CN116287076B - Silanization hydrolytic protein product and preparation method and application thereof - Google Patents

Silanization hydrolytic protein product and preparation method and application thereof Download PDF

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CN116287076B
CN116287076B CN202310206000.6A CN202310206000A CN116287076B CN 116287076 B CN116287076 B CN 116287076B CN 202310206000 A CN202310206000 A CN 202310206000A CN 116287076 B CN116287076 B CN 116287076B
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protein
protease
hair
hydrolysis
hydrolyzed
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CN116287076A (en
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邓声量
邓声敬
黄家强
吴鹏
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Guangzhou Diaoling Fine Chemical Co ltd
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Guangzhou Diaoling Fine Chemical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00Preparation of peptides or proteins
    • C12P21/06Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
    • 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
    • A61K8/645Proteins of vegetable origin; Derivatives or degradation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/002Preparations for repairing the hair, e.g. hair cure
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K1/00General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
    • C07K1/107General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides
    • C07K1/1072General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups
    • C07K1/1077General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups by covalent attachment of residues other than amino acids or peptide residues, e.g. sugars, polyols, fatty acids
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/80Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
    • Y02P60/87Re-use of by-products of food processing for fodder production

Abstract

The invention discloses a silanol hydrolysis protein product, a preparation method and application thereof. The invention carries out pretreatment of adding alkaline water to the vegetable protein raw material to obtain protein alkaline treatment clear liquid; adding compound protease into the obtained protein alkali treatment clear liquid for hydrolysis, and filtering to obtain hydrolyzed protein liquid; adding polyhydroxy silane and a catalyst into the obtained hydrolyzed protein liquid, and obtaining a crude product through reaction; the obtained crude product is subjected to neutralization treatment, decoloration and deodorization treatment, so that the silanol hydrolysis protein product which is safe and effective, high in utilization rate and strong in adsorptivity is prepared. The silanol hydrolysis protein product prepared by the invention has light color, can be dissolved in water, can be used as an additive for daily chemicals (such as skin care products, shampoo products and the like), and has good compatibility with the formula of the daily chemicals.

Description

Silanization hydrolytic protein product and preparation method and application thereof
Technical Field
The invention relates to the technical field of cosmetics, in particular to a silanization alcoholized hydrolyzed protein product and a preparation method and application thereof.
Background
In modern cosmetic aesthetics, hair is also one of the aesthetic elements, and is an important component of cosmetic appearance. With the increasing pursuit of hair aesthetics and environmental impact, overhead hair is subject to deterioration by a variety of factors, including frequent washing, harsh chemical treatments, harsh heat treatments, air pollution, UV exposure, and other factors. The swollen and cracked top coat hair scales and increased porosity tend to make the hair dry, soft and difficult to handle and cause bifurcation and loss of gloss. The hair contains a large amount of keratin which accounts for 65-95% of the hair, and many natural active proteins have high affinity to the hair, are easy to be absorbed by the hair, have nutrition and film forming effects, and are excellent hair conditioning agents. The function of protein in conditioning is closely related to the structural composition and molecular mass of the protein, and the key is that the protein forms hydrogen bonds with keratin in hair, and the water-soluble protein has a certain repairing effect on damaged hair. Proteins (such as hydrolyzed wheat and vegetable proteins) and amino acids have been used in hair care products as restoration components for damaged hair. Wheat proteins are known to have some firmness (substatiticity) to hair, while it is reported to penetrate the epidermis to provide conditioning benefits and improve breaking strength. Despite their firmness, proteins deposited on hair are easily washed off after one or more washes, along with any benefits they may provide.
