CN112521430A - Large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics - Google Patents
Large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics Download PDFInfo
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Abstract
The invention relates to a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics. Taking kelp as a raw material, quickly rinsing and degreasing the kelp by using an alkali solution in pretreatment, quickly removing all crude protein and partial mannitol and ash by using high-speed homogenization and pulverization and protease enzymolysis, quickly preparing sulfated kelp oligosaccharide primary extract from kelp residues obtained by the pretreatment through high-temperature oxidation and hydrolysis, separating and purifying the sulfated kelp oligosaccharide extract by using a continuous flow centrifugal synergistic membrane separation technology at normal temperature to obtain a sulfated kelp oligosaccharide solution, and finally quickly drying the sulfated kelp oligosaccharide solution by using a spray drying technology to form sulfated kelp oligosaccharide powder. The method has the advantages of simple and feasible process, high efficiency, energy conservation and suitability for large-scale production; the prepared sulfated kelp oligosaccharide has higher molecular weight concentration and can even be comparable to a dextran standard product; and the prepared sulfated laminarin oligosaccharide with the molecular weight less than 1000 is particularly suitable for being used in various cosmetics.
Description
Technical Field
The invention relates to a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics, belonging to the fields of chemical extraction technology and cosmetics.
Background
Laminarin is an intercellular polysaccharide inherent to brown algae such as kelp, is present in a cell wall matrix of brown algae, and is an active substance specific to brown algae. Laminarin is a multi-component mixture, and the composition and activity of the laminarin obtained from the kelp by different extraction methods are greatly different; in addition, laminarin has the defects of complex molecular structure, poor absorption, difficult quality control and the like, and needs to be solved urgently. Laminarin oligosaccharide is hydrolysate of laminarin, and low molecular weight Laminarin oligosaccharide has biological activity of resisting tumor, resisting oxidation, inhibiting bacteria, promoting growth, etc. Because of the low molecular weight, the kelp oligosaccharide has the advantages of strong water solubility, high stability, safety, no toxicity and the like, and has wide development prospect in the fields of medicine development, functional food and novel cosmetic development, agriculture and the like. Therefore, the kelp oligosaccharide can be used as a health-care product for enhancing the immunity of the human body and can also be a core raw material of a novel high-end cosmetic for removing free radicals with high added value.
At present, the preparation method of the kelp oligosaccharide mainly comprises the steps of taking kelp polysaccharide as a raw material, and degrading the kelp polysaccharide by a free radical degradation method, an acidolysis method, an alkaline hydrolysis method, a salt hydrolysis method, an enzymolysis method, an ultrasonic degradation method or a gamma-ray degradation method to obtain a mixture of various oligosaccharides, wherein the polymerization degree of the obtained kelp oligosaccharide is 2-30, and the molecular weight of the kelp oligosaccharide is 342 Da-8000 Da (the kelp oligosaccharide, the preparation method and the application thereof, CN201010213491. X); or preparing herba Zosterae Marinae oligosaccharide (oligosaccharide of herba Zosterae Marinae with effects of promoting growth of Stichopus japonicus and resisting stress, and its preparation method and application, CN201510259443.7) with average polymerization degree of 7 and average molecular weight of 2846 by fermenting crude enzyme solution with microorganism; and taking kelp as a raw material, inoculating special microorganisms into the kelp slurry, screening strains producing oligosaccharide, and separating and purifying to obtain a kelp oligosaccharide mixture (kelp oligosaccharide and a preparation method and application thereof, CN201710930007.7) with the polymerization degree of 2-20 and the molecular weight of 376-6500 Da. The kelp oligosaccharide prepared by the method has wide polymerization degree distribution and dispersed molecular weight distribution, loses the specific natural sulfate radical of kelp polysaccharide, and is not beneficial to the faster absorption of the kelp oligosaccharide by human bodies. At present, no patent literature reports on the preparation technology and process of sulfated kelp oligosaccharide particularly suitable for cosmetics have been found.
Disclosure of Invention
In order to solve the technical problems, the technical solution of the invention is as follows:
a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics comprises the following steps:
(1) pretreatment of
Putting a kelp raw material into a reaction kettle, adding an alkali solution or a strong base weak acid salt solution which is 2-10 times of the weight of the kelp, stirring for 15-60 minutes, washing away silt, impurities and mucus on the surface of the kelp, removing fat of the kelp, and rinsing with clear water, wherein the mass volume concentration of the alkali solution is 1-4%; putting the cleaned kelp into a reaction kettle, adding deionized water with the weight 3-15 times that of the kelp, homogenizing at high speed for 15-60 minutes at the speed of 10000-28000 r/min, heating to 50-60 ℃ after homogenizing, adjusting the pH to 6.0-7.0, adding protease with the weight 0.1-2% that of the kelp, and reacting for 30-60 minutes; and (3) after enzymolysis is finished, centrifuging at a high speed by using a continuous flow centrifuge, collecting the centrifuged kelp residues, putting the kelp residues into the reaction kettle again, adding deionized water with the weight 8-15 times that of kelp, stirring for 15-45 minutes, centrifuging at a high speed by using the continuous flow centrifuge, removing crude protein, part of mannitol and ash in the kelp, and collecting the centrifuged kelp residues for later use.
