A nano-functional material with strong non-toxic antibacterial and antiviral properties and its preparation and application

Abstract

The present invention discloses a strong, non-toxic, antibacterial and antiviral nano-functional material and a preparation method thereof. The nano-functional material is green, non-toxic and harmless, and its antibacterial and antiviral effect can reach more than 99%. The new nano-material innovatively uses the natural antibacterial agent meta-dichlorostyrene meta-dichloroacetophenone as the main body of the material to exert its antibacterial and antiviral effects. This makes the new nano-material not only have extremely strong antibacterial and antiviral effects, but also as a natural antibacterial agent, when it is used as a textile material, it can be non-toxic and harmless to the human body, green and healthy. It has a better inhibitory effect on both Gram-negative and Gram-positive bacteria than nano-copper oxide and meta-dichlorophenylethanol and meta-dichloroacetophenone. The present invention also provides a preparation method for the nano-functional material, which includes chemical reaction processes such as boron hydrolysis reaction, catalytic oxidation reaction, electrocarboxylation reaction, and esterification reaction.

Description

Technical Field

[0001] The present invention belongs to the field of nanomaterials, and particularly relates to a nanofunctional material with strong, non-toxic, antibacterial and antiviral properties, as well as its preparation and application. Background Art

[0002] With the development of the economy and society, people's awareness of self-care and the environment has continued to grow, and the demand for special functional textiles for various purposes has also increased dramatically. Health remains one of the most concerned topics. However, bacteria are everywhere, including many harmful bacteria, and their spread and spread seriously threatens human health. Therefore, in order to control the growth and reproduction of harmful bacteria and reduce the harm they may cause, the research and development of antibacterial functional textiles has become a hot topic in scientific research and production. Traditional methods of antibacterial and antiviral textiles mainly rely on the addition of chemical antibacterial or antiviral agents. However, these chemical additives may cause certain harm to human health, and the antibacterial effect on textiles will gradually weaken over time. Summary of the Invention

[0003] The purpose of the present invention is to provide a strong, non-toxic, antibacterial and antiviral nano-functional material for modifying textiles, as well as its preparation and application.

[0004] Specifically, the present invention provides, on one hand, a potent, non-toxic, antibacterial and antiviral nanofunctional material as described in formula (I).

[0005]

[0006] In one aspect, the present invention provides a method for preparing a potent, non-toxic, antibacterial and antiviral nanofunctional material as described in formula (I):

[0007] S1: Formula (A) The product is subjected to hydroboration and oxidation reaction with pinacol diboron ester, ferrous chloride, and alkaline organic solution, extracted, washed with saturated brine, dried, spin-dried, column purified, and rotary evaporated to obtain the product of formula (B).

[0008] S2: Take formula (D) Place in a reaction kettle, add acetonitrile and tetraethylammonium tetrafluoroborate, conduct electrocarboxylation reaction under constant voltage and CO2, extract, adjust pH value, and obtain formula (E) The formula (B) and formula (E) described in step S1 are mixed, distilled water is added, and the formula (C) is obtained under the action of a catalyst.

[0009] S3: dissolving the compound (C) obtained in step S2 in an organic solvent, adding pretreated nano-copper oxide, ultrasonically dispersing, and rotary evaporating to obtain a potent, non-toxic, antibacterial and antiviral nano-functional material of formula (I).

[0010] In one or more embodiments, the alkaline organic solution in step S1 is preferably one or more of triethylamine, triethylenediamine, lithium tert-butoxide, potassium tert-butoxide, and sodium tert-butoxide; and the organic solvent in step S3 is one of ethanol, acetone, ether, or ethylene glycol.

[0011] In one or more embodiments, in step S1, the molar ratio of the ferrous chloride solution, the alkaline organic solution and the pinacol diboron ester is preferably 1: (15-18): (20-25); the reaction temperature of step S1 is 30-45° C.; and the reaction time is 10-18 h.