Under the background, the research on a hydrolyzed protein product which is safe, effective, high in utilization rate and strong in adsorptivity is a problem to be solved in the field.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a silanization hydrolysis protein product and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a silanolated protein hydrolysate, comprising the steps of:
(1) Performing alkaline water pretreatment on the vegetable protein raw material to obtain protein alkaline treatment clear liquid;
(2) Adding compound protease into the protein alkali treatment clear liquid obtained in the step (1) for hydrolysis, and filtering to obtain hydrolyzed protein liquid;
(3) Adding polyhydroxy silane and a catalyst into the hydrolyzed protein solution obtained in the step (2), and obtaining a crude product through a grafting reaction;
(4) And (3) carrying out neutralization treatment, decoloration and deodorization treatment on the crude product obtained in the step (3) to obtain a silane purified hydrolyzed protein product.
Hair is a reticular long-chain polymer aggregate of amino acid polypeptide keratin protein, and its main component is keratin, accounting for about 97%; the keratin consists of a plurality of amino acids, wherein the content of cystine is the highest, and is generally more than 14%; the repair of keratin to hair is mainly achieved through the supplementation of cystine, the existing keratin is mainly extracted from sheep hair and fish scales, animals of the sources have main carriers of viruses, hormones, heavy metals and the like, and the risks are not negligible. Therefore, the vegetable protein raw material is hydrolyzed through a specific hydrolysis environment, so that the cystine/cysteine content in the hydrolysate is obviously improved, the same keratin restoration effect is achieved, the sulfur-rich amino acid content in the hydrolyzed protein product is high, the sulfur-rich amino acid in the hydrolyzed protein product can be absorbed transdermally and can be combined with disulfide bonds of damaged hair, the hair core is restored, the elasticity of the hair is restored, and the tensile strength of the hair is improved; meanwhile, the vegetable protein raw material source is safer, green and healthy; in addition, the polyhydroxy silane is grafted in the catalytic environment, and the silanization hydrolysate has strong adsorptivity to hair, can more effectively fill damaged hair scales, repair damaged hair quality, improve the brightness of hair and improve the tensile strength of hair; the silanol hydrolysis protein product can form a protective film on the surface layer of the hair flake, and effectively alleviate ultraviolet injury and thermal injury.
Preferably, the step (1) specifically includes: adding a vegetable protein raw material and an alkaline agent into hot water at 75-85 ℃, and stirring for 30-60 min at a constant temperature to obtain a protein alkali treatment clear liquid, wherein the mass ratio of the alkaline agent to the vegetable protein raw material is (2.2-2.7) mg/32 g; the alkaline agent is at least one selected from potassium hydroxide, sodium hydroxide, triethanolamine and ethanolamine. The plant protein raw material is subjected to heat treatment under alkaline conditions, so that peptide bonds in the plant protein are broken, the tight structure of the plant protein is destroyed, the plant protein is promoted to be dissolved in hot water, the addition amount of protease during hydrolysis is reduced, and the time for hydrolysis is shortened.
Further preferably, the mass ratio of the vegetable protein raw material to the hot water is 1:5-15.
Preferably, the vegetable protein material is selected from at least one of wheat protein and corn protein.
Preferably, the complex protease is selected from at least two of alkaline protease, neutral protease, flavourzyme and cysteine protease; the adding amount of the compound protease is 2-7% of the weight of the protein alkali treatment clear liquid.
Further preferably, the compound protease comprises alkaline protease, neutral protease, flavourzyme and cysteine protease, wherein the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (4-6) to (2-4) to 1:1. When the added compound protease meets the above conditions, the cystine/cysteine content in the hydrolyzed protein solution is significantly increased.
Preferably, the catalyst is at least one selected from hydrochloric acid solution, citric acid, lactic acid and sulfuric acid solution, wherein the mass concentration of hydrochloric acid in the hydrochloric acid solution is 10-30wt%, and the mass concentration of sulfuric acid in the sulfuric acid solution is 10-30wt%.
Preferably, the catalyst is added in an amount of 2 to 3% by mass of the hydrolyzed protein solution.
