Copper vanillate as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic copper, and particularly relates to copper vanillate as well as a preparation method and application thereof. The invention provides copper vanillate. The chemical formula of the copper vanillate is Cu2 (C8H7O4) 4 (H2O) 2. Copper and vanillic acid are combined to obtain copper vanillate, the multi-component structure can interact with several target positions in bacteria, and the risk of drug-resistant gene enrichment is effectively reduced. Meanwhile, copper and vanillic acid are combined to form copper vanillate, the bioavailability of copper can be improved, copper vanillate has excellent antioxidant activity, broad-spectrum antibacterial activity and excellent antibacterial performance, and organic copper can release Cu < 2 + > under different pH values, so that the risk that Cu induces toxicity can be effectively reduced. The preparation method of the copper vanillate is mild in reaction condition, capable of reacting at room temperature, simple to operate and suitable for large-scale production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic copper, and specifically relates to copper vanillate and a preparation method and application thereof. Background Art

[0002] Traditional inorganic metal compounds CuSO4 are often used as antibacterial agents. For example, 0.5-2.0 mg / L CuSO4 is often used as a fungicide, algaecide and insecticide in aquaculture. When CuSO4 is used as an algaecide, the dosage is 10-40 times the safety range for aquatic animals. When CuSO4·5H2O is added to the water, aquatic animals are exposed to excessive Cu. 2+ It activates the intestinal antioxidant system and inflammatory response, while reducing the composition and structure of the intestinal microbiota, inhibiting the abundance of probiotics, and promoting the growth of intestinal pathogens, thereby reducing the growth performance and survival rate of aquatic animals.

[0003] CuSO4 has high water solubility, resulting in Cu 2+ Too fast release increases the virulence of pathogens and induces the formation of biofilms to accelerate infection; and aquatic animals generally pass free Cu in water. 2+ It is reported that continuous use of CuSO4 may increase bacterial sensitivity to Cu. 2+ of drug resistance. Summary of the invention

[0004] In view of this, the object of the present invention is to provide copper vanillate and its preparation method and application. The copper vanillate of the present invention has good antioxidant and antibacterial effects, and can effectively reduce the risk of drug resistance gene enrichment.

[0005] The invention provides copper vanillate, the chemical formula of which is Cu2(C8H7O4)4(H2O)2.

[0006] The present invention also provides a method for preparing copper vanillate described in the above technical solution, comprising the following steps:

[0007] A solution containing vanillic acid and a copper source containing copper ions are mixed to react, and solid-liquid separation is performed to obtain copper vanillate.

[0008] Preferably, the solvent of the vanillic acid-containing solution is an aqueous solution of alcohol, and the volume fraction of alcohol in the aqueous solution of alcohol is 25-35%.

[0009] Preferably, the concentration of vanillic acid in the vanillic acid-containing solution is 0.01 to 0.03 g / mL.

[0010] Preferably, the copper source includes an insoluble copper source and a soluble copper source, the insoluble copper source includes one or more of copper oxide, copper hydroxide and basic copper carbonate, and the soluble copper source includes one or more of copper chloride, copper nitrate and copper sulfate.

[0011] Preferably, when the copper source is a soluble copper source, the step of adjusting the pH value of the solution containing vanillic acid to 6-9 before mixing is further included; and the copper source is used in the form of a copper source aqueous solution.

[0012] Preferably, the concentration of the copper source aqueous solution is 0.05-0.2 mol / L.

[0013] Preferably, the molar ratio of the vanillic acid to the copper ions in the copper source is (1-3):1.

[0014] Preferably, the reaction temperature is 20-70° C. and the reaction time is 0.5-3 h.

[0015] The present invention also provides the use of the copper vanillate described in the above technical solution or the copper vanillate obtained by the above preparation method in anti-oxidation or antibacterial.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention provides copper vanillate, the chemical formula of which is Cu2(C8H7O4)4(H2O)2. The present invention combines copper with vanillic acid to obtain copper vanillate. This multi-component structure can interact with several target locations in bacteria (such as cell walls and cell membranes), effectively reducing the risk of drug resistance gene enrichment. At the same time, copper combines with vanillic acid to form copper vanillate, which can improve the bioavailability of copper. Copper vanillate has excellent antioxidant activity and broad-spectrum antibacterial activity, excellent antibacterial performance, and this organic copper can control the release of Cu at different pH values. 2+ , which can effectively reduce the risk of Cu-induced toxicity.

