CN113402392B - P-coumarate and synthetic method and application thereof - Google Patents
P-coumarate and synthetic method and application thereof Download PDFInfo
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- CN113402392B CN113402392B CN202110721177.0A CN202110721177A CN113402392B CN 113402392 B CN113402392 B CN 113402392B CN 202110721177 A CN202110721177 A CN 202110721177A CN 113402392 B CN113402392 B CN 113402392B
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—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
- C07C69/73—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
- 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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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/06—Preservation of finished products
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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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
- A23L3/3517—Carboxylic acid esters
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
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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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Abstract
The invention discloses p-coumarate and a synthesis method and application thereof. The method comprises the following steps: adding methyl p-coumarate, alcohols and a catalyst into a solvent, uniformly mixing to obtain a mixed solution, and heating in an oscillating state to react to obtain the p-coumarate. The transesterification method adopts enzymatic transesterification reaction in a nonaqueous phase system, overcomes the obvious defects of poor selectivity, high reagent toxicity, harsh conditions and the like of the traditional chemical catalysis, maintains and enhances the activity, has mild conditions, high selectivity, simple operation, relatively high yield, shortens the reaction time and has good application prospect.
Description
Technical Field
The invention belongs to the field of research and development of food additives, and particularly relates to p-coumarate and a synthesis method and application thereof.
Background
P-coumaric acid (PCA) is a vegetable phenolic acid widely found in fruits and vegetables, such as apples, grapes, citrus, spinach and cereals, and is also abundant in some traditional Chinese medicines. It has rich bioactivity, including scavenging free radicals, inhibiting lipid peroxidation, protecting body from oxidative heart injury, and resisting inflammation. However, the hydrophilicity of coumaric acid is reported to be a serious disadvantage, thus limiting their antioxidant effect in fat and oil systems. To overcome this limitation, the addition of aliphatic side chain groups to phenolic acids by esterification has been reported to demonstrate the enhanced antioxidant activity of phenolic acids after modification, thereby producing valuable phenolic lipids with potential emulsifying action, improving antioxidant properties.
To date, it has been reported that the acylation of phenolic acid is mostly achieved through chemical catalysis or biological catalysis, but the traditional chemical catalysis has obvious defects of poor selectivity, high reagent toxicity, harsh conditions and the like. As is known, the enzyme catalysis can overcome the shortcomings of chemical catalysis, and has the obvious advantages of environmental friendliness, less side effects, high selectivity and the like.
The antioxidant capacity of phenolic acids in general has been well documented, and in particular in lipophilic systems, has a significant antioxidant capacity for coumaric acid, comparable to BHA/BHT. Meanwhile, many reports indicate that the effect of phenolic acid as an antioxidant is enhanced by esterification. Immobilized lipase is one of the most commonly used enzymes for synthesizing various phenolic esters. In this context, the stability and antioxidant activity of the modified compounds, in particular of the oil and fat system, can be substantially increased by enzymatically catalyzing p-coumaric acid of different chain lengths.
According to the prior report, the esterification reaction efficiency of phenolic acid and fatty alcohol is very low, and the transesterification reaction can not only increase the solubility of a substrate, but also replace the p-coumaric acid by the low-carbon fatty alcohol of the p-coumaric acid, so that the generated low-level alcohol is easy to volatilize or directly remove through a molecular sieve, thereby facilitating the continuous progress of the enzymatic reversible reaction, and simultaneously eliminating the inhibition effect of water generated in the direct esterification process on the enzyme activity, thereby shortening the reaction time and improving the reaction efficiency. The lipase-catalyzed transesterification synthesis method using lower alkyl esters of p-coumaric acid and octanol has not been reported yet.
Cao Jiankang et al research on the application of coumarate derivatives in fruit and vegetable sterilization and preservation agents (CN 107927149B), and found that the fruit and vegetable sterilization and preservation agents added with the coumarate derivatives can effectively inhibit infection of pathogenic bacteria so as to inhibit postharvest diseases of fruits and vegetables, are harmless to human health and free from causing environmental pollution, have high food safety, and can be used as substitutes of traditional synthetic bactericides and chemical preservatives; however, the traditional chemical catalytic synthesis method has the problems of poor selectivity, more byproducts, low efficiency and the like, so that the search for an efficient biocatalysis synthesis method is very necessary.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide p-coumarate and a synthesis method and application thereof.
