CN116813676B - Rumex plant extract and active compound, and preparation method and application thereof - Google Patents

Rumex plant extract and active compound, and preparation method and application thereof Download PDF

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CN116813676B
CN116813676B CN202310784811.4A CN202310784811A CN116813676B CN 116813676 B CN116813676 B CN 116813676B CN 202310784811 A CN202310784811 A CN 202310784811A CN 116813676 B CN116813676 B CN 116813676B
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extract
methanol
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CN116813676A (en
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朱宏涛
张颖君
李静娟
胡江苗
杨柳
王东
杨崇仁
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Kunming Institute of Botany of CAS
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    • 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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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • 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
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    • 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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    • A61Q19/08—Anti-ageing preparations
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Abstract

The invention provides 4 compounds shown in structural formula and Rumex plant extracts, and a preparation method and application thereof. Belongs to the technical field of cosmetics. The invention adopts an activity tracking method and combines a phytochemistry extraction and separation means to extract from flower thinning sorrelRumex nepalensis var.remotiflorus) Fructus Phyllanthi acid mouldR.dentatus) Henpol RumexR.nepalensis) The active extract is prepared from the sorrel plants, the extract contains 4 active compounds, the extract and the 4 compounds have obvious antioxidant activity, tyrosinase inhibitory activity and strong ultraviolet absorption capacity, and the extract and the 4 compounds can be used as functional additives to be added into cosmetics to realize the effects of delaying skin aging, whitening and sun protection. The product is derived from a plant source and,has good skin affinity and high absorption and utilization rate.

Description

Rumex plant extract and active compound, and preparation method and application thereof
Technical field:
the invention belongs to the field of cosmetics, and in particular relates to a Rumex plant extract and a compound, and preparation and application thereof in cosmetics.
The background technology is as follows:
skin color is white and glossy, and skin smoothness and elasticity are ideal skin conditions which are pursued by people. However, due to the influence of ultraviolet rays, environmental pollution, endocrine dyscrasia, inheritance and other factors, melanin metabolism abnormality is caused, and freckle, chloasma and senile plaque are generated by local skin blackening. The effect of the factors can also accelerate the rapid loss of skin moisture, cause death and aging of cells, make skin cells lose elasticity, and cause the generation and deepening of wrinkles on the skin surface. In order to alleviate and maximally eliminate the above skin problems, the skin is also colorful and beautiful, and the whitening skin care products on the market are layered endlessly. Traditional whitening active ingredients (such as mercury and compounds thereof, hydroquinone and the like) have the defects of cytotoxicity, irritation, sensitization, great adverse reaction and the like, and are forbidden to be used in cosmetics at present. Therefore, searching for new generation of natural, safe and efficient plant whitening active ingredients becomes one of the hot spots for research at home and abroad in recent years. However, many whitening active ingredients have a single mechanism of action, and it is difficult to meet the complex requirements for skin beauty. The exploration of natural plant extracts with various whitening mechanisms such as melanin accumulation inhibition, large amount of ultraviolet absorption, free radical removal and the like is an important direction for developing the current whitening products.
Rumex, rumex and Rumex are all plants of the genus Rumex of the family Polygonaceae, and are widely distributed in Asia, the middle east and the southeast European regions. The wild and cultivated resources of the plants in China are quite rich, and are mainly distributed in regions such as Yunnan, guizhou, xinjiang and the like. The sorrel is rich in quinone, flavonoid, tannin, terpenes, naphthalene and other compounds, and the secondary metabolites have remarkable anti-inflammatory, antibacterial and antioxidant activities and are often used for treating pharyngitis, dysentery, scabies and gynecological medicines by local folks. In recent years, although there have been reports on the addition of cosmetic raw materials in research and application of the genus plant, the raw materials are conceptually added in the form of crude extracts and mixtures. However, the prior art does not relate to the active sites of Rumex philippinensis, rumex nepalensis and Rumex occidentalis, active compounds thereof, processes for their preparation and their use for the delay of aging, whitening and sun protection.
The invention comprises the following steps:
the invention aims to provide an extract and an active compound of Rumex plants, a preparation method thereof and application thereof in cosmetics, and provides anti-aging, whitening and sun-screening activities of Rumex, rumex nepalensis and Rumex odontoides and compounds 1-4 for the first time, a preparation method thereof and application thereof in skin cosmetics with whitening and anti-aging effects.