[0018] The present invention also provides a method for preparing copper vanillate described in the above technical solution, which has mild reaction conditions, can react at room temperature, is simple to operate, and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0020] Figure 1FTIR spectra of VA and VA-Cu obtained in Example 1, wherein (i) is VA and (ii) is VA-Cu;

[0021] Figure 2 The Raman spectra of VA and VA-Cu obtained in Example 1, (i) is VA, (ii) is VA-Cu;

[0022] Figure 3 This is the thermal decomposition diagram of VA-Cu obtained in Example 1 under air atmosphere;

[0023] Figure 4 The simulated PXRD patterns of VA-Cu powder and crystal obtained in Example 1;

[0024] Figure 5 This is a schematic diagram of the structure of VA-Cu obtained in Example 1;

[0025] Figure 6 The morphology and microstructure of VA-Cu obtained in Example 1, wherein (a) the powder prepared in Example 1; (b) the SEM image of VA-Cu powder; (c-d) the SEM images of VA-Cu sea urchin-like crystals;

[0026] Figure 7 The effect of different concentrations of VA-Cu on ABTS + Clearing effect;

[0027] Figure 8 The inhibition zones (unit: mm) after VA and VA-Cu treatment of bacteria, where (a) Gram-negative bacteria; (b) Gram-positive bacteria;

[0028] Fig. 9 The colony growth of indicator strains after treatment with different concentrations of VA-Cu for 24 hours. DETAILED DESCRIPTION

[0029] The invention provides copper vanillate, the chemical formula of which is Cu2(C8H7O4)4(H2O)2.

[0030] The copper vanillate of the present invention has good anti-oxidation and antibacterial effects.

[0031] The present invention also provides a method for preparing copper vanillate described in the above technical solution, comprising the following steps:

[0032] A solution containing vanillic acid and a copper source containing copper ions are mixed to react, and solid-liquid separation is performed to obtain copper vanillate.

[0033] In the present invention, unless otherwise specified, the materials and equipment used are commercially available products in the art.

[0034] In the present invention, the solvent of the vanillic acid-containing solution is preferably an alcohol aqueous solution, and the volume fraction of alcohol in the alcohol aqueous solution is preferably 25-35%, more preferably 30%; the alcohol in the alcohol aqueous solution preferably includes ethanol or methanol.

[0035] In the present invention, the concentration of vanillic acid in the vanillic acid-containing solution is preferably 0.01 to 0.03 g / mL, more preferably 0.02 g / mL.

[0036] In the present invention, the copper source preferably includes an insoluble copper source and a soluble copper source. The insoluble copper source preferably includes one or more of copper oxide, copper hydroxide and basic copper carbonate, and the soluble copper source preferably includes one or more of copper chloride, copper nitrate and copper sulfate.

[0037] When the copper source is preferably copper oxide, copper hydroxide and basic copper carbonate, the reaction formulas are respectively as shown below:

[0038] 4C8H8O4+2CuO→[Cu2(C8H7O4)4(H2O)2]

[0039] 4C8H8O4+2Cu(OH)2→[Cu2(C8H7O4)4(H2O)2]+2H2O

[0040] 4C8H8O4+Cu2(OH)2CO3→[Cu2(C8H7O4)4(H2O)2]+H2O+CO2

[0041] When the copper source is preferably a soluble copper source, the mixing further includes adjusting the pH value of the solution containing vanillic acid before mixing. The pH value of the solution containing vanillic acid is preferably adjusted using potassium hydroxide solution or sodium hydroxide solution, and the concentration of the potassium hydroxide solution or sodium hydroxide solution is preferably 1 mol / L; the pH value of the solution after adjustment is preferably 6 to 9, more preferably 6.5 to 8.5, specifically 6.5, 7, 7.5, 8 or 8.5, and vanillic acid reacts with alkali to form a salt during the pH adjustment process; the pH value of the present invention has a high yield of copper vanillate. The copper source is preferably used in the form of a copper source aqueous solution, and the concentration of the copper source aqueous solution is preferably 0.05 to 0.2 mol / L, more preferably 0.1 mol / L. The present invention preferably slowly adds the copper source aqueous solution to the solution containing vanillic acid, and the rate of slow addition is preferably 2 mL / min. The reaction formula of the reaction is shown below:

[0042] OH-+C8H8O4→C8H7O4 - +H2O

[0043] 4C8H7O4 - +2Cu 2++2H2O→[Cu(C8H7O4)4(H2O)2]

[0044] In the present invention, the molar ratio of the vanillic acid to the copper ions in the copper source is preferably (1-3):1, more preferably (1.5-2.8):1, specifically 1.5:1, 1.8:1, 2:1, 2.1:1, 2.2:1 or 2.5:1. The molar ratio of the present invention has a high yield of copper vanillate.

[0045] In the present invention, the reaction is preferably carried out under stirring; the reaction temperature is preferably 20-70°C, more preferably 25-60°C, specifically 30°C, 35°C, 40°C, 50°C, 55°C or 60°C; the reaction time is preferably 0.5-3h, more preferably 0.5-2.5h, specifically 1h, 1.5h, 2h or 2.5h. The reaction temperature and time of the present invention have a high yield of copper vanillate.

[0046] In the present invention, the solid-liquid separation method is preferably filtration, and after the solid-liquid separation, it is preferably further included: washing and drying the obtained solid; the washing reagent is preferably water; the drying is preferably forced air drying, the drying temperature is preferably 40 to 80°C, more preferably 50 to 70°C, and the drying time is preferably 6 to 24 hours, more preferably 8 to 12 hours.

[0047] The present invention also provides the use of the copper vanillate described in the above technical solution or the copper vanillate obtained by the above preparation method in anti-oxidation or antibacterial.

[0048] The copper vanillate of the present invention has good antioxidant effect and antibacterial performance, and can reduce the bacterial cell to Cu 2+ tolerance.

[0049] In order to further illustrate the present invention, the copper vanillate and its preparation method and application provided by the present invention are described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0050] Examples 1 to 7

[0051] According to the reaction conditions shown in Table 1, vanillic acid copper (VA-Cu) was prepared:

[0052] (1) When the copper source is copper oxide, copper hydroxide and basic copper carbonate, the preparation steps are:

[0053] Vanillic acid (VA) was dissolved in a 30% volume fraction ethanol solution (concentration 0.02125 g / mL), stirred, solid copper source powder was added, and the reaction was stirred at a certain temperature to obtain a milky green precipitate. The precipitate was filtered, washed with water, and dried with air (drying temperature 50°C, time 8h) to obtain the product VA-Cu.

[0054] (2) When the copper source is copper chloride, copper nitrate and copper sulfate, the preparation steps are:

[0055] Vanillic acid (VA) was dissolved in 30% volume fraction ethanol solution (concentration 0.02125 g / mL), 1 mol / L potassium hydroxide solution was added to adjust the pH value, and the mixture was stirred. Then, a copper salt aqueous solution (concentration 0.1 mol / L) was slowly added (2 mL / min), and the reaction was stirred at a certain temperature to obtain a milky green precipitate. The precipitate was filtered, washed with water, and dried with air (drying temperature 50°C, time 8 h) to obtain the product VA-Cu.

[0056] Table 1 Reaction conditions of Examples 1 to 7

[0057]

[0058]

[0059] Note: The data in Table 1 are based on the reaction of 42.5 g of vanillic acid. The yield is obtained by multiplying the mass of the obtained product by the purity and then dividing it by the theoretical yield. The purity is the copper content of the obtained product divided by the theoretical copper content. The theoretical copper content is 15.28%.

[0060] Example 8

[0061] According to method (2) in Examples 1 to 7, copper vanillate (VA-Cu) was prepared according to the reaction conditions shown in Table 2:

[0062] Table 2 Reaction conditions of Example 8

[0063]

[0064]

[0065] When the VA:Cu molar ratio is greater than 2:1, the copper content tends to be stable. When the molar ratio is 1.5:1, the copper content is 15.09%, which is speculated to be due to the generation of impurities by side reactions. For economic considerations and to save raw material costs, the optimal molar ratio is selected as 2:1. Under this condition, the yield is 98.89% and the copper content is 15.26%, which is close to the theoretical copper content of 15.28%.