[0012] In one or more embodiments, step S1 further comprises a step of pumping and filling argon gas; the number of times of pumping and filling argon gas is preferably 2 to 5 times.

[0013] In one or more embodiments, in step S2, the CO2 flow time is 0.5 to 1 hour. The concentration of tetraethylammonium tetrafluoroborate is preferably 0.1 to 0.3 mol / L. The reaction temperature of formula (B) and formula (E) is 70 to 80°C. The reaction time is 4 to 6 hours. The pH value is 5.0 to 5.6. The volume ratio of acetonitrile to tetraethylammonium tetrafluoroborate is (10 to 20):1.

[0014] In one or more embodiments, step S2 further comprises a low-temperature water washing step, wherein the water washing temperature is 5 to 10° C. and the number of water washing times is 2 to 4 times.

[0015] In one or more embodiments, in step S3, the nano-copper oxide is preferably one of rod-shaped nano-copper oxide, needle-shaped nano-copper oxide and flake-shaped nano-copper oxide; the size of the nano-copper oxide is preferably one or more of 20 nm, 50 nm and 100 nm.

[0016] In one or more embodiments, in step S3, the ultrasonic frequency in the ultrasonic dispersion is 20 to 30 kHz, the ultrasonic power is 12 to 39 W, and the ultrasonic time is 10 to 20 min.

[0017] In one or more embodiments, the pretreatment process in step S3 includes: exposing the nano-copper oxide to 254nm ultraviolet light, and then placing the nano-copper oxide after ultraviolet light exposure in a glass dessicator containing a beaker containing a saturated potassium nitrate solution for surface treatment; the ultraviolet light exposure time is 2 to 5 hours; and the surface treatment time is 3 to 6 hours.

[0018] On one hand, the present invention provides the application of a strong, non-toxic, antibacterial and antiviral nano-functional material in textiles for preparing strong, non-toxic, antibacterial and antiviral textiles.

[0019] This patent proposes the use of potent, non-toxic, antibacterial and antiviral nanofunctional materials to improve the antibacterial and antiviral properties of textiles and better protect people's health. This patent prepares a potent, non-toxic, antibacterial and antiviral nanofunctional material by compounding nano-copper oxide with meta-dichlorostyrene-meta-dichlorophenyl ketone. Both have excellent antibacterial effects, and after nano-copper oxide is grafted onto meta-dichlorostyrene-meta-dichlorophenyl ketone, textiles treated with the potent, non-toxic, antibacterial and antiviral nanofunctional material will be more resistant to washing and have better antibacterial and antiviral effects. In addition, the raw material used, meta-dichlorostyrene-meta-dichlorophenyl ketone, is a natural antibacterial agent, which can ensure that the product is non-toxic and harmless to the human body, and is green and healthy.

[0020] The present invention has the following advantages over the prior art:

[0021] The composite product of nano copper oxide and meta-dichlorostyrene and meta-dichlorophenyl ketone in the present invention has better antibacterial effect.

[0022] The raw materials in the present invention are green and environmentally friendly. 1,2-dichlorostyrene and 1,2-dichlorophenyl ketone are natural plant-derived antibacterial agents that are non-toxic and harmless to the human body, and are green and healthy compared to chemical antibacterial agents.

[0023] The present invention connects the composite product of nano copper oxide and meta-dichlorostyrene and meta-dichlorophenyl ketone to various places of the textile, so that the textile can still maintain good antibacterial and antiviral effects after repeated use and washing. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the chemical reaction formula of the nano-functional material according to the embodiment of the present invention;

[0025] Figure 2 This is a process flow chart of the nano-functional material according to an embodiment of the present invention;

[0026] Figure 3 Comparison of the antibacterial and antiviral properties of experimental cloth pieces doped with different amounts of the nano-functional material according to the embodiment of the present invention before washing;

[0027] Figure 4 Comparison of the antibacterial and antiviral properties of experimental cloth pieces with different doping amounts after being washed 50 times with the nano-functional material according to the embodiment of the present invention;

[0028] Figure 5 This is a comparison chart of the antibacterial and antiviral properties of nanomaterials using different pretreatment methods of the present invention. DETAILED DESCRIPTION

[0029] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are for illustrative purposes only, and those skilled in the art will readily appreciate other obvious variations. The basic principles of the present invention defined in the following description may be applied to other embodiments, variations, improvements, equivalents, and other technical solutions that do not depart from the spirit and scope of the present invention.

