CN113200840A - Anthraquinone compound with antibacterial activity and preparation method and application thereof - Google Patents
Anthraquinone compound with antibacterial activity and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anthraquinone compound with antibacterial activity, a preparation method and application thereof, wherein the compound has a structural formula as follows:
. The method is characterized in that bean tea cassia is used as a raw material and is obtained by extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation. The application is the application of the anthraquinone compound with antibacterial activity in preparing antibacterial products. The compound has strong activity on propionibacterium, staphylococcus, corynebacterium, bacillus, pseudomonas, malassezia furfur, malassezia blumea and malassezia pachydermatis; the inhibition rates are all over 82.5%.
Description
Technical Field
The invention belongs to the technical field of extraction of effective components of plants, and particularly relates to an anthraquinone compound with antibacterial activity and a preparation method and application thereof.
Background
The cassia seed, bean tea, is a wild herb plant, and the whole plant can be used as medicine. The plant can be harvested in autumn, washed and dried in the sun to be used as a medicine, can clear heat, promote diuresis, remove blood stasis and relieve pain after being used as the medicine, and can also be used for treating various diseases such as dyspepsia and diarrhea of human beings. In addition, the bean tea cassia seed extract is safe and non-toxic, has obvious antibacterial effect, and is also an ideal additive for face washing cream, beauty cream, astringent, shampoo, facial mask and the like. Therefore, the continuous and intensive research on the plants in the genus is very important.
Disclosure of Invention
The first object of the present invention is to provide an anthraquinone compound having antibacterial activity; the second purpose is to provide a preparation method of the anthraquinone compound with antibacterial activity; the third purpose is the application of the anthraquinone compound with antibacterial activity.
The first purpose of the invention is realized by that the anthraquinone compound with antibacterial activity is obtained by taking cassia occidentalis as a raw material and carrying out extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation, and is named as: 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, english name: 2- (3-hydroxyproyl) -3, 6-dimethoxy-5-methyllantraquinone, molecular formula: c20H20O5The compound is dark red jelly and has a structural formula as follows:
the second purpose of the invention is realized by taking bean tea cassia as a raw material and carrying out extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography separation on the raw material, and the method comprises the following specific steps:
A. extraction: crushing raw material bean tea cassia seed to 20-40 meshes, carrying out ultrasonic extraction for 2-5 times by using an organic solvent for 30-60 min each time, combining extracting solutions, filtering, and concentrating under reduced pressure to 1/4-1/2 of the volume; standing for 20-60 min, filtering out precipitates, and filtering out the precipitates to obtain an extracting solution a;
B. MCI decoloration: loading the extracting solution a on an MCI column, collecting effluent liquid, and concentrating under reduced pressure to obtain extract b;
C. silica gel column chromatography: dissolving the extract b with acetone or methanol which is 1.5-3 times of the weight of the extract b, performing silica gel column chromatography, loading the silica gel into a column with 160-200 meshes, using the amount of the silica gel which is 6-10 times of the weight of the extract b, performing gradient elution by using a chloroform-acetone mixed organic solvent with the volume ratio of 1: 0-0: 1, collecting gradient eluent, concentrating, monitoring by TLC, and combining the same parts;
D. high performance liquid chromatography separation: and (3) separating and purifying the eluent obtained by gradient elution with a chloroform-acetone mixed organic solvent of 9:1 by high performance liquid chromatography to obtain the target anthraquinone compound with antibacterial activity.
The third object of the invention is realized by the application of the anthraquinone compound with antibacterial activity in the preparation of antibacterial products.