The invention provides a method for synthesizing p-coumarate, which is a safer additive process for food synthesis by using a biocatalysis method, in particular to a method for synthesizing p-coumarate by transesterification based on nonaqueous phase lipase.
The object of the invention is achieved by at least one of the following technical solutions.
The invention aims at overcoming the defects and the defects of the application of the p-coumaric acid, and provides a method for synthesizing the p-coumaric acid octyl ester by transesterification based on nonaqueous phase lipase for realizing efficient obtaining of the p-coumaric acid octyl ester.
The structural general formula of the p-coumarate provided by the invention is shown as follows:
The p-coumarate provided by the invention is one of butyl p-coumarate, hexyl p-coumarate, octyl p-coumarate, decyl p-coumarate and lauric p-coumarate.
The invention provides a method for synthesizing p-coumarate, which comprises the following steps:
adding methyl p-coumarate, alcohols and a catalyst into a solvent, uniformly mixing to obtain a mixed solution, and heating in an oscillating state to react to obtain the p-coumarate.
Further, the alcohol is one of n-butanol, n-hexanol, n-octanol, decanol and lauryl alcohol.
Further, the catalyst is lipase.
Preferably, the lipase is lipase Novozyme435.
Further, the solvent is a mixture of pyridine and cyclohexane.
Further, the volume ratio of the pyridine to the cyclohexane is 5:5-1:9;
further preferably, the volume ratio of pyridine to cyclohexane is 1:9.
Further, the mass ratio of the p-coumarate methyl ester to the alcohol is 1:1-1:20;
preferably, the mass ratio of methyl p-coumarate to alcohols is 1:10.
Further, in the mixed solution, the concentration of the catalyst is 20mg/ml to 80mg/ml, and the concentration of the p-coumaric acid methyl ester is 20 mu M to 200 mu M;
preferably, the concentration of the catalyst in the mixed solution is 40mg/ml.
Preferably, the concentration of methyl p-coumarate in the mixed solution is 20 μm.
Further, the rotation speed of the vibration is 150-200 rpm, the reaction temperature is 20-70 ℃, and the reaction time is 24-96 h.
Preferably, the rotation speed of the oscillation is 180rpm, the temperature of the reaction is 50 ℃, and the reaction time is 72 hours.
The p-coumarate provided by the invention can be applied to antioxidation treatment in emulsion or grease.
The method of the invention is to use pyridine: cyclohexane is used as a reaction medium in a ratio of 1:9, lipase is used as a catalyst, and the catalyst is prepared by reacting methyl p-coumarate and octanol in a pyridine and cyclohexane system. The method overcomes the obvious defects of poor selectivity, high reagent toxicity, harsh conditions and the like of the traditional chemical method, greatly improves the solubility of the substrate and the enzymatic reaction efficiency, is simple and convenient to operate, and is easy to prepare a large amount of high-purity products.
The synthesis method provided by the invention is a method for synthesizing octyl p-coumarate by transesterification based on nonaqueous phase lipase. The method takes a mixed solution of pyridine and cyclohexane as a reaction medium, takes lipase as a catalyst, and prepares a product by reacting methyl p-coumarate and octanol in a pyridine and cyclohexane system.
The synthesized p-coumaric acid fatty alcohol ester comprises: butyl p-coumarate, hexyl p-coumarate, octyl p-coumarate, decyl p-coumarate, lauric p-coumarate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The method is prepared by transesterification in the synthesis process of the octyl coumarate, so that the solubility and conversion rate of the substrate are greatly improved, the reaction conversion rate can reach more than 90%, the defects of poor selectivity, more byproducts and the like in the traditional chemical synthesis are overcome, the defect of low conversion rate in the traditional direct esterification reaction is overcome, the operation is simple, and the method is easier to prepare a large amount of high-purity products.
(2) The method has few byproducts in the whole reaction process, is favorable for product separation, is convenient for industrial continuous production, and has good market application prospect.
Drawings
FIG. 1 is a flow chart of a synthesis reaction according to an embodiment of the present invention.