(2) High temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 5-10 times of the weight of the kelp residue, adding dilute alkali liquor or dilute acid liquor to adjust the pH to 5.0-7.0, adding hydrogen peroxide which is 0.2-2% of the weight of the kelp residue, reacting at the temperature of 80-100 ℃ for 6-8 hours; and obtaining sulfated kelp oligosaccharide primary extract after the hydrolysis is finished.
(3) Separating and purifying
Combining continuous flow centrifugation with a nanofiltration membrane with the relative molecular mass of 10 kD-5 kD to remove macromolecular impurities and solid fiber residues in the sulfated kelp oligosaccharide primary extract, removing micromolecular impurities and partial inorganic salts in the obtained clear liquid by using the nanofiltration membrane with the relative molecular mass of 500 DA-200 DA, and further concentrating to obtain a sulfated kelp oligosaccharide solution with the content of more than or equal to 95% and the molecular weight of less than 1000.
Preferably, the scale-up preparation method of the present invention further comprises:
(4) quick drying and sterilizing package
Rapidly drying the sulfated kelp oligosaccharide solution by spray drying to obtain sulfated kelp oligosaccharide powder; and then the rapid sterilization is carried out through the light radiation, and finally the sterile subpackaging is carried out.
The Latin raw material used in the step (1) is named Laminaria japonica Aresch by Laminaria japonica Laminaria.
The alkali or the strong base and weak acid salt used for adjusting the pH value by adding the alkali liquor or the strong base and weak acid salt solution in the step (1) and the step (2) is at least one of sodium bicarbonate, potassium bicarbonate, sodium hydroxide or potassium hydroxide; the acid is hydrochloric acid or nitric acid.
The protease used in the step (2) is one or a combination of two of papain, neutral protease, acid protease, bromelain and flavourzyme.
The flow rate of the nanofiltration membrane with the relative molecular mass of 10 kD-5 kD used in the step (3) is 5-14 cubic meters per hour, the membrane pressure is 0.552-0.931Mpa, and the temperature is 20-50 ℃; the flow rate of the nanofiltration membrane with the relative molecular mass of 500 DA-200 DA is 5-14 cubic meters per hour, the membrane pressure is 0.483-2.758 Mpa, and the temperature is 20-50 ℃.
The continuous flow centrifuge used in the step (1) and the step (3) has a centrifugation rate of 10000-15000 rpm.
The air inlet temperature of the spray drying used in the step (4) is 120-180 ℃, and the air outlet temperature is 70-95 ℃; the used light radiation can be ultraviolet radiation, gamma-ray or electron beam radiation, the radiation dose is 0.01-40 kGy, and the radiation time is 1-60 minutes.
The invention takes kelp rich in sources as a raw material of sulfated kelp oligosaccharide, adopts high-speed homogenization combined with biological enzymolysis technology for pretreatment, quickly removes all crude protein and partial mannitol and ash in the kelp, and then develops a high-temperature oxidation hydrolysis process for quickly preparing the sulfated kelp oligosaccharide for cosmetics in one step, and the prepared sulfated kelp oligosaccharide has high concentration of molecular weight distribution and molecular weight lower than 1000, and is more beneficial to absorption of human skin.
The test shows that: the cosmetic cream, the cosmetic lotion and the cosmetic lotion added with the sulfated kelp oligosaccharide (2%) are superior to glycerin cosmetics (2%) with the same content in moisture absorption and moisture retention performance, and the antioxidant activity of different mechanisms is superior to vitamin E cosmetics (2%) with the same content.
Compared with the prior art, the invention has the following advantages:
1. based on the analysis result of main components of kelp, the invention utilizes different chemical properties among protein, fat and carbohydrate, and quickly rinses and degreases by alkali liquor, quickly homogenizes and crushes at a high speed, and quickly removes crude protein and partial mannitol as well as partial ash (potassium iodide, sodium iodide and the like) by protease enzymolysis, so that kelp residue after pretreatment is almost sulfated laminarin solid.
2. Based on the characteristic that the glycosidic bond of laminarin is relatively stable, the invention selects the high-temperature oxidation hydrolysis method as the extraction method of the laminarin oligosaccharide, thereby not only avoiding the lengthy time cost and expensive material cost brought by the complex enzymatic hydrolysis method advocated by the prior patents and documents, but also realizing the effective improvement of the extraction rate and the great reduction of the extraction time; on the other hand, the process from the degradation of laminarin to the laminarin oligosaccharide is essentially the process of damaging the glucosidic bonds of the laminarin, so that although the high-temperature oxidation hydrolysis method adopted by the invention belongs to the chemical hydrolysis method, the problem of environmental pollution caused by strong acid and strong base in the general chemical method can be effectively avoided, and meanwhile, any toxic and harmful substance is not generated.