[0030] In the examples of the present invention, if the specific conditions are not specified, the experiments were carried out according to conventional conditions or the conditions recommended by the manufacturer. All raw materials and reagents used without specifying the manufacturer are conventional products that can be purchased from the market.

[0031] The compound of formula A, 5-vinyl-3-hexanone trimethoxysilane, is synthesized according to the following steps: 1. Vinyl trimethoxysilane is added to hydrogen peroxide solution and hydrogen bromide solution, and the mixture is stirred to react to obtain 1-bromoethyl trimethoxysilane. 2. 3-Butenoic acid and excess thionyl chloride are heated to reflux in an organic solvent. After the reaction, the excess thionyl chloride and organic solvent are evaporated to obtain 3-butenoyl chloride. 3. 1-Bromoethyl trimethoxysilane and 3-butenoyl chloride are added to anhydrous ether, and nitrogen is introduced to react to obtain formula A.

[0032] References:

[0033] [1] Zhang Heng, Xing Zhirong, Liu Dong, Zhou Zhibin, Feng Wenfang. Improvement of the synthetic experiment of Grignard reagent[J]. University Chemistry, 2023, 38(2): 177-184

[0034] [2]Xin Jianfeng, Ma Jihai, Zhang Shufen, Chen Shaorui, Li Haiyu. Review of preparation methods of acyl chlorides[J]. Hebei Chemical Industry, 2006, 29(11):16-1820

[0035] [3]Fiandanese V, Marchese G, Martina V, et al.Iron catalyzed cross-coupling reactions of acyl chlorides with Grignard reagents.A mild, general, and convenient synthesis of aliphatic and aromatic ketones[J].Tetrahedronletters,1984,25(42):4805-4808.

[0036] Formula D compound 2,6-dichlorostyryl 2,6-dichlorophenyl ketone was prepared by referring to the following literature: A.KAISER, P.BIELMEIER, W.WIEGREBE, 1,3-Diphenylpropane-1,3-diamines. Part 11. Conversion of a 3-Hydroxy-1,3-diphenylpropan-1-one to

[0037] 1,3-Diphenylpropane-1,3-diamines.,Monatsh.Chem.,1997,128,1247-1254.

[0038] Example 1

[0039] Step 1

[0040]

[0041] 10 mL of a 5 mmol / L ferrous chloride solution, 0.061 g of lithium tert-butoxide, and 0.25 g of pinacol diboron ester were weighed into a Schlenk reaction tube at a molar ratio of ferrous chloride, alkaline organic solvent, and pinacol diboron ester of 1:15:20. While ensuring airtightness, the tube was evacuated and filled with argon twice. Then, 50 mL of methyl tert-butyl ether and 1.9 g of formula (A) were added. The mixture was heated to 30°C and stirred for 10 hours. After extraction with ethyl acetate, 25 mL of a 2 mol / L sodium hydroxide solution and 25 mL of a 30% hydrogen peroxide solution were added to the organic phase and stirred. After extraction, the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and dried by spin drying. Purified by column chromatography, evaporation was performed to obtain 2.05 g of formula (B).

