CN113480579A - Phenolic acid active substance and preparation method and application thereof - Google Patents
Phenolic acid active substance and preparation method and application thereof Download PDFInfo
- Publication number
- CN113480579A CN113480579A CN202110748350.6A CN202110748350A CN113480579A CN 113480579 A CN113480579 A CN 113480579A CN 202110748350 A CN202110748350 A CN 202110748350A CN 113480579 A CN113480579 A CN 113480579A
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- CN
- China
- Prior art keywords
- acid
- lignin
- reaction
- phenolic
- phenolic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000007965 phenolic acids Chemical class 0.000 title claims abstract description 75
- 239000013543 active substance Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 21
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- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 claims abstract description 20
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims abstract description 20
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 15
- DOUMFZQKYFQNTF-WUTVXBCWSA-N (R)-rosmarinic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-WUTVXBCWSA-N 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 claims abstract description 7
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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Classifications
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- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
- A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
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- A—HUMAN NECESSITIES
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- A61Q19/08—Anti-ageing preparations
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/74—Biological properties of particular ingredients
- A61K2800/78—Enzyme modulators, e.g. Enzyme agonists
- A61K2800/782—Enzyme inhibitors; Enzyme antagonists
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
- C07C59/48—Unsaturated compounds containing hydroxy or O-metal groups containing six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
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- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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Abstract
The invention provides a phenolic acid active substance and a preparation method and application thereof, and relates to the technical field of extraction preparation and application of natural active ingredients. The phenolic acid active substance provided by the invention comprises at least one compound of p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, danshensu and rosmarinic acid, and the total content of the compound is 100 mg/g. The total content of phenolic hydroxyl groups in the phenolic acid active substance prepared by the invention is 7.0-14.0mmol/g, has excellent biological activities of antioxidation, bacteriostasis, anti-inflammation, whitening and the like, and can be applied to the development of cosmetics such as anti-inflammation, allergy relief, acne removal, whitening, spot lightening, wrinkle removal, anti-aging and the like.
Description
Technical Field
The invention relates to the technical field of extraction preparation and application of natural active ingredients, in particular to a phenolic acid active substance and a preparation method and application thereof.
Background
The phenolic acid active substances comprise p-coumaric acid, caffeic acid, protocatechuic acid, gallic acid, ellagic acid, danshensu, salvianolic acid, rosmarinic acid and the like, have excellent biological activities of resisting oxidation, inflammation and bacteria, whitening and fading speckles, reducing blood fat, resisting tumors, preventing and treating cardiovascular and cerebrovascular diseases and the like, and are widely applied to the fields of medicines, food health care, cosmetics, animal and plant nutrition and the like.
The phenolic acid active substance is usually separated and extracted from natural products, or is produced by organic synthesis or biosynthesis. Lignin is the most abundant aromatic compound in nature, and can generate 6 × 10 of lignin every year14About t lignin is a renewable carbon resource with great potential. In industrial production in China, the annual yield of lignin exceeds 1100 million tons, and part of lignin is used for burning energy supply, low-value chemical products and the like, is abandoned in large quantities and is beneficial to effectivelyThe utilization rate is less than 20 percent, which causes huge waste of biomass resources and ecological environment pollution. Because the lignin intrinsic structure has a structural unit similar to that of the phenolic acid compound, the preparation of the phenolic acid compound by taking lignin as a raw material is an effective way for realizing high-value utilization of lignin wastes, and has technical feasibility.