FIGS. 2a and 2b are, respectively, high performance liquid chromatograms and nuclear magnetic chromatograms of methyl p-coumarate synthesized in example 1;
FIGS. 3a and 3b are, respectively, high performance liquid chromatograms and nuclear magnetic chromatograms of hexyl p-coumarate synthesized in example 2;
FIGS. 4a and 4b are, respectively, high performance liquid chromatograms and nuclear magnetic patterns of octyl p-coumarate synthesized in example 3;
FIGS. 5a and 5b are, respectively, high performance liquid chromatograms and nuclear magnetic chromatograms of decyl p-coumarate synthesized in example 4;
FIGS. 6a and 6b are, respectively, high performance liquid chromatograms and nuclear magnetic chromatograms of lauryl p-coumarate synthesized in example 5;
FIG. 7 is a graph showing the change in absorbance of the beta-carotene-linoleic acid system after addition of various p-coumaric acid derivatives in example 6;
FIG. 8 is a graph showing the effect of various antioxidants on corn oil induction time in example 7.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but are not intended to limit the practice and protection of the invention. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
The HPLC method is used for detecting the p-coumarate which is an enzymatic synthesis product in the implementation process of the invention. The reaction mixture was subjected to high performance liquid chromatography using a (5 μm) ZorbaxSB-C18 column (4.6 mm. Times.250 mm) and a Waters2996 UV/photodiode array detector at 308 nm. The mobile phase adopts a mixture of methanol and water (85:15 v/v), the flow rate is 0.9mL/min, the detection wavelength is 308nm, and the sample injection amount is 20 mu L.
The method for calculating the conversion rate and the yield of the product to coumarate comprises the following steps:
example 1
Referring to fig. 1, methyl p-coumarate is used as a reaction substrate, the reaction is carried out in a 40ml system, methyl p-coumarate is butanol=1:10 (mass ratio), lipase Novozym435 is added in an amount of 1600mg/ml, and the reaction medium is pyridine: cyclohexane is prepared into a reaction system according to the volume ratio of 1:9, the oscillation speed is 180rpm at 50 ℃, and the reaction is carried out for 72 hours, so that a reaction liquid is obtained, wherein p-coumarate is contained in the reaction liquid. After the reaction is finished, the reaction liquid sample is detected by HPLC, the retention time is 5.057min, the product is p-coumarate methyl ester, the conversion rate is 98.69%, and the yield is 85.7%. Fig. 2a and 2b are high performance liquid chromatograms and nuclear magnetic resonance chromatograms of butyl p-coumarate synthesized in example 1, respectively.
Example 2
Methyl p-coumarate is used as a reaction substrate, a 40ml system is adopted for reaction, and the addition amount of lipase Novozym435 is 800mg/ml according to the mass ratio of methyl p-coumarate to hexanol=1:8, and the reaction medium pyridine: cyclohexane is prepared into a reaction system according to the volume ratio of 2:8, the oscillation speed is 180rpm at 40 ℃, and the reaction is carried out for 36 hours, so that a reaction liquid is obtained, wherein p-coumarate is contained in the reaction liquid. After the reaction is finished, the reaction liquid sample is detected by HPLC, the retention time is 7.456min, the product is hexyl p-coumarate, the conversion rate is 91.26%, and the yield is 82.19%. Fig. 3a and 3b are respectively high performance liquid chromatograms and nuclear magnetic resonance chromatograms of butyl p-coumarate synthesized in example 2.
Example 3
Methyl p-coumarate is used as a reaction substrate, a 40ml system is adopted for reaction, and the addition amount of lipase Novozym435 is 1200mg/ml according to the mass ratio of methyl p-coumarate to octanol=1:12, and the reaction medium pyridine: cyclohexane is prepared into a reaction system according to a volume ratio of 3:7, and the reaction is carried out for 96 hours at 40 ℃ with an oscillating rotation speed of 180rpm, so as to obtain a reaction liquid, wherein p-coumarate is contained in the reaction liquid. After the reaction is finished, the reaction liquid sample is detected by HPLC, the retention time is 12.302min, the product is octyl p-coumarate, the conversion rate is 96.57%, and the yield is 83.4%. Fig. 4a and 4b are respectively high performance liquid chromatograms and nuclear magnetic resonance chromatograms of butyl p-coumarate synthesized in example 3.