The anthraquinone compound with antibacterial activity is separated for the first time, is determined to be the anthraquinone compound with antibacterial activity by a nuclear magnetic resonance and mass spectrometry method, and is characterized in that the specific structure is as follows:
the anthraquinone compound with antibacterial activity is dark red jelly,
the spectrum analysis was carried out by infrared, ultraviolet and mass spectrometry and 1H-NMR, 13C-NMR and HMBC, and the data of 1H-NMR and 13C-NMR spectra are shown in FIGS. 2 and 3, respectively, and the data of 1H NMR and 13C NMR are shown in Table 1. Infrared, ultraviolet and mass spectral data of compounds: violet spectrum (methanol), λ max (log ∈) 215 (4.11), 254 (3.82), 278 (3.60), 403 (3.15) nm; infrared spectroscopy (potassium bromide pellet): ν max 3410, 3058, 2962, 1664, 1616, 1567, 1443, 1348, 1154, 1057, 838 cm-1; 1H and 13C NMR data (500 and 125 MHz in CDCl3 as solvent) in Table 1; positive ion mode ESIMS M/z 363 [ M + Na ]]+; positive ion mode HRESIMS M/z 363.1214 [ M + Na ]]+ (calculated 363.1208, C)20H20O5Na)。
The structure analysis process is as follows: compound 1 is a dark red gum, and HRESI-MS shows that the peak of the excimer ion is 349.1052 [ M + Na ]]+, 1H and 13C NMR combined to give the formula C20H20O5. The infrared spectrum shows that the compound has signals of hydroxyl (3410 cm-1), carbonyl (1664 cm-1) and aromatic ring (1616, 1567, 1443 cm-1), and the ultraviolet spectrum has maximum absorption at 215, 254, 278 and 403 nm and also confirms that the aromatic ring structure exists in the compound. The 1H and 13C NMR spectra of the compound (Table 1) show that it contains 20 carbons and 20 hydrogens, including a 1,2,4, 5-quartSubstituted benzene rings (C-1-C-4, C-4a and C-10 a; H-1, H-4), a 1,2,3, 4-tetra-substituted benzene ring (C-5-C-8, C-9a and C-10 a; H-7 and H-8), a methyl (C-13, H3-13), two methoxy groups (delta C56.2 q, 56.4 q; delta H3.80, 3.84 s), and 1 hydroxypropyl group (C-11-C-13, H2-11-H2-13). According to nuclear magnetic resonance data of two benzene rings and typical carbonyl signals (C-5 and C-10), the compound can be preliminarily presumed to be an anthraquinone compound. This speculation can be confirmed based on the HMBC correlation of H-1 and C-1a, C-4a, C-9, H-4 and C-1a, C-4a, C-10, H-8 and C-9, C-9a, C-10a (FIG. 3).
After the parent structure of the compound is confirmed, two methoxy groups are substituted at C-3 and C-6 positions according to the correlation of two methoxy hydrogens (delta H3.78, 3.82) and HMBC of C-3 and C-6; the methyl substitution at the C-5 position can be confirmed by the correlation of the methyl hydrogen signal (H3-14) with HMBC at C-5, C-6 and C-10 a; furthermore, the substitution of hydroxypropyl at the C-2 position was confirmed based on the correlation of H2-11 with HMBC at C-1, C-2, C-3, H2-12 and C-2. Thus far, the structure of the compounds of the present invention was confirmed and identified as: 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone.
1H NMR and 13C NMR data (CDCl3) for the compounds of Table 1
The compound is screened for antibacterial activity, and an in vitro antibacterial experiment is carried out by an agar diffusion method, wherein test bacteria are firstly uniformly coated on a flat plate of a common agar culture medium (beef extract, peptone, sodium chloride, serum and agar), then a tablet (the diameter is 5 mm) soaked by a compound to be tested (the compound is dissolved by 10 mL DMSO and diluted into 50 mu g/mL solution by adding water) is placed on the culture medium with bacteria, the culture medium is placed in a constant temperature box, and the size of an antibacterial ring is observed after incubation is carried out for 24-72 h at 25 ℃. The results show that: the compound has strong activity on propionibacterium, staphylococcus, corynebacterium, bacillus, pseudomonas, malassezia furfur, malassezia blumea and malassezia pachydermatis; the inhibition rates are all over 82.5%.
Dandruff is one of the clinical common diseases of dermatology; manifested by increased dandruff, itching of the scalp, greasy or dry hair. In order to test the dandruff removing and itching relieving effects of the shampoo disclosed by the invention. 20 volunteers were collected, and when the shampoo of the invention was used for washing hair three times a week, 7 volunteers showed the regression of dandruff, the regression of scalp itch, and the improvement of greasy hair and dry hair; the antibacterial shampoo disclosed by the invention is proved to have practical effects.