At present, chemical methods and biological methods are mostly adopted for preparing phenolic acid compounds by using lignin. The chemical method depolymerizes lignin into micromolecular phenolic compounds by pyrolysis, gasification, hydrolysis, reduction, oxidation and other methods, wherein phenolic acid compounds such as p-hydroxybenzoic acid, vanillic acid and the like can be obtained by the catalytic oxidation method, the yield of products is less than 15%, high-activity phenolic acid compounds such as p-coumaric acid, caffeic acid, protocatechuic acid, gallic acid and the like cannot be obtained, and because a homogeneous metal salt catalyst and an organic solvent are adopted in the preparation process, a large amount of waste liquid, waste residues and the like are generated in the subsequent separation and extraction operation, and the environmental pollution is large. The biological method mostly adopts enzyme engineering such as lignin oxidase, manganese catalase, laccase and the like or fermentation mode of microorganisms such as thermophilic bacillus and the like to convert lignin into compounds such as small molecular acids such as muconic acid and the like, phenols, phenolic acids and the like, the content of the obtained phenolic acid compounds such as p-coumaric acid, caffeic acid, protocatechuic acid, gallic acid and the like is very low, usually less than or equal to 200 mu g/g, the content of target products is low, the separation and extraction difficulty of the products from fermentation liquor is increased, the energy consumption is increased, and the waste liquid amount in the fermentation and extraction processes is greatly increased. Therefore, there is a need to develop a green and efficient synthesis method for preparing high-activity phenolic acid compounds such as p-coumaric acid, caffeic acid, protocatechuic acid and gallic acid by using lignin. In addition, the application of the mixed raw materials of the phenolic acid compounds to the production of cosmetics is not seen at present.
Disclosure of Invention
The invention mainly aims to provide a phenolic acid active substance and a preparation method thereof, and aims to solve the problems of low content of effective components, difficult separation, more waste, great environmental pollution and the like in the prior chemical method or biological method for preparing phenolic acid compounds.
In order to achieve the above objects, in a first aspect, the present invention provides a phenolic acid active substance, comprising at least one compound selected from the group consisting of p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, tanshinol, and rosmarinic acid, wherein the total content of the compounds is 100-500 mg/g.
The p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, danshensu and rosmarinic acid contained in the phenolic acid active substance provided by the invention belong to high-activity phenolic acid compounds, and have excellent biological activities of antioxidation, bacteriostasis, anti-inflammation, whitening and the like.
As a preferable embodiment of the phenolic acid active material of the present invention, the total content of phenolic hydroxyl groups in the phenolic acid active material is 7.0 to 14.0 mmol/g.
In a second aspect, the present invention further provides a method for preparing a phenolic acid active substance, comprising the following steps:
(1) adding lignin, a catalyst and a reaction solvent into a reaction container, replacing oxygen to exhaust air in the kettle, introducing 0.5-1.5MPa oxygen, stirring and reacting at 120-180 ℃ for 2-12h, cooling to room temperature, filtering and separating the catalyst, collecting the reaction liquid, washing a filter cake with the reaction solvent, combining an eluate and the reaction liquid, and carrying out reduced pressure distillation and vacuum drying to obtain an intermediate product A;
(2) and adding the intermediate product A, iodocyclohexane and N, N-dimethylformamide into a reaction container, stirring and refluxing for reaction for 12-36h, stopping the reaction, cooling to room temperature, washing with N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain the phenolic acid active substance.
In the technical solution of the present invention, as a preferred embodiment of the method for preparing the phenolic acid active material according to the present invention, the mass ratio of the lignin to the catalyst is lignin: the catalyst is 1:0.1-1, and the ratio of the mass of the lignin to the volume of the reaction solvent is lignin: 20-50ml of reaction solvent; the ratio of the mass of lignin to the volume of iodocyclohexane is lignin: 1g of iodocyclohexane, wherein the ratio of the mass of the lignin to the volume of the N, N-dimethylformamide is lignin: n, N-dimethylformamide is 1g, and 10-40ml is obtained.