[0042] Step 2

[0043]

[0044] 2.54g of formula (D), 25mL of acetonitrile, and 2.5mL of 0.1mol / L tetraethylammonium tetrafluoroborate solution were placed in an electrolytic cell. CO2 was introduced at atmospheric pressure for 0.5h, and then electrolysis was performed at a constant potential of -1.75V. The resulting mixture was extracted with acetone, and the aqueous phase was acidified to a pH of 5.0 by adding 4mol / L hydrochloric acid. The aqueous layer was extracted again with an organic solvent, and the organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to obtain 2.86g of formula (E). Formula (E) and formula (B) were placed in a reaction kettle, distilled water was added, and stirred evenly. Formic acid was added, and the reaction was heated to 70°C for 4h. After the reaction was complete, the reaction was cooled for 3h to obtain a reaction solution. The resulting reaction solution was extracted with an organic solvent, and the organic phase was washed twice with 5°C distilled water, separated, dehydrated, filtered, and purified by distillation. Formula (C) was obtained by rotary evaporation.

[0045] Step 3

[0046]

[0047] 2.5g of 20nm nano-copper oxide was exposed to 254nm ultraviolet light for 2 hours. The exposed nano-copper oxide was then placed in a glass desiccator containing a beaker of saturated potassium nitrate solution for surface treatment for 3 hours. The pretreated nano-copper oxide and formula (C) were added sequentially to an acetone solution. Ultrasonic dispersion was performed at an ultrasonic frequency of 20kHz and a power of 12W for 10 minutes. After filtration, the solid was dried in a vacuum drying oven at 80°C for 24 hours to obtain a potent, non-toxic, antibacterial and antiviral nano-functional material of formula (I) for textile modification.

[0048] Example 2

[0049] Step 1

[0050] 10 mL of a 5 mmol / L ferrous chloride solution, 0.064 g of lithium tert-butoxide, and 0.292 g of pinacol diboron ester were weighed into a Schlenk reaction tube in a molar ratio of ferrous chloride, alkaline organic solvent, and pinacol diboron ester of 1:16:23. While ensuring airtightness, the tube was evacuated and filled with argon three times. Then, 50 mL of methyl tert-butyl ether and 4 g of formula (A) were added. The mixture was heated to 40°C and stirred for 12 hours. After extraction with ethyl acetate, the organic phase was added with 25 mL of a 2 mol / L sodium hydroxide solution and 25 mL of a 30% hydrogen peroxide solution, and stirred. After extraction, the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and dried by spin drying. Purified by column chromatography, evaporation was performed to obtain 4.2 g of formula (B).

[0051] Step 2

[0052] 4.08g of formula (D), 25mL of acetonitrile, and 1.67mL of 0.2mol / L tetraethylammonium tetrafluoroborate solution were placed in an electrolytic cell. CO2 was introduced at atmospheric pressure for 0.7h, followed by constant voltage electrolysis at -1.75V. The resulting mixture was extracted with acetone, and the aqueous phase was acidified to a pH of 5.3 by adding 4mol / L hydrochloric acid. The aqueous layer was then extracted again with an organic solvent, and the organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to yield 5.65g of formula (E). Formula (E) and formula (B) were placed in a reaction kettle, distilled water was added, and the mixture was stirred evenly. Formic acid was added, and the reaction mixture was heated to 75°C for 5h. After completion of the reaction, the mixture was cooled for 3h to yield a reaction solution. The resulting reaction solution was extracted with an organic solvent, and the organic phase was washed three times with 7°C distilled water, separated, dehydrated, filtered, and purified by distillation. After rotary evaporation, formula (C) was obtained.

[0053] Step 3

[0054] 6g of 50nm nano-copper oxide was exposed to 254nm ultraviolet light for 3 hours. The exposed nano-copper oxide was then placed in a glass desiccator containing a beaker of saturated potassium nitrate solution for surface treatment for 4 hours. The pretreated nano-copper oxide and formula (C) were added sequentially to an ether solution. Ultrasonic dispersion was performed at an ultrasonic frequency of 30 kHz and a power of 39 W for 15 minutes. After filtration, the solid was dried in a vacuum drying oven at 80°C for 24 hours to obtain a potent, non-toxic, antibacterial and antiviral nano-functional material of formula (I) for textile modification.