Shampoo, also known as shampoo and shampoo, is a hair washing product which is most widely applied and is one of the most commonly used hair cosmetics. It can be used for cleaning human body secreted oil, sweat scale, cells detached from scalp, foreign dust, microorganism, and residue and unpleasant odor of styling product, etc. attached to scalp and hair, and keeping scalp and hair clean and beautiful. The shampoo has various formulations, and the commercially available shampoo is mainly liquid shampoo. Most liquid shampoos have structural components in which surfactants, foam stabilizers, thickeners, preservatives and perfumes are essential ingredients. Other ingredients depend on consumer needs and cost economics.
Along with the continuous improvement of living standard of people, the demand on daily chemical products is more and more, the requirement on quality is higher and more, and products such as cosmetics, shampoo, shower gel are daily consumer goods commonly used by people, and are used on healthy skin almost every day, so the quality requirement on the washing and protecting products is higher, and the first requirement is that the products are safe and reliable, do not hinder the health of human bodies, and have no side effect when in use. The development trend of daily chemicals reflects the pursuit of fashion: the natural, comprehensive and functional products are the development trend of daily chemicals.
The shampoo prepared by the anthraquinone compound with antibacterial activity has the following beneficial effects:
(1) the shampoo is simple to prepare, and the components are uniformly mixed according to the proportion to obtain the shampoo. The shampoo can form different fragrance types by selectively adding different plant essential oils (or essences) so as to meet the personalized preferences of different consumers. In addition, the added anthraquinone compounds have dyeing effect, so that the shampoo can present bright light orange color, and pigments are not required to be added into the shampoo.
(2) Except for 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, the raw materials of the shampoo can be purchased from the market, the shampoo has mature production and supply, and the preparation cost of the shampoo is low. The key component 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone in the shampoo can be separated from the cassia occidentalis serving as a raw material, the cassia occidentalis is easy to plant, the biological yield is high, the raw material source is very wide, and the cost is low.
(3) The shampoo provided by the invention has the advantages that all the components of the shampoo are natural products, and the shampoo is safe and reliable; besides good decontamination effect, the shampoo also has the effects of inhibiting the propagation of harmful microorganisms on the head, removing dandruff and relieving itching.
Drawings
FIG. 1 nuclear magnetic resonance carbon spectrum (13C NMR) of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum (1H NMR) of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone according to the present invention;
FIG. 3 key HMBC correlation scheme for 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any variations or modifications which are based on the teachings of the present invention are intended to fall within the scope of the invention.
The anthraquinone compound with antibacterial activity is obtained by taking cassia occidentalis as a raw material through extraction, MCI (methanol to olefins) decoloration, silica gel column chromatography and high performance liquid chromatography separation, and is named as: 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, english name: 2- (3-hydroxyproyl) -3, 6-dimethoxy-5-methyllantraquinone, molecular formula: c20H20O5The compound is dark red jelly and has a structural formula as follows:
the method for preparing the anthraquinone compound with antibacterial activity takes the cassia occidentalis as a raw material and obtains the compound by extraction, MCI decoloration, silica gel column chromatography and high performance liquid chromatography, and comprises the following specific steps:
A. extraction: crushing raw material bean tea cassia seed to 20-40 meshes, carrying out ultrasonic extraction for 2-5 times by using an organic solvent for 30-60 min each time, combining extracting solutions, filtering, and concentrating under reduced pressure to 1/4-1/2 of the volume; standing for 20-60 min, filtering out precipitates, and filtering out the precipitates to obtain an extracting solution a;
B. MCI decoloration: loading the extracting solution a on an MCI column, collecting effluent liquid, and concentrating under reduced pressure to obtain extract b;
C. silica gel column chromatography: dissolving the extract b with acetone or methanol which is 1.5-3 times of the weight of the extract b, performing silica gel column chromatography, loading the silica gel into a column with 160-200 meshes, using the amount of the silica gel which is 6-10 times of the weight of the extract b, performing gradient elution by using a chloroform-acetone mixed organic solvent with the volume ratio of 1: 0-0: 1, collecting gradient eluent, concentrating, monitoring by TLC, and combining the same parts;
D. high performance liquid chromatography separation: and (3) separating and purifying the eluent obtained by gradient elution with a chloroform-acetone mixed organic solvent of 9:1 by high performance liquid chromatography to obtain the target anthraquinone compound with antibacterial activity.