In a third aspect, the present invention further provides a method for preparing a phenolic acid active substance, comprising the following steps:
(1) adding lignin, iodocyclohexane and N, N-dimethylformamide into a reaction container, stirring and refluxing for reaction for 12-36h, stopping the reaction, cooling to room temperature, washing with N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate product B;
(2) adding the intermediate product B, a catalyst and a reaction solvent into a reaction container, introducing 0.5-1.5MPa oxygen after the air in the kettle is completely discharged by oxygen replacement, stirring and reacting at the temperature of 120-180 ℃ for 2-12h, cooling to room temperature, filtering and separating the catalyst, collecting the reaction liquid, washing a filter cake by using the reaction solvent, combining the eluate and the reaction liquid, and carrying out reduced pressure distillation and vacuum drying to obtain the phenolic acid active substance.
As a preferred embodiment of the method for producing a phenolic acid active material according to the present invention, the ratio of the mass of lignin to the volume of iodocyclohexane is lignin: 1g of iodocyclohexane, wherein the ratio of the mass of the lignin to the volume of the N, N-dimethylformamide is lignin: 10-40ml of N, N-dimethylformamide; the mass ratio of the lignin to the catalyst is lignin: the catalyst is 1:0.1-1, and the ratio of the mass of the lignin to the volume of the reaction solvent is lignin: the reaction solvent is 1g and 20-50 ml.
In the preparation method of the phenolic acid active substance, lignin serving as a reaction raw material can be mixed with a catalyst and a reaction solvent for reaction to obtain an intermediate product A, and then the intermediate product A is reacted with iodocyclohexane and N, N-dimethylformamide to prepare the phenolic acid active substance; or mixing lignin, iodocyclohexane and N, N-dimethylformamide for reaction to obtain an intermediate product B, and mixing the intermediate product B with a catalyst and a reaction solvent for reaction to obtain the phenolic acid active substance. I.e., the timing of addition of the catalyst, reaction solvent, iodocyclohexane, N-dimethylformamide can be adjusted as described above without affecting the composition and properties of the product.
In a preferred embodiment of the method for producing a phenolic acid-based active material according to the present invention, the lignin includes at least one of lignosulfonic acid, alkali lignin, organosolv lignin, and enzymatic lignin.
As a preferred embodiment of the preparation method of the phenolic acid active substance, the catalyst is at least one of MnOx/C, MoOx/C, VOx/C, CuOx/C.
Mn in the metal oxide active component of MnOx/C, MoOx/C, VOx/C, CuOx/C catalyst4+、Mo6+、V5+、Cu2+C in isoenergetic and lignin structural unitα-O、Cβ-O、CγOxygen atoms such as-O coordinate and activate corresponding and adjacent chemical bonds such as C-O, C-C, C-H to promote Cα-Cβ、CβOxidative cleavage of-O bond, promotion of CγOxidation of-OH to form CαOOH、CγPhenolic carboxylic acids such as OOH; the surface of the carbon-based carrier in the catalyst contains functional groups such as aromatic ring, hydroxyl, carbonyl, carboxyl and the like, and lignin can be promoted to diffuse to the surface of the catalyst and to be adsorbed and reacted with the active center of the metal oxide of the catalyst through intermolecular forces such as hydrogen bond, pi-pi accumulation and the like. On the whole, the MnOx/C, MoOx/C, VOx/C, CuOx/C catalyst is selected to be beneficial to the catalytic oxidative depolymerization of lignin to generate phenolic acid substances such as vanillic acid, ferulic acid and the like.
In a preferred embodiment of the method for producing a phenolic acid active material according to the present invention, the reaction solvent is at least one of methanol, ethylene glycol, dimethyl sulfoxide, and γ -valerolactone.
The reaction solvent selected by the invention has good dissolution and dispersion on lignin, and is beneficial to contact reaction of reaction substrate lignin molecules and a catalyst in a liquid phase solution.
In a fourth aspect, the invention also provides an application of the phenolic acid active substance in cosmetics and health care products.
