CN113068744A - Modified milk powder with antioxidant and anti-aging effects - Google Patents

Modified milk powder with antioxidant and anti-aging effects Download PDF

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CN113068744A
CN113068744A CN202110468535.1A CN202110468535A CN113068744A CN 113068744 A CN113068744 A CN 113068744A CN 202110468535 A CN202110468535 A CN 202110468535A CN 113068744 A CN113068744 A CN 113068744A
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mixed solution
stirring
dichloroethane
milk powder
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陈清香
沈五雄
黄豪德
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Goldmax Guangzhou Dairy Co ltd
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00Milk preparations; Milk powder or milk powder preparations
    • A23C9/152Milk preparations; Milk powder or milk powder preparations containing additives
    • A23C9/1526Amino acids; Peptides; Protein hydrolysates; Nucleic acids; Derivatives thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C3/00Preservation of milk or milk preparations
    • A23C3/08Preservation of milk or milk preparations by addition of preservatives
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23CDAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00Milk preparations; Milk powder or milk powder preparations
    • A23C9/152Milk preparations; Milk powder or milk powder preparations containing additives
    • A23C9/156Flavoured milk preparations ; Addition of fruits, vegetables, sugars, sugar alcohols or sweeteners

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Abstract

The invention discloses a modified milk powder with antioxidant and anti-aging effects, which comprises the following raw materials: desalted whey powder, concentrated whey protein powder, sodium hyaluronate, papaya fruit powder, rose powder with double red petals, milk mineral salt, compound nutrient package, antioxidant component, skimmed milk powder and the like; the antioxidant component is prepared by the following steps: step one, preparing chitosan oligosaccharide Schiff base; secondly, dissolving the auxiliary agent in dimethylformamide to obtain a mixed solution A, dissolving the Schiff base of the oligosaccharides in dimethylformamide to obtain a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, and reacting to obtain a crude product; and thirdly, adding a hydrochloric acid ethanol mixed solution into the crude product obtained in the second step, stirring at room temperature, and treating to obtain the antioxidant component. The auxiliary agent contains a sesame phenol analog structure, the oligosaccharide is used as a natural antiseptic antibacterial agent, and besides biodegradability, biocompatibility and biological non-toxicity, the auxiliary agent with antibacterial activity is introduced to the chain, so that a high-efficiency antioxidant component is obtained.

Description

Modified milk powder with antioxidant and anti-aging effects
Technical Field
The invention belongs to the technical field of food, and particularly relates to modified milk powder with antioxidant and anti-aging effects.
Background
The modified milk powder is a powdery product prepared by processing raw cow (sheep) milk or a processed product thereof serving as a main raw material, adding other raw materials, and optionally adding a food additive and a nutrition enhancer, and the conventional modified milk powder still needs to be improved. In addition, hyaluronic acid is also commonly known as Hyaluronic Acid (HA), and is widely present in tissues such as joint cavities, skin, vitreous eye, cartilage, umbilical cord, etc. of the human body. The content of hyaluronic acid in human body gradually decreases with age, and when the age is 30, 50 and 60 years old, the content of hyaluronic acid in human body decreases to 65%, 45% and 25% of 20 years old respectively. The reduction of hyaluronic acid can lead to arthritis, skin aging, increased wrinkles, and eye puffiness.
The problems of preservation and oxidation resistance of food are key to food preservation. Because the prepared milk powder contains a large amount of nutrient substances, the prepared milk powder is very suitable for the growth of microorganisms. If the modified milk powder is not preserved properly, a large number of microorganisms will be propagated, resulting in putrefaction and deterioration.
Disclosure of Invention
The invention provides modified milk powder with antioxidant and anti-aging effects.
The technical problems to be solved by the invention are as follows:
the problems of preservation and oxidation resistance of food are key to food preservation. Because the prepared milk powder contains a large amount of nutrient substances, the prepared milk powder is very suitable for the growth of microorganisms. If the modified milk powder is not preserved properly, a large number of microorganisms will be propagated, resulting in putrefaction and deterioration.
