Antibacterial cotton cellulose material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of biological antibacterial cotton fiber preparation, and particularly relates to an antibacterial cotton cellulose material and a preparation method and application thereof. The antibacterial cotton fiber product with good antibacterial activity is obtained by adopting ethyl acetate to extract antibacterial active ingredients in scutellaria baicalensis and loading the antibacterial active ingredients in the cotton fiber product, the diameter of an inhibition zone of the antibacterial cotton fiber to staphylococcus aureus is as high as 3.1 mm, the diameter of an inhibition zone of the antibacterial cotton fiber to escherichia coli is 2.8 mm, and the antibacterial cotton fiber product has good antibacterial activity. A good broad-spectrum antibacterial effect is shown.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of biological antibacterial cotton fiber preparation, and particularly relates to an antibacterial cotton cellulose material and a preparation method and application thereof. BACKGROUND

[0002] Cotton fiber, as a natural cellulose fiber, is widely used in the fields of textile and clothing, medical and health care, home decoration, etc. due to its excellent moisture absorption and air permeability, biocompatibility and biodegradability.

[0003] However, the porous structure and chemical characteristics of cotton fiber, which are rich in hydroxyl groups, make it easy to adsorb water and nutrients, and it is an ideal environment for the growth of bacteria, fungi and other microorganisms. At the same time, the large-scale reproduction of microorganisms can also cause problems such as odor, mold, and mechanical property degradation of cotton fiber products, and more likely to cause skin infection, cross infection and other health risks. Especially in the fields of medical dressings and infant clothing, the antibacterial performance of cotton fiber has become a key indicator.

[0004] Antibacterial cotton fiber is a kind of cotton fiber material with antibacterial effect prepared by introducing antibacterial active ingredients into the surface or interior of the fiber through physical or chemical methods. At present, the antibacterial ingredients loaded on the cotton fiber material mainly include chemical synthetic antibacterial ingredients and natural antibacterial ingredients. With the enhancement of human environmental protection consciousness and safety consciousness and the improvement of research level, the application of natural antibacterial agents in antibacterial fibers has become a research hotspot.

[0005] The loading of natural antibacterial agents is the core link to realize the antibacterial function of cotton fiber, and the key is to stably combine natural antibacterial ingredients (such as plant extracts, polysaccharides, polypeptides, etc.) on the surface or inside of cotton fiber through appropriate technical means, while retaining the original physical and mechanical properties and biocompatibility of the fiber.

[0006] At present, the loading of natural antibacterial agents mainly adopts physical adsorption and chemical grafting as the mainstream method, but each method has significant differences in loading efficiency, antibacterial durability and fiber damage. For example, in patent CN112176728A, phytic acid and inorganic antibacterial agents are added to realize the chemical grafting of natural antibacterial agents and cotton fiber with the help of β-cyclodextrin. Although the durability of the antibacterial effect is improved, the excessive crosslinking agent may increase the brittleness of the fiber, and the residual chemical reagents may affect the biocompatibility, and even cause skin sensitivity after long-term contact with the skin. In addition, the adsorption amount of antibacterial drugs on the surface of cotton fiber is limited, and a large number of hydroxyl groups of cellulose are still embedded in the interior of the fiber and do not fully play a role in combination with the drugs, resulting in poor antibacterial effect of the cotton fiber. SUMMARY

[0007] The present application provides an antibacterial cotton cellulose material and a preparation method and application thereof to solve the above technical problems.

[0008] The application provides an antibacterial cotton cellulose material, which is prepared by using traditional Chinese medicine bacteriostatic components and a cotton cellulose solution, and the antibacterial cotton cellulose material includes but is not limited to any one of the following forms: fiber filaments, fiber aerogel and fiber film, and the traditional Chinese medicine bacteriostatic components are extracted from at least one of the following traditional Chinese medicinal materials: Huangqi, Chuanxinlian, Xiaakucao and Jinyinhua.