[0055] Example 3

[0056] Step 1

[0057] 10 mL of a 5 mmol / L ferrous chloride solution, 0.072 g of lithium tert-butoxide, and 0.317 g of pinacol diboron ester were weighed into a Schlenk reaction tube in a molar ratio of ferrous chloride, alkaline organic solvent, and pinacol diboron ester of 1:18:25. While ensuring airtightness, the tube was evacuated and filled with argon five times. Then, 50 mL of methyl tert-butyl ether and 2.85 g of formula (A) were added. The mixture was heated to 45°C and stirred for 18 hours. After extraction with ethyl acetate, the organic phase was added with 25 mL of a 2 mol / L sodium hydroxide solution and 25 mL of a 30% hydrogen peroxide solution, and stirred. After extraction, the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and dried by spin drying. Purified by column chromatography, evaporation was performed to obtain 3.1 g of formula (B).

[0058] Step 2

[0059] 3.79g of formula (D), 25mL of acetonitrile, and 1.25mL of 0.3mol / L tetraethylammonium tetrafluoroborate solution were placed in an electrolytic cell. CO2 was introduced at atmospheric pressure for 1h, and then electrolysis was performed at a constant potential of -1.75V. The resulting mixture was extracted with acetone, and the aqueous phase was acidified to a pH of 5.6 by adding 4mol / L hydrochloric acid. The aqueous layer was then extracted again with an organic solvent, and the organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to obtain 4.25g of formula (E). Formula (E) and formula (B) were placed in a reaction kettle, distilled water was added, and the mixture was stirred evenly. Formic acid was added, and the reaction mixture was heated to 80°C for 6h. After the reaction was complete, the mixture was cooled for 3h to obtain a reaction solution. The resulting reaction solution was extracted with an organic solvent, and the organic phase was washed three times with 10°C distilled water, separated, dehydrated, filtered, and purified by distillation. After rotary evaporation, formula (C) was obtained.

[0060] Step 3

[0061] 5g of 100nm nano-copper oxide was exposed to 254nm ultraviolet light for 5 hours. The exposed nano-copper oxide was then placed in a glass desiccator containing a beaker of saturated potassium nitrate solution for surface treatment for 6 hours. The pretreated nano-copper oxide and formula (C) were added sequentially to an ethanol solution. Ultrasonic dispersion was performed at an ultrasonic frequency of 25 kHz and a power of 30 W for 20 minutes. After filtration, the solid was dried in a vacuum drying oven at 80°C for 24 hours to obtain a potent, non-toxic, antibacterial and antiviral nano-functional material of formula (I) for textile modification.

[0062] In order to evaluate the antibacterial and antiviral performance of the present invention, we used the cloth piece of the present invention to evaluate its antibacterial and antiviral performance according to national standards. The experimental results are listed in Table 1 and Figure 3 shown.

[0063] (1) The evaluation of antibacterial performance refers to the national standard: "Oscillating method for evaluation of antibacterial properties of textiles GB / T20944.3-2008".

[0064] Three samples (each 10 cm x 10 cm, cut into two pieces) were taken from the antimicrobial fabric sample and washed according to test condition A1M in GB / T 12490, using an ECE standard phosphate-free detergent. The washing time was 45 minutes using a water temperature of 40°C ± 3°C, a detergent concentration of 0.2%, 150 mL of solution, and 10 steel balls. After washing, the samples were removed and rinsed twice in 100 mL of water at 40°C ± 3°C for 1 minute each. This procedure was repeated until the specified number of washes had been reached. To prevent residual detergent from interfering with the antimicrobial performance test, the samples were thoroughly rinsed at the end of the final wash cycle and then air-dried or air-dried.