In order to achieve the above object of the present invention, the present invention provides the following technical solutions:
4 compounds of the following structural formula,
a process for the preparation of said 4 compounds, comprising the steps of:
(1) Crushing dried root of Rumex philippinensis, and leaching with 0-100% acetone water at room temperature for 4 times (7 days each time), wherein the weight ratio w of Rumex philippinensis root to acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution on Fr.1-6 by using a methanol-dichloromethane volume ratio v/v of 0:1-1:0, performing gradient elution on Sephadex LH20 by using Fr.5 under reduced pressure, and performing gradient elution on the methanol-water volume ratio v/v of 0:1-1:0 to obtain Fr.5-1-5-10;
or crushing the dried roots of the odontoseisis, and leaching with 0-100% acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the odontoseisis roots to the acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution on Fr.1-6 by using a methanol-dichloromethane volume ratio v/v of 0:1-1:0, performing gradient elution on Sephadex LH20 by using Fr.5 under reduced pressure, and performing gradient elution on the methanol-water volume ratio v/v of 0:1-1:0 to obtain Fr.5-1-5-10;
or crushing the dried plants of the Nepal sorrel, and leaching the dried plants of the Nepal sorrel with 0 to 100 percent of acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the dried plants of the Nepal sorrel to the acetone water is 1:1 to 1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0 to obtain Fr.1-6, performing gradient elution with the volume ratio v/v of methanol to water of 0:1-1:0 to obtain Fr.5-1-5-10, and performing vacuum concentration on the Fr.5 to obtain Sephadex LH 20;
(2) Loading the active site extract Fr.5-8 obtained in the step (1) on an Rp-18 chromatographic column, eluting Fr.5-8-1-10 with methanol to chloroform volume ratio v/v of 0:1-1:0, combining semi-preparative HPLC, eluting with 35% acetonitrile water, and eluting at t R When 24.0min compound 1, fr.5-8-2 was obtained, concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 20% acetonitrile water at t R Compound 2 was obtained when=17.5 min, fr.5-8-1 was concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 18% acetonitrile water at t R Compound 3 was obtained when=21.0 min, fr.5-8-6 was concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 35% acetonitrile water at t R Compound 4 was obtained when=20.0 min.
The Rumex plant extract comprises Rumex philippinensis active site extract, rumex philippinensis active site extract and Rumex nepalensis active site extract, and is prepared by the following method:
crushing dried root of Rumex philippinensis, and leaching with 0-100% acetone water at room temperature for 4 times (7 days each time), wherein the weight ratio w of Rumex philippinensis root to acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain an extract, stirring the extract with a silica gel column, performing gradient elution on Fr.1-6 with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0, performing gradient elution on Sephadex LH20 with the volume ratio v/v of methanol to water of 0:1-1:0, performing gradient elution on Fr.5-1-5-10, and performing gradient elution on Fr.5-8 parts under reduced pressure to obtain an extract of the active part of the flower thinning die;
crushing dried roots of the odontoseisis rupestris, and leaching with 0-100% acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the odontoseisis rupestris roots to the acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain an extract, stirring the extract with a silica gel column, performing gradient elution on Fr.1-6 with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0, performing gradient elution on Sephadex LH20 with the volume ratio v/v of methanol to water of 0:1-1:0, performing gradient elution on Fr.5-1-5-10, and performing gradient elution on Fr.5-8 parts under reduced pressure to obtain an active part extract of the odontoseisis;
crushing the dried plants of the Nepal sorrel, and leaching the dried plants of the Nepal sorrel with 0 to 100 percent of acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the dried plants of the Nepal sorrel to the acetone water is 1:1 to 1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain an extract, stirring the extract with a silica gel column, performing gradient elution on the methanol-dichloromethane with the volume ratio v/v of 0:1-1:0 to obtain Fr.1-6, performing gradient elution on the Fr.5 with the Sephadex LH20 under reduced pressure, performing gradient elution on the methanol-water with the volume ratio v/v of 0:1-1:0 to obtain Fr.5-1-5-10, and performing gradient elution on the Fr.5-8 part to obtain the nepal acid mould active part extract.
The cosmetic is composed of any one of the compounds 1-4 or the combination of any two of the compounds, and is added into a common carrier for cosmetics, wherein the addition amount of the compound is 0.01% -0.08%.
The cosmetic is prepared from any one or a combination of any two of the extracts of the Rumex plants, and is added with a common carrier for the cosmetic, wherein the addition amount of the extracts is 0.1-0.8%.
The application of the compounds 1-4 in the preparation of cosmetics for whitening, anti-aging and sun protection.
The application of the Rumex plant extract in preparing cosmetics for whitening, resisting aging and preventing sunburn.
The compounds 1-4 are applied to the preparation of antioxidants, tyrosinase inhibitors and ultraviolet resistant products.
The application of the Rumex plant extract in preparing antioxidant, tyrosinase inhibitor and ultraviolet resistant products.
The extract and the compound have remarkable antioxidant activity, tyrosinase inhibitory activity and ultraviolet absorption effect.
The antioxidation activity evaluation adopts a DPPH free radical scavenging method, namely, a drug to be tested is mixed with DPPH (the final concentration is 100 mu M) for reaction, 3 repeated holes are set, a blank control hole without the drug and a Trolox (vitamin E) positive control hole are set at the same time, the OD value is measured at 30 ℃ for 1h by an enzyme-labeled instrument, the detection wavelength is 515nm, and the antioxidation rate is calculated. Antioxidant rate (%) = (1-experimental well OD) 515nm Blank well OD 515nm )×100。
The method for evaluating the tyrosinase inhibition activity comprises the steps of mixing a drug to be tested with L-Dopa, adding tyrosinase (the final concentration is 25U/mL) to start reaction, setting 3 repeated holes, setting a blank control without the drug and a Kojic Acid positive control, measuring an OD value at room temperature for 5min by an enzyme-labeling instrument, and measuring the detection wavelength to be 490nm. And calculating to obtain the tyrosinase activity inhibition rate. Tyrosinase activity inhibition rate (%) = (1-sample OD 490nm Experimental control well OD 490nm )×100
The ultraviolet absorption activity evaluation method is to dissolve a sample to be tested with 50% ethanol to make the final concentration of the sample to be tested be 2g/L, and taking 50% ethanol as a blank control; dissolving ethylhexyl methoxycinnamate in ethanol to a final concentration of 2g/L, and dissolving in ethanolAs a blank for this compound, absorbance A was measured at intervals of 10nm in the UVB region (280-320 nm) and the UVA region (320-400 nm). Absorbance a=a 1 -A 0 Wherein A is 1 For absorbance of the sample, A 0 Absorbance was used as solvent blank.