The purpose of the invention can be realized by the following technical scheme:
the modified milk powder with the effects of resisting oxidation and ageing comprises the following raw materials in percentage by weight:
20-26% of desalted whey powder, 18-20% of whole milk powder, 10-16% of solid corn syrup, 3-7% of lactose, 3-6% of collagen peptide, 3-6% of galacto-oligosaccharide, 3-5% of concentrated whey protein powder, 0.1-0.4% of sodium hyaluronate, 0-0.3% of pawpaw fruit powder, 0-0.3% of double red rose pollen, 0.3-0.6% of milk mineral salt, 0.5% of compound nutrient package, 0.2-0.6% of antioxidant component and the balance of skimmed milk powder to be 100%;
accurately weighing the raw materials according to the formula, respectively sieving the raw materials with a 60-80 mesh sieve, adding the raw materials into a mixer according to an equivalent progressive method, uniformly mixing, and directly packaging to obtain the modified milk powder with the effects of resisting oxidation and ageing.
The antioxidant component is prepared by the following steps:
dissolving chitosan oligosaccharide in an acetic acid solution, adding methanol, uniformly stirring, dropwise adding a methanol solution of benzaldehyde at the temperature of 60 ℃, stirring and reacting at the constant temperature of 60 ℃, and performing aftertreatment after the reaction is finished, wherein the aftertreatment process comprises the following steps: cooling the reaction liquid to room temperature, volatilizing the organic solvent, adjusting the pH value to 7 by using a sodium hydroxide solution with the mass fraction of 5%, continuously stirring until no flocculent precipitate is generated, performing suction filtration, collecting the precipitate, performing Soxhlet extraction on the precipitate by using absolute ethyl alcohol for 12h, washing to be neutral, performing vacuum drying, and grinding to obtain powder, thereby obtaining the chitosan oligosaccharide Schiff base;
the reaction process is as follows:
Figure BDA0003044397350000021
and secondly, dissolving an auxiliary agent in dimethylformamide to obtain a mixed solution A, dissolving the Schiff base of the oligosaccharides in dimethylformamide to obtain a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, stirring and reacting for 6 hours at the temperature of 25 ℃, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: adding excessive acetone to terminate the reaction, generating solid, performing vacuum filtration, performing Soxhlet extraction on the obtained solid with acetone, removing dimethylformamide, and finally performing vacuum drying to obtain a crude product;
the reaction process is as follows:
Figure BDA0003044397350000031
and thirdly, adding a hydrochloric acid ethanol mixed solution into the crude product obtained in the second step, stirring at room temperature for 12 hours, adjusting the pH value to 7 by using sodium carbonate, washing by using acetone, filtering, and drying in vacuum to obtain the antioxidant component.
The reaction process is as follows:
Figure BDA0003044397350000032
further, the mass fraction of the acetic acid solution in the first step is 1%, and the methanol solution of benzaldehyde is prepared by mixing benzaldehyde and methanol according to a volume ratio of 1: 10, mixing the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol and benzaldehyde, wherein the dosage ratio of the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol to benzaldehyde is 15 g: 70mL of: 120mL of: 120 mL; in the second step, the mixed solution A is taken as an auxiliary agent and dimethylformamide according to the weight ratio of 1 g: 10mL, wherein the mixed solution B is formed by mixing the schiff base of the sub-packaging oligosaccharide and dimethylformamide according to the weight ratio of 1 g: 10mL of the mixture is mixed, and the volume ratio of the mixed solution A to the mixed solution B is 1: 3; in the third step, the hydrochloric acid-ethanol mixed solution is 0.25mol/L hydrochloric acid solution and absolute ethanol according to the volume ratio of 1: 4, and mixing.