3. The sulfated kelp oligosaccharide produced by the method has high content (sugar content and sulfate radical content) of not less than 95 percent, has higher molecular weight concentration, and can even be compared with a dextran standard product.
4. The molecular weight of the sulfated kelp oligosaccharide produced by the invention is less than 1000 (average molecular weight 618, polymerization degree: 4), through detection, the moisture absorption and retention performance of the sulfated kelp oligosaccharide is stronger than that of glycerol, the antioxidant activity of the sulfated kelp oligosaccharide is better than that of vitamin E, the sulfated kelp oligosaccharide can effectively permeate skin and better supplement skin moisture, and the sulfated kelp oligosaccharide is particularly suitable for being used in various cosmetics.
5. On the basis of the produced sulfated kelp oligosaccharide, the invention develops kelp oligosaccharide series cosmetics (cosmetic liquid, cosmetic emulsion and cosmetic cream); through detection, the moisture absorption and retention performances of the kelp oligosaccharide series cosmetics are higher than those of the same type of glycerin cosmetics, and the antioxidant activity of the kelp oligosaccharide series cosmetics is better than that of the same type of vitamin E cosmetics, so that the kelp oligosaccharide produced by the invention is proved to be particularly suitable for being used in various cosmetics.
6. The sulfated kelp oligosaccharide produced by the invention is particularly suitable for being used as a functional raw material of cosmetics, but can also be directly eaten as clinical nourishment, health-care food, sports food and carbohydrate nutrition supplement.
In addition, many current methods for preparing kelp by enzymolysis adopt alginate lyase for enzymolysis (CN201811137102.2, CN201810566502.9 and the like), and the used alginate lyase is high in price and not beneficial to large-scale preparation. The enzyme used in the invention is protease, and the cost of the enzyme is far lower than that of alginate lyase.
Drawings
Table 1 shows the main components of the kelp raw material of the present invention.
FIG. 1 is a process of the invention: a process flow chart of a large-scale preparation method of sulfated kelp oligosaccharide.
Fig. 2 is a chromatogram of four standards: 1. dextran (Mw 405700); 2. dextran (Mw 45800); 3. dextran (Mw 1200); 4. dextran (Mw 342). Chromatographic conditions are as follows: a chromatographic column: TSKgel GMPWXL column; mobile phase: deionized water; isocratic elution for 20 minutes; a difference detector. This is also the chromatographic conditions of fig. 4, 5, 6 and 10 below.
FIG. 3 is a standard curve for four standards.
FIG. 4 is a process of the invention: chromatogram of primary extract of kelp oligosaccharide extracted by high-temperature oxidation hydrolysis method.
FIG. 5 is a chromatogram of primary extract of Laminaria oligosaccharide extracted by complex enzyme hydrolysis.
FIG. 6 is a chromatogram of primary extract of Laminaria oligosaccharide extracted by high temperature strong acid hydrolysis.
Table 2 shows the comparison of extraction time and extraction rate for different methods of extraction of kelp oligosaccharide.
FIG. 7 is a method of the invention: the influence of the extraction time of the high-temperature oxidation hydrolysis method on the extraction rate of sulfated kelp oligosaccharide, and other extraction conditions are as follows: the material-liquid ratio: 1:10, hydrogen peroxide content: 1%, pH 7, temperature: 80 ℃.
FIG. 8 is a method of the invention: the influence of the extraction temperature of the high-temperature oxidation hydrolysis method on the extraction rate of sulfated kelp oligosaccharide, and other extraction conditions are as follows: the material-liquid ratio: 1:10, hydrogen peroxide content: 1%, pH 7, time: for 6 hours.
FIG. 9 is the method of the present invention: the influence of the extraction pH of the high-temperature oxidation hydrolysis method on the extraction rate of sulfated kelp oligosaccharide, and other extraction conditions are as follows: the material-liquid ratio: 1:10, hydrogen peroxide content: 1%, temperature: 80 ℃, time: for 6 hours.
FIG. 10 is a method of the invention: chromatogram of sulfated kelp oligosaccharide prepared by high-temperature oxidation hydrolysis method.
FIG. 11 is a method of the invention: sulfated kelp oligosaccharide (simply called kelp oligosaccharide) and a series of cosmetics thereof.
FIG. 12 shows the effect of the molecular weight of laminarin and laminarin on their hygroscopic properties (1-1 kilo-laminarin; 2-glycerol; 3-1-2 ten thousand laminarin; 4-20 ten thousand laminarin).
FIG. 13 shows the effect of the molecular weight of laminarin and laminarin on the moisture retention properties (1-1 kilo-laminarin; 2-glycerol; 3-1-2 ten thousand laminarin; 4-20 ten thousand laminarin).