The organic solvent in the step A is an acetone aqueous solution with the volume percentage concentration of 70-100%, an ethanol aqueous solution with the volume percentage concentration of 70-100% or a methanol aqueous solution with the volume percentage concentration of 70-100%.
And C, before the extractum is subjected to silica gel column chromatography, dissolving the extractum by using acetone or methanol which is 1.5 to 3 times of the weight of the extractum b, mixing the sample by using 80 to 100 meshes of silica gel which is 0.8 to 1.2 times of the weight of the extractum b, and then performing silica gel column chromatography.
The gradient proportion of the chloroform-acetone mixed organic solvent in the step C is 20:1, 9:1, 8:2, 7:3, 6:4 and 1: 1. Each ratio needs to be eluted until no component flows out, namely no component remains in a distillation flask after solvent is evaporated, and then the next gradient ratio is changed.
And D, performing high performance liquid chromatography separation and purification by taking 55-65% methanol aqueous solution as a mobile phase, taking a Zorbax PrepHT GF reversed-phase preparation column of 21.2 x 250 mm and 5 mu m as a stationary phase at the flow rate of 15-25 mL/min, taking a detection wavelength of 403 nm by an ultraviolet detector and feeding 0.5-1.0 mL each time, collecting chromatographic peaks for 30-45 min, and performing multiple accumulation and evaporation to dryness.
The application of the anthraquinone compound with antibacterial activity is the application of the anthraquinone compound with antibacterial activity in preparing antibacterial products.
The antibacterial activity is antibacterial activity to propionibacterium, staphylococcus, corynebacterium, bacillus, pseudomonas, malassezia furfur, malassezia blumea or malassezia pachydermatis, and the inhibition rate is more than 82.5%.
The antibacterial product is a daily chemical product.
The daily chemical product is shampoo with an itching relieving effect, and the formula of the shampoo with the itching relieving effect is as follows: 4-6% of Tween-60, 10-15% of amino acid surfactant, 3-5% of coconut oil thickening foaming agent, 3-5% of amino acid humectant, 1-2% of chitosan fibroin protein, 2-3% of water-soluble olive ester, 2.5-3.5% of pullulan, 0.5-1% of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, 0.8-2% of vegetable essential oil (or essence), 0.5-1% of vitamin B5, and the balance of water.
In the formula composition of the shampoo with the itch relieving effect:
tween-60 is a mixture of polyoxyethylene sorbitan monolaurate and a part of polyoxyethylene bissorbitan monolaurate, is a nonionic surfactant, has good decontamination effect, can also be used as an emulsifier in the fields of food, medicine and the like, and can increase the stability of the emulsion.
The amino acid surfactant is a novel green environment-friendly surfactant, and has the advantages of small toxic and side effects, mild performance, small irritation and good biodegradability; and the good properties of emulsification, wetting, solubilization, dispersion, foaming and the like are currently attracting people's attention, and the good properties are gradually applied to various fields of washing, personal care, food industry and the like.
The coconut oil thickening foaming agent is a high-molecular water-accumulating substance; the low irritation, the good dissolubility and compatibility, the good foamability and the obvious thickening property; the compatibility of medicines can obviously improve the softness, conditioning and low-temperature stability of the washing products.
The amino acid humectant is chemically named as trimethylglycine, is a natural structural substance zwitterionic moisturizing component, can rapidly improve the moisture retention of skin and hair and stimulate cell activity in the application of personal care products, and has the effects of keeping skin moist and smooth and preventing dryness and darkness.
The chitosan silk fibroin is a silk fibroin composite material, and because hairs belong to protein, the silk fibroin not only has a good hair care effect on hair quality, but also has a good hair care effect on scalp.