[0066] The reaction temperature has little effect on the yield and copper content of the product. When the reaction temperature is 30°C, the copper content is 15.28% and the yield is 97.99%. When the temperature continues to rise, the copper content of VA-Cu increases, reaching a maximum of 15.77%. This may be because as the temperature increases, side reactions also increase. At a certain temperature, VA will esterify with ethanol in the reaction solvent to form ethyl vanillate and chelate with metal ions through phenolic hydroxyl and o-methoxy groups.

[0067] The yield of VA-Cu increases with the increase of pH value. When the pH value is 7.5, the copper content of VA-Cu is 15.28% and the yield is 98.84%. As the pH value increases, the copper content begins to increase, and the product gradually changes from light green to dark green. On the one hand, the phenolic hydroxyl group of VA may participate in the complexation reaction after protonation under strong alkaline conditions. On the other hand, when the reaction pH is too high, Cu 2+ Copper hydroxide is generated under alkaline conditions.

[0068] As the reaction time increases, the yield first increases and then decreases. When the reaction time is 2h, the yield of VA-Cu reaches a maximum of 96.96%. If the reaction time is too long, the yield decreases and the copper content increases. When the reaction time is 3h, the copper content is 15.63%, which is greater than the theoretical copper content. Phenolic groups are easily oxidized under certain conditions and become semiquinone or quinone structures. It is inferred that the phenolic hydroxyl groups in VA are easily oxidized to benzoquinone when exposed to air for a long time.

[0069] Copper content test method:

[0070] The copper content in copper vanillate was determined by EDTA complexometric titration. 0.0500 g to 0.1000 g of the sample was accurately weighed in a conical flask, added to 20 mL of deionized water, 10.0 mL of ammonia-ammonium chloride buffer solution with a pH of ≈ 10, 2 drops of PAN indicator, shaken well, and titrated with 0.0100 mol / EDTA standard solution; preheated at 40 ° C, the solution color changed from blue to green at the titration endpoint; the metal content (ρ) was expressed as mass percentage (%) and calculated according to the following formula:

[0071]

[0072] In the formula: C------concentration of EDTA standard solution (mol / L); V------volume of EDTA standard solution used to titrate the sample (L); m------sample mass (g); M------mass in grams per mole of metal (g / mol), Cu is 63.55.

[0073] Results Characterization

[0074] The molecular structure of VA-Cu was analyzed by FTIR and Raman. Figure 1 The infrared absorption curves of VA (i) and VA-Cu (ii) obtained in Example 1 are shown in Table 1. VA is located at 3483 cm -1 The peak at 1679 cm is the stretching vibration absorption peak of phenolic hydroxyl group. -1 The C=O stretching vibration absorption peaks conjugated with the benzene ring are 1597, 1521 and 1431 cm -1It is the absorption peak of benzene ring skeleton, 1204cm -1 The OCO stretching vibration absorption peak of -OCH3 is 1108cm -1 The CO stretching vibration absorption peak of the carboxyl group is at 3465 cm. In contrast, the phenolic hydroxyl stretching vibration absorption peak of VA-Cu is red-shifted to 3465 cm -1 3535cm -1 The -OH stretching vibration peak of the coordinated water molecule is at 1573 cm-1. In addition, the C=O characteristic absorption peak of VA-Cu disappears, and the absorption peaks at 1573 cm-1, 1423 cm-1, and 1400 cm-1 are -1 The anti-stretching vibration of the carboxyl group appears at as (COO - ) and stretching vibration ν s (COO - ). At the same time, the CO stretching vibration absorption peak of VA-Cu carboxyl group blue-shifted to 1120 cm -1 , indicating that Cu may react with the protonated carboxyl group of VA. In addition, due to the introduction of Cu, the absorption vibration peak of the benzene ring skeleton of VA-Cu blue-shifted to 1604 cm -1 . Figure 2 Figure 2 is the Raman spectra of VA (i) and VA-Cu (ii) obtained in Example 1. Compared with VA, the C=O characteristic absorption peak in the Raman spectrum of VA-Cu disappears. In addition, the absorption peak at 361 cm -1 The peak is the Cu-O absorption vibration peak, indicating that VA and Cu are successfully coordinated.

