick lime and white lime storage are convenient, and source is wide, is reacted fastly with water, obtains uniformity soon Milk of lime, can be with extemporaneous preparation.
Embodiment as one preferred, in the step 3), organic acid be citric acid, acetic acid, lactic acid, in malic acid Any one or a few.The present invention carries out carrying out fish scale the processing of degreasing deliming under the action of organic acid, and organic acid is acid Mildly, easy post-processing, it is easy to use;By milk of lime and organic acid treated fish scale, degreasing deliming effect is good;Restore Neutrallty condition and then extraction collagen, reduce the destruction of amino acid structure in polypeptide molecule.
It is every during stewing process in embodiment as one preferred, the step 2) and the step 3) It is primary every 0.5~1h stirring, mix it uniformly.The present invention carries out the process of stewing process in milk of lime and organic acid to fish scale In, by way of batch type, fish scale is made to be mixed with uniformity consistency when uniformly having fully ensured that processing, improved Treatment effect.
A kind of fish scale collagen of the invention, is mainly realized by the following technical programs: the fish scale Collagen is that the preparation method of the fish scale collagen according to any of the above one is prepared.
The resulting fish scale collagen of the present invention is colourless, it is tasteless, there is good transparency, appearance is beautiful, during pH value is Property, not fatty, carbohydrate content is lower, and safe and secure, the collagen hydrogels of formation show good rheology Performance is learned, moreover, this fish scale collagen hydrogel can mutually turn with variation of ambient temperature between colloidal sol and gel Change, this property is directly to use fish scale collagen hydrogel or mix fish scale collagen hydrogel with other materials Using providing convenient condition.
A kind of application of fish scale collagen of the invention, is mainly realized by the following technical programs: institute Fish scale collagen is stated as food additives, cosmetic additive agent or products and health products additive agent.
Fish scale collagen of the invention is a kind of good natural biologic material, may be used as food additives, makeup Product additive and bioengineered tissue expand the application of fish scale collagen;Moreover, this fish scale collagen hydrogel with Variation of ambient temperature can be mutually converted between colloidal sol and gel, using convenient.
Compared with prior art, the beneficial effects of the present invention are: fish scale of the present invention use freeze thawing treatment, do not need strong acid or Highly basic impregnates, and not will cause environmental pollution, will not lead to the heavy-metal residual of collagen product;Without enzymatic hydrolysis, technique stream Journey is short, easy to operate, and convenient for control, process cycle is short, high production efficiency, and less energy consumption is at low cost, it is easy to accomplish industrialization;Energy Enough collagens effectively extracted in fish scale, reduce the destruction of amino acid structure in polypeptide molecule.Resulting fish glue from scale Former albumen is colourless, it is tasteless, there is good transparency, appearance is beautiful, and pH value is neutrality, can be hydrogel and is also possible to solid Substance, not fatty, carbohydrate content is lower, maintains the original strand of collagen, solid matter is by adding water Hydrogel can also be obtained after being adjusted to.The resulting collagen hydrogels of the present invention show good rheologic behavio(u)r, can For use as food additives, cosmetic additive agent or products and health products additive agent, the application of fish scale collagen is expanded;Moreover, this Kind fish scale collagen hydrogel can be mutually converted with variation of ambient temperature between colloidal sol and gel, using convenient.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiments of the present invention, is shown So, described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) take fish scale, clean, drain, seal freeze thawing at -4~-20 DEG C, thaw, be repeated in sealing freeze thawing and Thaw operation, repeated several times, the fish scale after obtaining freeze thawing treatment;
2) milk of lime is added in the fish scale after the resulting freeze thawing treatment of step 1), the mass ratio of fish scale and milk of lime is 1: 1~6, it is uniformly mixed, stewing process, 1~5h of coprocessing, washing, until the pH value of washing water is neutrality;
3) the resulting fish scale of step 2) is soaked in aqueous solutions of organic acids, the mass ratio of fish scale and aqueous solutions of organic acids is 1:3~30, the mass concentration of organic acid are 1~10%, stir evenly, stewing process, 0.5~10h of coprocessing, wash, until washing The pH value of water is washed as neutrality;
4) the resulting fish scale of step 3) is used to 100~125 DEG C of steam treatment, the processing time is 5~15min, hot water It is incubated for and extracts, mass ratio 1:2~30 of fish scale and water, the temperature of water is 70~100 DEG C, every 10~20min, using power For 60~120s of ultrasonication of 150~300W, it is incubated for 0.5~2h, is separated by solid-liquid separation, liquid is fish scale collagen, solid Continue hot water and be incubated for extraction, repeat 0~2 time, collect liquid and merge, concentration obtains fish scale collagen.