The water-soluble olive ester is water-soluble oil prepared by reacting olive oil hydrolysis fatty acid with ethylene oxide, has a structure similar to that of naturally existing oil of skin, and can improve hair luster and combing property.
The pullulan is extracellular water-soluble mucopolysaccharide which is produced by fermentation of aureobasidium pullulans and is similar to glucan and xanthan gum, has good film-forming property, can replace glycerin to be used as a perfuming and antifreezing humectant, and is widely applied to daily chemicals such as face washing cream, beauty cream, lotion, shampoo, facial mask and the like.
The plant essential oil (or essence) has fragrance, different value types and ratios, and can endow the shampoo with different fragrance characteristics.
Vitamin B5 is one of the common 13 vitamins, has remarkable effect on preventing and treating alopecia, can make the hair thicker and increase the luster of the hair, and has very important effect on the health of the scalp.
2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone is a novel compound separated from the cassia occidentalis of the bean tea, and the compound has remarkable antibacterial activity. And the hair dye has a dyeing effect, so that the shampoo presents bright light orange color, and pigments are not required to be added into the shampoo.
The compound synthesized by taking the anthraquinone compound with antibacterial activity as a template can also achieve the aim of the invention.
The invention is further illustrated by the following specific examples:
example 1
Preparation of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone: taking whole bean tea cassia, drying in the sun, crushing to 20-50 meshes, carrying out ultrasonic extraction for 2-5 times by using a solvent, wherein the solvent amount of each extraction is 2-6 times of that of a sample, the extraction time is 30-60 minutes, combining the extracting solutions, filtering, concentrating the filtrate under reduced pressure until just precipitate is separated out, standing for 20-60 minutes, and filtering the precipitate to obtain a sample extracting solution. Filtering to remove precipitate, loading the sample extractive solution on MCI column, collecting eluate, and concentrating under reduced pressure to obtain extract.
Performing silica gel column chromatography on the extract, wherein silica gel filled in the column is 160-200 meshes, and the weight of the silica gel is 6-10 times that of the extract; performing gradient elution by using a chloroform-acetone mixed organic solvent with a volume ratio of 1: 0-0: 1, collecting gradient eluents of all gradients, concentrating, monitoring by TLC, and combining the same parts. And (3) separating and purifying the part eluted by using a chloroform-acetone mixed organic solvent with the volume ratio of 9:1 by using high performance liquid chromatography to obtain the 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone.
Example 2
Structural identification of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone: taking the prepared dark red jelly, and carrying out spectrum analysis to identify the structure by infrared, ultraviolet and mass spectrums, 1H-NMR, 13C-NMR and HMBC.
The structure analysis process is as follows: compound 1 is a dark red gum, and HRESI-MS shows that the peak of the excimer ion is 349.1052 [ M + Na ]]+, 1H and 13C NMR combined to give the formula C20H20O5. The infrared spectrum shows that the compound has signals of hydroxyl (3410 cm-1), carbonyl (1664 cm-1) and aromatic ring (1616, 1567, 1443 cm-1), and the ultraviolet spectrum has maximum absorption at 215, 254, 278 and 403 nm and also confirms that the aromatic ring structure exists in the compound. The 1H and 13C NMR spectra of the compounds (Table-1) showed 20 carbons and 20 hydrogens, including a 1,2,4, 5-tetrasubstituted benzene ring (C-1 to C-4, C-4a and C-10 a; H-1, H-4), a 1,2,3, 4-tetrasubstituted benzene ring (C-5 to C-8, C-9a and C-10 a; H-7 and H-8)) One methyl group (C-13, H3-13), two methoxy groups (Δ C56.2 q, 56.4 q; delta H3.80, 3.84 s), 1 hydroxypropyl group (C-11 to C-13, H2-11 to H2-13). According to nuclear magnetic resonance data of two benzene rings and typical carbonyl signals (C-5 and C-10), the compound can be preliminarily presumed to be an anthraquinone compound. This speculation was confirmed by HMBC correlation of H-1 with C-1a, C-4a, C-9, H-4 with C-1a, C-4a, C-10, H-8 with C-9, C-9a, C-10a (FIG. 3).