Further preferably, the catalyst is hydrochloric acid solution, and the mass concentration of hydrochloric acid in the hydrochloric acid solution is 20wt%. Hydrochloric acid is used as a catalyst, so that an acidic embrittlement environment is provided for the silanol reaction, and the catalyst is easy to separate, thereby being beneficial to obtaining a silanol hydrolyzed protein product with high purity and low odor.
Preferably, the addition amount of the polyhydroxy silane is 5-25% of the mass of the hydrolyzed protein liquid.
Preferably, the polyhydroxy silane is at least one selected from 3- (2, 3-epoxypropoxy) propyl trihydroxy silane, propyl silanetriol and propyl methyl silanediol.
Further preferably, the polyhydroxy silane is 3- (2, 3-glycidoxy) propyl trihydroxy silane.
Compared with other polyhydroxy silanes, the invention selects 3- (2, 3-epoxypropoxy) propyl trihydroxy silane to carry out grafting reaction, the prepared silanolate hydrolysis protein product has stronger adsorptivity to hair, can more effectively repair damaged hair, and has better effects of resisting ultraviolet injury and heat injury.
Preferably, when the step (2) is performed, the hydrolysis temperature is 40-60 ℃, the hydrolysis time is 2-6 h, and the pH is controlled to be 6.8-9.2. The pH of the system is controlled in a proper range in the process of hydrolyzing the plant protein, so that the content of soluble nitrogen in the final product can be effectively improved; if the pH of the system is too low, too little soluble nitrogen is obtained during hydrolysis, resulting in too low a content of soluble nitrogen in the final product; and too high a pH of the system can easily cause off-flavors in the hydrolysate.
Preferably, in the step (3), the reaction temperature is 60-120 ℃, the reaction time is 2-6 h, and the air pressure is 1-1.2 MPa. Under the reaction conditions, the polyhydroxy silane can fully react with the hydrolyzed protein liquid under the catalysis of the catalyst, so that amino acid and protein in the hydrolyzed protein liquid can be fully silanized.
Preferably, the decoloring and deodorizing treatment in the step (4) specifically includes: and (3) passing the neutralized crude product through an activated carbon porous adsorption device, wherein the residence time in the activated carbon porous adsorption device is 8-22 h.
Preferably, the step (4) further includes: and adding a preservative after the decoloring and deodorizing treatment.
In a second aspect, the present invention provides a silanized protein hydrolysate prepared by the process for preparing a silanized protein hydrolysate according to the first aspect.
In a third aspect, the present invention provides the use of a silanized protein hydrolysate as described in the second aspect for the preparation of a commodity chemical.
The daily chemical comprises any one of a shampoo product and a skin care product.
Compared with the prior art, the invention has the beneficial effects that:
(1) The vegetable protein pigment disclosed by the invention is safer in source, green and healthy and free of pollution;
(2) The plant protein raw material is hydrolyzed in a specific hydrolysis environment, so that hydrolyzed protein liquid with high purity and strong activity can be obtained, the cystine/cysteine content in the hydrolyzed product is obviously improved, the same keratin restoration effect is achieved, the sulfur-rich amino acid content in the hydrolyzed protein product is high, the sulfur-rich amino acid in the hydrolyzed protein product can be absorbed transdermally and can be combined with disulfide bonds of damaged hair, hair cores are restored, the elasticity of hair is restored, and the tensile strength of hair is improved;
(3) The polyhydroxy silane is grafted in the catalytic environment, the silanization hydrolysate has strong adsorptivity to hair, can more effectively fill damaged hair scales, repair damaged hair quality, improve the brightness of hair and improve the tensile strength of hair; the silanol hydrolysis protein product can form a protective film on the surface layer of the hair flake, so that ultraviolet injury and thermal injury can be effectively relieved;
(4) The silanol hydrolysis protein product prepared by the invention has light color, can be dissolved in water, can be used as an additive for daily chemicals (such as skin care products, shampoo products and the like), and has good compatibility with the formula of the daily chemicals.