The phenolic acid active substance prepared by the invention shows excellent biological activities of antioxidation, bacteriostasis, anti-inflammation, whitening and the like, and can be applied to the development of cosmetics and health care products with anti-inflammation, allergy relief, acne and scar removal, whitening, spot lightening, wrinkle removal, anti-aging and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the technical scheme, the lignin is used as a raw material to prepare the phenolic acid active substance containing high-activity phenolic acid compounds such as p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, danshensu, rosmarinic acid and the like, the prepared phenolic acid active substance has high phenolic hydroxyl content and excellent biological activities such as oxidation resistance, bacteriostasis, inflammation resistance, whitening and the like, and can be applied to the fields of health and beauty industry such as health care products, cosmetics and the like;
(2) the method for preparing the lignin source of the phenolic acid active substance has the characteristics of novel route method, low-carbon and green preparation process, high preparation process efficiency, low raw material and production cost, simple product post-treatment, low energy, environmental protection and the like, the yield of the prepared phenolic acid active substance is more than 75%, and the content of the high-activity phenolic acid compound is 100-400 mg/g.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of organic solvolysis lignin, 0.5g of MoOx/C and 40mL of gamma-valerolactone (GVL) into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring and reacting at 180 ℃ for 3 hours, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of gamma-valerolactone (GVL), combining filtrates, distilling under reduced pressure and drying in vacuum to obtain an intermediate;
(2) putting the intermediate into a round-bottom flask, adding 20mL of N, N-Dimethylformamide (DMF) and 6mL of iodocyclohexane, stirring and refluxing for 24h, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing with 20mL of N-hexane for 3 times, and distilling the washed reaction solution under reduced pressure and drying in vacuum to obtain 0.802g of yellow phenolic acid active substances.
Example 2
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of enzymatic hydrolysis lignin, 1.0g of CuOx/C and 40mL of ethylene glycol into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring and reacting at 180 ℃ for 5h, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of ethylene glycol, combining filtrates, distilling under reduced pressure, and drying under vacuum to obtain an intermediate;
(2) putting the intermediate into a round-bottom flask, adding 20mL of N, N-Dimethylformamide (DMF) and 6mL of iodocyclohexane, stirring and refluxing for 24h, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing with 20mL of N-hexane for 3 times, and distilling the washed reaction solution under reduced pressure and drying in vacuum to obtain 0.753g of yellow phenolic acid active substances.
Example 3
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of alkali lignin, 0.5g of VOx/C and 40mL of methanol into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring and reacting at 150 ℃ for 8h, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of methanol, combining filtrates, carrying out reduced pressure distillation and vacuum drying to obtain an intermediate;
(2) and (3) putting the intermediate into a round-bottom flask, adding 20mL of N, N-Dimethylformamide (DMF) and 6mL of iodocyclohexane, stirring and refluxing for 24h, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing the solution for 3 times by 20mL of N-hexane, and distilling the washed reaction solution under reduced pressure and drying the reaction solution in vacuum to obtain 0.798g of yellow phenolic acid active substances.
Example 4
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1g of lignosulfonic acid, 1.0g of MnOx/C and 40mL of DMSO (dimethyl sulfoxide) into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring at 150 ℃ for 8 hours, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of DMSO, combining filtrates, carrying out reduced pressure distillation and vacuum drying to obtain an intermediate;
(2) putting the intermediate into a round-bottom flask, adding 20mL of N, N-Dimethylformamide (DMF) and 6mL of iodocyclohexane, stirring and refluxing for 24h, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing the solution for 3 times by 20mL of N-hexane, and distilling the washed reaction solution under reduced pressure and drying the reaction solution in vacuum to obtain 0.818g of yellow phenolic acid active substances.
Example 5
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of organic solvolysis lignin, 8mL of iodocyclohexane and 20mL of N, N-Dimethylformamide (DMF) into a round-bottom flask, stirring and refluxing for 24 hours, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing for 3 times by using 20mL of N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate;
(2) adding the intermediate, 0.5g of MoOx/C and 40mL of gamma-valerolactone (GVL) into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring at 180 ℃ for 3h, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of gamma-valerolactone (GVL), combining filtrates, distilling under reduced pressure, and drying in vacuum to obtain 0.812g of yellow phenolic acid active substances.