Further, the auxiliary agent is prepared by the following steps:
step S11, adding 1, 2-dichloroethane and N-methylpyrrolidine into a three-neck flask, heating to reflux temperature, dropwise adding a mixed solution of 3, 4-dihydroxybenzyl alcohol and sodium hydroxide solution while stirring, stirring and reacting for 10 hours at the temperature of 91 ℃ after dropwise adding, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: firstly, decompressing and filtering, decompressing and concentrating the obtained filtrate to recover unreacted dichloroethane solution, and then drying the dichloroethane solution by using anhydrous sodium sulfate to obtain an intermediate 1;
the reaction process is as follows:
Figure BDA0003044397350000041
step S12, adding the intermediate 1 and thionyl chloride into a flask, stirring for reaction, stirring at room temperature until solid is precipitated, and performing post-treatment, wherein the post-treatment process comprises the following steps: adding petroleum ether, washing, filtering, discarding filtrate until the washing liquid is colorless, and recrystallizing the obtained filter cake in boiling water to obtain an intermediate 2;
the reaction process is as follows:
Figure BDA0003044397350000042
step S13, adding anhydrous aluminum chloride and nitrobenzene into a three-neck flask, adding acetyl chloride under the condition of ice-water bath, stirring and reacting for 30min, then adding a nitrobenzene solution of the intermediate 2, removing the ice-water bath after dropwise adding, stirring and reacting for 16h under the condition of room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment specific steps are as follows: mixing the obtained reaction solution with a hydrochloric acid solution with the mass fraction of 10%, extracting with dichloromethane, washing the obtained organic phase with deionized water, a sodium hydroxide solution with the mass fraction of 5% and deionized water to be neutral, performing rotary evaporation to remove dichloromethane to obtain a solid, and recrystallizing with an ethanol solution with the volume fraction of 40% to obtain an intermediate 3;
the reaction process is as follows:
Figure BDA0003044397350000043
step S14, adding the dichloroethane solution of the intermediate 3 into a three-neck flask, dropwise adding the dichloroethane solution of chloroperoxybenzoic acid at 0 ℃, stirring and reacting for 10 hours at room temperature, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: filtering, washing the obtained filtrate with saturated sodium sulfite, a sodium hydroxide solution with the mass fraction of 10% and distilled water respectively to be neutral, then carrying out rotary evaporation to remove the solvent, then adding the filtrate into a sodium hydroxide solution with the mass fraction of 15%, stirring the mixture at room temperature until the mixture is dissolved and saponified, adjusting the pH value to 3 with persulfuric acid, extracting the mixture with dichloromethane, washing an organic phase with a sodium bicarbonate solution with the mass fraction of 15% and deionized water to be neutral, and carrying out rotary evaporation to remove the solvent to obtain the auxiliary agent.
The reaction process is as follows:
Figure BDA0003044397350000051
further, the mass fraction of the sodium hydroxide solution in step S11 is 50%; the dosage ratio of the 1, 2-dichloroethane, the N-methylpyrrolidine, the 3, 4-dihydroxybenzyl alcohol and the sodium hydroxide solution is 80 mL: 150mL of: 28 g: 30 mL;
in the step S12, the dosage mass ratio of the intermediate 1 to the thionyl chloride is 16: 12;
the dosage ratio of the anhydrous aluminum chloride, nitrobenzene, acetyl chloride and the nitrobenzene solution of the intermediate 2 in the step S13 was 22.2 g: 250mL of: 20mL of: 50 mL; the nitrobenzene solution of intermediate 2 was intermediate 2 and nitrobenzene solution in 19 g: 50mL of the mixture is mixed;
the dichloroethane solution of chloroperoxybenzoic acid in step S14 was prepared from chloroperoxybenzoic acid and dichloroethane in an amount of 2.8 g: 30mL of the mixture, and the dichloroethane solution of the intermediate 3 is the mixture of the intermediate 3 and dichloroethane according to a ratio of 2.2 g: 50mL of the intermediate 3, and the volume ratio of the dichloroethane solution of chloroperoxybenzoic acid to the dichloroethane solution of the intermediate 3 is 3: 5.
further, the compound nutrient package contains 1000g of vitamin A acetate: 0.2-1.13g, vitamin D3: 0.00042-0.00133g, vitamin E: 0.6-1.47g, pyridoxine hydrochloride: 0.6-1.47g, sodium L-ascorbate: 0.6-01.47g, ferrous lactate: 0.8-1.14g, zinc sulfate: 0.8-1.14g and sodium selenite: 0.3-1 g; the balance is glucose to make up to 1000 g.
The invention has the beneficial effects that:
although both collagen and hyaluronic acid are located in the dermis, collagen more like an "elastic mesh" maintains facial elasticity and helps the skin resist sagging and wrinkling. The collagen fiber net formed by the collagen in the skin structure provides a basic structure for the hyaluronic acid, so that the hyaluronic acid has a better water retention effect on the skin and helps the skin to moisturize and moisturize. Meanwhile, the hyaluronic acid also helps the collagen fiber net to be better stretched in water and environment, and the collagen and the hyaluronic acid provide nutrition for the skin.
The prepared milk powder added with the collagen peptide and the sodium hyaluronate can be absorbed by human tissues; increasing skin moisture; the content of superoxide dismutase and glutathione peroxidase in serum is increased, and the antioxidant effect is achieved; increasing skin elasticity and resisting aging.