Drawings
FIG. 1 is a scanning electron microscope image of hair after being repaired by sample A provided in effect example 2 of the present invention;
FIG. 2 is a scanning electron microscope image of hair after being repaired by sample B provided in effect example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of hair after being repaired by sample C provided in effect example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of hair after the hair is repaired by sample D provided in effect example 2 of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
In the following examples and comparative examples, the vegetable protein material was a vegetable protein powder obtained by washing wheat and corn flour with water to remove starch and then oven drying, wherein the mass ratio of the wheat to the corn flour was 3:2.
The 3- (2, 3-glycidoxy) propyl trihydroxy silane of the following examples and comparative examples was prepared by the following method: mixing commercially available 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and deionized water according to the mass ratio of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane to deionized water=100:28, stirring at a rotating speed of 400r/min for 60-100 min at neutral (pH=7.0) and normal temperature (25 ℃), standing for layering, and removing an upper layer in a tilting filtration mode to obtain a lower clear solution, namely 3- (2, 3-epoxypropoxy) propyl trihydroxy silane. Separating the hydrolysate 3- (2, 3-epoxypropoxy) propyl trihydroxy silane in a tilting way, and immediately adding the hydrolysate into hydrolyzed protein liquid to participate in grafting reaction; 3- (2, 3-epoxypropoxy) propyltrimethoxysilane was obtained from Shanghai Michael Biochemical technology Co.
Example 1
The present example provides a process for the preparation of a silanolated protein hydrolysate comprising the steps of:
(1) Adding a vegetable protein raw material and sodium hydroxide into hot water at 80 ℃, and stirring for 50min at a constant temperature to obtain a protein alkali treatment clear liquid, wherein the mass ratio of the sodium hydroxide to the vegetable protein raw material is 2.4 mg/32 g, and the mass ratio of the vegetable protein raw material to the hot water is 1:10;
(2) Adding compound protease into the protein alkali treated clear liquid obtained in the step (1), hydrolyzing for 3 hours at 52 ℃, controlling the pH value of the system to be 8.2 in the hydrolysis process, separating by a membrane, and collecting a liquid phase to obtain clear hydrolyzed protein liquid; the adding amount of the compound protease is 4.8% of the weight of the protein alkali treatment clear liquid; the composite protease consists of alkaline protease, neutral protease, flavourzyme and cysteine protease, wherein the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (1:1:1) and the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (5:3:1);
(3) Adding 3- (2, 3-glycidoxy) propyl trihydroxy silane and hydrochloric acid solution into the hydrolyzed protein solution obtained in the step (2), wherein the addition amount of the 3- (2, 3-glycidoxy) propyl trihydroxy silane is 15% of the hydrolyzed protein solution; the mass concentration of hydrochloric acid in the hydrochloric acid solution is 20wt%, the adding amount of the hydrochloric acid solution is 2.3% of the hydrolyzed protein solution, and the raw product is obtained after the reaction for 4 hours at the temperature of 80 ℃ and the air pressure of 1.2MPa;
(4) Adding sodium hydroxide solution into the crude product obtained in the step (3) for neutralization, wherein the mass concentration of sodium hydroxide in the sodium hydroxide solution is 10wt%, the addition amount of the sodium hydroxide solution is 4.2% of the mass of the crude product, and the pH value of the neutralized crude product is 6.2-6.6; and (3) passing the neutralized crude product through an activated carbon porous adsorption device (such as an activated carbon porous adsorption column), wherein the residence time of the neutralized crude product in the activated carbon porous adsorption device is 12h, collecting filtrate, and adding a preservative into the collected filtrate to obtain a silane purification hydrolyzed protein product, wherein the addition amount of the preservative is 2% of that of the silane purification hydrolyzed protein product.