Example 6
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of enzymatic hydrolysis lignin, 8mL of iodocyclohexane and 20mL of N, N-Dimethylformamide (DMF) into a round-bottom flask, stirring and refluxing for 24 hours, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing for 3 times by using 20mL of N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate;
(2) adding the intermediate, 1.0g of CuOx/C and 40mL of glycol into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring at 180 ℃ for 5h, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of glycol, combining filtrates, distilling under reduced pressure, and drying in vacuum to obtain 0.764g of yellow phenolic acid active substance.
Example 7
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1.0g of alkali lignin, 8mL of iodocyclohexane and 20mL of N, N-Dimethylformamide (DMF) into a round-bottom flask, stirring and refluxing for 24 hours, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing for 3 times by using 20mL of N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate;
(2) adding the intermediate, 0.5g VOx/C and 40mL of methanol into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring and reacting for 8h at 150 ℃, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of methanol, combining filtrates, distilling under reduced pressure, and drying in vacuum to obtain 0.808g of yellow phenolic acid active substances.
Example 8
This example provides a phenolic acid active.
The preparation method of the phenolic acid active substance comprises the following steps:
(1) adding 1g of lignosulfonic acid, 8mL of iodocyclohexane and 20mL of N, N-Dimethylformamide (DMF) into a round-bottom flask, stirring and refluxing for 24 hours, stopping stirring, cooling the solution to room temperature, transferring the solution into a separating funnel, washing with 20mL of N-hexane for 3 times, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate;
(2) adding the intermediate, 1.0g of MnOx/C and 40mL of DMSO (dimethyl sulfoxide) into a high-pressure reaction kettle, charging 1MPa of oxygen, stirring and reacting for 8 hours at 150 ℃, stopping stirring, cooling to room temperature, filtering and separating reaction liquid, washing a filter cake for 2 times by using 10mL of DMSO, combining filtrates, distilling under reduced pressure, and drying in vacuum to obtain 0.826g of yellow phenolic acid active substance.
Effect example 1
The yields of the phenolic acid-based active materials prepared in examples 1 to 8 were calculated according to the following formula, the yield being (mass of the phenolic acid-based active material/mass of the lignin raw material) × 100%, and the yields of the yellow phenolic acid-based active materials prepared in examples 1 to 8 are shown in table 1 below.
TABLE 1 yield (%)
| Serial number | Yield of | Serial number | Yield of |
| Example 1 | 80.2 | Example 5 | 81.2 |
| Example 2 | 75.3 | Example 6 | 76.4 |
| Example 3 | 79.8 | Example 7 | 80.8 |
| Example 4 | 81.8 | Example 8 | 82.6 |
Effect example 2
The compositions of the phenolic acid active substances prepared in examples 1 to 8 were analyzed by HPLC-UV analysis, and the specific analytical test methods were as follows: accurately weighing 50mg of phenolic acid compound sample, fixing the volume to 25mL by using chromatographic grade methanol, carrying out ultrasonic treatment for 10min to completely dissolve the phenolic acid compound, and quantitatively analyzing the content of the active ingredients of the phenolic acid compound by using HPLC-UV (high performance liquid chromatography-ultraviolet): the chromatographic column adopts C18 column, acetonitrile/0.1% phosphoric acid water solution is used as mobile phase, 272nm is used as detection wavelength, and the amount of each active component is calculated by standard curve method.
The test shows that the phenolic acid active substances prepared in examples 1-8 all contain p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, danshensu and rosmarinic acid. The total content of the above-mentioned phenol-based active ingredients in the phenol-based active materials prepared in examples 1 to 8 is shown in table 2 below.