FIG. 14 shows the influence of the molecular weight of laminarin and laminarin on their antioxidant activity (a-FRAP method for determining the iron ion reduction/antioxidant ability of laminarin and laminarin; b-ABTS method for determining the antioxidant ability of laminarin and laminarin; c-T-AOC method for determining the total antioxidant ability of laminarin and laminarin; d-Fenton method for determining the hydroxyl radical inhibition ability of laminarin and laminarin).
FIG. 15 shows the moisture absorption properties of the kelp oligosaccharide cosmetic liquid (1-1 thousand kelp oligosaccharide (2%) cosmetic liquid; 2-glycerin (2%) cosmetic liquid).
FIG. 16 shows the moisturizing properties of the kelp oligosaccharide cosmetic liquid (1-1 thousand kelp oligosaccharide (2%) cosmetic liquid; 2-glycerin (2%) cosmetic liquid).
FIG. 17 is the moisture absorption properties of a kelp oligosaccharide cosmetic emulsion (1-1 thousand kelp oligosaccharide (2%) cosmetic emulsion; 2-glycerin (2%) cosmetic emulsion).
FIG. 18 is the moisturizing properties of a kelp oligosaccharide cosmetic emulsion (1-1 thousand kelp oligosaccharide (2%) cosmetic emulsion; 2-glycerin (2%) cosmetic emulsion).
FIG. 19 is the hygroscopic properties of a kelp oligosaccharide cream (1-1 thousand kelp oligosaccharide (2%) cream; 2-glycerol (2%) cream).
FIG. 20 shows the moisturizing properties of the kelp oligosaccharide cream (1-1 thousand kelp oligosaccharide (2%) cream; 2-glycerol (2%) cream).
FIG. 21 shows the antioxidant activity of the cosmetic liquid of sea tangle oligosaccharide (a-FRAP method for determining the iron ion reduction/antioxidant ability of the cosmetic liquid of sea tangle oligosaccharide; b-ABTS method for determining the antioxidant ability of the cosmetic liquid of sea tangle oligosaccharide; c-T-AOC method for determining the total antioxidant ability of the cosmetic liquid of sea tangle oligosaccharide; d-Fenton method for determining the hydroxyl radical inhibition ability of the cosmetic liquid of sea tangle oligosaccharide).
FIG. 22 shows the antioxidant activity of a cosmetic emulsion of sea tangle oligosaccharide (a-FRAP method for determining iron ion reduction/antioxidant ability of cosmetic emulsion of sea tangle oligosaccharide; b-ABTS method for determining antioxidant ability of cosmetic emulsion of sea tangle oligosaccharide; c-T-AOC method for determining total antioxidant ability of cosmetic emulsion of sea tangle oligosaccharide; d-Fenton method for determining hydroxyl radical inhibition ability of cosmetic emulsion of sea tangle oligosaccharide).
FIG. 23 shows the antioxidant activity of the kelp oligosaccharide cream (a-FRAP method for determining iron ion reduction/antioxidant ability of kelp oligosaccharide cream, b-ABTS method for determining antioxidant ability of kelp oligosaccharide cream, c-T-AOC method for determining total antioxidant ability of kelp oligosaccharide cream, and d-Fenton method for determining hydroxyl radical inhibition ability of kelp oligosaccharide cream).
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1:
a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics comprises the following steps:
(1) pretreatment of
Putting the kelp raw material into a reaction kettle, adding a sodium bicarbonate solution which is 10 times of the weight of the kelp, stirring for 30 minutes, and rinsing with clear water, wherein the mass volume concentration of the sodium bicarbonate solution is 1%; putting the cleaned kelp into a reaction kettle, adding deionized water with the weight 10 times that of the kelp, homogenizing at high speed for 30 minutes at 16000 rpm, heating to 55 ℃ after homogenizing, adjusting the pH value to 6.5, adding papain with the weight 0.5 percent of that of the kelp, and reacting for 60 minutes; and (3) after enzymolysis is finished, centrifuging at high speed of 14000rpm by using a continuous flow centrifuge, collecting the centrifuged kelp residue, putting the kelp residue into the reaction kettle again, adding deionized water with the weight 10 times of that of kelp, stirring for 25 minutes, centrifuging at high speed of 14000rpm by using the continuous flow centrifuge, and collecting the centrifuged kelp residue for later use.
(2) High temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 10 times of the weight of the kelp residue, adding dilute alkali liquor (NaOH) to adjust the pH to 7.0, adding hydrogen peroxide which is 1 percent of the weight of the kelp residue, reacting at the temperature of 80 ℃ for 6 hours; and obtaining sulfated kelp oligosaccharide primary extract after the hydrolysis is finished.