Preferably, in the step 4), after concentration, obtain concentrate, in concentrate the mass content of protein be 1.5~ 15%, 80~120 DEG C of progress sterilization processings are heated to, are sealed, cooling obtains fish scale collagen hydrogel.
Further, in the step 4), after concentration, obtain concentrate, in concentrate the mass content of protein be 3~ 15%, spray drying or freeze-drying, sealing obtain fish scale collagen hydrogel solid.
Specifically, in the step 1), thaw is carried out in 20~35 DEG C of water.
Again less preferably, in the step 1), the number of repetition for sealing freeze thawing and thaw operation is 0~2 time.
Still further, milk of lime is the mixing that quick lime and water are formed according to mass ratio 1:3~5 in the step 2) The mixture that object either white lime and water are formed according to mass ratio 1:2.5~3.
Again specifically, in the step 3), organic acid be citric acid, acetic acid, lactic acid, in malic acid any one or it is several Kind.
It is highly preferred that stirring one every 0.5~1h during stewing process in the step 2) and the step 3) It is secondary, mix it uniformly.
A kind of fish scale collagen of the invention, the fish scale collagen are the fish scales according to any of the above one What the preparation method of collagen was prepared.
A kind of application of fish scale collagen of the invention, the fish scale collagen are used as food additives, cosmetics Additive or products and health products additive agent.
Embodiment one
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -4 DEG C, the thaw at 25 DEG C must freeze The fish scale that melts that treated;
2) addition is formed with 0.75 part of water by 0.25 part of quick lime in the fish scale after the resulting freeze thawing treatment of step 1) Milk of lime made of mixture is uniformly mixed, stewing process, and primary, coprocessing 5h, washing, until washing water are stirred at interval of 1h PH value be neutrality, drain;
3) the resulting fish scale of step 2) is soaked in by 5.4 parts of water and 0.6 part of aqueous solutions of organic acids formed of citric acid, It stirs evenly, stewing process, is stirred once at interval of 1h, coprocessing 4.5h, washing drains until the pH value of washing water is neutrality;
4) the resulting fish scale of step 3) is used to 125 DEG C of steam treatment, the processing time is 5min, takes out, is added 70 DEG C 5 parts of hot water, carry out hot water be incubated for extract, every 10min, use power for the ultrasonication 90s of 150W, incubation 1.5h, It is separated by solid-liquid separation, liquid is fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collects liquid and merges, is concentrated into The mass content of protein is 3%, is heated to 100 DEG C of progress sterilization processings, is sealed, and cooling obtains fish scale collagen hydrogel.