[0065] 40 mL of E. coli culture prepared in PBS buffer was added to the antibacterial and antiviral textiles washed at different times and a blank sample. The mixture was incubated at 37°C with shaking at 150 rpm for 18 hours. After 24 hours of incubation at 37°C, the E. coli concentration was measured and the removal rate was calculated using the nutrient agar plate method.

[0066] (2) Antiviral evaluation refers to the international standard: "Textiles - Determination of antiviral activity of textiles ISO 18184".

[0067] 40 mL of MS2 phage suspension prepared in PBS buffer was added to the antibacterial and antiviral textiles washed at different times and a blank sample. The suspension was incubated at 37°C with shaking at 150 rpm for 12 hours. Using the double-plate method, the cells were incubated in a 37°C incubator for 6-8 hours before counting, measuring the MS2 phage concentration, and calculating the removal rate.

[0068] We washed the experimental cloth pieces with different doping amounts fifty times and then tested their antibacterial and antiviral properties. Then we compared them with the cloth pieces before washing. Figure 4 It can be seen that the antibacterial and antiviral effects of the modified cloth piece of the present invention are still very strong after being washed fifty times.

[0069] Table 1 shows the antibacterial and antiviral effects of each piece of cloth before washing

[0070]

[0071] Table 2 Antibacterial and antiviral effects of each cloth piece after washing 50 times

[0072]

[0073] To determine the toxicity of the product, we evaluated cytotoxicity according to ISO 10993. The method is as follows: 50 μL of a well-stirred human epidermal cell suspension was inoculated into culture medium, cultured for 24 hours, and counted. A further 50 μL of the same concentration of human epidermal cell suspension was added to the well-stirred human epidermal cell suspension. Three replicates of each were prepared, inoculated into culture medium, cultured for 24 hours, and counted. The number of surviving cells in the culture medium without the experimental nanomaterial was compared with the number of surviving cells in the culture medium with the experimental nanomaterial, and the survival rate was calculated.

[0074] Table 3 Cytotoxicity test

[0075]

[0076] As shown in Table 3, the antibacterial and antiviral nanomaterials obtained in this experiment had little effect on the growth and reproduction of human epidermal cells. According to the ISO 10993 standard, antibacterial and antiviral nanomaterials can be classified as non-cytotoxic. This demonstrates that the antibacterial and antiviral nanomaterials synthesized in this experiment are truly non-toxic, harmless, and green and healthy.

[0077] To further verify that the experimentally synthesized antibacterial and antiviral nanomaterial is non-toxic, harmless, and environmentally friendly, we conducted sweat leaching experiments to measure the heavy metal and TOC content in the leached sweat. Heavy metal leaching was determined using the national standard "Textiles—Determination of Heavy Metals—Atomic Absorption Spectrophotometry" (GB / T17593.1-2006). TOC was determined using the combustion oxidation-non-dispersive infrared absorption method.

[0078] Take a 5 mm x 5 mm textile sample modified with the antibacterial and antiviral nanomaterial of the present invention, mix thoroughly, and weigh two 4 g samples (for parallel testing) to the nearest 0.01 g. Place the sample in a stoppered Erlenmeyer flask. Add 80 mL of prepared simulated acidic sweat solution to thoroughly soak the fiber. Oscillate the sample in a constant temperature water bath for 60 minutes, remove the sample, allow it to cool to room temperature, and filter it for analysis.

[0079] Dilute the prepared copper standard working solution with water to create a series of working solutions of appropriate concentrations. Measure the absorbance of copper in the series of working solutions in ascending order of concentration using a graphite furnace atomic absorption spectrophotometer at a wavelength of 324.7 nm (Cu). Plot a working curve with absorbance as the ordinate and concentration (μg / mL) as the abscissa. Measure the absorbance of each analyte in the blank solution and sample solution, and calculate the concentration of each analyte from the working curve.