(3) Separating and purifying
Centrifuging the primary sulfated kelp oligosaccharide extract at high speed of 14000rpm by using a continuous flow centrifuge, removing macromolecular impurities from the obtained clear liquid by using a nanofiltration membrane with the relative molecular mass of 5kD, wherein the flow rate is 8 cubic meters per hour, the membrane pressure is 0.931Mpa, and the temperature is 30 ℃; removing small molecular impurities and inorganic salts with nanofiltration membrane with relative molecular mass of 200DA at flow rate of 5 cubic meter/hr, membrane pressure of 2.758MPa and temperature of 30 deg.C, and concentrating to obtain sulfated kelp oligosaccharide solution with content of 96%.
(4) Quick drying and sterilizing package
Spray drying to rapidly dry oligosaccharide solution, setting air inlet temperature at 160 deg.C and air outlet temperature at 90 deg.C to obtain sulfated sea tangle oligosaccharide powder; and then the rapid sterilization is carried out through gamma-ray radiation, the radiation dose is 10kGy, the radiation time is 30 minutes, and finally the sterile subpackaging is carried out.
Example 2:
a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics comprises the following steps:
(1) pretreatment of
Putting the kelp raw material into a reaction kettle, adding a potassium bicarbonate solution which is 5 times of the weight of the kelp, stirring for 45 minutes, and rinsing with clear water, wherein the mass volume concentration of the potassium bicarbonate solution is 1%; putting the cleaned kelp into a reaction kettle, adding deionized water which is 5 times of the weight of the kelp, homogenizing at high speed for 60 minutes at 12000 r/min, heating to 60 ℃ after homogenizing, adjusting the pH to 7.0, adding papain which is 0.5 percent of the weight of the kelp and neutral protease which is 0.5 percent of the weight of the kelp, and reacting for 45 minutes; and (3) after enzymolysis is finished, centrifuging at high speed of 14000rpm by using a continuous flow centrifuge, collecting the centrifuged kelp residue, putting the kelp residue into the reaction kettle again, adding deionized water with the weight 15 times that of kelp, stirring for 15 minutes, centrifuging at high speed of 14000rpm by using the continuous flow centrifuge, and collecting the centrifuged kelp residue for later use.
(2) High temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 5 times of the weight of the kelp residue, adding dilute acid (HCl) to adjust the pH to 5.5, adding hydrogen peroxide which is 1 percent of the weight of the kelp residue, reacting at the temperature of 85 ℃ for 8 hours; and obtaining sulfated kelp oligosaccharide primary extract after the hydrolysis is finished.
(3) Separating and purifying
Centrifuging the primary sulfated kelp oligosaccharide extract at high speed of 14000rpm by using a continuous flow centrifuge, removing macromolecular impurities from the obtained clear liquid by using a nanofiltration membrane with the relative molecular mass of 5kD, wherein the flow rate is 6 cubic meters per hour, the membrane pressure is 0.931Mpa, and the temperature is 35 ℃; removing small molecular impurities and inorganic salts with nanofiltration membrane with relative molecular mass of 200DA at flow rate of 5 cubic meter/hr, membrane pressure of 2.758MPa and temperature of 35 deg.C, and concentrating to obtain sulfated kelp oligosaccharide solution with content of 97.8%.
(4) Quick drying and sterilizing package
Spray drying to rapidly dry oligosaccharide solution, setting air inlet temperature at 150 deg.C and air outlet temperature at 85 deg.C to obtain sulfated sea tangle oligosaccharide powder; and performing rapid sterilization through ultraviolet radiation, wherein the radiation dose is 5kGy, the radiation time is 60 minutes, and finally performing sterile subpackaging.
Example 3:
a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics comprises the following steps:
(1) pretreatment of
Putting the kelp raw material into a reaction kettle, adding a sodium hydroxide solution which is 10 times of the weight of the kelp, stirring for 15 minutes, and rinsing with clear water, wherein the mass volume concentration of the sodium hydroxide solution is 4%; putting the cleaned kelp into a reaction kettle, adding deionized water with the weight 3 times that of the kelp, homogenizing at high speed for 60 minutes at 10000 r/min, heating to 53 ℃ after homogenizing, adjusting the pH to 6.5, adding papain with the weight 1.0% of that of the kelp feed and flavourzyme with the weight 1.0% of that of the kelp feed, and reacting for 30 minutes; and (3) after enzymolysis is finished, centrifuging at high speed of 14000rpm by using a continuous flow centrifuge, collecting the centrifuged kelp residue, putting the kelp residue into the reaction kettle again, adding deionized water with the weight 15 times that of kelp, stirring for 15 minutes, centrifuging at high speed of 14000rpm by using the continuous flow centrifuge, and collecting the centrifuged kelp residue for later use.
(2) High temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 5 times of the weight of the kelp residue, adding dilute hydrochloric acid to adjust the pH to 5.0, adding hydrogen peroxide which is 1% of the weight of the kelp residue, and reacting for 6 hours at the reaction temperature of 100 ℃; and obtaining sulfated kelp oligosaccharide primary extract after the hydrolysis is finished.