The cosmetic dosage forms for whitening, anti-aging and sun protection comprise all cosmetic types such as face cream, emulsion, ointment, facial mask and the like.
When the Rumex plant extract is applied to cosmetics for whitening, resisting aging and preventing sunburn, the addition amount of the extract is 0.1-0.8%.
When the compounds 1-4 are independently or randomly applied to cosmetics for whitening, anti-aging and sun protection, the addition amount of the compounds is 0.01-0.08%.
Compared with the prior art, the invention has the following advantages:
1. the present invention provides extracts of sorrel plants comprising novel compounds 1-4 and comprising 4 novel compounds. The extract contains 4 chemical components shown in figure 1, has remarkable antioxidant activity, tyrosinase inhibitory activity and strong ultraviolet absorption capacity, and can be used as a functional additive to be added into cosmetics to realize the effects of delaying skin aging, whitening and sun protection. The product combines the triple effects of resisting oxidation, delaying aging, inhibiting tyrosinase, whitening skin, absorbing ultraviolet rays, preventing sunburn and the like to comprehensively protect skin health, and the extract is derived from plants, has good skin affinity and high absorption and utilization rate.
2. The present invention provides a novel process for preparing an active site extract containing novel compounds, which is easily available in raw materials, easy to operate, and suitable for industrial production, and a novel process for preparing the compounds.
3. The invention provides a novel compound and a cosmetic containing an active site of the novel compound as an active ingredient, and provides a material basis for preparing novel whitening and sun-screening cosmetics.
Drawings
FIG. 1 shows 4 novel compounds according to the invention: acidoin-8-O-beta-D- (6 ' -O-malonyl) glucopyranoside (musizin-8-O-beta-D- (6 ' -O-malonyl-3 ' -methoxy) glucopyranoside 1, 2-acetyl-3-methyl-1, 4-naphthoquinone-8-O-beta-D-glucopyranoside (2-acetyl-3-methyl-1, 4-nano-quinone-8-O-beta-D-glucopyranoside) 2, (2 ' R) -7-hydroxy-5-methyl acetate-2- (2 ' -hydroxypropyl) chromanone ((2 ' R) -7-hydroxy-2- (2 ' -hydroxypropyl) -5-methyl acetate chromone) 3 and 2,7-dimethyl-3,5-dihydroxySchematic structural formula of ketone (2, 7-dimethyl-3, 5-dihydroxyxanthone) 4.
FIG. 2 UV absorption of Rumex philippinensis extract;
FIG. 3 UV absorption of a fruit acid mold extract;
FIG. 4 UV absorption of Nepal Rumex extract;
the ultraviolet absorption of compounds 1 to 4 in FIG. 5.
Detailed Description
In order to better understand the essence of the present invention, the active site of the extract of Rumex plant of the present invention and its preparation method, preparation and structural identification of novel compounds 1 to 4, pharmacological effects and its application in cosmetics will be further described with reference to the accompanying drawings, but the present invention is not limited by this test example and examples.
The technical scheme of the invention is clearly and completely described in combination with the embodiment of the invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of Rumex nepalensis var. Remotiforus extract and evaluation of its activity.
Step 1, preparation of a flower thinning acid mould extract. 9kg of dried root of the sorrel is crushed, 60% acetone water is leached for 4 times at room temperature for 7 days, the extracting solution is decompressed and concentrated to remove the organic solvent, the obtained aqueous solution is extracted by ethyl acetate, the ethyl acetate part is decompressed and concentrated to obtain extract (450 g), the extract is stirred and put on a silica gel column, the methanol-dichloromethane volume ratio v/v is 0:1-1:0 gradient elution is carried out to obtain Fr.1-6, fr.5 (150 g) is decompressed and concentrated on Sephadex LH20, the methanol-water volume ratio v/v is 0:1-1:0 gradient elution is carried out to obtain Fr.5-1-5-10, and Fr.5-8 part is compressed and concentrated to obtain the active part extract (25 g) of the sorrel.
And 2, evaluating the activity of the Rumex philippinensis extract.
Mixing samples of the flower-thinning acid die extracts with different concentrations (0.010-0.200 mg/mL) with DPPH (final concentration is 100 mu M) for reaction by adopting a DPPH free radical scavenging method, setting 3 repeated holes, setting blank control without the samples and Trolox (vitamin E) positive control, measuring an OD value at 30 ℃ for 1h by using an enzyme-labeled instrument, detecting the wavelength to be 515nm, and calculating to obtain the antioxidation rate. Antioxidant rate (%) = (1-experimental well OD) 515nm Blank well OD 515nm ) X 100. And the IC50 value (the concentration of the sample required for eliminating half of DPPH free radicals) is used for reflecting the oxidation resistance of the test sample, and the IC50 value is calculated by a Reed-Muench method. The test results showed that DPPH radical scavenging IC50 value of the Rumex solvay extract was 0.0186+ -0.0012 mg/mL, which was stronger than positive control Trolox (IC50= 0.0332 + -0.0011 mg/mL).