[0009] Preferably, the traditional Chinese medicine bacteriostatic components are extracted from Huangqi, and more preferably, the traditional Chinese medicine bacteriostatic components are ethyl acetate extracts of Huangqi.

[0010] Preferably, the application further provides a preparation method of the antibacterial cotton cellulose material, which includes the following steps: S1. Preparation of traditional Chinese medicine bacteriostatic components: traditional Chinese medicinal material is crushed, ethyl acetate is added to immerse the traditional Chinese medicinal material, the traditional Chinese medicinal material is extracted by reflux for 3-4 times, the extract is combined, the solvent is evaporated, and the traditional Chinese medicine bacteriostatic components are obtained by purification through a silica gel chromatographic column, using petroleum ether and ethyl acetate as elution solvents, gradually increasing the proportion of ethyl acetate, 50 mL as one fraction, and combining the fractions containing the same components into five components through thin layer chromatography, and drying; S2. Preparation of a cotton cellulose solution: cotton or waste cotton products are used as raw materials, which are soaked in deionized water after being cut, the deionized water is squeezed out after centrifugation, the raw materials are immersed in N,N-dimethylacetamide again, and the raw materials are soaked repeatedly for 2-3 times after centrifugation, N,N-dimethylacetamide and LiCl are finally added, the temperature is heated to 50-70°C and stirred until LiCl is completely dissolved, the mixture is filtered while hot, the filter residue is squeezed, and the LiCl N,N-dimethylacetamide solution is added, the mixture is stirred at 50-70°C until the raw materials are dissolved, and the cotton cellulose solution is obtained by filtration. S3. Loading of traditional Chinese medicine bacteriostatic components: the cotton cellulose solution prepared in S1 is mixed with the N,N-dimethylacetamide solution of the traditional Chinese medicine bacteriostatic components, the mixture is condensed in a mold, and then the antibacterial cotton cellulose aerogel is obtained by rapid freezing under liquid nitrogen conditions. Or the cotton cellulose solution prepared in S1 is mixed with the traditional Chinese medicine bacteriostatic components, and then the antibacterial cotton fiber filaments are obtained by wet spinning.

[0011] Preferably, in the preparation method of the antibacterial cotton cellulose material, the volume ratio of petroleum ether to ethyl acetate is 10:1-0:1 in S1.

[0012] Preferably, the heating temperature is 60°C in S2.

[0013] Preferably, the condensation in S3 is to place the mixture in room temperature and avoid light for 12-36 hours, and the temperature condition of the liquid nitrogen rapid freezing is-120--40°C.

[0014] As preferred, in S3, the volume ratio of the cotton cellulose solution to the N,N-dimethylacetamide solution of the traditional Chinese medicine bacteriostatic component is 3-5:1, the concentration of the cotton cellulose solution is 1%-1.5%, and the concentration of the traditional Chinese medicine bacteriostatic component in the N,N-dimethylacetamide solution of the traditional Chinese medicine bacteriostatic component is 8-15 mg / mL.

[0015] The application of the above-mentioned antibacterial cotton cellulose material in preparing bacteriostatic products is also the technical content protected by the present application.

[0016] The present application has the following advantages and effects relative to the prior art: (1) The present application extracts traditional Chinese medicine components such as Scutellaria baicalensis Georgi, Andrographis paniculata, Prunella vulgaris and honeysuckle by using organic solvents, and screens the bacteriostatic properties of different traditional Chinese medicine extracts obtained by extraction, and finally obtains a Scutellaria baicalensis ethyl acetate extract with high bacteriostatic activity. The Scutellaria baicalensis extract obtained by further purifying the component by chromatography has a staphylococcus aureus inhibition ring diameter of up to 2.4 mm and an escherichia coli inhibition ring diameter of up to 1.9 mm. (2) The present application loads the Scutellaria baicalensis ethyl acetate extract on cotton fibers, and the bacteriostatic effect of the antibacterial cotton fiber material, especially the antibacterial cotton cellulose aerogel, is further improved. The results show that the staphylococcus aureus inhibition ring of the material reaches 3.1 mm, and the escherichia coli inhibition ring reaches 2.8 mm. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The figure is the bacteriostatic effect of the Scutellaria baicalensis ethyl acetate extract in Example 1 of the present application on staphylococcus aureus and escherichia coli. Figure 2 The figure is a scanning electron microscope image of the antibacterial cotton cellulose aerogel containing Scutellaria baicalensis antibacterial components prepared in Example 3 of the present application. Figure 3 The figure is the bacteriostatic effect of the antibacterial cotton cellulose aerogel prepared in Example 3 of the present application on escherichia coli and staphylococcus aureus. Figure 4 The figure is a picture of the cellulose morphology of each step in the spinning process using waste cotton textiles in Example 4 of the present application. DETAILED DESCRIPTION