TABLE 2 Total content (mg/g) of active ingredients in the phenolic acid active substances prepared in examples 1 to 8
| Serial number | Total content of active ingredients | Serial number | Total content of active ingredients |
| Example 1 | 454 | Example 5 | 423 |
| Example 2 | 338 | Example 6 | 308 |
| Example 3 | 274 | Example 7 | 242 |
| Example 4 | 198 | Example 8 | 161 |
Comparative example 1
The comparative example provides resveratrol which is a compound with antioxidant function and is commonly used in cosmetics.
Comparative example 2
The comparative example provides a commonly used antibacterial and anti-inflammatory functional compound salicylic acid for cosmetics, and the concentration is 1%.
Comparative example 3
The comparative example provides a commonly used whitening functional compound niacinamide.
Effect example 3
The phenolic acid active substances prepared in examples 1 to 8 and the phenolic hydroxyl group content of comparative examples 1 to 3 were analyzed by a Folin-Ciocalteu (Folin-Ciocalteu) test method, which was as follows: mixing 15mL of F-C phenol reagent with 135mL of methanol to prepare an F-C solution; mixing 4mL of F-C solution with 0.1mg/mL of phenolic acid compound sample methanol solution, stirring at room temperature for 5min, adding 3.2mL of 7.5% sodium carbonate aqueous solution, stirring at room temperature for 30min, and measuring the absorbance value of the sample at 765 nm. And calculating the phenolic hydroxyl content of the phenolic acid compound by adopting a catechol standard curve.
The phenolic hydroxyl group content of the phenolic acid active materials prepared in examples 1-8 is shown in table 3 below.
TABLE 3 phenolic hydroxyl group content (mmol/g) in the phenolic acid active substances prepared in examples 1 to 8
| Serial number | Total content of phenolic hydroxyl groups | Serial number | Total content of phenolic hydroxyl groups |
| Example 1 | 13.4 | Example 7 | 9.7 |
| Example 2 | 12.0 | Example 8 | 7.6 |
| Example 3 | 10.8 | Comparative example 1 | 8.9 |
| Practice ofExample 4 | 8.7 | Comparative example 2 | 7.2 |
| Example 5 | 12.5 | Comparative example 3 | - |
| Example 6 | 11.0 |
Effect example 4
The phenolic acid active substances prepared in examples 1 to 8 and the substances in comparative examples 1 to 3 were used as test subjects to evaluate the antioxidant effect, bacteriostatic effect, anti-inflammatory effect, and whitening effect. The relevant test data are shown in table 4 below.
(1) Antioxidant efficacy evaluation method
DPPH free radical scavenging: preparing 0.01mg/mL, 0.025mg/mL, 0.05mg/mL and 0.1mg/mL of methanol solution of a sample to be detected, sequentially transferring 3.0mL of the sample solution to be detected into a 10mL colorimetric tube, respectively adding 3.0mL of 0.15mM DPPH-methanol solution, shaking up, reacting at room temperature in a dark place for 30min, and measuring the absorbance value A1 of the sample at 517 nm; under the same conditions, methanol replaces DPPH solution to measure the background absorbance value A2; the sample solvent was substituted for the sample to determine the blank value a 0. DPPH · clearance (%) (a0- (a1-a2))/a0 × 100%. And fitting a curve of the DPPH clearance rate and the concentration of the sample to be detected, wherein the IC50 value is obtained when the concentration of the sample to be detected is 50% of the DPPH clearance rate.
(2) Antibacterial efficacy evaluation method
In vitro inhibition of propionibacterium acnes experiments: inoculating Propionibacterium acnes on a clostridium enrichment culture medium slope added with agar powder, and performing anaerobic culture at 37 +/-1 ℃ for 48-72 h. After the colonies were grown up, the colonies were eluted with 5mL of a clostridial enrichment medium. The eluate was collected and adjusted to a concentration of 106CFU/mL, and viable bacteria were counted by plate method. Weighing 1g of test sample, adding the test sample into 0.1mL of the bacterial suspension, adding 9mL of PBS, mixing, placing 1mL of test sample into 3 parallel plates, adding a clostridium enrichment medium, performing anaerobic culture at 37 +/-1 ℃ for 48-72h, counting colonies, repeating the experiment for 3 times, taking the average number of the colonies, and setting physiological saline as a blank control.