Mixing the flower-thinning Acid die extract samples with different concentrations (0.008-1.000 mg/mL) with L-Dopa by adopting a tyrosinase inhibition activity evaluation method, adding tyrosinase (final concentration 25U/mL) to start reaction, setting 3 repeated holes, setting a blank control without medicine and a Kojic Acid positive control, measuring an OD value by using an enzyme-labeling instrument at room temperature for 5min, and measuring the detection wavelength to be 490nm. And calculating to obtain the tyrosinase activity inhibition rate. Tyrosinase activity inhibition rate (%) = (1-sample OD 490nm Experimental control well OD 490nm ) X 100. And the tyrosinase inhibition strength of the test sample is reflected by an IC50 value (the concentration of the sample required for half inhibition of tyrosinase activity), and the IC50 value is calculated by a Reed-Muench method. The detection result shows that the tyrosinase inhibition IC50 value of the sorrel extract is 0.035+/-0.003 mg/mL, which is stronger than that of positive control Kojic Acid Kojic Acid (IC 50)＝0.090±0.007mg/mL)。
Dissolving a sample to be detected by using 50% ethanol by adopting an ultraviolet absorption method to ensure that the final concentration is 0.2mg/mL, and taking 50% ethanol as a blank control; ethylhexyl methoxycinnamate was dissolved in ethanol at a final concentration of 0.2mg/mL, and absorbance A was measured at 10nm intervals in the UVB region (280-320 nm) and the UVA region (320-400 nm) using an ethanol solution as a blank for the compound. Absorbance a=a 1 -A 0 Wherein A is 1 For absorbance of the sample, A 0 Absorbance was used as solvent blank. As shown in FIG. 2, the ultraviolet absorption value of the extract of Rumex philippinensis is similar to that of ethylhexyl methoxycinnamate, and the absorption range is larger than that of the compound, so that the ultraviolet absorption activity of the extract of Rumex philippinensis is better than that of ethylhexyl methoxycinnamate.
Example 2
Preparation of a dental acid mould (R.dentatus) extract and evaluation of its activity.
Step 1, preparing a tooth fruit acid mould extract. Crushing 6kg of dried roots of the odontoseisis rupestris, leaching with 8L of 60% acetone water at room temperature for 4 times, concentrating the extracting solution under reduced pressure for 7 days each time to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract (303 g), stirring the extract with a silica gel column, carrying out gradient elution on methanol-dichloromethane with the volume ratio v/v of 0:1-1:0 to obtain Fr.1-6, carrying out gradient elution on Fr.5 (98 g) with Sephadex LH20, carrying out gradient elution on methanol-water with the volume ratio v/v of 0:1-1:0 to obtain Fr.5-1-5-10, and carrying out gradient concentration on Fr.5-8 parts to obtain the active part extract (17 g) of the odontoseisis rupestris.
And 2, evaluating the activity of the tooth fruit acid mould extract.
And (3) mixing different concentrations (0.010-0.200 mg/mL) of the odontoseisis extract samples with DPPH (final concentration of 100 mu M) for reaction by adopting a DPPH free radical scavenging method, setting 3 repeated holes, setting a blank control without the samples and a Trolox (vitamin E) positive control, measuring an OD value at 30 ℃ for 1h by using an enzyme-labeling instrument, detecting the wavelength of 515nm, and calculating to obtain the antioxidation rate. Antioxidant rate (%) = (1-experimental well OD) 515nm Blank well OD 515nm ) X 100. And with IC50 value (concentration of sample required for scavenging half DPPH radical)Degree) reflects the strength of the antioxidant capacity of the test sample, and the IC50 value is calculated by a Reed-Muench method. The detection result shows that the DPPH free radical scavenging IC50 value of the fructus kochiae extract is 0.0302 +/-0.0017 mg/mL, which is slightly stronger than that of a positive control Trolox (IC50= 0.0332 +/-0.0011 mg/mL).
Mixing the odontoseisis extract samples with different concentrations (0.008-1.000 mg/mL) with L-Dopa by adopting a tyrosinase inhibition activity evaluation method, adding tyrosinase (final concentration 25U/mL) to start reaction, setting 3 repeated holes, setting a blank control without medicine and a Kojic Acid positive control, measuring an OD value by using an enzyme-labeling instrument at room temperature for 5min, and measuring the detection wavelength to be 490nm. And calculating to obtain the tyrosinase activity inhibition rate. Tyrosinase activity inhibition rate (%) = (1-sample OD 490nm Experimental control well OD 490nm ) X 100. And the tyrosinase inhibition strength of the test sample is reflected by an IC50 value (the concentration of the sample required for half inhibition of tyrosinase activity), and the IC50 value is calculated by a Reed-Muench method. The detection result shows that the tyrosinase inhibition IC50 value of the odontoseisis extract is 0.097+/-0.007 mg/mL, which is similar to that of positive control Kojic Acid Kojic Acid (IC50=0.090+/-0.007 mg/mL).
Dissolving a sample to be detected by using 50% ethanol by adopting an ultraviolet absorption method to ensure that the final concentration is 0.2mg/mL, and taking 50% ethanol as a blank control; ethylhexyl methoxycinnamate was dissolved in ethanol at a final concentration of 0.2mg/mL, and absorbance A was measured at 10nm intervals in the UVB region (280-320 nm) and the UVA region (320-400 nm) using an ethanol solution as a blank for the compound. Absorbance a=a 1 -A 0 Wherein A is 1 For absorbance of the sample, A 0 Absorbance was used as solvent blank. As shown in FIG. 3, the absorption value of the extract of the odontoseisis is larger than that of ethylhexyl methoxycinnamate at 280-300 nm, the absorption value of the extract of the odontoseisis at 310-340 nm is larger than that of ethylhexyl methoxycinnamate, and the absorption value of the extract of the odontoseisis at 350-400 nm is larger than that of ethylhexyl methoxycinnamate.