[0018] In order to enable those skilled in the art to better understand the present application, the present application will be further described in conjunction with specific embodiments.

[0019] Example 1 Take 150 g of Huangqi, crush it and put it into a 500 mL round bottom flask. Use n-hexane, dichloromethane, methanol, ethyl acetate, water, etc. as extraction solvents to immerse the medicine, and reflux extract three times. Combine the extract and evaporate the solvent in a water bath below 40°C using a rotary evaporator to obtain Huangqi extract.

[0020] Take 10 mg of Huangqi extract and put it into a 2 mL sample vial. Add 1 mL of dimethyl sulfoxide (DMSO) and ultrasonically treat it to fully dissolve it. Then conduct an antibacterial test. The specific operation of the antibacterial test is as follows: Prepare a culture medium containing a suitable concentration of Staphylococcus aureus and Escherichia coli. Use a puncher to punch holes in the culture medium. Take 100 μL of Huangqi extract in different solvents and drop them into the holes, with two parallel tests. Drop pure DMSO into the holes as a blank. Place the culture dish in an incubator and incubate the Escherichia coli and Staphylococcus aureus at 37°C for 24 hours. After the incubation, observe the inhibition zone and record it. The antibacterial effects of different Huangqi extracts are shown in Table 1.

[0021] Table 1 Antibacterial effects of different Huangqi extracts (inhibition zone diameter / mm) n-hexane methylene chloride methanol ethyl acetate water staphylococcus aureus 1.5 1.4 0.6 1.4 no bacteriostatic effect escherichia coli 0.6 0.6 0.9 1.1 no bacteriostatic effect

[0022] The results in Table 1 show that Huangqi extracts obtained by using various organic solvents all have certain antibacterial effects. The methanol extract has low antibacterial effect on both strains. The n-hexane, dichloromethane, and ethyl acetate extracts have little difference in antibacterial effect on Staphylococcus aureus, but have large differences in antibacterial effect on Escherichia coli. The ethyl acetate extract has the best antibacterial effect on Escherichia coli.

[0023] The inhibition effects of Huangqi ethyl acetate extract on Staphylococcus aureus and Escherichia coli are shown in the left and right graphs of Figure 1 Figure 1 In the left and right graphs, codes 1 and 2 represent the antibacterial effects of two parallels of Andrographis acetic ether extract, and codes 3 and 4 represent the antibacterial effects of two parallels of Huangqi acetic ether extract. It can be seen that the Huangqi acetic ether extract has significant antibacterial properties. Take 150 g of Huangqi, crush it and put it into a 500 mL round bottom flask. Add ethyl acetate to immerse the medicine, and reflux extract three times. Combine the extract and evaporate the solvent in a water bath below 40°C using a rotary evaporator to obtain Huangqi extract. ​The obtained Scutellaria extract in S1 was purified by using a silica gel chromatographic column, 30 times the mass of the Scutellaria extract was used to fill the silica gel column with 200-300 mesh silica gel by wet method, then the extract was mixed with 3 times the mass of 100-200 mesh silica gel, and then the mixture was poured into the filled silica gel column, petroleum ether: ethyl acetate = 10:1-0:1 was used as the eluent, and the proportion of ethyl acetate was gradually increased from low polarity to high polarity, and the silica gel column was eluted, 50 mL for each fraction, and the fractions containing the same components were combined into 5 components by thin layer chromatography, and then dried by a rotary evaporator to obtain the antibacterial components of Scutellaria.