Example 4
Methyl p-coumarate is used as a reaction substrate, a 40ml system is adopted for reaction, and the addition amount of lipase Novozym435 is 1600mg/ml according to the mass ratio of methyl p-coumarate to decanol=1:15, and the reaction medium pyridine: cyclohexane is prepared into a reaction system according to the volume ratio of 2:8, the oscillation speed is 180rpm at 60 ℃, and the reaction is carried out for 24 hours, so that a reaction liquid is obtained, wherein p-coumarate is contained in the reaction liquid. After the reaction is finished, the reaction liquid sample is detected by HPLC, the retention time is 22.121min, the product is decyl p-coumarate, the conversion rate is 95.22%, and the yield is 83.1%. Fig. 5a and 5b show high performance liquid chromatograms and nuclear magnetic resonance spectra of butyl p-coumarate synthesized in example 4.
Example 5
Methyl p-coumarate is used as a reaction substrate, a 40ml system is adopted for reaction, and the addition amount of lipase Novozym435 is 2000mg/ml according to the mass ratio of methyl p-coumarate to laurinol=1:20, and the reaction medium pyridine: cyclohexane is prepared into a reaction system in a volume ratio of 5:5, and the reaction is carried out for 72 hours at 45 ℃ with an oscillating rotation speed of 180rpm, so as to obtain a reaction liquid, wherein p-coumarate is contained in the reaction liquid. After the reaction is finished, the reaction liquid sample is detected by HPLC, the retention time is 42.083min, the product is p-coumarate lauryl ester, the conversion rate is 91.23%, and the yield is 81.7%. Fig. 6a and 6b are respectively high performance liquid chromatograms and nuclear magnetic resonance chromatograms of butyl p-coumarate synthesized in example 5.
Example 6
Antioxidant application assays were performed on examples 1-5 using a carotene-linoleic acid antioxidant model system. The measuring method comprises the following steps:
2.0mg of carotene was dissolved in 10mL of chloroform to prepare a carotene solution. Then transferring one milliliter of carotene solution into a round-bottom flask, vacuumizing to remove chloroform, and then adding 20mg of purified linoleic acid, 200mg of Tween40 emulsifier and 50mL of aerated distilled water into the flask on a rotary evaporator at 40 ℃ to obtain emulsion by shaking uniformly; then, the prepared emulsion (4.9 mL of each part) is respectively added into a butyl p-coumarate solution, a hexyl p-coumarate solution, a octyl p-coumarate solution, a decyl p-coumarate solution, a lauryl p-coumarate solution, a BHA (butyl hydroxy anisole) solution and absolute ethyl alcohol (serving as a control group) for comparison, the volumes of the solutions and the absolute ethyl alcohol are 0.1mL, and the solutions are uniformly mixed to obtain mixed solutions of different groups. The compositions are respectively a butyl p-coumarate group, a hexyl p-coumarate group, a octyl p-coumarate group, a decyl p-coumarate group, a lauryl p-coumarate group, a BHA group and a control group. The concentration of butyl p-coumarate in the mixed solution of butyl p-coumarate group was 0.2mM, the concentration of hexyl p-coumarate in the mixed solution of hexyl p-coumarate group was 0.2mM, the concentration of octyl p-coumarate in the mixed solution of octyl p-coumarate group was 0.2mM, the concentration of decyl p-coumarate in the mixed solution of decyl p-coumarate group was 0.2mM, the concentration of lauryl p-coumarate in the mixed solution of lauryl p-coumarate group was 0.2mM, the concentration of BHA in the mixed solution of BHA group was 0.2mM, and the concentration of absolute ethanol in the mixed solution of control group was 0.2mM.
After the emulsion was added to each tube, the volume of solution per tube was 5mL and the absorbance was read at 470nm for zero time. The samples were stored in a water bath at 50 ℃ and subsequent absorbance readings were recorded every 15 minutes until the visual color of the carotene in the control sample containing 0.2mM absolute ethanol disappeared (about 120 minutes).