The auxiliary agent contains a sesame phenol analog structure, has good safety and antioxidant activity, can effectively remove free radicals, has antioxidant activity in a phenolic hydroxyl structure, shows multiple physiological activities of bacteriostasis, antivirus and the like in a benzodioxole derivative, is introduced into an antioxidant component, improves the action of the antioxidant component, has an O-alkylation reaction with chitosan oligosaccharide Schiff base, is introduced onto a chitosan oligosaccharide molecular chain, is deprotected by using an acid-alcohol solution, releases an active amino group, obtains the antioxidant component, is used as a natural antiseptic antibacterial agent, has biodegradability, biocompatibility and biological non-toxicity, and is introduced onto the chain to obtain a high-efficiency antioxidant component.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The auxiliary agent is prepared by the following steps:
step S11, adding 1, 2-dichloroethane and N-methylpyrrolidine into a three-neck flask, heating to reflux temperature, dropwise adding a mixed solution of 3, 4-dihydroxybenzyl alcohol and sodium hydroxide solution while stirring, stirring and reacting for 10 hours at the temperature of 91 ℃ after dropwise adding, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: firstly, decompressing and filtering, decompressing and concentrating the obtained filtrate to recover unreacted dichloroethane solution, and then drying the dichloroethane solution by using anhydrous sodium sulfate to obtain an intermediate 1;
step S12, adding the intermediate 1 and thionyl chloride into a flask, stirring for reaction, stirring at room temperature until solid is precipitated, and performing post-treatment, wherein the post-treatment process comprises the following steps: adding petroleum ether, washing, filtering, discarding filtrate until the washing liquid is colorless, and recrystallizing the obtained filter cake in boiling water to obtain an intermediate 2;
step S13, adding anhydrous aluminum chloride and nitrobenzene into a three-neck flask, adding acetyl chloride under the condition of ice-water bath, stirring for reaction for 30min, then adding a nitrobenzene solution of the intermediate 2, removing the ice-water bath after dropwise adding, stirring for reaction for 16h under the condition of room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment specific steps are as follows: mixing the obtained reaction solution with a hydrochloric acid solution with the mass fraction of 10%, extracting with dichloromethane, washing the obtained organic phase with deionized water, a sodium hydroxide solution with the mass fraction of 5% and deionized water to be neutral, performing rotary evaporation to remove dichloromethane to obtain a solid, and recrystallizing with an ethanol solution with the volume fraction of 40% to obtain an intermediate 3;
step S14, adding the dichloroethane solution of the intermediate 3 into a three-neck flask, dropwise adding the dichloroethane solution of chloroperoxybenzoic acid at 0 ℃, stirring and reacting for 10 hours at room temperature, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: filtering, washing the obtained filtrate with saturated sodium sulfite, a sodium hydroxide solution with the mass fraction of 10% and distilled water respectively to be neutral, then carrying out rotary evaporation to remove the solvent, then adding the filtrate into a sodium hydroxide solution with the mass fraction of 15%, stirring the mixture at room temperature until the mixture is dissolved and saponified, adjusting the pH value to 3 with persulfuric acid, extracting the mixture with dichloromethane, washing an organic phase with a sodium bicarbonate solution with the mass fraction of 15% and deionized water to be neutral, and carrying out rotary evaporation to remove the solvent to obtain the auxiliary agent.
Wherein the mass fraction of the sodium hydroxide solution in the step S11 is 50%; the dosage ratio of the 1, 2-dichloroethane, the N-methylpyrrolidine, the 3, 4-dihydroxybenzyl alcohol and the sodium hydroxide solution is 80 mL: 150mL of: 28 g: 30 mL;
in the step S12, the dosage mass ratio of the intermediate 1 to the thionyl chloride is 16: 12;
the dosage ratio of the anhydrous aluminum chloride, nitrobenzene, acetyl chloride and the nitrobenzene solution of the intermediate 2 in the step S13 was 22.2 g: 250mL of: 20mL of: 50 mL; the nitrobenzene solution of intermediate 2 was intermediate 2 and nitrobenzene solution in 19 g: 50mL of the mixture is mixed;
the dichloroethane solution of chloroperoxybenzoic acid in step S14 was prepared from chloroperoxybenzoic acid and dichloroethane in an amount of 2.8 g: 30mL of the mixture, and the dichloroethane solution of the intermediate 3 is the mixture of the intermediate 3 and dichloroethane according to a ratio of 2.2 g: 50mL of the intermediate 3, and the volume ratio of the dichloroethane solution of chloroperoxybenzoic acid to the dichloroethane solution of the intermediate 3 is 3: 5.