After the parent structure of the compound is confirmed, two methoxy groups are substituted at C-3 and C-6 positions according to the correlation of two methoxy hydrogens (delta H3.78, 3.82) and HMBC of C-3 and C-6; the methyl substitution at the C-5 position can be confirmed by the correlation of the methyl hydrogen signal (H3-14) with HMBC at C-5, C-6 and C-10 a; furthermore, the substitution of hydroxypropyl at the C-2 position was confirmed based on the correlation of H2-11 with HMBC at C-1, C-2, C-3, H2-12 and C-2. Thus far, the structure of the compounds of the present invention was confirmed and identified as: 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone.
Example 2
The formula of the antibacterial shampoo comprises the following components: the shampoo in the embodiment is prepared from the following raw materials in percentage by mass: 4-6% of tween-60, 10-15% of amino acid surfactant, 3-5% of coconut oil thickening foaming agent, 3-5% of amino acid humectant, 1-2% of chitosan silk fibroin, 2-3% of water-soluble olive ester, 2.5-3.5% of pullulan, 0.5-1% of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, 0.8-2% of vegetable essential oil (or essence), 0.5-1% of vitamin B5, and the balance of water. The components are uniformly mixed according to a certain proportion and fully dissolved to obtain an orange transparent viscous solution, and the shampoo liquid of the invention can be obtained. The shampoo can form different fragrance types by selectively adding different plant essential oils (or essences) so as to meet the requirements of individual preference of different consumers.
Example 3
The shampoo in the embodiment is prepared from the following raw materials: 12% of buckwheat flower honey, 0.25% of chlorogenic acid, 0.2% of phenethyl propionate, 0.08% of phenethyl formate, 0.4% of scopoletin, 0.2% of ethyl vanillin, 0.5% of vanilla extract, 12% of propylene glycol, 1.0% of beeswax absolute, 0.4% of bean tea cassia pyranolide-A, 1.5% of fructus phyllanthi extract and the balance of water. The components are uniformly mixed according to a certain proportion and fully dissolved to obtain a light yellow transparent solution with elegant bean fragrance and slightly sweet fragrance; thus obtaining the finished product of the shampoo. 1.5% of the shampoo of the embodiment is added into a certain Yunnan brand cigarette paper. Rolling into cigarette, performing sensory evaluation according to GB5606.4-2005 standard, and using cigarette without shampoo as control. The evaluation results show that: the shampoo is added into cigarette paper, so that cigarettes are full of fragrance, the bean fragrance style characteristics are outstanding, and the cigarettes slightly have back sweet taste; the aftertaste of the oral cavity is comfortable and clean, the throat irritation is reduced, the smoke is smoother and smoother, and the suction comfort is improved.
Example 4
And (3) testing the antibacterial effect of the shampoo: the shampoo is tested for antibacterial effect, and in vitro antibacterial experiments are carried out by an agar diffusion method, wherein test bacteria are uniformly coated on a flat plate of a common agar culture medium (beef extract, peptone, sodium chloride, serum and agar), soaked tablets (with the diameter of 5 mm) are placed on the culture medium with bacteria, the culture medium is placed in a constant temperature box, and the size of an antibacterial zone is observed after incubation is carried out for 24-72 h at the temperature of 25 ℃. The results show that: the shampoo has strong activity on propionibacterium, staphylococcus, corynebacterium, bacillus, pseudomonas, malassezia furfur, malassezia blumea and malassezia pachydermatis; the inhibition rates are all over 89.2%.
Example 5
And (3) testing the dandruff removing and itching relieving effects of the shampoo: in order to test the dandruff removing and itching relieving effects of the shampoo disclosed by the invention. 20 volunteers were collected, and when the shampoo of the invention was used for washing hair three times a week, 7 volunteers showed the regression of dandruff, the regression of scalp itch, and the improvement of greasy hair and dry hair; the antibacterial shampoo disclosed by the invention is proved to have practical effects.