Example 3
Preparation of Rumex nepalensis (R.nepalensis) extract and evaluation of activity thereof.
Step 1, preparation of a Rumex nepalensis extract. Crushing 9kg of dried plants of the nephelometric herb, leaching with 60% acetone water for 4 times at room temperature for 7 days, concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract (460 g), stirring the extract with a silica gel column, carrying out gradient elution on methanol-dichloromethane with the volume ratio v/v of 0:1-1:0 to obtain Fr.1-6, carrying out gradient elution on Fr.5 (150 g) with Sephadex LH20, carrying out gradient elution on methanol-water with the volume ratio v/v of 0:1-1:0 to obtain Fr.5-1-5-10, and carrying out pressure concentration on Fr.5-8 parts to obtain the extract (28 g) of active parts of the nephelometric herb.
And 2, evaluating the activity of the Rumex nepalensis extract.
Mixing nephelometric extracts with different concentrations (0.010-0.200 mg/mL) with DPPH (final concentration of 100 mu M) for reaction by adopting a DPPH free radical scavenging method, setting 3 repeated holes, setting blank control without sample and Trolox (vitamin E) positive control, measuring OD value at 30 ℃ for 1h by an enzyme-labeled instrument, detecting wavelength to 515nm, and calculating to obtain the antioxidation rate. Antioxidant rate (%) = (1-experimental well OD) 515nm Blank well OD 515nm ) X 100. And the IC50 value (the concentration of the sample required for eliminating half of DPPH free radicals) is used for reflecting the oxidation resistance of the test sample, and the IC50 value is calculated by a Reed-Muench method. The test results showed that the DPPH radical scavenging IC50 value of the nephelometric extract was 0.0267.+ -. 0.0014mg/mL, which was stronger than the positive control Trolox (IC50= 0.0332.+ -. 0.0011 mg/mL).
Mixing samples of Nepal Rumex extract with different concentrations (0.008-1.000 mg/mL) with L-Dopa, adding tyrosinase (final concentration 25U/mL) to start reaction, setting 3 repeated holes, setting a blank control without medicine and a Kojic Acid positive control, measuring OD value at room temperature for 5min by an enzyme-labeling instrument, and detecting wavelength as 490nm. And calculating to obtain the tyrosinase activity inhibition rate. Tyrosinase activity inhibition rate (%) = (1-sample OD 490nm Experimental control well OD 490nm ) X 100. And the tyrosinase inhibition strength of the test sample is reflected by an IC50 value (the concentration of the sample required for half inhibition of tyrosinase activity), and the IC50 value is calculated by a Reed-Muench method. The detection result shows that tyramine of the Rumex nepalensis extractThe IC50 value of the inhibition of the Acid enzyme is 0.065+/-0.009 mg/mL, which is stronger than that of positive control Kojic Acid Kojic Acid (IC50=0.090+/-0.007 mg/mL).
Dissolving a sample to be detected by using 50% ethanol by adopting an ultraviolet absorption method to ensure that the final concentration is 0.2mg/mL, and taking 50% ethanol as a blank control; ethylhexyl methoxycinnamate was dissolved in ethanol at a final concentration of 0.2mg/mL, and absorbance A was measured at 10nm intervals in the UVB region (280-320 nm) and the UVA region (320-400 nm) using an ethanol solution as a blank for the compound. Absorbance a=a 1 -A 0 Wherein A is 1 For absorbance of the sample, A 0 Absorbance was used as solvent blank. As shown in FIG. 4, the ultraviolet absorption range and the absorption value of the Nepal Rumex extract are both larger than those of ethylhexyl methoxycinnamate, and the ultraviolet absorption activity of the extract is better than that of ethylhexyl methoxycinnamate.
Example 4
The monomeric compounds of Rumex plants Rumex Acidon-8-O-beta-D- (6 ' -O-malonyl) glucopyranoside (1), 2-acetyl-3-methyl-1, 4-naphthoquinone-8-O-beta-D-glucopyranoside (2), (2 ' R) -7-hydroxy-5-methyl acetate-2- (2 ' -hydroxypropyl) chromone (3) and 2,7-dimethyl-3,5-dihydroxyPreparation of ketone (4) and evaluation of activity thereof.
Step 1, preparation of the compounds 1-4. The active site extracts Fr.5-8 (25 g) obtained in examples 1 and/or 2 and/or 3 were subjected to Rp-18 column chromatography, methanol: fr.5-8-1-10 is obtained by the volume ratio v/v of 0:1-1:0, fr.5-8-3 (2.5 g) is put on a silica gel column, methanol is used for: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 35% acetonitrile water at t R Compound 1 (16 mg) was obtained when=24.0 min, fr.5-8-2 was concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 20% acetonitrile water at t R Compound 2 (14 mg) was obtained when=17.5 min, fr.5-8-1 was concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 18% acetonitrile water at t R ＝21Compound 3 (11.5 mg) was obtained at 0min, fr.5-8-6 was concentrated under reduced pressure on a silica gel column, and methanol was used: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 35% acetonitrile water at t R Compound 4 (12 mg) was obtained when=20.0 min.