Embodiment two
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -20 DEG C, the thaw at 20 DEG C, successively Sealing freeze thawing and thaw operation are repeated, is repeated 2 times, the fish scale after obtaining freeze thawing treatment;
2) added in the fish scale after the resulting freeze thawing treatment of step 1) by 0.85 part of white lime with 2.3 parts of water form mix Milk of lime made of object to be closed, is uniformly mixed, stewing process, primary, coprocessing 4h is stirred at interval of 1h, washing is washed 4 times, until The pH value of washing water is neutrality, is drained;
3) the resulting fish scale of step 2) is soaked in by 13 parts of water and 0.9 part of aqueous solutions of organic acids formed of malic acid, It stirs evenly, stewing process, is stirred once at interval of 0.5h, coprocessing 2h, washing drains until the pH value of washing water is neutrality;
4) the resulting fish scale of step 3) is used to 100 DEG C of steam treatment, the processing time is 15min, takes out, is added 100 DEG C 2 parts of hot water, carry out hot water be incubated for extract, every 20min, use power for the ultrasonication 60s of 300W, incubation 0.5h is separated by solid-liquid separation, and liquid is fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collects liquid and merges, dense The mass content for being reduced to protein is 3%, is heated to 80 DEG C of progress sterilization processings, seals, and cooling obtains fish scale collagen water-setting Glue.
Embodiment three
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -10 DEG C, the thaw at 25 DEG C, successively Sealing freeze thawing and thaw operation are repeated, is repeated 1 times, the fish scale after obtaining freeze thawing treatment;
2) addition is formed with 0.83 part of water by 0.17 part of quick lime in the fish scale after the resulting freeze thawing treatment of step 1) Milk of lime made of mixture is uniformly mixed, stewing process, and primary, coprocessing 1h, washing, until washing are stirred at interval of 0.5h The pH value of water is neutrality, is drained;
3) the resulting fish scale of step 2) is soaked in by 29.7 parts of water and 0.3 part of aqueous solutions of organic acids formed of lactic acid, It stirs evenly, stewing process, primary, coprocessing 2.5h, washing is stirred at interval of 0.5h, until the pH value of washing water is neutrality, drip It is dry;
4) the resulting fish scale of step 3) is used to 120 DEG C of steam treatment, the processing time is 10min, takes out, is added 70 DEG C 30 parts of hot water, carry out hot water be incubated for extract, every 15min, use power for the ultrasonication 120s of 200W, incubation 2h, It is separated by solid-liquid separation, liquid is fish scale collagen, and the mass content for being concentrated into protein is 1.5%, is heated to 120 DEG C and is sterilized Processing seals, and cooling obtains fish scale collagen hydrogel.
Example IV
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -15 DEG C, the thaw at 35 DEG C must freeze The fish scale that melts that treated;
2) addition is formed with 3.75 parts of water by 1.25 parts of white lime in the fish scale after the resulting freeze thawing treatment of step 1) Milk of lime made of mixture is uniformly mixed, stewing process, and primary, coprocessing 4h, washing, until washing water are stirred at interval of 1h PH value be neutrality, drain;
3) the resulting fish scale of step 2) is soaked in by 2.85 parts of water and 0.15 part of aqueous solutions of organic acids formed of citric acid In, it stirs evenly, stewing process, primary, coprocessing 0.5h, washing is stirred at interval of 0.5h, until the pH value of washing water is neutrality, It drains;
4) the resulting fish scale of step 3) is used to 125 DEG C of steam treatment, the processing time is 5min, takes out, is added 90 DEG C 5 parts of hot water, carry out hot water be incubated for extract, every 10min, use power for the ultrasonication 90s of 300W, incubation 1h, Gu Liquid separation, liquid are fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collect liquid and merge, are concentrated into egg The mass content of white matter is 15%, is spray-dried, and sealing obtains fish scale collagen powder.