Claims (10)
1. An anthraquinone compound with antibacterial activity is characterized in that the anthraquinone compound with antibacterial activity is prepared by taking cassia occidentalis as a raw material and carrying out extraction, MCI (methanol-to-ethanol) decoloration, silica gel column chromatography, mass spectrometry, and the like,Obtained by high performance liquid chromatography separation, and is named as: 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, english name: 2- (3-hydroxyproyl) -3, 6-dimethoxy-5-methyllantraquinone, molecular formula: c20H20O5The compound is dark red jelly and has a structural formula as follows:
2. the preparation method of anthraquinone compounds with antibacterial activity according to claim 1, which is characterized by taking cassia occidentalis as a raw material, and performing extraction, MCI (methanol-to-ethanol) decoloration, silica gel column chromatography and high performance liquid chromatography separation to obtain the anthraquinone compounds, and comprises the following specific steps:
A. extraction: crushing raw material bean tea cassia seed to 20-40 meshes, carrying out ultrasonic extraction for 2-5 times by using an organic solvent for 30-60 min each time, combining extracting solutions, filtering, and concentrating under reduced pressure to 1/4-1/2 of the volume; standing for 20-60 min, filtering out precipitates, and filtering out the precipitates to obtain an extracting solution a;
B. MCI decoloration: loading the extracting solution a on an MCI column, collecting effluent liquid, and concentrating under reduced pressure to obtain extract b;
C. silica gel column chromatography: dissolving the extract b with acetone or methanol which is 1.5-3 times of the weight of the extract b, performing silica gel column chromatography, loading the silica gel into a column with 160-200 meshes, using the amount of the silica gel which is 6-10 times of the weight of the extract b, performing gradient elution by using a chloroform-acetone mixed organic solvent with the volume ratio of 1: 0-0: 1, collecting gradient eluent, concentrating, monitoring by TLC, and combining the same parts;
D. high performance liquid chromatography separation: and (3) separating and purifying the eluent obtained by gradient elution with a chloroform-acetone mixed organic solvent of 9:1 by high performance liquid chromatography to obtain the target anthraquinone compound with antibacterial activity.
3. The method according to claim 2, wherein the organic solvent in step A is an aqueous solution of acetone with a concentration of 70 to 100% by volume, an aqueous solution of ethanol with a concentration of 70 to 100% by volume, or an aqueous solution of methanol with a concentration of 70 to 100% by volume.
4. The preparation method according to claim 2, wherein in the step C, before the extractum is subjected to silica gel column chromatography, acetone or methanol which is 1.5-3 times of the weight of the extractum b is used for dissolving, then 80-100 mesh silica gel which is 0.8-1.2 times of the weight of the extractum b is used for mixing, and then the mixture is subjected to silica gel column chromatography.
5. The method according to claim 2, wherein the chloroform-acetone mixed organic solvent in step C is prepared in a step ratio of 20:1, 9:1, 8:2, 7:3, 6:4, and 1: 1.
6. The preparation method according to claim 2, wherein the high performance liquid chromatography separation and purification in step D is performed by taking 55-65% methanol aqueous solution by volume concentration as a mobile phase, flowing at 15-25 mL/min, using a 21.2 × 250 mm, 5 μm Zorbax prep ph t GF reverse phase preparation column as a stationary phase, detecting at 403 nm by an ultraviolet detector, feeding 0.5-1.0 mL each time, collecting 30-45 min chromatographic peaks, accumulating for multiple times, and evaporating to dryness.
7. Use of an anthraquinone compound having antibacterial activity according to claim 1, in the preparation of an antibacterial product.
8. An application of anthraquinone compounds with antibacterial activity according to claim 7, characterized by that said antibacterial activity is that it has antibacterial activity for propionibacterium, staphylococcus, corynebacterium, bacillus, pseudomonas, malassezia furfur, malassezia inactive or malassezia pachydermatis, and its inhibition rate is above 82.5%.
9. Use of an anthraquinone compound having antibacterial activity according to claim 7 or 8, wherein the antibacterial product is a daily chemical product.