[0024] In this embodiment, when different concentration gradients of ethyl acetate were used to elute the Scutellaria extract, the antibacterial effect of the obtained fractions was shown in Table 2.

[0025] Table 2 Antibacterial effect of different elution fractions of Scutellaria (diameter of inhibition zone / mm) elution fractions component 1 component 2 component 3 component 4 component 5 staphylococcus aureus 1.7 2.4 0.9 0.6 0.6 escherichia coli 1.1 1.9 0.6 0.6 0.6

[0026] The experimental data in Table 2 shows that when elution is performed with a ratio of petroleum ether: ethyl acetate = 10-0:1, 5 antibacterial components can be obtained, among which component 2 has the best antibacterial effect on the two bacteria, with an inhibition zone diameter of 2.4 mm for Staphylococcus aureus and 1.9 mm for Escherichia coli.

[0027] Example 3 An antibacterial cotton cellulose material was prepared by the following method: 1 g of cotton was cut into pieces and soaked in a conical flask with deionized water for 16 h, then centrifuged to squeeze out the deionized water, and then immersed in N,N-dimethylacetamide (DMAC) and centrifuged to squeeze out the DMAC, and then immersed in DMAC again, and repeated 2-3 times, and finally soaked in DMAC for 16 h.

[0028] 40 mL of DMAC and 3.2 g of LiCl were added to a conical flask, heated and stirred until the LiCl was completely dissolved, and then filtered with a microporous filter while hot, and then the cotton was taken out of the DMAC and squeezed to remove the excess DMAC, and then placed in a conical flask, and then 40 mL of DMAC containing 8% LiCl was added, and then the conical flask was placed on a magnetic stirrer with heating function, and then heated and stirred at 60°C until the cotton was dissolved, and then the undissolved fibers were separated from the cellulose solution using a centrifuge or a sand core funnel, and thus a cotton cellulose solution was obtained, with a concentration of about 2.5%.

[0029] The cotton cellulose solution is diluted with DMAC to a concentration of 1.25%, 4 mL is taken out, and the extracted part of the antibacterial effective Scutellaria extract component is dissolved in 1 mL of DMAC to a concentration of 10 mg / mL. After mixing, pour it into the mold, and place it in the dark for 16 h. After the cellulose coagulates, take it out and put it in deionized water. Change the water every 12 h until no Li + is detected in the water, that is, the antibacterial component-containing cotton cellulose hydrogel is obtained. Use liquid nitrogen to freeze it quickly, transfer it to a freeze-drying machine cold trap pre-cooled to -50°C, and run the freeze-drying program. After 24 h, the cotton cellulose material containing traditional Chinese medicine antibacterial components, that is, the antibacterial cotton cellulose aerogel, is obtained.

[0030] The scanning electron microscope image of the antibacterial cotton cellulose aerogel is shown in Figure 2 . From the scanning electron microscope image, it can be seen that the antibacterial cotton cellulose aerogel has a good pore structure.

[0031] After the Scutellaria elution fraction is loaded on the cotton cellulose, the antibacterial effect of the obtained antibacterial cotton cellulose aerogel is shown in Figure 3 .

[0032] Figure 3 The left graph in the figure is the inhibition effect of the antibacterial cotton cellulose aerogel on Escherichia coli, and the right graph is the inhibition effect on Staphylococcus aureus. It can be seen from the figure that the antibacterial cotton cellulose aerogel loaded with Scutellaria antibacterial components has obvious antibacterial effect. The antibacterial ring of Staphylococcus aureus reaches 3.1 mm, and that of Escherichia coli reaches 2.8 mm.