[0075] The thermal stability of VA-Cu at 40-500°C in air atmosphere was further analyzed by thermogravimetric analyzer to evaluate the composition, thermal stability and degradation behavior of VA-Cu. Figure 3 This is the thermal decomposition diagram of VA-Cu obtained in Example 1 under air atmosphere. The first weight loss of VA-Cu in the range of 130-190°C is attributed to the coordinated water. The second weight loss occurs in the range of 200-250°C, which is due to the degradation of the remaining coordinated water and ligands, and the corresponding DTG peak is 231°C. The third weight loss occurs in the range of 250-316°C, and the corresponding DTG peak is 272°C. The final black component remaining after thermal decomposition of VA-Cu is CuO, with a residual amount of 18.98%, and the converted copper content is 15.16%. VA-Cu has characteristic diffraction peaks at 2θ values ​​of 8.87°, 10.02° and 12.27°, and the PXRD of crystal simulation is basically consistent with the PXRD of powdered VA-Cu prepared in Example 1 ( Figure 4 ), indicating the successful preparation of VA-Cu.

[0076] Figure 5 Schematic diagram of the structure of VA-Cu obtained in Example 1. Figure 6The morphology and microstructure of VA-Cu obtained in Example 1, wherein (a) the powder prepared in Example 1; (b) the SEM image of VA-Cu powder; (c-d) the SEM images of VA-Cu sea urchin-like crystals.

[0077] Application Examples

[0078] 1. Antioxidant test

[0079] Preparation of ABTS stock solution: weigh 0.0384 g ABTS and dilute to 10 mL volumetric flask with deionized water to obtain 7.0 mmol / L ABTS + Stock solution, weigh 0.0134g potassium persulfate and dilute to 10mL volumetric flask with deionized water, then add the prepared ABTS + The stock solution and potassium persulfate solution were mixed in equal volumes in a brown bottle and placed in a dark place at room temperature for 12 hours to generate ABTS. + · Before use, dilute ABTS 20 times with PBS buffer (pH = 7.4) + Working solution, ready for use. Accurately weigh 5 mg of VA and VA-Cu respectively into a 100 mL volumetric flask and dilute to volume with deionized water to prepare a 0.05 mg / mL sample solution. Pipette 200 μL, 300 μL, 400 μL, 500 μL, 600 μL, 700 μL, 800 μL, 900 μL, and 1 mL of the sample solution into a 15 mL centrifuge tube, and then fill to 5 mL with deionized water to prepare sample solutions of different concentrations, and then add 5 mL of ABTS + The working solution was shaken evenly and reacted in a shaker at 37°C, 200 r / min in the dark for 15 min. The absorbance of the product and ABTS was measured at 734 nm using a UV spectrophotometer. + The absorbance of the mixed solution is A i ; The absorbance A0 of the product mixed with blank solvent and 5mL deionized water and 5mL ABTS + Absorbance A after mixing the working solution j . Calculate the effects of VA and VA-Cu on ABTS by the following formula: + Free radical scavenging rate:

[0080]

[0081] 2. Antibacterial test

[0082] The antibacterial effect of VA-Cu was evaluated using standard strains of Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Vibrio alginolyticus (V. alginolyticus) and aquatic animal pathogen isolates of Aeromonas veronii (MS-A. veronii), Citrobacter freundii (MS-C. freundii), Streptococcus agalactiae (TM-S. agalactiae), Staphylococcus warneri (TM-S. warneri) and Vibrio parahaemolyticus (SV. parahaemolyticus) as experimental objects.

[0083] Test Results

[0084] Figure 7 The effect of different concentrations of VA-Cu on ABTS + ·Clearing effect.

[0085] Figure 7 It shows that VA-Cu has a great influence on ABTS + The free radical scavenging rate increases with the concentration. At a drug concentration of 3.5 mg / L, the scavenging rate of VA-Cu reached 93.90%, while the maximum scavenging rate of VA at 3.5 mg / L was only 81.79%. The EC of VA-Cu was obtained from the curve 50 is 1.70 mg / L. Similarly, the EC of VA 50 VA-Cu to ABTS + The cleaning effect is better than VA.