Example 2
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: the example hydrolyzes for 4 hours at 52 ℃, the pH value of the system is controlled at 7.0 during the hydrolysis,
example 3
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: the mass ratio of alkaline protease, neutral protease, flavourzyme and cysteine protease in the added composite protease of the example is alkaline protease to neutral protease to flavourzyme to cysteine protease=4:2:1:1.
Example 4
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: the mass ratio of alkaline protease, neutral protease, flavourzyme and cysteine protease in the composite protease added in this example is alkaline protease to neutral protease to flavourzyme to cysteine protease=6:4:1:1.
Example 5
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: in this example, 3- (2, 3-glycidoxy) propyltrihydroxysilane was added in an amount of 5% of the hydrolyzed protein solution.
Example 6
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: in this example, 3- (2, 3-glycidoxy) propyltrihydroxysilane was added in an amount of 25% of the hydrolyzed protein solution.
Example 7
The present example provides a process for the preparation of a silanolated protein hydrolysate comprising the steps of:
(1) Adding a vegetable protein raw material and sodium hydroxide into hot water at 85 ℃, and stirring for 30min at a constant temperature to obtain a protein alkali treatment clear liquid, wherein the mass ratio of the sodium hydroxide to the vegetable protein raw material is 2.2 mg/32 g, and the mass ratio of the vegetable protein raw material to the hot water is 1:5;
(2) Adding compound protease into the protein alkali treated clear liquid obtained in the step (1), hydrolyzing for 6 hours at 40 ℃, controlling the pH value of the system to be 6.8 in the hydrolysis process, separating by a membrane, and collecting a liquid phase to obtain clear hydrolyzed protein liquid; the adding amount of the compound protease is 2.0% of the weight of the protein alkali treatment clear liquid; the composite protease consists of alkaline protease, neutral protease, flavourzyme and cysteine protease, wherein the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (1:1:1) and the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (5:3:1);
(3) Adding 3- (2, 3-glycidoxy) propyl trihydroxy silane and hydrochloric acid solution into the hydrolyzed protein solution obtained in the step (2), wherein the addition amount of the 3- (2, 3-glycidoxy) propyl trihydroxy silane is 15% of the hydrolyzed protein solution; the mass concentration of hydrochloric acid in the hydrochloric acid solution is 20wt%, the adding amount of the hydrochloric acid solution is 1.5% of the hydrolyzed protein solution, and the raw product is obtained after the reaction for 6 hours at the temperature of 60 ℃ and the air pressure of 1.2MPa;
(4) Adding sodium hydroxide solution into the crude product obtained in the step (3) to neutralize, so that the pH value of the neutralized crude product is 6.2-6.6, and the mass concentration of sodium hydroxide in the sodium hydroxide solution is 10wt%; and (3) passing the neutralized crude product through an activated carbon porous adsorption device (such as an activated carbon porous adsorption column), wherein the residence time of the neutralized crude product in the activated carbon porous adsorption device is 8 hours, collecting filtrate, and adding a preservative into the collected filtrate to obtain a silane purification hydrolyzed protein product, wherein the addition amount of the preservative is 1% of that of the silane purification hydrolyzed protein product.
