阅读说明：本技术 一种海洋生物精华及其制备方法 (Marine organism essence and preparation method thereof ) 是由 封金才 于 2020-12-01 设计创作，主要内容包括：本发明公开了一种海洋生物精华及其制备方法,其中各组分包括改性海带多糖、自制增稠剂、明胶、海藻酸钠、透明质酸衍生物、海带渣、防腐剂、香精、去离子水和超纯水。海带多糖采用水提后柠檬酸法从海带渣中提取,再将海带多糖进行特殊的硫酸化处理,大幅度的提高抗氧化能力。使用改性明胶与海藻酸钠制备的自制增稠剂,将水状精华改为凝胶状精华,增加活性成分的附着力,而经过改性的明胶细胞亲和力增加,使得明胶可以很好的发挥效用,又因为海藻酸钠的协同作用,克服了单一明胶的不稳定性。经过表面修饰的透明质酸具备两亲性,在凝胶体系中可以更好的发挥效用。本发明制备的海洋生物精华虽然成分简单,却有优异的抗氧化和保湿能力。(The invention discloses marine organism essence and a preparation method thereof, wherein each component comprises modified laminarin, a self-made thickening agent, gelatin, sodium alginate, a hyaluronic acid derivative, kelp residue, a preservative, essence, deionized water and ultrapure water. The laminarin is extracted from the laminarin residue by a citric acid method after water extraction, and then the laminarin is subjected to special sulfation treatment, thereby greatly improving the oxidation resistance. The homemade thickener prepared from the modified gelatin and the sodium alginate changes the aqueous essence into the gel essence, increases the adhesive force of the active ingredients, increases the affinity of the modified gelatin cells, ensures that the gelatin can well play a role, and overcomes the instability of single gelatin due to the synergistic effect of the sodium alginate. The hyaluronic acid subjected to surface modification has amphipathy, and can better play a role in a gel system. The marine organism essence prepared by the invention has excellent oxidation resistance and moisturizing capability although the components are simple.)

1. The marine organism essence is characterized by comprising the following raw materials in parts by weight: 10-20 parts of modified laminarin, 10-15 parts of self-made thickening agent, 20-30 parts of gelatin, 5-10 parts of sodium alginate, 5-10 parts of hyaluronic acid derivative, 30-50 parts of kelp residue, 2-5 parts of preservative, 1-2 parts of essence, 10-20 parts of deionized water and 10-20 parts of ultrapure water.

2. The marine organism essence of claim 1, wherein: the laminarin is extracted from the kelp residue by a citric acid method after water extraction.

3. The essence of marine organisms according to claim 1, wherein: the modified polysaccharide is prepared by firstly carrying out ultrasonic treatment on purified laminarin, then carrying out sulfation, and carrying out ultrasonic treatment while sulfating.

4. The essence of marine organisms according to claim 1, wherein: the self-made thickener is prepared by compounding modified gelatin and sodium alginate, and has the mass concentration of 8: 1.

5. the essence of marine organisms according to claim 1, wherein: the hyaluronic acid derivative is prepared by introducing pyrene functional groups to perform surface modification on hyaluronic acid.

6. The preparation method of the marine organism essence is characterized by comprising the following specific steps:

(1) extracting with 120 ℃ hot water for 3h, adding the filtered kelp residue into a triangular flask, and mixing the kelp residue with the water according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, filtering, adjusting to neutrality, adding 95% ethanol, standing at low temperature overnight, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(6) Adding the modified gelatin and sodium alginate into deionized water at 25 ℃ to swell for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(7) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(8) And (3) uniformly mixing the modified laminarin, the self-made thickening agent and the hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain a finished product.

7. The method for preparing marine organism essence according to claim 6, wherein in the step (1): after suction filtration, the pH was adjusted using KOH solution, and 95% ethanol was added in a volume fraction of 70%.

8. The method for preparing marine organism essence according to claim 6, wherein in the step (4): measuring 2.5mL of n-butanol, placing the n-butanol in a 500mL round-bottom flask, adding 1.25g of ammonium sulfate, shaking for dissolution, and adding 7.5mL of concentrated sulfuric acid for preparing a reaction solution; during dialysis, tap water is firstly used for dialysis for 24 hours, and then deionized water is used for dialysis for 24 hours.

9. The method for preparing marine organism essence according to claim 6, wherein in the step (6): the mass of the modified gelatin and the sodium alginate is 8: and 1, obtaining the home-made thickening agent with the pH value of 6-7.