(3) Separating and purifying
Centrifuging the primary sulfated kelp oligosaccharide extract at high speed of 14000rpm by using a continuous flow centrifuge, removing macromolecular impurities from the obtained clear liquid by using a nanofiltration membrane with the relative molecular mass of 5kD, wherein the flow rate is 6 cubic meters per hour, the membrane pressure is 0.931Mpa, and the temperature is 35 ℃; and removing small molecular impurities and inorganic salts by using a nanofiltration membrane with the relative molecular mass of 500DA, wherein the flow rate is 8 cubic meters per hour, the membrane pressure is 2.5Mpa, the temperature is 35 ℃, and the sulfated kelp oligosaccharide solution with the content of 96.8 percent is obtained by concentration.
(4) Quick drying and sterilizing package
Spray drying to rapidly dry oligosaccharide solution, setting air inlet temperature at 165 deg.C and air outlet temperature at 88 deg.C to obtain sulfated sea tangle oligosaccharide powder; and then performing rapid sterilization through gamma-ray radiation, wherein the radiation dose is 15kGy, the radiation time is 15 minutes, and finally performing sterile subpackaging.
Example 4:
a large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics comprises the following steps:
(1) pretreatment of
Putting the kelp raw material into a reaction kettle, adding a potassium hydroxide solution which is 5 times of the weight of the kelp, stirring for 20 minutes, and rinsing with clear water, wherein the mass volume concentration of the potassium hydroxide solution is 3%; putting the cleaned kelp into a reaction kettle, adding deionized water 15 times the weight of the kelp, homogenizing at high speed for 45 minutes at 15000rpm, heating to 50 ℃ after homogenizing, adjusting the pH to 6.0, adding papain 1.0% and bromelain 1.0% of the weight of the kelp, and reacting for 60 minutes; and (3) after enzymolysis is finished, centrifuging at high speed of 14000rpm by using a continuous flow centrifuge, collecting the centrifuged kelp residue, putting the kelp residue into the reaction kettle again, adding deionized water with the weight 8 times that of kelp, stirring for 45 minutes, centrifuging at high speed of 14000rpm by using the continuous flow centrifuge, and collecting the centrifuged kelp residue for later use.
(2) High temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 5 times of the weight of the kelp residue, adding dilute hydrochloric acid to adjust the pH to 6.0, adding hydrogen peroxide which is 1.5 percent of the weight of the kelp residue, reacting at the temperature of 80 ℃ for 7 hours; and obtaining sulfated kelp oligosaccharide primary extract after the hydrolysis is finished.
(3) Separating and purifying
Centrifuging the primary sulfated kelp oligosaccharide extract at high speed of 14000rpm by using a continuous flow centrifuge, removing macromolecular impurities from the obtained clear liquid by using a nanofiltration membrane with the relative molecular mass of 10kD, wherein the flow rate is 8 cubic meters per hour, the membrane pressure is 0.931Mpa, and the temperature is 25 ℃; and removing small molecular impurities and inorganic salts by using a nanofiltration membrane with the relative molecular mass of 500DA, wherein the flow rate is 5 cubic meters per hour, the membrane pressure is 2.75Mpa, the temperature is 45 ℃, and the sulfated kelp oligosaccharide solution with the content of 95.6 percent is obtained by concentration.
(4) Quick drying and sterilizing package
Spray drying to rapidly dry oligosaccharide solution, setting air inlet temperature at 165 deg.C and air outlet temperature at 92 deg.C to obtain sulfated sea tangle oligosaccharide powder; and performing rapid sterilization by electron beam radiation, wherein the radiation dose is 10kGy, the radiation time is 15 minutes, and finally performing sterile subpackaging.
As shown in table 1, more than two thirds of the components in kelp are carbohydrates including alginic acid, algin, kelp fiber, mannitol, etc., and crude protein and ash respectively account for about 10% and 15% of the components, while the fat content is very low, so that the present invention designs a process flow capable of large-scale preparation of sulfated kelp oligosaccharide.
TABLE 1
As shown in figure 1, the method comprises the steps of firstly washing silt, impurities and mucus on the surface of kelp by using dilute alkali liquor, removing trace fat in the kelp, then quickly removing non-negligible crude protein components and partial mannitol and water-soluble ash (potassium iodide, sodium iodide and the like) in the kelp by using high-speed homogenization crushing and protease enzymolysis, then quickly preparing sulfated kelp oligosaccharide primary extract from the centrifuged kelp residue through high-temperature oxidation hydrolysis, then separating, purifying and desalting the sulfated kelp oligosaccharide extract by using a continuous flow centrifugation and membrane separation technology at normal temperature to obtain a sulfated kelp oligosaccharide solution with the content of more than or equal to 95 percent and the molecular weight of less than 1000, finally quickly drying by using a spray drying technology to form sulfated kelp oligosaccharide powder, and quickly sterilizing, sealing and storing by using a light radiation technology.