FIG. 7 is a graph showing the change in absorbance of the beta-carotene-linoleic acid system after addition of various p-coumaric acid derivatives. As can be seen from fig. 7, the lauryl p-coumarate showed a better antioxidant activity in the linoleic acid emulsion system, and the lipid peroxidation rate was 82.7%, which is superior to that of BHA group. At the same concentration, BHA has an antioxidant rate of only 69.8% for linoleic acid emulsion. In the process of autoxidation of linoleic acid emulsion without PCA (p-coumaric acid) and its derivatives or standard compounds, the peroxide content is rapidly increased, which shows that the oxidation induction period of p-coumaric acid is prolonged and the oxidation resistance is greatly improved after long-chain alcohol is introduced. This is probably due to the fact that the lauryl p-coumarate, after having been incorporated into the long chain alkyl group, is able to penetrate into the molecular layer and further combine with the free radicals to form a stable product, preventing chain transfer of the free radicals when linoleic acid peroxidation occurs and thus achieving a stronger antioxidant activity.
Example 7
The antioxidant effect of decyl p-coumarate and lauryl p-coumarate synthesized in examples 4 to 5 in corn oil was verified. The Racimart method is adopted, the condition is that the temperature is 135 ℃, the air flow is set to 25L/h, the conventional Switzerland Metrohm743Rancimat grease oxidation stability tester is adopted for testing, and the testing principle is as follows: and (3) introducing dry air into the grease at constant temperature at constant speed, oxidizing substances which are easy to oxidize in the grease into micromolecule volatile acid, introducing the volatile acid into a conductivity measuring pool containing water by air, measuring the conductivity in the measuring pool on line, recording an oxidation curve of the conductivity to the reaction time, and obtaining a second derivative of the curve, thereby measuring the induction time of the sample.
Taking commercial corn oil, equally dividing 6 parts, adding 5 mug of samples to be tested into each 2g part, and uniformly stirring to form 6 groups of test objects; the samples to be tested are BHA (butyl hydroxy anisole), BHT (2, 6-di-tert-butyl p-cresol), TBHQ (tert-butyl hydroquinone), p-coumaric acid laurate, p-coumaric acid decyl ester and p-coumaric acid respectively;
FIG. 8 is a graph showing the effect of various antioxidants on corn oil induction time in example 7. As can be seen from fig. 8, the induction times of the addition of BHA, BHT, TBHQ, p-coumaric acid laurate, and p-coumaric acid decate to the oxidative rancidity of corn oil were 3.6h, 2.2h, 3.7h, 3.1h, 5.1h, and 4.4h, respectively. It can be seen that the induction time of lauryl p-coumarate to corn oil was 5.1h, followed by decyl p-coumarate, TBHQ, BHA, PCA and BHT. BHT has comparatively lowest antioxidant activity in corn oil and induction time of 2.2h, indicating that the BHT has more excellent grease antioxidant property on lauryl coumarate.
The embodiments given above are preferred examples for realizing the present invention, and the present invention is not limited to the above-described embodiments. Any immaterial additions and substitutions made by those skilled in the art according to the technical features of the technical scheme of the invention are all within the protection scope of the invention. The above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.
Claims (4)
1. A method for synthesizing p-coumarate, which is characterized by comprising the following steps:
adding methyl p-coumarate, alcohols and a catalyst into a solvent, uniformly mixing to obtain a mixed solution, and heating in an oscillating state to react to obtain the p-coumarate;
the alcohol is one of n-butanol, n-hexanol, n-octanol, decanol and lauryl alcohol;
the catalyst is lipase;
the solvent is a mixture of pyridine and cyclohexane; the volume ratio of the pyridine to the cyclohexane is 5:5-1:9.
2. The method for synthesizing p-coumarate according to claim 1, wherein the lipase is lipase Novozyme435.
3. The method for synthesizing p-coumarate according to claim 1, wherein the mass ratio of the p-coumarate to the alcohol is 1:1-1:20; in the mixed solution, the concentration of the catalyst is 20 mg/ml-80 mg/ml, and the concentration of the p-coumaric acid methyl ester is 20 uM-200 uM.
4. The method for synthesizing p-coumarate according to claim 1, wherein the rotation speed of the oscillation is 150-200 rpm, the reaction temperature is 20-70 ℃, and the reaction time is 24-96 h.
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