And 2, identifying the structure of the compound.
Compound 1 was a yellow amorphous powder. (+) -HRESIMS m/z 501.1370[ M+Na ] according to high resolution mass spectrometry] + (C 23 H 26 O 11 Na, calcd.for 501.1367) bond 13 The C-NMR data speculates that the molecular formula is C 23 H 26 O 11 The unsaturation was 11. The infrared absorption spectrum showed the presence of hydroxyl groups (3412 cm -1 ) And carbonyl (1738 cm) -1 ) And the like. From the slave 13 The C-NMR spectrum data indicated that Compound 1 had 23 carbon signals, including two methyl carbon signals (delta) C 23.6 and 20.0), four aromatic ring methine carbon signals (delta) C 128.8 124.2, 121.1 and 112.4), 6 aromatic ring quaternary carbon signals (delta) C 156.2 152.9, 138.2, 134.8, 126.4 and 115.2), 3 carbonyl carbon signals (delta C 208.4 168.2 and 168.9), 1 methylene carbon signal (delta) C 41.4 And 6 carbon signals on glucose (delta) C 104.4 78.1, 76.0, 75.0, 71.5 and 65.6). From the slave 1 The H-NMR spectrum data showed that Compound 1 had two single-peak methyl protons (. Delta.) H 2.60 and 2.31), a unimodal methoxy proton signal (delta) H 3.69 1,2, 3-substituted benzene ring segment [ delta ] H 7.43(1H,d,J＝8.1H Z ),7.39(1H,t,J＝8.1,7.6H Z ) And 7.26 (1H, d, j=7.6h Z )]And an aromatic ring proton signal (delta) which is unimodal H 7.15 And a series of sugar matrix sub-signals (delta) H 5.10 to 3.42). The nuclear magnetic resonance data features above are similar to those reported for 6-hydroxy-sorangin-8-O-beta-D- (6' -O-malonyl) glucoside structure, but compound 1 has a continuous coupling proton signal [ delta ] H 7.43(1H,d,J＝8.1H Z ),7.39(1H,t,J＝8.1,7.6H Z ) And 7.26 (1H, d, j=7.6h Z )]And HMBC pattern shows H-5,H-7 and C-6 (delta), respectively C 128.8 Related, confirm that the structure of Compound 1 does not have 6-position extractionAnd (3) replacing. In summary, the structure of compound 1 was determined and named acid-8-O-beta-D- (6' -O-malonyl) glucopyranoside (Table 1).
Compound 2 was an orange amorphous powder. (+) -HRESIMS M/z415.1002[ M+Na ] according to high resolution mass spectrometry] + (C 19 H 20 O 9 Na, calcd.for 415.1000) is presumed to have the molecular formula C 19 H 20 O 9 The degree of unsaturation was 10. The infrared absorption spectrum showed the presence of hydroxyl groups (3431 cm -1 ) And carbonyl (1699 cm) -1 ) And the like. 13 C-NMR and DEPT spectra showed that Compound 2 has three carbonyl carbon signals (delta) C 203.7 186.1 and 184.6), two methyl carbon signals (delta C 31.8 and 12.9), three aromatic methine carbon signals (delta) C 122.5 136.9 and 124.9), five aromatic quaternary carbon signals (delta) C 148.4 142.0, 158.9, 135.0 and 121.5), and 6 carbon signals on glucose (delta) C 103.6 78.8, 77.7, 74.8, 71.3 and 62.7). 1 H-NMR spectra showed that in compound 2 there are two monomodal methyl proton signals (. Delta.) in addition to a set of glucose matrix proton signals H 2.45 and 2.02) and 1,2, 3-substituted aromatic proton signals [ delta ] H 7.83(1H,d,J＝7.5H Z ),7.76(1H,dd,J＝8.0,7.5H Z )and 7.73(1H,d,J＝8.0H Z )]. The nuclear magnetic resonance data of the compound 2 is similar to the structure of the known 6-methoxy-2-acetyl-3-methyl-1, 4-naphthoquinone-8-O-beta-D-glucopyranoside, and is prepared from 1 The difference between the three coupled aromatic proton signals in the H-NMR spectrum can be seen in that compound 2 has one less methoxy signal. H-6 and C-10 (delta) in HMBC spectra C 121.4 Related H-12 and C-2 (delta) C 148.4)，C-11(δ C 203.7 Related to H-13 and C-2 (delta) C 148.4)，C-3(δ C 142.0)，C-4(δ C 186.1 Related, H-1' and C-8 (. Delta.) C 158.9 The correlation can further confirm the structure of 2. Accordingly, the structure of compound 2 was identified and designated 2-acetyl-3-methyl-1, 4-naphthoquinone-8-O- β -D-glucopyranoside (Table 1).