example 2
The antioxidant component is prepared by the following steps:
dissolving chitosan oligosaccharide in an acetic acid solution, adding methanol, uniformly stirring, dropwise adding a methanol solution of benzaldehyde at the temperature of 60 ℃, stirring and reacting at the constant temperature of 60 ℃, and performing aftertreatment after the reaction is finished, wherein the aftertreatment process comprises the following steps: cooling the reaction liquid to room temperature, volatilizing the organic solvent, adjusting the pH value to 7 by using a sodium hydroxide solution with the mass fraction of 5%, continuously stirring until no flocculent precipitate is generated, performing suction filtration, collecting the precipitate, performing Soxhlet extraction on the precipitate by using absolute ethyl alcohol for 12h, washing to be neutral, performing vacuum drying, and grinding to obtain powder, thereby obtaining the chitosan oligosaccharide Schiff base;
and secondly, dissolving an auxiliary agent in dimethylformamide to obtain a mixed solution A, dissolving the Schiff base of the oligosaccharides in dimethylformamide to obtain a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, stirring and reacting for 6 hours at the temperature of 25 ℃, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: adding excessive acetone to terminate the reaction, generating solid, performing vacuum filtration, performing Soxhlet extraction on the obtained solid with acetone, and removing dimethylformamide to obtain a crude product;
and thirdly, adding a hydrochloric acid ethanol mixed solution into the crude product obtained in the second step, stirring at room temperature for 12 hours, adjusting the pH value to 7 by using sodium carbonate, washing by using acetone, filtering, and drying in vacuum to obtain the antioxidant component.
Wherein, the mass fraction of the acetic acid solution in the first step is 1%, and the methanol solution of benzaldehyde is prepared by mixing benzaldehyde and methanol according to the volume ratio of 1: 10, mixing the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol and benzaldehyde, wherein the dosage ratio of the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol to benzaldehyde is 15 g: 70mL of: 120mL of: 120 mL; in the second step, the mixed solution A is taken as an auxiliary agent and dimethylformamide according to the weight ratio of 1 g: 10mL, wherein the mixed solution B is formed by mixing the schiff base of the sub-packaging oligosaccharide and dimethylformamide according to the weight ratio of 1 g: 10mL of the mixture is mixed, and the volume ratio of the mixed solution A to the mixed solution B is 1: 3; in the third step, the hydrochloric acid-ethanol mixed solution is 0.25mol/L hydrochloric acid solution and absolute ethanol according to the volume ratio of 1: 4, wherein the auxiliary agent is prepared in the example 1.
Example 3
The modified milk powder with the effects of resisting oxidation and ageing comprises the following raw materials in percentage by weight:
20% of desalted whey powder, 18% of whole milk powder, 10% of solid corn syrup, 3% of lactose, 3% of collagen peptide, 3% of galacto-oligosaccharide, 3% of concentrated whey protein powder, 0.1% of sodium hyaluronate, 0.3% of milk mineral salt, 0.5% of compound nutrient package, 0.2% of antioxidant component and the balance of skimmed milk powder to make up to 100%; wherein the antioxidant component is obtained in example 2.
Accurately weighing the raw materials according to the formula, respectively sieving the raw materials with a 60-mesh sieve, adding the raw materials into a mixer according to an equivalent progressive method, uniformly mixing, and directly packaging to obtain the modified milk powder with the effects of resisting oxidation and resisting aging.
Example 4
The modified milk powder with the effects of resisting oxidation and ageing comprises the following raw materials in percentage by weight:
23% of desalted whey powder, 19% of whole milk powder, 3% of solid corn syrup, 5% of lactose, 4% of collagen peptide, 5% of galacto-oligosaccharide, 4% of concentrated whey protein powder, 0.2% of sodium hyaluronate, 0.2% of pawpaw fruit powder, 0.2% of bivalvia red rose pollen, 0.5% of milk mineral salt, 0.5% of compound nutrient package, 0.5% of antioxidant component and the balance of skimmed milk powder to be 100%; wherein the antioxidant component is obtained in example 2.