The bacteriostasis rate X is (A-B)/A X100%
Wherein A is the average number of recovered colonies of the control sample; b is the average number of recovered colonies of the test sample.
(3) Method for evaluating anti-inflammatory efficacy
The lipopolysaccharide LPS is adopted to induce RAW264.7 mouse macrophage model for anti-inflammatory efficacy test. The method comprises the following steps: culturing macrophage Raw264.7 in vitro, treating Raw264.7 with LPS with different concentrations (0.1mg/L, 0.5mg/L, 1mg/L, 2mg/L, 5mg/L and 10mg/L), determining the optimal stimulation response condition of LPS according to the cell viability and the change degree of inflammation related factors (NO, TNF-alpha) and the like, and evaluating the efficacy of anti-inflammatory standard substances and the activity to be tested through the change of the levels of the inflammation factors before and after the treatment of the test object based on the stimulation condition (5mg/L LPS).
The evaluation method comprises the following steps: the cells are inoculated for 24h, then the sample is treated for 1h, then 5mg/L LPS is added, and the mixture is placed at 37 ℃ and 5% CO2Culturing for 24h in an incubator, collecting cell culture supernatant, analyzing the contents of inflammation-related factors NO and TNF-alpha by using a nitric oxide kit and an ELISA kit respectively, and simultaneously evaluating corresponding blank groups, wherein each group of experiments are independently repeated for 3 times.
(4) Whitening efficacy evaluation method
A. In vitro tyrosinase inhibition assay: adding PBS buffer solution, 0.5g/L L-tyrosinase solution and sample solutions with different concentrations, placing in a water bath at 37 ℃ for 10min, adding 500U/mL tyrosinase solution, mixing, placing in a water bath at 37 ℃ for reaction for 10min, quickly transferring into a cuvette, and measuring the absorbance value at 475 nm.
B. alpha-MSH induces inhibition of melanin synthesis in B16-F10 cell model: selecting B16-F10 cells in logarithmic growth phase, digesting with trypsin with a mass fraction of 0.25%, preparing a cell suspension with a density of 5 × 104 cells/mL in DMEM complete medium, inoculating the cell suspension into a 96-well culture plate with 2 mL/well, and culturing at 37 ℃ and 5% CO in a 5% CO system2Culturing in an incubator for 24 h. After observing cell adherence under a lens, adding culture media containing a test object and alpha-MSH respectively, and setting a blank control group and a positive control group, wherein each hole is 2mL, and each concentration is performed in 3 parallels. At 37 ℃ with 5% CO2After incubation in an incubator for 72h, the supernatant was discarded and the cells were collected, 400. mu.L of a 1mol/L NaOH solution (containing 10% DMSO by mass) was added thereto, the temperature was maintained at 80 ℃ for 2h, and 100. mu.L of the solution was measured for absorbance at 490nm using a microplate reader.
TABLE 4 evaluation results of efficacy of examples 1 to 8 and comparative examples 1 to 3
Note: evaluation of whitening efficacy: examples 1-8 phenolic acid compounds and comparative example 3 the tested concentration of nicotinamide was 0.5%;
② evaluating the bacteriostatic and anti-inflammatory efficacy: examples 1-8 phenolic acid compounds and comparative example 2 were tested at a concentration of 0.05%.