Compound 3 was a yellow amorphous powder. By high resolution mass spectrometry (-) -HRESIMS m/z 291.0878[ M-H ]] - (C 15 H 15 O 6 Calcd.for 291.0874) is presumed to have the formula C 15 H 16 O 6 . The UV absorption spectrum shows typical chromone backbone absorption (lambda) max 240 247, 290 nm). The infrared absorption spectrum showed that 3 had hydroxyl groups (3413 cm -1 ) And two carbonyl groups (1722, 1644 cm) -1 ) And the like. 13 C-NMR and HSQC data indicated that Compound 3 had two carbonyl carbon signals (. Delta.) C 181.5 and 174.1), three aromatic methine carbon signals (delta) C 119.8 112.3 and 103.2), five aromatic quaternary carbon signals (delta) C 167.9 138.8, 163.5, 161.5 and 115.9), two methylene carbon signals (δ C 44.4 and 42.0), a methyl-oxygen-methylene-carbon signal (delta) C 66.5 A methyl carbon signal (delta) C 23.7 And a methoxy carbon signal (delta) C 52.4)。 1 H-NMR data showed 3 having two meta-coupled aromatic protons (delta) H 6.78 and 6.80, d, j=3.6h Z ) A unimodal aromatic proton signal (delta H 6.01 Two methylene protons [ delta ] H (4.08，s)，(2.67，dd，J＝14.3，8.0H Z )]One oxygen-methyl proton delta H (4.19, m), a methyl proton (delta) H 1.28 And a methoxy proton signal (delta) H 3.67). From the above nuclear magnetic data, it can be assumed that compound 3 is a chromone derivative, similar to the planar structure of the known compound (2 'S) -7-hydroxy-5-hydroxymethyl-2- (2' -hydroxypropyl) chromone. H-11 and C-6 (delta) in HMBC data C 119.8)，C-12(δ C 174.1 Related H-13 and C-12 (delta) C 174.1 Correlation confirmed that compound 3 had one COOCH more than (2 'S) -7-hydroxy-5-hydroxymethyl-2- (2' -hydroxypropyl) chromanone on C-11 3 A group. Determination of the absolute configuration of Compound 3 in combination with the Horeau method, the optical rotation value of Compound 3 was(c 0.04, meOH) in the opposite direction and with the equivalent magnitude of the optical value of (2 'S) -7-hydroxy-5-hydroxymethyl-2- (2' -hydroxypropyl) chromanone, thereby defining the R configuration of 3. Thus, the structure of Compound 3 was determined and designated (2' R) -7-hydroxyMethyl-5-acetate-2- (2' -hydroxypropyl) chromone (Table 1).
Compound 4 was a yellow solid. Its molecular formula is C 15 H 12 O 4 255.0662[ M-H ] by high resolution mass spectrometry (-) -HRESIMS m/z - (C 15 H 11 O 4 Calcd.for 255.0663) and 13 C-NMR data were deduced and had 10 unsaturations. IR spectrum shows hydroxy (3428 cm) -1 ) And carbonyl (1651 cm) -1 ) A group signal. 1 The H-NMR spectrum gave four aromatic proton signals (. Delta.) each of which was unimodal H 7.19,6.23,6.60,6.55), and two methyl proton signals delta H 2.77,2.47 (3H, s). 13 The C-NMR spectrum showed 15 carbon signals including a carbonyl carbon signal (delta C 181.5 Four aromatic methine carbon signals (delta) C 126.6 112.8, 108.3 and 104.2), 8 aromatic quaternary carbon signals (delta) C 166.0 159.2, 158.2, 140.7, 136.0, 136.0, 117.5 and 117.5) and two methyl carbon signals (δ C 23.6 and 19.9). The above nuclear magnetic data shows that Compound 4 is tetrasubstitutedA ketone derivative. From H-1 and C-1a (delta) C 117.5)，C-2(δ C 136.0)，C-3(δ C 166.0)，C-9(δ C 182.1 HMBC related, H-6 and C-5 (delta) C 159.2)，C-5a(δ C 140.9)，C-7(δ C 136.0)，C-8(δ C 108.0 HMBC related, H-12 and C-6 (delta) C 126.5)，C-9(δ C 182.1 HMBC correlation confirmed the four-substituted attachment positions of the compounds. In summary, the structure of Compound 4 was determined and designated 2,7-dimethyl-3, 5-dihydroxyl ∈ ->Ketones (Table 2).
TABLE 1 Compounds 1-3 1 H- (600 MHz) and 13 c- (150 MHz) NMR spectroscopic data (CD 3 OD，δin ppm)
a The determination of the structure of the compounds is based on HSQC and HMBC data.
TABLE 2 Compound 4 1 H- (600 MHz) and 13 c- (150 MHz) NMR spectroscopic data (CD 3 OD，δin ppm)
Step 3, evaluation of Activity of Compounds 1-4.
And (3) mixing 1-4 samples of compounds with different concentrations (0.008-1.000 mg/mL) with DPPH (final concentration of 100 mu M) for reaction by adopting a DPPH free radical scavenging method, setting 3 repeated holes for each concentration gradient of each compound, setting a blank control without the sample and a Trolox positive control, measuring an OD value at 30 ℃ for 1h by using an enzyme-labeled instrument, detecting the wavelength to be 515nm, and calculating to obtain the antioxidation rate. Antioxidant rate (%) = (1-experimental well OD) 515nm Blank well OD 515nm ) X 100. And the IC50 value (the concentration of the sample required for eliminating half of DPPH free radicals) is used for reflecting the oxidation resistance of the test sample, and the IC50 value is calculated by a Reed-Muench method. The test results are shown in Table 3:
TABLE 3 antioxidant Activity of Compounds 1 to 4
Mixing 1-4 samples of compounds with different concentrations (0.008-1.000 mg/mL) with L-Dopa, adding tyrosinase (final concentration 25U/mL) to start reaction, setting 3 repeated holes for each concentration gradient of each compound, setting blank control without medicine and Kojic Acid positive control at room temperature for 5min,the OD value is measured by an enzyme-labeled instrument, and the detection wavelength is 490nm. And calculating to obtain the tyrosinase activity inhibition rate. Tyrosinase activity inhibition rate (%) = (1-sample OD 490nm Experimental control well OD 490nm ) X 100. And the tyrosinase inhibition strength of the test sample is reflected by an IC50 value (the concentration of the sample required for half inhibition of tyrosinase activity), and the IC50 value is calculated by a Reed-Muench method. The test results are shown in Table 4:
TABLE 4 tyrosinase inhibitory activity of Compounds 1 to 4
Using ultraviolet absorption method to dissolve the sample to be tested (compound 1-4) with 50% ethanol to make its final concentration be 0.2mg/mL, using 50% ethanol as blank control; ethylhexyl methoxycinnamate was dissolved in ethanol at a final concentration of 0.2mg/mL, and absorbance A was measured at 10nm intervals in the UVB region (280-320 nm) and the UVA region (320-400 nm) using an ethanol solution as a blank for the compound. Absorbance a=a 1 -A 0 Wherein A is 1 For absorbance of the sample, A 0 Absorbance was used as solvent blank. As shown in FIG. 5, compounds 1 to 4 have an absorption value in the entire ultraviolet absorption region similar to or slightly higher than that of ethylhexyl methoxycinnamate, compared with the control.