Accurately weighing the raw materials according to the formula, respectively sieving the raw materials with a 70-mesh sieve, adding the raw materials into a mixer according to an equivalent progressive method, uniformly mixing, and directly packaging to obtain the modified milk powder with the effects of resisting oxidation and resisting aging.
Example 5
The modified milk powder with the effects of resisting oxidation and ageing comprises the following raw materials in percentage by weight:
26% of desalted whey powder, 20% of whole milk powder, 16% of solid corn syrup, 7% of lactose, 6% of collagen peptide, 6% of galacto-oligosaccharide, 5% of concentrated whey protein powder, 0.4% of sodium hyaluronate, 0.3% of pawpaw fruit powder, 0.3% of bivalvia red rose pollen, 0.6% of milk mineral salt, 0.5% of compound nutrient package, 0.6% of antioxidant component and the balance of skimmed milk powder to be 100%; wherein the antioxidant component is obtained in example 2.
Accurately weighing the raw materials according to the formula, respectively sieving the raw materials with a 80-mesh sieve, adding the raw materials into a mixer according to an equivalent progressive method, uniformly mixing, and directly packaging to obtain the modified milk powder with the effects of resisting oxidation and resisting aging.
Comparative example 1
The antioxidant component of example 3 was replaced with potassium sorbate, the remainder being unchanged.
The milk powder of examples 3-5 and comparative example 1 was subjected to a corrosion resistance test; the results of the microbial detection in the storage experiment are shown in table 1 below:
TABLE 1
Figure BDA0003044397350000101
From the above table 1, it can be seen that the modified milk powder with antioxidant and anti-aging effects prepared by the invention has long storage time, the auxiliary agent contains a sesame phenol analog structure, has good safety and antioxidant activity, can effectively remove free radicals, the phenolic hydroxyl structure has antioxidant activity, the benzodioxole derivative also shows multiple physiological activities such as bacteriostasis, antivirus and the like, the auxiliary agent is introduced into the antioxidant component to improve the antiseptic effect of the antioxidant component, the auxiliary agent and chitosan oligosaccharide schiff base undergo an O-alkylation reaction, the auxiliary agent is introduced onto the chitosan oligosaccharide molecular chain, then the acid alcohol solution is used for deprotection to release active amino groups to obtain the antioxidant component, the chitosan oligosaccharide is used as a natural antiseptic, besides biodegradability, biocompatibility and biological non-toxicity, the auxiliary agent with antibacterial activity is introduced onto the chain to obtain a high-efficiency antioxidant component, the storage time is improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (5)

1. The modified milk powder with the effects of resisting oxidation and ageing is characterized by comprising the following raw materials in percentage by weight:
20-26% of desalted whey powder, 18-20% of whole milk powder, 10-16% of solid corn syrup, 3-7% of lactose, 3-6% of collagen peptide, 3-6% of galacto-oligosaccharide, 3-5% of concentrated whey protein powder, 0.1-0.4% of sodium hyaluronate, 0-0.3% of pawpaw fruit powder, 0-0.3% of double red rose pollen, 0.3-0.6% of milk mineral salt, 0.5% of compound nutrient package, 0.2-0.6% of antioxidant component and the balance of skimmed milk powder to be 100%;
the antioxidant component is prepared by the following steps:
dissolving chitosan oligosaccharide in an acetic acid solution, adding methanol, stirring uniformly, dropwise adding a methanol solution of benzaldehyde at the temperature of 60 ℃, stirring at the constant temperature of 60 ℃ for reaction, and performing post-treatment after the reaction is finished to obtain chitosan oligosaccharide Schiff base;
secondly, dissolving an auxiliary agent in dimethylformamide to obtain a mixed solution A, dissolving the Schiff base of the oligosaccharides in dimethylformamide to obtain a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, stirring and reacting for 6 hours at the temperature of 25 ℃, and performing post-treatment after the reaction is finished to obtain a crude product;
and thirdly, adding a hydrochloric acid ethanol mixed solution into the crude product obtained in the second step, stirring at room temperature for 12 hours, adjusting the pH value to 7 by using sodium carbonate, washing by using acetone, filtering, and drying in vacuum to obtain the antioxidant component.