[0086] Figure 8 The inhibition zones of bacteria after VA and VA-Cu treatment (unit: mm): (a) Gram-negative bacteria; (b) Gram-positive bacteria.

[0087] The partial enlarged images of the inhibition zones of VA, CuSO4 and VA-Cu show that 1% DMSO as a solvent control did not show any inhibition zone. Figure 8 It can be observed that the CuSO4 treatment group showed multiple inhibition rings against E. coli, MS-A. veronii, V. alginolyticus, S. aureus, TM-S. agalactiae and TM-S. warneri, indicating that the antibacterial effect of CuSO4 is not long-lasting. Table 3 shows the results of the inhibition zone diameters of VA, VA-Cu and CuSO4 against 8 indicator bacteria. The results of the inhibition zone experiment showed that under the same Cu concentration, VA-Cu coordinated with Cu showed stronger antibacterial activity even if the drug was not fully diffused, indicating that VA reduced the bacterial cell's resistance to Cu. 2+ tolerance.

[0088] Table 3 Diameters of inhibition zones of VA, VA-Cu and CuSO4 against 8 indicator bacteria

[0089]

[0090] Fig. 9 The colony growth of the indicator strain after being treated with different concentrations of VA-Cu for 24 hours, and the MBC / MIC ratio are shown in Table 4:

[0091] Table 4 MIC and MBC of VA and VA-Cu against indicator strains (unit: mg / mL)

[0092]

[0093] Except for TM-S. agalactiae, the MIC of VA-Cu against the other 7 strains was lower than that of VA. The antibacterial activity was further evaluated based on the MBC / MIC ratio. When the MBC / MIC of a drug against a certain bacterium is ≤4, it can be judged as a bactericide, otherwise it is an antibacterial agent. The MBC / MIC ratios are shown in Table 4. VA and VA-Cu have bactericidal effects on all strains. Although the MIC of VA-Cu against TM-S. agalactiae and MS-C. freundii is relatively large, the MBC / MIC ratio is in the range of 1.5 to 2, and it still has a good bactericidal effect.

[0094] Although the above-mentioned embodiments have made a detailed description of the present invention, they are only some embodiments of the present invention, rather than all embodiments. People can also obtain other embodiments based on the embodiments of the present invention without creative work, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A copper vanillate, characterized in that The chemical formula is Cu2(C8H7O4)4(H2O)2.

2. The method for preparing copper vanillate according to claim 1, characterized in that: The following steps are involved: A solution containing vanillic acid and a copper source containing copper ions are mixed to react, and solid-liquid separation is performed to obtain copper vanillate.

3. The preparation method according to claim 2, characterized in that: The solvent of the vanillic acid-containing solution is an alcohol aqueous solution, and the volume fraction of alcohol in the alcohol aqueous solution is 25-35%.

4. The preparation method according to claim 3, characterized in that: The concentration of vanillic acid in the vanillic acid-containing solution is 0.01-0.03 g / mL.

5. The preparation method according to claim 2, characterized in that: The copper source includes an insoluble copper source and a soluble copper source. The insoluble copper source includes one or more of copper oxide, copper hydroxide and basic copper carbonate. The soluble copper source includes one or more of copper chloride, copper nitrate and copper sulfate.

6. The preparation method according to claim 5, characterized in that: When the copper source is a soluble copper source, the pH value of the solution containing vanillic acid is adjusted to 6-9 before mixing; the copper source is used in the form of a copper source aqueous solution.

7. The preparation method according to claim 6, characterized in that: The concentration of the copper source aqueous solution is 0.05-0.2 mol / L.

8. The preparation method according to claim 2, characterized in that: The molar ratio of the vanillic acid to the copper ions in the copper source is (1-3):

1.

9. The preparation method according to claim 2 or 8, characterized in that: The reaction temperature is 20-70° C. and the reaction time is 0.5-3 h.

10. Use of the copper vanillate according to claim 1 or the copper vanillate obtained by the preparation method according to any one of claims 2 to 9 in anti-oxidation or antibacterial applications.

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