Embodiment five
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -4 DEG C, the thaw at 25 DEG C, successively Sealing freeze thawing and thaw operation are repeated, is repeated 2 times, the fish scale after obtaining freeze thawing treatment;
2) in the fish scale after the resulting freeze thawing treatment of step 1) addition by 1 part of quick lime and 3 parts of mixtures formed of water Manufactured milk of lime is uniformly mixed, stewing process, and primary, coprocessing 4h, washing, until the pH value of washing water are stirred at interval of 1h For neutrality, drain;
3) the resulting fish scale of step 2) is soaked in by 4.8 parts of water and 0.2 part of aqueous solutions of organic acids formed of citric acid, It stirs evenly, stewing process, is stirred once at interval of 1h, coprocessing 3h, washing drains until the pH value of washing water is neutrality;
4) the resulting fish scale of step 3) is used to 110 DEG C of steam treatment, the processing time is 8min, takes out, is added 70 DEG C 10 parts of hot water, carry out hot water be incubated for extract, every 10min, use power for the ultrasonication 90s of 300W, incubation 1.5h, It is separated by solid-liquid separation, liquid is fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collects liquid and merges, is concentrated into The mass content of protein is 10%, is freeze-dried, and sealing obtains fish scale collagen block.
Embodiment six
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -4 DEG C, the thaw at 25 DEG C must freeze The fish scale that melts that treated;
2) in the fish scale after the resulting freeze thawing treatment of step 1) addition by 1 part of quick lime and 5 parts of mixtures formed of water Manufactured milk of lime is uniformly mixed, stewing process, and primary, coprocessing 5h, washing, until the pH value of washing water are stirred at interval of 1h For neutrality, drain;
3) the resulting fish scale of step 2) is soaked in by stirring in 5 parts of water and 0.2 part of aqueous solutions of organic acids formed of acetic acid Uniformly, stewing process stirs once at interval of 1h, and coprocessing 5h, washing drains until the pH value of washing water is neutrality;
4) the resulting fish scale of step 3) is used to 110 DEG C of steam treatment, the processing time is 8min, takes out, is added 70 DEG C 10 parts of hot water, carry out hot water be incubated for extract, every 10min, use power for the ultrasonication 90s of 300W, incubation 1.5h, It is separated by solid-liquid separation, liquid is fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collects liquid and merges, is concentrated into The mass content of protein is 5%, and spray drying obtains fish scale collagen powder.
Embodiment seven
A kind of preparation method of fish scale collagen of the invention, comprising the following steps:
1) 1 part of fresh clean fish scale is taken, is cleaned, is drained, freeze thawing is sealed at -4 DEG C, the thaw at 25 DEG C must freeze The fish scale that melts that treated;
2) in the fish scale after the resulting freeze thawing treatment of step 1) addition by 1 part of white lime and 2.5 parts of mixing formed of water Milk of lime made of object is uniformly mixed, stewing process, and primary, coprocessing 5h, washing, until the pH of washing water are stirred at interval of 1h Value is neutrality, is drained;
3) the resulting fish scale of step 2) is soaked in by 4.95 parts of water and 0.05 part of aqueous solutions of organic acids formed of acetic acid, It stirs evenly, stewing process, primary, coprocessing 10h, washing is stirred at interval of 0.8h, until the pH value of washing water is neutrality, drip It is dry;
4) the resulting fish scale of step 3) is used to 110 DEG C of steam treatment, the processing time is 8min, takes out, is added 70 DEG C 10 parts of hot water, carry out hot water be incubated for extract, every 10min, use power for the ultrasonication 90s of 300W, incubation 1.5h, It is separated by solid-liquid separation, liquid is fish scale collagen, and solid continues hot water and is incubated for extraction, is repeated 2 times, and collects liquid and merges, is concentrated into The mass content of protein is 8%, is heated to 100 DEG C of progress sterilization processings, is sealed, and cooling obtains fish scale collagen hydrogel.
Six resulting three parts of embodiment of the present invention four, embodiment five and embodiment fish scale collagen solids are added respectively Water is configured to the fish scale collagen hydrogel that the mass concentration of solid matter is 1%, and by embodiment one to three He of embodiment The mass concentration that the concentration of seven resulting four parts of fish scale collagen hydrogels of embodiment is also separately adjusted to angularly solid matter is 1%, then, this seven parts of fish scale collagen hydrogels are measured into its gelling temperature and gelation time, experimental result such as table 1 respectively It is shown.