10. An application of anthraquinone compounds with antibacterial activity according to claim 9, wherein said daily chemical products are shampoos with itch-relieving efficacy, and the formulations of said shampoos with itch-relieving efficacy are as follows: 4-6% of Tween-60, 10-15% of amino acid surfactant, 3-5% of coconut oil thickening foaming agent, 3-5% of amino acid humectant, 1-2% of chitosan fibroin protein, 2-3% of water-soluble olive ester, 2.5-3.5% of pullulan, 0.5-1% of 2- (2-hydroxypropyl) -3, 6-dimethoxy-5-methylanthraquinone, 0.8-2% of vegetable essential oil (or essence), 0.5-1% of vitamin B5, and the balance of water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173843A (en) * | 2021-05-19 | 2021-07-27 | 云南民族大学 | Tobacco black shank resistant active compound and preparation method and application thereof |
| CN114736110A (en) * | 2022-05-10 | 2022-07-12 | 云南中烟工业有限责任公司 | Anthraquinone compound, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603525A (en) * | 2012-01-05 | 2012-07-25 | 中国海洋大学 | Anthraquinone derivative, as well as preparation method and application of anthraquinone derivative serving as antibacterial agent |
| CN106966888A (en) * | 2017-04-28 | 2017-07-21 | 云南民族大学 | A kind of preparation method and application of the novel anthraquinone analog compound with activity of resisting tobacco mosaic virus |
| CN107011143A (en) * | 2017-05-05 | 2017-08-04 | 云南民族大学 | The preparation method and application of two kinds of anthraquinone analog compounds |
| CN107032976A (en) * | 2017-05-18 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of anthraquinone analog compound with antioxidation activity and its preparation method and application |
| CN107129428A (en) * | 2017-05-18 | 2017-09-05 | 云南中烟工业有限责任公司 | A kind of anthraquinone analog compound and its preparation method and application |
| CN111533720A (en) * | 2020-05-09 | 2020-08-14 | 云南中烟工业有限责任公司 | Pyranolide compound, preparation method thereof, additive containing pyranolide compound and application of pyranolide compound |
-
2021
- 2021-05-19 CN CN202110547989.8A patent/CN113200840A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603525A (en) * | 2012-01-05 | 2012-07-25 | 中国海洋大学 | Anthraquinone derivative, as well as preparation method and application of anthraquinone derivative serving as antibacterial agent |
| CN106966888A (en) * | 2017-04-28 | 2017-07-21 | 云南民族大学 | A kind of preparation method and application of the novel anthraquinone analog compound with activity of resisting tobacco mosaic virus |
| CN107011143A (en) * | 2017-05-05 | 2017-08-04 | 云南民族大学 | The preparation method and application of two kinds of anthraquinone analog compounds |
| CN107032976A (en) * | 2017-05-18 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of anthraquinone analog compound with antioxidation activity and its preparation method and application |
| CN107129428A (en) * | 2017-05-18 | 2017-09-05 | 云南中烟工业有限责任公司 | A kind of anthraquinone analog compound and its preparation method and application |
| CN111533720A (en) * | 2020-05-09 | 2020-08-14 | 云南中烟工业有限责任公司 | Pyranolide compound, preparation method thereof, additive containing pyranolide compound and application of pyranolide compound |
Non-Patent Citations (4)
| Title |
|---|
| PAL TARASANKAR等: "Selective hydroxymethylation of emodin", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
| PAL TARASANKAR等: "Selective hydroxymethylation of emodin", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 64, no. 12, 31 December 1991 (1991-12-31), pages 3755 - 3757 * |
| ZHOU MIN等: "Three new anthraquinones from the twigs of Cassia fistula and their bioactivities", 《JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH》 * |
| ZHOU MIN等: "Three new anthraquinones from the twigs of Cassia fistula and their bioactivities", 《JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH》, vol. 19, no. 11, 2 February 2017 (2017-02-02), pages 1073 - 1078 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173843A (en) * | 2021-05-19 | 2021-07-27 | 云南民族大学 | Tobacco black shank resistant active compound and preparation method and application thereof |
| CN113173843B (en) * | 2021-05-19 | 2022-08-09 | 云南民族大学 | Tobacco black shank resistant active compound and preparation method and application thereof |
| CN114736110A (en) * | 2022-05-10 | 2022-07-12 | 云南中烟工业有限责任公司 | Anthraquinone compound, preparation method and application thereof |
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