2. The modified milk powder with antioxidant and anti-aging effects as claimed in claim 1, wherein the mass fraction of the acetic acid solution in the first step is 1%, and the methanol solution of benzaldehyde is prepared by mixing benzaldehyde and methanol according to a volume ratio of 1: 10, mixing the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol and benzaldehyde, wherein the dosage ratio of the chitosan oligosaccharide, the acetic acid solution and the methanol solution of methanol to benzaldehyde is 15 g: 70mL of: 120mL of: 120 mL; in the second step, the mixed solution A is taken as an auxiliary agent and dimethylformamide according to the weight ratio of 1 g: 10mL, wherein the mixed solution B is formed by mixing the schiff base of the sub-packaging oligosaccharide and dimethylformamide according to the weight ratio of 1 g: 10mL of the mixture is mixed, and the volume ratio of the mixed solution A to the mixed solution B is 1: 3; in the third step, the hydrochloric acid-ethanol mixed solution is 0.25mol/L hydrochloric acid solution and absolute ethanol according to the volume ratio of 1: 4, and mixing.
3. The modified milk powder with antioxidant and antiaging effects as claimed in claim 2, characterized in that the adjuvant is prepared by the following steps:
step S11, adding 1, 2-dichloroethane and N-methylpyrrolidine into a three-neck flask, heating to a reflux temperature, then dropwise adding a mixed solution of 3, 4-dihydroxybenzyl alcohol and a sodium hydroxide solution while stirring, stirring and reacting for 10 hours at the temperature of 91 ℃ after dropwise adding, and performing post-treatment after the reaction is finished to obtain an intermediate 1;
step S12, adding the intermediate 1 and thionyl chloride into a flask, stirring for reaction, stirring at room temperature until solid is precipitated, and performing aftertreatment to obtain an intermediate 2;
step S13, adding anhydrous aluminum chloride and nitrobenzene into a three-neck flask, adding acetyl chloride under the condition of ice-water bath, stirring and reacting for 30min, then adding a nitrobenzene solution of the intermediate 2, removing the ice-water bath after dropwise adding, stirring and reacting for 16h under the condition of room temperature, and performing post-treatment after the reaction is finished to obtain an intermediate 3;
and step S14, adding the dichloroethane solution of the intermediate 3 into a three-neck flask, dropwise adding the dichloroethane solution of chloroperoxybenzoic acid at 0 ℃, stirring and reacting for 10 hours at room temperature, and performing post-treatment after the reaction is finished to obtain the assistant.
4. The modified milk powder with antioxidant and anti-aging effects as claimed in claim 3, wherein the mass fraction of the sodium hydroxide solution in step S11 is 50%; the dosage ratio of the 1, 2-dichloroethane, the N-methylpyrrolidine, the 3, 4-dihydroxybenzyl alcohol and the sodium hydroxide solution is 80 mL: 150mL of: 28 g: 30 mL; in the step S12, the dosage mass ratio of the intermediate 1 to the thionyl chloride is 16: 12; the dosage ratio of the anhydrous aluminum chloride, nitrobenzene, acetyl chloride and the nitrobenzene solution of the intermediate 2 in the step S13 was 22.2 g: 250mL of: 20mL of: 50 mL; the nitrobenzene solution of intermediate 2 was intermediate 2 and nitrobenzene solution in the following weight ratio of 19 g: 50mL of the mixture is mixed; the dichloroethane solution of chloroperoxybenzoic acid in step S14 was prepared from chloroperoxybenzoic acid and dichloroethane in an amount of 2.8 g: 30mL of the mixture, and the dichloroethane solution of the intermediate 3 is the mixture of the intermediate 3 and dichloroethane according to a ratio of 2.2 g: 50mL of the intermediate 3, and the volume ratio of the dichloroethane solution of chloroperoxybenzoic acid to the dichloroethane solution of the intermediate 3 is 3: 5.
5. the modified milk powder with antioxidant and anti-aging effects as claimed in claim 1, wherein the compound nutrient package contains 1000g of vitamin A acetate: 0.2-1.13g, vitamin D3: 0.00042-0.00133g, vitamin E: 0.6-1.47g, pyridoxine hydrochloride: 0.6-1.47g, sodium L-ascorbate: 0.6-01.47g, ferrous lactate: 0.8-1.14g, zinc sulfate: 0.8-1.14g and sodium selenite: 0.3-1 g; the balance is glucose to make up to 1000 g.
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