10. The method for preparing essence of marine organism according to claim 6, wherein in the step (7): the volume ratio of the mixed solvent of pyridine is 2: 1.

Technical Field

The invention relates to the technical field of cosmetics, in particular to marine organism essence and a preparation method thereof.

Background

In the daily skin care process, people often neglect the use of essence and pay more attention to the use of toning lotion and emulsion. Lotions and creams can only achieve basic moisturizing effects, and improper use can also accelerate facial water loss. But the effect of the essence is greater than that of these basic skin care products. Furthermore, the essences on the market at present pursue complex components and multiple efficacies, so that a certain effect is difficult to achieve to the best under multiple actions.

Polysaccharide and hyaluronic acid are natural moisturizing factors, and if the essence can be utilized by combining with marine organisms, the prepared essence is simple in components and single in effect and high in efficiency, and the essence is welcomed by people and draws attention to the essence for people. Therefore, it is necessary to design a marine organism essence with simple components and remarkable antioxidant and moisturizing effects.

Disclosure of Invention

The invention aims to provide marine organism essence to solve the problems in the background technology.

In order to solve the technical problems, the invention provides the following technical scheme of marine organism essence in a first aspect, which comprises the following raw materials in parts by weight:

10-20 parts of modified laminarin, 10-15 parts of self-made thickening agent, 20-30 parts of gelatin, 5-10 parts of sodium alginate, 5-10 parts of hyaluronic acid derivative, 30-50 parts of kelp residue, 2-5 parts of preservative, 1-2 parts of essence, 10-20 parts of deionized water and 10-20 parts of ultrapure water.

Preferably, the laminarin is extracted from the kelp residue by a citric acid method after water extraction.

Preferably, the modified polysaccharide is prepared by performing ultrasonic treatment on purified laminarin, then performing sulfation, and performing ultrasonic treatment while performing sulfation.

Preferably, the self-made thickening agent is prepared by compounding modified gelatin and sodium alginate, and the mass concentration is 8: 1.

preferably, the hyaluronic acid derivative is prepared by introducing pyrene functional groups to perform surface modification on hyaluronic acid.

Preferably, the preservative is one of an alcohol preservative, a formaldehyde donor and an aldehyde derivative preservative, and benzoic acid and a derivative preservative thereof.

The invention provides a preparation method of marine organism essence, which comprises the following steps:

(1) extracting with 120 ℃ hot water for 3h, adding the filtered kelp residue into a triangular flask, and mixing the kelp residue with the water according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, filtering, adjusting to neutrality, adding 95% ethanol, standing at low temperature overnight, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(6) Adding the modified gelatin and sodium alginate into deionized water at 25 ℃ to swell for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(7) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(8) And (3) uniformly mixing the modified laminarin, the self-made thickening agent and the hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain a finished product.

In the step (1): after suction filtration, the pH was adjusted using KOH solution, and 95% ethanol was added in a volume fraction of 70%.

In the step (4): measuring 2.5mL of n-butanol, placing the n-butanol in a 500mL round-bottom flask, adding 1.25g of ammonium sulfate, shaking for dissolution, and adding 7.5mL of concentrated sulfuric acid for preparing a reaction solution; during dialysis, tap water is firstly used for dialysis for 24 hours, and then deionized water is used for dialysis for 24 hours.

In the step (6): the mass of the modified gelatin and the sodium alginate is 8: 1, the pH value of the obtained self-made thickening agent is 6-7, and the pH value is moderate, so that the skin cannot be damaged.

In the step (7): the volume ratio of the mixed solvent of pyridine is 2: 1.

compared with the prior art, the invention has the following beneficial effects:

the invention discloses marine organism essence, which comprises components such as modified laminarin, a self-made thickening agent, gelatin, sodium alginate, laminarin residue, a preservative, essence and the like, wherein the laminarin is extracted from the laminarin residue by a citric acid method after water extraction, so that the low extraction rate of a water extraction method is avoided, and the complex repeated extraction of all acid extraction methods is avoided. The hydroxyl on the sugar chain of the laminarin modified by sulfuric acid acidification is replaced by a sulfuric acid group, a new active group is introduced on the sugar chain, the antioxidant capacity of the laminarin is enhanced, and the introduction of the sulfuric acid group enables the conformation of the laminarin to be more extended, so that the water solubility is improved; the degree of substitution is one of important factors influencing the biological activity of sulfated laminarin, and after ultrasonic treatment, the degree of substitution of the laminarin after ultrasonic-sulfation is more than 3 times of that of sulfated modified polysaccharide, and the laminarin has stronger reducing capability and oxygen radical absorption capability than the sulfated modified polysaccharide. This is because the rearrangement of the sugar chains by sonication increases the hydroxyl activity of C-2 and C-4 groups, making substitution by sulfate groups more likely.