As shown in fig. 2, four dextran standards of different molecular weights spaced peaks on the TSKgel GMPWXL column without coincidence.
As shown in fig. 3, the regression equation for the standard curve is: y-1.0306 x +13.973 (R)20.998), shows a molecular weight in the range of 405700 to 342, and the accuracy of the measurement results is high.
As shown in fig. 4, 5 and 6, by comparing the molecular weight distribution of the laminarin oligosaccharides prepared by different extraction methods, the main peak positions (hooked positions in the figures) of the laminarin oligosaccharides prepared by the high-temperature oxidation hydrolysis method (the method of the present invention), the complex enzymatic hydrolysis method and the high-temperature strong acid hydrolysis method are all consistent, and the chromatographic effect of the laminarin oligosaccharides prepared by the high-temperature oxidation hydrolysis method is significantly better than that of the laminarin prepared by the complex enzymatic hydrolysis method and the high-temperature strong acid hydrolysis method. In addition, as shown in table 2, the time for extracting the kelp oligosaccharide by the high-temperature oxidation hydrolysis method is shortest, and the extraction rate is highest; therefore, the invention selects a high-temperature oxidation hydrolysis method as an extraction method of sulfated kelp oligosaccharide.
TABLE 2
As shown in fig. 7, the extraction time was extended from 1 hour to 6 hours, and the extraction rate of sulfated kelp oligosaccharide increased from 10.97% ± 1.04% to 61.25% ± 1.11%, in the course of which the extraction rate rapidly increased as the extraction time was extended. While the extraction time is prolonged from 6 hours to 8 hours, the extraction rate of the sulfated kelp oligosaccharide is basically kept unchanged.
As shown in fig. 8, the extraction temperature was increased from 30 ℃ to 80 ℃, and the extraction rate of sulfated kelp oligosaccharide was increased from 1.92% ± 0.09% to 61.25% ± 1.11%, during which the extraction rate rapidly increased as the extraction temperature increased. While the extraction temperature is increased from 80 ℃ to 100 ℃, the extraction rate of sulfated kelp oligosaccharide is slowly increased.
As shown in fig. 9, the extraction pH increased from 1 to 7 and the extraction yield of sulfated kelp oligosaccharide remained substantially unchanged; while the pH further increased from 7 to 14, the extraction rate of sulfated kelp oligosaccharide decreased from 61.25% ± 1.11% to 19.11% ± 2.06%, because hydrogen peroxide was easily decomposed under alkaline high temperature conditions, resulting in a sharp decrease in extraction rate.
As shown in FIG. 10, the Laminaria oligosaccharide did not have any peak pattern at wavelengths of 280nm, 220nm and 214nm, indicating that: the prepared sulfated kelp oligosaccharide has no protein or peptide, and the sulfated kelp oligosaccharide only has a narrow single peak in a TSKgel GMPWXL column, which indicates that the prepared sulfated kelp oligosaccharide has high molecular weight concentration and can even be compared with a dextran standard product; calculated from the standard curve of fig. 3: the average molecular weight of the sulfated kelp oligosaccharide is 618.
As shown in FIG. 11, the invention prepares kelp oligosaccharide cosmetic liquid, kelp oligosaccharide cosmetic lotion and kelp oligosaccharide cosmetic cream on the basis of sulfated kelp oligosaccharide (hereinafter referred to as kelp oligosaccharide), and researches moisture absorption and moisture retention performance and antioxidant activity.
As shown in fig. 12 and 13, the moisture absorption and retention performances of laminarin and laminarin with different molecular weights are, from strong to weak: more than 1 thousand kelp oligosaccharide (prepared by the method of the invention) > glycerin >1 million to 2 million kelp polysaccharide >20 million kelp polysaccharide.
As shown in FIG. 14, by four antioxidant activity measurement methods (FRAP method, ABTS method, T-AOC method and Fenton method) with different mechanisms, the results of the influence of the molecular weight of laminarin oligosaccharide and laminarin on the antioxidant activity are consistent; the antioxidant activity of the composition is from strong to weak: less than 1 thousand kelp oligosaccharide (prepared by the method of the invention) > vitamin E >1 million to 2 million kelp polysaccharide >20 million kelp polysaccharide.
As shown in fig. 15, 16, 17, 18, 19 and 20, all the cosmetics (lotion, lotion and cream) added with laminarin oligosaccharide (2%) had better moisture absorption and retention performance than the glycerin cosmetics (2%) of the same content.
As shown in fig. 21, 22 and 23, the results of measuring the antioxidant activity of three kelp oligosaccharide cosmetics (cosmetic liquid, cosmetic emulsion and cosmetic cream) by four antioxidant activity detection methods (FRAP method, ABTS method, T-AOC method and Fenton method) with different mechanisms are consistent, and the antioxidant activity is from strong to weak: more than 1 thousand kelp oligosaccharide cosmetics (prepared by the method of the invention) > vitamin E cosmetics >1 million to 2 million kelp polysaccharide cosmetics >20 million kelp polysaccharide cosmetics.