[0080] Table 4 Metal copper leaching analysis

[0081] sample Copper precipitation content (mg / kg) Containing 5wt% of the product of Example 1 1.71 Containing 5wt% of the product of Example 2 1.65 Containing 5wt% of the product of Example 3 1.54 Containing 7.5wt% of the product of Example 1 1.70 Containing 7.5wt% of the product of Example 2 1.66 Containing 7.5wt% of the product of Example 3 1.60 Containing 10wt% of the product of Example 1 1.81 Containing 10wt% of the product of Example 2 1.70 Containing 10wt% of the product of Example 3 1.59

[0082] As shown in Table 4, the heavy metal leaching content of the cloth after being subjected to simulated sweat is far lower than the national standard, which proves that the textile modified by the present invention is green, healthy, non-toxic and harmless.

[0083] Prepare two identical sample solutions using the same method as above. Inject the two sample solutions into the high-temperature combustion tube and the low-temperature reaction tube, respectively, to obtain the total carbon and inorganic carbon contents of the sample solutions. Subtract the two to obtain the organic carbon content.

[0084] Table 5 Organic carbon leaching analysis

[0085] sample Organic carbon content (μg / L) Containing 5wt% of the product of Example 1 45.12 Containing 5wt% of the product of Example 2 45.36 Containing 5wt% of the product of Example 3 46.67 Containing 7.5wt% of the product of Example 1 42.56 Containing 7.5wt% of the product of Example 2 43.99 Containing 7.5wt% of the product of Example 3 44.45 Containing 10wt% of the product of Example 1 46.67 Containing 10wt% of the product of Example 2 47.34 Containing 10wt% of the product of Example 3 47.56

[0086] As can be seen from Table 5, the organic carbon leaching content of the cloth piece leached with simulated sweat is extremely low, proving that the present invention is extremely stable and will not precipitate due to sweat and cause harm to the human body, once again proving that the present invention is green, healthy, non-toxic and harmless.

[0087] To verify that the pretreatment step of the nano-copper oxide in the present invention can improve the antibacterial and antiviral effects of the final synthetic material, the present invention compared the antibacterial and antiviral properties of the final products synthesized from nano-copper oxide after undergoing different pretreatment steps. The experimental method is as follows: three identical nano-copper oxides were subjected to four different pretreatments: 254nm ultraviolet light exposure for 2 hours, surface treatment in a glass desiccator containing a beaker of saturated potassium nitrate solution, and then 254nm ultraviolet light exposure followed by surface treatment in a glass desiccator containing a beaker of saturated potassium nitrate solution. Four antibacterial and antiviral nanomaterials were synthesized from the three nano-copper oxides that had undergone different pretreatments and the nano-copper oxide that had not undergone pretreatment. These four antibacterial and antiviral nanomaterials were then tested for their antibacterial and antiviral properties, and their antibacterial and antiviral properties were compared.

[0088] Figure 5 Middle: Experimental group: Nanomaterials synthesized from nano-copper oxide that was irradiated with UV light and surface-treated with saturated potassium nitrate solution; Surface treatment group: Nanomaterials synthesized from nano-copper oxide that was not irradiated with UV light and surface-treated with saturated potassium nitrate solution; UV light group: Nanomaterials synthesized from nano-copper oxide that was irradiated with UV light and surface-treated with saturated potassium nitrate solution; Untreated group: Nanomaterials synthesized from nano-copper oxide that was not irradiated with UV light and surface-treated with no saturated potassium nitrate solution; Log removal rate: Log removal rate of bacteria or viruses.

[0089] Table 6 Comparison of antibacterial and antiviral properties of nanomaterials by different pretreatment methods

[0090]

[0091]