Example 5:
cosmetic 1: the cosmetic formulations (W%) of the whitening cream containing the active extracts obtained in examples 1 and 2 and 3 were prepared according to the conventional method for preparing cosmetics as shown in table 5, and the following formulations were prepared.
Table 5 cosmetic 1 formulation composition
Cosmetic 2: the cosmetic formulations (W%) of the whitening cream containing the compounds 1 to 4 obtained in example 4 alone and/or in random combination were prepared according to the conventional method for preparing cosmetics as shown in table 6.
TABLE 6 cosmetic 2 formulation composition
Cosmetic 3
Emulsion formulations (W%) containing the extract of the sorhium vulgare active site and/or the extract of the nephelometric active site or compounds 1-4 of the invention, alone and/or in random combination:
the cosmetic with the formula is prepared according to a conventional method for preparing cosmetics.

Claims (5)

1. Compounds 1 to 4 shown in the following structural formula,
2. a process for the preparation of 4 compounds according to claim 1, characterized in that it comprises the following steps:
(1) Crushing dried root of Rumex philippinensis, and leaching with 0-100% acetone water at room temperature for 4 times (7 days each time), wherein the weight ratio w of Rumex philippinensis root to acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0 to obtain Fr.1-6, performing gradient elution with the volume ratio v/v of methanol to water of 0:1-1:0 to obtain Fr.5-1-5-10, and performing vacuum concentration on the Fr.5 to obtain Sephadex LH 20;
or crushing the dried roots of the odontoseisis, and leaching with 0-100% acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the odontoseisis roots to the acetone water is 1:1-1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0 to obtain Fr.1-6, performing gradient elution with the volume ratio v/v of methanol to water of 0:1-1:0 to obtain Fr.5-1-5-10, and performing vacuum concentration on the Fr.5 to obtain Sephadex LH 20;
or crushing the dried plants of the Nepal sorrel, and leaching the dried plants of the Nepal sorrel with 0 to 100 percent of acetone water for 4 times at room temperature for 7 days each time, wherein the weight ratio w of the dried plants of the Nepal sorrel to the acetone water is 1:1 to 1:1.5; concentrating the extracting solution under reduced pressure to remove the organic solvent, extracting the obtained aqueous solution with ethyl acetate, concentrating the ethyl acetate part under reduced pressure to obtain extract, stirring the extract with a silica gel column, performing gradient elution with the volume ratio v/v of methanol to dichloromethane of 0:1-1:0 to obtain Fr.1-6, performing gradient elution with the volume ratio v/v of methanol to water of 0:1-1:0 to obtain Fr.5-1-5-10, and performing vacuum concentration on the Fr.5 to obtain Sephadex LH 20;
(2) Loading the active site extract Fr.5-8 obtained in the step (1) on an Rp-18 chromatographic column, eluting Fr.5-8-1-10 with methanol to chloroform volume ratio v/v of 0:1-1:0, combining semi-preparative HPLC, eluting with 35% acetonitrile water, and eluting at t R When 24.0min compound 1, fr.5-8-2 was obtained, concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 20% acetonitrile water at t R Compound 2 was obtained when=17.5 min, fr.5-8-1 was concentrated under reduced pressure on a silica gel column, purified with methanol: chloroform volume ratio v/v of 0:1-1:0, combined with semi-preparative HPLC, eluting with 18% acetonitrile water at t R Compound 3 was obtained when=21.0 min, fr.5-8-6 was concentrated under reduced pressure on a silica gel column, purified with methanol: eluting with chloroform at volume ratio v/v of 0:1-1:0, combining with semi-preparative HPLC, eluting with 35% acetonitrile waterAt t R Compound 4 was obtained when=20.0 min.
3. A cosmetic comprising any one of the compounds 1 to 4, or a combination of any two or more thereof, according to claim 1, and a carrier ordinarily used in cosmetics, wherein the amount of the compound added is 0.01 to 0.08%.
4. The use of compounds 1 to 4 according to claim 1 for the preparation of cosmetics for whitening, anti-aging and sun protection.
5. The use of compounds 1 to 4 according to claim 1 for the preparation of antioxidants, tyrosinase inhibitors and UV-resistant cosmetics.
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