Example 8
The present example provides a process for the preparation of a silanolated protein hydrolysate comprising the steps of:
(1) Adding a vegetable protein raw material and sodium hydroxide into hot water at 75 ℃, and stirring for 60 minutes at a constant temperature to obtain a protein alkali treatment clear liquid, wherein the mass ratio of the sodium hydroxide to the vegetable protein raw material is 2.7 mg/32 g, and the mass ratio of the vegetable protein raw material to the hot water is 1:15;
(2) Adding compound protease into the protein alkali treatment clear liquid obtained in the step (1), hydrolyzing for 2 hours at 60 ℃, controlling the pH value of the system to be 9.2 in the hydrolysis process, separating by a membrane, and collecting a liquid phase to obtain clear hydrolyzed protein liquid; the adding amount of the compound protease is 7% of the weight of the protein alkali treatment clear liquid; the composite protease consists of alkaline protease, neutral protease, flavourzyme and cysteine protease, wherein the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (1:1:1) and the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is (5:3:1);
(3) Adding 3- (2, 3-glycidoxy) propyl trihydroxy silane and hydrochloric acid solution into the hydrolyzed protein solution obtained in the step (2), wherein the addition amount of the 3- (2, 3-glycidoxy) propyl trihydroxy silane is 15% of the hydrolyzed protein solution; the mass concentration of hydrochloric acid in the hydrochloric acid solution is 20wt%, the adding amount of the hydrochloric acid solution is 4% of the hydrolyzed protein solution, and the raw product is obtained after the reaction for 2 hours at the temperature of 120 ℃ and the air pressure of 1.0 MPa;
(4) Adding sodium hydroxide solution into the crude product obtained in the step (3) to neutralize, so that the pH value of the neutralized crude product is 6.2-6.6, and the mass concentration of sodium hydroxide in the sodium hydroxide solution is 10wt%; and (3) passing the neutralized crude product through an activated carbon porous adsorption device (such as an activated carbon porous adsorption column), wherein the residence time of the neutralized crude product in the activated carbon porous adsorption device is 22h, collecting filtrate, and adding a preservative into the collected filtrate to obtain a silane purification hydrolyzed protein product, wherein the addition amount of the preservative is 2% of that of the silane purification hydrolyzed protein product.
Example 9
This example provides a process for the preparation of a silanolated protein hydrolysate which differs from example 1 in that: the polyhydroxy silane employed in this example was methylsilanetriol.
Comparative example 1
The comparative example provides a method for preparing a hydrolyzed protein product, comprising the following steps:
preparing hydrolyzed protein solution according to step (1) to step (2) of example 1; and adding a preservative into the hydrolyzed protein solution to obtain a hydrolyzed protein product.
Effect example 1
The physicochemical properties of the products of the above examples and comparative examples were tested, and the test results are shown in table 1:
(1) Protein content testing method: the Kjeldahl nitrogen determination method is that under the condition of catalyst, organic nitrogen is converted into inorganic ammonium salt by using sulfuric acid to digest a sample, then the ammonium salt is converted into ammonia under the alkaline condition, distilled and separated, and absorbed by using excessive acid liquor, and then the total nitrogen content of the sample is calculated by using standard acid titration, wherein the nitrogen content in the true protein is about 6.25%, and the protein content of the sample=total nitrogen content is 6.25%;
(2) Average molecular weight determination: the gel filtration chromatography is adopted for testing, and the principle of separating protein by the gel filtration chromatography is based on the molecular weight of the protein; since sephades of different exclusion ranges have a specific range of protein molecular weights, there is a linear relationship between the logarithm of molecular weight and elution volume within this range; thus, gel chromatography was performed using several proteins of known molecular weight as standard, and standard elution curves were plotted as the elution volume of each protein versus the logarithm of their molecular weight; gel chromatography is carried out on the unknown protein under the same condition, and the molecular weight corresponding to the unknown protein can be obtained from a standard elution curve according to the elution volume used by the unknown protein;
(3) Soluble solids content: 5mg of a sample (mass recorded as m) 0 ) Heat-insulating for 3 hours at 105℃in an oven, and weighing (mass is denoted as m 1 ) A soluble solids content of m 1 /m 0 *100%。
(4) Sulfur-containing amino acid determination: the protein contains sulfur amino acids (cystine, cysteine, methionine), which are oxidized with performic acid and hydrolyzed with hydrochloric acid to form cysteic acid and methionine sulfone, and the disulfo-alanine and methionine sulfone are separated and measured by particle exchange chromatography.
The above test methods are all conventional test methods, and the test conditions are the same when the products of examples 1 to 8 and comparative example 1 are tested.