1 fish scale collagen hydrogel gelling temperature of table and gelation time
As can be seen from Table 1, fish scale collagen hydrogel gelling temperature of the invention is high, and solid masses concentration is 1% Fish scale collagen hydrogel place 110min or so at a temperature of 15 DEG C can plastic;Improve the dense of fish scale collagen Degree, 15 DEG C at a temperature of place when, the gelation time that is averaged will be lower than 110min, also, since concentration increase leads to glue The reason of interaction force enhances between former protein molecular can also form collagen water-setting under the conditions of being higher than 15 DEG C of temperature Glue.In addition, fish scale collagen hydrogel of the invention can mutually turn with variation of ambient temperature between colloidal sol and gel Change, this property is directly to use fish scale collagen hydrogel or mix fish scale collagen hydrogel with other materials Using convenient condition is provided, keeps its application convenient, expand its application range.
Six resulting three parts of embodiment of the present invention four, embodiment five and embodiment fish scale collagen solids are added respectively Water is configured to fish scale collagen hydrogel, and with seven resulting four parts of scale collagens of embodiment one to embodiment three and embodiment Protein hydrogel, respectively according to method as defined in National Standard of the People's Republic of China GB5009.5-2016 detect its mainly at Point, experimental result is as shown in table 2.
2 fish scale collagen hydrogel Nutrition monitoring of table
As can be seen from Table 2, the obtained fish scale collagen product of the present invention it is colourless, it is tasteless, have it is good transparent Degree, appearance is beautiful, and pH value is neutrality, and not fatty, fat content is 0, and carbohydrate content is lower, and carbohydrate contains Amount is no more than 3.0g/100g;Fish scale collagen product of the invention solves the mankind to edible mammalian collagen The misgivings of safety substantially increase the added value of fish aquatic products.
By seven resulting four parts of fish scale collagen hydrogel difference of the embodiment of the present invention one to embodiment three and embodiment It is dry, collagen solids are obtained, and solid with six resulting three parts of example IV, embodiment five and embodiment fish scale collagens Body adds water respectively, and the mass concentration according to solid matter is 1%, is configured to fish scale collagen hydrogel, is risen using Shanghai The Universal TA type Texture instrument for pulling out the production of instrument Science and Technology Ltd. tests and analyzes its food quality;Then, with Existing same concentrations fish scale collagen hydrogel data compare (abbreviation control sample), and experimental result is as shown in table 3.
The texture of 3 fish scale collagen hydrogel of table is analyzed
Detection project Hardness (g) Cohesion Adhesiveness (mJ) Elastic (mm) Adhesivity (g) Chewiness (mJ)
Embodiment one 266 0.34 0.75 2.92 139 2.4
Embodiment two 255 0.32 0.70 2.90 104 2.2
Embodiment three 263 0.34 0.71 2.92 133 2.3
Example IV 251 0.32 0.68 2.87 122 2.1
Embodiment five 248 0.30 0.62 2.55 106 1.7
Embodiment six 249 0.32 0.62 2.53 124 1.9
Embodiment seven 267 0.35 0.77 2.91 136 2.9
Control sample 246 0.30 0.60 2.18 83 1.8
As can be seen from Table 3, the obtained fish scale collagen product of the present invention has physically better gelation, puts down For equal hardness in 257g or so, this illustrates its high mechanical strength;The average adhesion of the obtained fish scale collagen product of the present invention Property for 0.69mJ or so, for cohesion more than 0.30, average elasticity value is 2.80mm or so, hence it is evident that is better than control sample, this explanation It is with good viscoplasticity;The shoes of the obtained fish scale collagen product of the present invention is 120g or so, hence it is evident that is higher than Control sample, this illustrates it with good glue sense;The average mastication of the obtained fish scale collagen product of the present invention is 2.2mJ or so is higher than control sample, this illustrates that it has significantly chewable property.