Most of the common essences in the market are water-shaped essences, the water-shaped essences are changed into gel-shaped essences by using a thickening agent to form a space network structure, liquid serving as a dispersion medium is filled in structural gaps, and the components in the essence are firmly locked on the surface of the skin on the face. Gelatin, as a protein, can utilize the steric hindrance and viscosity of polysaccharides to increase the stability of the active ingredient. However, gelatin has poor temperature resistance, the resulting gel system becomes unstable due to temperature changes, and when gelatin is used as a single thickener, the solution tends to form large droplets, resulting in poor system stability. The oxazolidine cross-linked and modified gelatin changes the temperature resistance of the gelatin, relieves the degradation speed of the gelatin, and enables the system to be in an excellent gel state in a wider temperature range. The modified gelatin is compounded with the sodium alginate, and the solution has uniform droplet shape, good elutriation stability and low elutriation rate through the synergistic effect of the modified gelatin and the sodium alginate, and small aggregation occurs below 50 ℃, so that the stability of the marine organism essence is improved.

The natural moisturizing factor hyaluronic acid is added into the essence, and the hyaluronic acid is used as an important component of extracellular matrix and has natural biocompatibility. As a natural moisturizing factor, the pyrene functional group is introduced into hyaluronic acid, and the hyaluronic acid is an amphiphilic biomacromolecule by utilizing the structure with a large number of pi-pi conjugated structures, so that hyaluronic acid derivatives can be better combined in the gel system of marine organism essence. The marine organism essence prepared by the modified laminarin and the hyaluronic acid derivative under the action of the self-made thickening agent has excellent oxidation resistance and moisturizing capability although the components are simple.

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.

The marine organism essence comprises the following raw materials in parts by weight:

10-20 parts of modified laminarin, 10-15 parts of self-made thickening agent, 20-30 parts of gelatin, 5-10 parts of sodium alginate, 5-10 parts of hyaluronic acid derivative, 30-50 parts of kelp residue, 2-5 parts of preservative, 1-2 parts of essence, 10-20 parts of deionized water and 10-20 parts of ultrapure water.

Preferably, the laminarin is extracted from the kelp residue by a citric acid method after water extraction.

Preferably, the modified polysaccharide is prepared by performing ultrasonic treatment on purified laminarin, then performing sulfation, and performing ultrasonic treatment while performing sulfation.

Preferably, the self-made thickening agent is prepared by compounding modified gelatin and sodium alginate, and the mass concentration is 8: 1.

preferably, the hyaluronic acid derivative is prepared by introducing pyrene functional groups to perform surface modification on hyaluronic acid.

Preferably, the preservative is one of an alcohol preservative, a formaldehyde donor and an aldehyde derivative preservative, and benzoic acid and a derivative preservative thereof.

The invention provides a preparation method of marine organism essence, which comprises the following steps:

(1) extracting with 120 ℃ hot water for 3h, adding the filtered kelp residue into a triangular flask, and mixing the kelp residue with the water according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, filtering, adjusting to neutrality, adding 95% ethanol, standing at low temperature overnight, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(6) Adding the modified gelatin and sodium alginate into deionized water at 25 ℃ to swell for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(7) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(8) And (3) uniformly mixing the modified laminarin, the self-made thickening agent and the hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain a finished product.

In the step (1): after suction filtration, the pH was adjusted using KOH solution, and 95% ethanol was added in a volume fraction of 70%.

In the step (4): measuring 2.5mL of n-butanol, placing the n-butanol in a 500mL round-bottom flask, adding 1.25g of ammonium sulfate, shaking for dissolution, and adding 7.5mL of concentrated sulfuric acid for preparing a reaction solution; during dialysis, tap water is firstly used for dialysis for 24 hours, and then deionized water is used for dialysis for 24 hours.

In the step (6): the mass of the modified gelatin and the sodium alginate is 8: 1, the pH value of the obtained self-made thickening agent is 6-7, and the pH value is moderate, so that the skin cannot be damaged.

In the step (7): the volume ratio of the mixed solvent of pyridine is 2: 1.

example 1: marine organism essence I:

the marine organism essence comprises the following components in parts by weight:

the modified laminarin-containing kelp residue-containing kelp paste comprises, by weight, 10 parts of modified laminarin, 10 parts of a self-made thickener, 20 parts of gelatin, 5 parts of sodium alginate, 5 parts of hyaluronic acid derivative, 30 parts of kelp residue, 2 parts of a preservative, 1 part of essence, 10 parts of deionized water and 10 parts of ultrapure water.