TABLE 1
Effect example 2
The silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 1:99 to prepare sample A, the silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 3:97 to prepare sample B, the commercially available wheat protein liquid and deionized water were dispersed at a mass ratio of 3:97 to prepare sample C, a blank control sample D was additionally set, and the repairing effect of the sample on damaged hair tresses was tested as follows:
(1) Taking a plurality of natural hair bundles with the length of 15cm, mixing with the bleaching powder at the temperature of 9 ℃ and the ratio of 1:1, carrying out post treatment for 40 minutes, cleaning, and placing in a constant temperature and humidity box for drying completely at the temperature of 25 ℃;
(2) Soaking the sample for 15 minutes, washing the sample with deionized water, drying the sample in a constant temperature and humidity drying oven at 25 ℃, and circulating for 5 times;
(3) And (5) observing the hair surface hair scale repairing effect through a Scanning Electron Microscope (SEM).
The test results are shown in FIGS. 1 to 4.
The test results show that both the example 1 and the commercial wheat protein liquid can effectively repair the hair surface hairiness.
Effect example 3
The silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 1:99 to prepare sample A, the silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 5:95 to prepare sample B, and the commercially available wheat protein liquid and deionized water were dispersed at a mass ratio of 5:95 to prepare sample C, and a blank control sample D was additionally set to test the color protection effect of each sample, and the specific test procedure was as follows:
preparing eight hair bundles with the length of 3-5 g and the length of 15cm, dyeing with the same commercial hair dye, dividing 8 hair bundles into four groups, marking each group of two hair bundles as A, B, C, D, measuring with an x-rite color difference meter, and recording the values of L, a and b;
treating the hair bundle with a sample for 10 times, and measuring the values of L, a and b of the hair bundle by an x-rite color difference meter after each treatment;
the color difference of the dyed hair after sample care is tested and compared, the color difference is characterized by a color difference symbol delta E, delta E is defined as the total color difference of the sample, and the larger the delta E value is, the larger the color difference is, and the lower the color protection degree is;
the corresponding results of the color difference calculation formula and the variation are as follows:
ΔE=[ΔL 2 +Δa 2 +Δb 2 ] 1/2
the larger ΔE, the greater the color difference, indicating a higher degree of hair color fade;
the smaller ΔE, the smaller the color difference, indicating a lower degree of hair color fade;
wherein L, a, b have the meanings: l represents color brightness, a represents color redness-greenness, and b represents color yellowness-blueness.
The color protection rate is calculated through the change of the total color difference delta E, and the calculation formula is as follows:
color retention% = [ (Δe) Control -ΔE Experiment )/ΔE Control ]*100%;
The sample was prepared by dispersing the silanol-hydrolyzed protein products of examples 2 to 9 and deionized water at a mass ratio of 1:99, and the sample was prepared by dispersing the wheat protein liquid of comparative example 1 and deionized water at a mass ratio of 1:99, and the test was performed according to the above-described test procedure.
The test results of this effect example are shown in tables 2 to 3.
TABLE 2
TABLE 3 Table 3
As can be seen from tables 2 to 3, the color protection effect of the silane purified hydrolyzed protein products prepared in examples 1 to 9 of the present invention is significantly better than that of comparative example 1 and the commercially available wheat protein liquid.
Effect example 4
The silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 5:95 to prepare sample A, the silanol hydrolysis protein product and deionized water of example 1 were dispersed at a mass ratio of 10:90 to prepare sample B, and the commercially available wheat protein liquid and deionized water were dispersed at a mass ratio of 10:90 to prepare sample C, and a blank sample D was set to test the thermal protection effect of each sample on hair tress, and the specific test procedure was as follows:
(1) Eight hair bundles with the length of 20cm and 5g are taken, cleaned by SLES solution and then placed in a constant temperature and humidity box for drying;
(2) Carding the hair bundles for 20 times until no hair falls; spraying the test sample to the hair bundles by the test group, spraying the hair bundles by pure water by the blank control group, and drying slowly;
(3) And (3) heat treatment: heating the splint to 205 ℃, clamping the hair bundle from the beginning to the end at a frequency of 5 times per minute, naturally cooling the hair bundle during the period, and repeating the process for 5 times;
(4) Placing a plastic plate under the hair bundle, carding for 100 times by using a comb, collecting the number of broken hair, and calculating the broken hair reduction rate according to the following formula;
the hair breakage reduction rate (%) = (c-t)/c is 100%, wherein c is the average hair breakage number of the blank control group, and t is the average hair breakage number of the sample group; the results are shown in Table 4.