Compared with prior art, the beneficial effects of the present invention are: fish scale of the present invention use freeze thawing treatment, do not need strong acid or Highly basic impregnates, and not will cause environmental pollution, will not lead to the heavy-metal residual of collagen product;Without enzymatic hydrolysis, technique stream Journey is short, easy to operate, and convenient for control, process cycle is short, high production efficiency, and less energy consumption is at low cost, it is easy to accomplish industrialization;Energy Enough collagens effectively extracted in fish scale, reduce the destruction of amino acid structure in polypeptide molecule.Resulting fish glue from scale Former albumen is colourless, it is tasteless, there is good transparency, appearance is beautiful, and pH value is neutrality, can be hydrogel and is also possible to solid Substance, not fatty, carbohydrate content is lower, maintains the original strand of collagen, solid matter is by adding water Hydrogel can also be obtained after being adjusted to.The resulting collagen hydrogels of the present invention show good rheologic behavio(u)r, can For use as food additives, cosmetic additive agent or products and health products additive agent, the application of fish scale collagen is expanded;Moreover, this Kind fish scale collagen hydrogel can be mutually converted with variation of ambient temperature between colloidal sol and gel, using convenient.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of fish scale collagen, it is characterised in that: the following steps are included:
1) fish scale is taken, cleans, drains, freeze thawing is sealed at -4~-20 DEG C, thaw is repeated in sealing freeze thawing and defrosting Melt operation, repeated several times, the fish scale after obtaining freeze thawing treatment;
2) add milk of lime in the fish scale after the resulting freeze thawing treatment of step 1), the mass ratio of fish scale and milk of lime be 1:1~ 6, it is uniformly mixed, stewing process, 1~5h of coprocessing, washing, until the pH value of washing water is neutrality;
3) the resulting fish scale of step 2) is soaked in aqueous solutions of organic acids, the mass ratio of fish scale and aqueous solutions of organic acids is 1:3 ~30, the mass concentration of organic acid is 1~10%, is stirred evenly, stewing process, 0.5~10h of coprocessing, is washed, until washing water PH value be neutrality;
4) the resulting fish scale of step 3) is used to 100~125 DEG C of steam treatment, the processing time is 5~15min, and hot water is incubated for Extract, mass ratio 1:2~30 of fish scale and water, the temperature of water is 70~100 DEG C, every 10~20min, use power for 60~120s of ultrasonication of 150~300W is incubated for 0.5~2h, is separated by solid-liquid separation, and liquid is fish scale collagen, solid after Continuous hot water, which is incubated for, to be extracted, and is repeated 0~2 time, is collected liquid and is merged, and concentration obtains fish scale collagen.
2. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 4), after concentration, concentrate is obtained, the mass content of protein is 1.5~15% in concentrate, is heated to 80 ~120 DEG C of progress sterilization processings seal, and cooling obtains fish scale collagen hydrogel.
3. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 4), after concentration, obtain concentrate, in concentrate the mass content of protein be 3~15%, spray drying or Freeze-drying, sealing, obtains fish scale collagen solid.
4. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 1), thaw is carried out in 20~35 DEG C of water.
5. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 1), the number of repetition for sealing freeze thawing and thaw operation is 0~2 time.
6. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 2), mixture either white lime that milk of lime, which is quick lime and water, to be formed according to mass ratio 1:3~5 with The mixture that water is formed according to mass ratio 1:2.5~3.
7. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
In the step 3), organic acid is citric acid, acetic acid, lactic acid, any one or a few in malic acid.
8. the preparation method of fish scale collagen according to claim 1, it is characterised in that:
It is primary every 0.5~1h stirring during stewing process in the step 2) and the step 3), mix it uniformly It closes.
9. a kind of fish scale collagen, it is characterised in that: the fish scale collagen be according to claim 1~8 in it is any one What the preparation method of the fish scale collagen described in was prepared.
10. the application of fish scale collagen according to claim 9, it is characterised in that:
The fish scale collagen is used as food additives, cosmetic additive agent or products and health products additive agent.
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