Claims (10)
1. A large-scale preparation method of sulfated kelp oligosaccharide suitable for cosmetics is characterized by comprising the following steps:
(1) pretreatment of
Putting a kelp raw material into a reaction kettle, adding an alkali solution or a strong base weak acid salt solution which is 2-10 times of the weight of the kelp, stirring for 15-60 minutes, washing away silt, impurities and mucus on the surface of the kelp, removing fat of the kelp, and rinsing with clear water, wherein the mass volume concentration of the alkali solution or the strong base weak acid salt solution is 1-4%; putting the cleaned kelp into a reaction kettle, adding deionized water with the weight 3-15 times that of the kelp, homogenizing at high speed for 15-60 minutes at the speed of 10000-28000 r/min, heating to 50-60 ℃ after homogenizing, adjusting the pH to 6.0-7.0, adding protease with the weight 0.1-2% that of the kelp, and reacting for 30-60 minutes; after enzymolysis is finished, centrifuging at a high speed by using a continuous flow centrifuge, collecting the centrifuged kelp residue, putting the kelp residue into the reaction kettle again, adding deionized water with the weight 8-15 times that of kelp, stirring for 15-45 minutes, centrifuging at a high speed by using the continuous flow centrifuge, and collecting the centrifuged kelp residue for later use;
(2) high temperature oxidative hydrolysis
Putting the kelp residue after pretreatment, cleaning and centrifugation into a reaction kettle, adding deionized water which is 5-10 times of the weight of the kelp residue, adding dilute alkali liquor or dilute acid liquor to adjust the pH to 4.0-7.0, adding hydrogen peroxide which is 0.2-2% of the weight of the kelp residue, reacting at the temperature of 80-100 ℃ for 6-8 hours; obtaining sulfated kelp oligosaccharide primary extract after hydrolysis;
(3) separating and purifying
Combining continuous flow centrifugation with a nanofiltration membrane with the relative molecular mass of 10 kD-5 kD to remove macromolecular impurities and solid fiber residues in the sulfated kelp oligosaccharide primary extract, removing micromolecular impurities and partial inorganic salts in the obtained clear liquid by using the nanofiltration membrane with the relative molecular mass of 500 DA-200 DA, and further concentrating to obtain a sulfated kelp oligosaccharide solution with the content of more than or equal to 95% and the molecular weight of less than 1000.
2. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to claim 1, wherein: adding alkali liquor in the step (1) and the step (2) to adjust the pH value, wherein the alkali or strong alkali weak acid salt is sodium bicarbonate, potassium bicarbonate, sodium hydroxide or potassium hydroxide; the acid is hydrochloric acid or nitric acid.
3. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to claim 1, wherein: the protease used in the step (2) is one or two of papain, neutral protease, acid protease, bromelain and flavourzyme.
4. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to claim 1, wherein: the flow rate of the nanofiltration membrane with the relative molecular mass of 10 kD-5 kD used in the step (3) is 5-14 cubic meters per hour, the membrane pressure is 0.552-0.931Mpa, and the temperature is 20-50 ℃; the flow rate of the nanofiltration membrane with the relative molecular mass of 500 DA-200 DA is 5-14 cubic meters per hour, the membrane pressure is 0.483-2.758 Mpa, and the temperature is 20-50 ℃.
5. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to claim 1, wherein: and (3) the high-speed centrifugal speed of the continuous flow centrifugal machine in the step (1) and the step (3) is 10000-15000 rpm.
6. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to any one of claims 1 to 5, wherein: further comprises the following steps of (4) quick drying and sterilization packaging: rapidly drying the sulfated kelp oligosaccharide solution by spray drying to obtain sulfated kelp oligosaccharide powder; and then the rapid sterilization is carried out through the light radiation, and finally the sterile subpackaging is carried out.
7. The method for the large-scale preparation of sulfated kelp oligosaccharide suitable for cosmetics according to claim 6, wherein: the air inlet temperature of the spray drying used in the step (4) is 120-180 ℃, and the air outlet temperature is 70-95 ℃; the used light radiation is ultraviolet radiation, gamma-ray or electron beam radiation, the radiation dose is 0.01-40 kGy, and the radiation time is 1-60 minutes.
8. A sulfated kelp oligosaccharide suitable for cosmetics, which is characterized by being produced by the method for producing a sulfated kelp oligosaccharide suitable for cosmetics according to any one of claims 1 to 5.
9. A cosmetic characterized by containing the sulfated kelp oligosaccharide according to claim 8 in an amount of 0.01 to 99% by weight.
10. A cosmetic product according to claim 9, said cosmetic product comprising at least one of a lotion, cream and lotion.
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