In this effect example, the silanol hydrolyzed protein products of examples 2 to 9 and deionized water were prepared as samples by dispersing them at a mass ratio of 10:90, and the wheat protein liquid of comparative example 1 and deionized water were prepared as samples by dispersing them at a mass ratio of 10:90, and the test was performed according to the above-mentioned test procedure, and the test results are shown in Table 5.
TABLE 4 Table 4
Project Sample D Sample A Sample B Sample C
Hair breakage number of hair bundle 1 #) 12 7 6 10
Hair breakage number of hair bundle 2# 8 9 5 9
Average number of broken hair 10 8 5.5 9.5
Rate of hair loss - 20.00% 45.00% 5.00%
SD 2.8284 1.4142 0.7071 0.7071
Error of 1.6330 0.8165 0.4082 0.4082
TABLE 5
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As can be seen from tables 4 to 5, the heat protection effect of the silane purified hydrolyzed protein products prepared in examples 1 to 9 of the present invention on hair tresses is significantly better than that of comparative example 1 and commercial wheat protein liquid.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (4)

1. A process for the preparation of a silanolated protein hydrolysate comprising the steps of:
(1) Adding a vegetable protein raw material and an alkaline agent into hot water at 75-85 ℃, and preserving heat for 30-60 min to obtain a protein alkaline treatment clear liquid; the plant protein raw material is plant protein powder prepared by washing wheat and corn flour with water to remove starch and then drying;
(2) Adding compound protease into the protein alkali treatment clear liquid obtained in the step (1) for hydrolysis, and filtering to obtain hydrolyzed protein liquid;
the composite protease consists of alkaline protease, neutral protease, flavourzyme and cysteine protease, wherein the mass ratio of the alkaline protease to the neutral protease to the flavourzyme to the cysteine protease is as follows: neutral protease: flavourzyme: cysteine protease= (4-6): (2-4): 1:1, a step of; the adding amount of the compound protease is 2-7% of the weight of the protein alkali treatment clear liquid;
when the step (2) is performed with hydrolysis, the hydrolysis temperature is 40-60 ℃ and the hydrolysis time is 2-6 h;
(3) Adding polyhydroxy silane and a catalyst into the hydrolyzed protein solution obtained in the step (2), and obtaining a crude product through a grafting reaction; the polyhydroxy silane is 3- (2, 3-glycidoxy) propyl trihydroxy silane; the catalyst is hydrochloric acid solution;
in the step (3), the reaction temperature is 60-120 ℃, the reaction time is 2-6 h, and the air pressure is 1-1.2 MPa;
(4) And (3) carrying out neutralization treatment, decoloration and deodorization treatment on the crude product obtained in the step (3) to obtain a silanolated hydrolyzed protein product.
2. The method for producing a silanol hydrolyzed protein product according to claim 1, wherein the mass ratio of the alkaline agent to the vegetable protein material is (2.2 to 2.7) mg:32g; the alkaline agent is at least one selected from potassium hydroxide, sodium hydroxide, triethanolamine and ethanolamine.
3. A silanolated protein hydrolysate, characterized in that it is obtained by the process for the preparation of a silanolated protein hydrolysate according to any one of claims 1-2.
4. Use of the silanized protein hydrolysate according to claim 3 for preparing daily chemicals for repairing hair.
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