The preparation method of the essence comprises the following steps:

(1) extracting 30 parts by weight of kelp residue with 120 ℃ hot water for 3 hours, adding the filtered kelp residue into a triangular flask, and mixing the materials according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, performing suction filtration, adjusting to neutrality, adding 95% ethanol until the volume fraction is 70%, standing overnight at 0 deg.C, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving 10 parts by weight of laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(6) Mixing the modified gelatin with 5 parts by weight of sodium alginate in a mass ratio of 8: 1, adding the mixture into deionized water at the temperature of 25 ℃ for swelling for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(7) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(8) Uniformly mixing 10 parts by weight of modified laminarin, 10 parts by weight of self-made thickening agent and 5 parts by weight of hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain the finished product.

The reaction solution is prepared by weighing 2.5mL of n-butanol, placing the n-butanol in a 500mL round-bottom flask, adding 1.25g of ammonium sulfate, shaking for dissolution, and adding 7.5mL of concentrated sulfuric acid.

The volume ratio of the mixed solvent of the pyridine is 2: 1.

example 2: marine organism essence II:

the marine organism essence comprises the following components in parts by weight:

the modified laminarin-containing kelp residue-containing kelp paste comprises 15 parts of modified laminarin, 15 parts of self-made thickener, 10 parts of gelatin, 10 parts of sodium alginate, 10 parts of hyaluronic acid derivative, 50 parts of kelp residue, 5 parts of preservative, 2 parts of essence, 20 parts of deionized water and 20 parts of ultrapure water.

The preparation method of the essence comprises the following steps:

(1) extracting 50 parts by weight of kelp residues by hot water at 120 ℃ for 3 hours, adding the filtered kelp residues into a triangular flask, and mixing the materials according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, performing suction filtration, adjusting to neutrality, adding 95% ethanol until the volume fraction is 70%, standing overnight at 0 deg.C, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving 20 parts by weight of laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(6) Mixing the modified gelatin and 10 parts of sodium alginate by mass ratio of 8: 1, adding the mixture into deionized water at the temperature of 25 ℃ for swelling for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(7) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(8) Uniformly mixing 20 parts by weight of modified laminarin, 15 parts by weight of self-made thickening agent and 10 parts by weight of hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain the finished product.

The reaction solution is prepared by weighing 2.5mL of n-butanol, placing the n-butanol in a 500mL round-bottom flask, adding 1.25g of ammonium sulfate, shaking for dissolution, and adding 7.5mL of concentrated sulfuric acid.

The volume ratio of the mixed solvent of the pyridine is 2: 1.

comparative example 1:

(1) extracting with 120 deg.C hot water for 3 hr, centrifuging, vacuum filtering, adding 95% ethanol, standing at low temperature overnight, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin; purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(2) dissolving laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(3) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(4) dissolving 10% of gelatin in phosphate buffer solution at 60 ℃, slowly dripping 90% of oxazolidine for crosslinking reaction for 12h to obtain the modified gelatin.

(5) Adding the modified gelatin and sodium alginate into deionized water at 25 ℃ to swell for 1h, then heating to 40 ℃ and stirring for 12h to obtain the self-made thickening agent.

(6) Dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(7) And (3) uniformly mixing the modified laminarin, the self-made thickening agent and the hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain a finished product.

Comparative example 2:

(1) extracting with 120 ℃ hot water for 3h, adding the filtered kelp residue into a triangular flask, and mixing the kelp residue with the water according to a material-liquid ratio of 1: 30 adding citric acid solution with pH of 2.0 into a bottle, wrapping, heating to 120 deg.C, extracting for 2 hr, intermittently shaking and mixing during extraction, cooling to room temperature, mixing the solutions, centrifuging at 8000rpm for 10min, collecting supernatant and residue of herba Zosterae Marinae, and repeatedly extracting for 3 times. Collecting all centrifugates, filtering, adjusting to neutrality, adding 95% ethanol, standing at low temperature overnight, centrifuging, collecting precipitate, washing with 95% ethanol, centrifuging, and lyophilizing to obtain crude product of laminarin;

(2) purifying the crude laminarin product by using macroporous resin to obtain laminarin freeze-dried powder;