As can be seen from the results in Table 4, the phenolic acid compounds prepared using lignin have a low DPPH.clear IC50 value and exhibit high antioxidant activity, as compared to the actives provided in the comparative examples; the inhibition rate of the propionibacterium acnes is 99.99 percent, and the propionibacterium acnes has high bacteriostatic activity; LPS induces RAW264.7 mouse macrophage model evaluation, the content of NO and TNF-alpha inflammatory factor is lower, and high anti-inflammatory activity is shown; in vitro tyrosinase inhibition experiments and alpha-MSH induction B16-F10 cell model melanin synthesis inhibition experiments evaluate that the tyrosinase inhibition rate IC50 and B16-F10 cell melanin secretion inhibition rate of the phenolic acid compounds are lower under the same tested concentration, and the whitening effect is good.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A phenolic acid active substance is characterized by comprising at least one compound of p-hydroxybenzoic acid, protocatechuic acid, gallic acid, ellagic acid, p-coumaric acid, caffeic acid, ferulic acid, danshensu and rosmarinic acid, wherein the total content of the compound is 100-500 mg/g.
2. The phenolic acid active material of claim 1, wherein the total phenolic hydroxyl group content of the phenolic acid active material is from 7.0 to 14.0 mmol/g.
3. The method for producing a phenolic acid active material according to any one of claims 1 or 2, comprising the steps of:
(1) adding lignin, a catalyst and a reaction solvent into a reaction container, replacing oxygen to exhaust air in the kettle, introducing 0.5-1.5MPa oxygen, stirring and reacting at 120-180 ℃ for 2-12h, cooling to room temperature, filtering and separating the catalyst, collecting the reaction liquid, washing a filter cake with the reaction solvent, combining an eluate and the reaction liquid, and carrying out reduced pressure distillation and vacuum drying to obtain an intermediate product A;
(2) and adding the intermediate product A, iodocyclohexane and N, N-dimethylformamide into a reaction container, stirring and refluxing for reaction for 12-36h, stopping the reaction, cooling to room temperature, washing with N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain the phenolic acid active substance.
4. The method for producing a phenolic acid active material according to any one of claims 1 or 2, comprising the steps of:
(1) adding lignin, iodocyclohexane and N, N-dimethylformamide into a reaction container, stirring and refluxing for reaction for 12-36h, stopping the reaction, cooling to room temperature, washing with N-hexane, and carrying out reduced pressure distillation and vacuum drying on the washed reaction solution to obtain an intermediate product B;
(2) adding the intermediate product B, a catalyst and a reaction solvent into a reaction container, introducing 0.5-1.5MPa oxygen after the air in the kettle is completely discharged by oxygen replacement, stirring and reacting at the temperature of 120-180 ℃ for 2-12h, cooling to room temperature, filtering and separating the catalyst, collecting the reaction liquid, washing a filter cake by using the reaction solvent, combining the eluate and the reaction liquid, and carrying out reduced pressure distillation and vacuum drying to obtain the phenolic acid active substance.
5. The method of any one of claims 3 or 4, wherein the lignin comprises at least one of lignosulfonic acid, alkali lignin, organosolv lignin, and enzymatic lignin.
6. The method of any of claims 3 or 4, wherein the catalyst is at least one of MnOx/C, MoOx/C, VOx/C, CuOx/C.
7. The method according to any one of claims 3 or 4, wherein the reaction solvent is at least one of methanol, ethylene glycol, dimethyl sulfoxide, and γ -valerolactone.
8. The method according to any one of claims 3 or 4, wherein the mass ratio of lignin to catalyst is lignin: the catalyst is 1:0.1-1, and the ratio of the mass of the lignin to the volume of the reaction solvent is lignin: the reaction solvent is 1g and 20-50 ml.
9. The method of any one of claims 3 or 4, wherein the ratio of the mass of lignin to the volume of iodocyclohexane is lignin: 1g of iodocyclohexane, wherein the ratio of the mass of the lignin to the volume of the N, N-dimethylformamide is lignin: n, N-dimethylformamide is 1g, and 10-40ml is obtained.
10. Use of phenolic acid active substances according to any of claims 1 or 2 in cosmetics, nutraceuticals.
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