[0092] From Table 6 and Figure 5It can be seen that the nano-copper oxide treated with ultraviolet light and not treated with a saturated potassium nitrate solution has an increased surface activity, resulting in a performance improvement of approximately 60% over the nano-copper oxide produced by reacting with the nano-copper oxide treated with ultraviolet light and not treated with a saturated potassium nitrate solution. The nano-copper oxide that has not been treated with ultraviolet light and not treated with a saturated potassium nitrate solution has an increased surface load of water molecules, which increases the number of surface reaction sites. This results in a performance improvement of approximately 65% ​​over the nano-copper oxide produced by reacting with the nano-copper oxide treated with a saturated potassium nitrate solution. The nano-copper oxide treated with ultraviolet light and surface treated with saturated potassium nitrate solution not only increases the surface activity of the nano-copper oxide, but also increases the reaction sites on the surface of the nano-copper oxide, resulting in a performance improvement of about 100% in the nano-material generated by the nano-copper oxide treated with ultraviolet light and surface treated with saturated potassium nitrate solution compared to the nano-copper oxide not treated with ultraviolet light and surface treated with saturated potassium nitrate solution.

Claims

1. A method for preparing a non-toxic antibacterial and antiviral nanofunctional material, characterized in that: The following steps are involved: S1: Formula (A) The product is subjected to hydroboration and oxidation reaction with pinacol diboron ester, ferrous chloride, and alkaline organic solution, extracted, washed with saturated brine, dried, spin-dried, column purified, and rotary evaporated to obtain the product of formula (B). S2: Take formula (D) Place in a reaction kettle, add acetonitrile and tetraethylammonium tetrafluoroborate, conduct electrocarboxylation reaction under constant voltage and CO2, extract, adjust pH value, and obtain formula (E) The formula (B) and formula (E) described in step S1 are mixed, distilled water is added, and the formula (C) is obtained under the action of a catalyst. S3: dissolving the compound of formula (C) obtained in step S2 in an organic solvent, adding the pretreated nano-copper oxide, ultrasonically dispersing the compound while stirring continuously, and rotary evaporating the compound to obtain a non-toxic, antibacterial, and antiviral nano-functional material; The pretreatment process in step S3 includes: exposing the nano-copper oxide to 254nm ultraviolet light, and then placing the nano-copper oxide after ultraviolet light exposure in a glass desiccator containing a beaker containing a saturated potassium nitrate solution for surface treatment; the ultraviolet light exposure time is 2 to 5 hours; and the surface treatment time is 3 to 6 hours.

2. The preparation method according to claim 1, characterized in that The alkaline organic solution in step S1 is one or more of triethylamine, triethylenediamine, lithium tert-butoxide, potassium tert-butoxide, and sodium tert-butoxide.

3. The preparation method according to claim 1, characterized in that In step S1, the molar ratio of ferrous chloride, alkaline organic solution and pinacol diboron ester is 1: (15-18): (20-25); the reaction temperature of step S1 is 30-45° C.; and the reaction time is 10-18 hours.

4. The preparation method according to claim 1, characterized in that Step S1 also includes the step of pumping and filling argon gas; the number of times of pumping and filling argon gas is 2 to 5 times.

5. The preparation method according to claim 1, characterized in that In step S2, the CO2 passage time is 0.5 to 1 h; the concentration of tetraethylammonium tetrafluoroborate is 0.1 to 0.3 mol / L; the reaction temperature of formula (B) and formula (E) is 70 to 80°C, and the reaction time is 4 to 6 h; the pH value is 5.0 to 5.6; and the volume ratio of acetonitrile to tetraethylammonium tetrafluoroborate is (10 to 20):

1.

6. The preparation method according to claim 1, characterized in that Step S2 also includes a low-temperature water washing step, where the water washing temperature is 5-10° C. and the number of water washing times is 2-4 times.

7. The preparation method according to claim 1, characterized in that In step S3, the ultrasonic frequency in the ultrasonic dispersion is 20 to 30 kHz, the ultrasonic power is 12 to 39 W, and the ultrasonic time is 10 to 20 minutes.

8. Use of the non-toxic antibacterial and antiviral nano-functional material prepared by the method for preparing the non-toxic antibacterial and antiviral nano-functional material according to any one of claims 1 to 7 in textiles, characterized in that: Used to prepare non-toxic antibacterial and antiviral textiles.

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