(3) dissolving laminarin freeze-dried powder in deionized water, and carrying out ultrasonic treatment for 30min at the power of 400W and the temperature of 30 ℃;

(4) and (2) preparing a reaction solution, placing the reaction solution in cold water for cooling, slowly adding laminarin subjected to ultrasonic treatment into the reaction solution, keeping the constant temperature at 0 ℃ for reaction for 30min, and simultaneously placing the reaction solution in an ultrasonic instrument for ultrasonic auxiliary treatment, wherein the ultrasonic power is 400W, and the ultrasonic temperature is 30 ℃. After the reaction is finished, adding a proper amount of NaOH solution for neutralization. The reaction solution was dialyzed. Concentrating the dialyzate under reduced pressure, and precipitating with ethanol to obtain modified laminarin;

(5) dissolving hyaluronic acid in ultrapure water, adding a mixed solvent of pyridine, and sequentially adding EDC, NHS and 1-aminomethyl pyrene. Reacting the mixture at room temperature for 72h under argon atmosphere, putting the reacted solution into a freeze dryer to remove the solvent to obtain a solid product, re-dissolving the solid product into ultrapure water, and dialyzing in a large amount of deionized water to obtain the hyaluronic acid derivative.

(6) And (3) uniformly mixing the modified laminarin and the hyaluronic acid derivative, and homogenizing by using a homogenizer at a homogenizing speed of 212000 r/min for 10min to obtain a finished product.

Comparative example 3:

the formulation of comparative example 3 was the same as example 1. The preparation method of the essence is different from that of the example 1 only in that the preparation treatment of the step (7) is not carried out, the step (8) directly uses the modified laminarin to mix with the self-made thickening agent and the hyaluronic acid, and the rest preparation steps are the same as the example 1.

Test example 1 oxidation resistance comparison

1. Test method

(1) Preparing a DPPH solution;

(2) adding 10mL of absolute ethyl alcohol into 10mL of 0.2mmol/LDPPH solution, stirring uniformly, standing for 1h, and detecting absorbance A_C(ii) a Adding 10mL of the marine organism essence I prepared in the example 1 into 10mL of 0.2mmol/LDPPH solution, uniformly stirring, standing for 3h, and detecting the absorbance A₁Mixing 10mL of the marine organism essence A prepared in the example 1 and 10mL of absolute ethyl alcohol, and uniformly stirring, wherein the absorbance A is detected₂。

According to the formula,% clearance ═ 1- (A)₁-A₂)/A_C]X%, the clearance of the marine organism essence one prepared in example 1 was calculated.

(3) Adding 10mL of absolute ethanol into 10mL of 0.2mmol/L DPPH solution, stirring uniformly, standing for 1h, and detecting absorbance A_C(ii) a Adding 10mL of the essence prepared in the comparative example 1 into 10mL of 0.2mmol/LDPPH solution, uniformly stirring, standing for 3h, and detecting the absorbance A₃Mixing 10mL of the essence prepared in comparative example 1 with 10mL of absolute ethanol, and uniformly stirring, wherein the detected absorbance is A₄。

According to the formula,% clearance ═ 1- (A)₃-A₄)/A_C]X%, the clearance of the essence prepared in comparative example 1 was calculated.

2. Test results

The radical scavenging values for example 1 and comparative example 1 are shown in table 1.

Table 1 comparison of radical scavenging rates of example 1 and comparative example 1

Compared with the comparative example 1, the marine organism essence has stronger free radical scavenging capacity by comparing the free radical scavenging capacity, and shows that the extraction rate of the laminarin extracted by the citric acid extraction method is higher than that of the laminarin extracted by the comparative example 1. The marine organism essence disclosed by the invention is indicated to have stronger oxidation resistance.

Test example 2 comparison of moisturizing ability

1. Test method

(1) Human allergy test.

(2) Example 1, comparative example 2 and comparative example 3 were applied to different sites, and skin moisture content was recorded after 3 hours for comparison.

2. Test results

The percent skin moisture for example 1 and comparative examples 2 and 3 are shown in table 1.

Table 1 example 1 comparison of skin moisture content with comparative examples 2 and 3

Comparative examples 2 and 3 formed a control test with example 1, comparative example 2 was in a gel state, comparative example 3 was in a state of adding hyaluronic acid without surface modification, and other process parameters and component contents were identical to those of example 1. The comparison of the water content change of the skin under the same environment shows that the marine organism essence has extremely strong moisturizing capability, and the adoption of the gelatin gel state and the hyaluronic acid derivative can improve the moisturizing capability of the marine organism essence.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.