[0033] Example 4 An antibacterial cotton cellulose material is prepared by the following method: Take 1 g of waste cotton fabric (pure cotton towel), cut it into pieces, and soak it in a conical flask with deionized water for 16 h. After centrifugation, try to squeeze out the water. Add DMAC to immerse the waste cotton fabric, centrifuge to squeeze out the DMAC, and then add DMAC to immerse the waste cotton fabric again. Repeat 2-3 times, and finally soak the waste cotton fabric in DMAC for 16 h.

[0034] Add 40 mL of DMAC and 3.2 g of LiCl to the conical flask, heat and stir until the LiCl is completely dissolved, and then filter it with a microporous filter while hot.

[0035] Squeeze out the DMAC soaked in the waste cotton fabric, put the waste cotton fabric into the conical flask, add 40 mL of DMAC containing 8% LiCl, and place the conical flask on a magnetic stirrer with heating function. Heat and stir at 60°C until the waste cotton fabric is completely dissolved. Use a centrifuge or sand core funnel to separate the undissolved fibers from the cellulose solution, and obtain the cellulose solution of the waste cotton fabric with a concentration of about 2.5%.

[0036] DMAC in the cellulose solution and LiCl are exchanged into the spinning bath by solvent exchange, and since the boiling point of DMAC is higher than that of water, DMAC can be recovered by fractional distillation. After the fractional distillation, LiCl remains in the heating container, and the dissolution solution is recycled by this method.

[0037] Figure 4 In the figure, a is the morphology of the pure cotton towel after being dissolved in the DMAC solution containing 8% LiCl, b is the cellulose solution obtained after the pure cotton towel is dissolved, and c is the fiber morphology after the cellulose solution is spun into fibers by the wet spinning method.

[0038] Comparative Example 1 Different from Example 1, andradix andrographolides, prunella vulgaris and honeysuckle are used to replace scutellaria baicalensis, and the rest of the operations are the same as those in Example 1.

[0039] The antibacterial effects of different traditional Chinese medicine antibacterial components obtained in Comparative Example 1 are shown in Table 3 below.

[0040] Table 3 Comparison of antibacterial effects of different traditional Chinese medicine antibacterial components (diameter of inhibition zone / mm)

[0041] Note: In Table 3, A, B, C, D and E respectively represent n-hexane, dichloromethane, methanol, ethyl acetate and water as extraction solvents.

[0042] It can be seen from the results of Table 3 that although the organic solvent extracts of andradix andrographolides, prunella vulgaris and honeysuckle have certain antibacterial effects on staphylococcus aureus and escherichia coli, the antibacterial effects are not as good as those of the organic solvent extracts of scutellaria baicalensis, especially the ethyl acetate extract of scutellaria baicalensis. Therefore, scutellaria baicalensis is more suitable as a traditional Chinese medicine antibacterial component carrier for antibacterial cotton materials to improve the broad-spectrum antibacterial effect of cotton products.

[0043] The above are only preferred embodiments of the present application, and do not limit the patent scope of the present application. Any equivalent changes and modifications made within the scope of the present application should still fall within the scope of the present application.

Claims

1. An antibacterial cotton cellulose material, characterized in that, It is prepared using antibacterial components of traditional Chinese medicine and cotton cellulose solution. The antibacterial cotton cellulose material is in the form of, but is not limited to, any one of fiber filaments, fiber aerogels, and fiber films. The antibacterial components of traditional Chinese medicine are extracted from at least one of the following traditional Chinese medicinal materials: Scutellaria baicalensis, Andrographis paniculata, Prunella vulgaris, and Lonicera japonica.

2. The method for preparing the antibacterial cotton cellulose material according to claim 1, characterized in that, The steps include the following: Preparation of S1 antibacterial component of traditional Chinese medicine: Take the raw material of traditional Chinese medicine, crush it and add ethyl acetate to just submerge the raw material. Reflux and extract 3-4 times, then combine the extracts, evaporate the solvent, and purify by silica gel column chromatography. Use petroleum ether and ethyl acetate as elution solvents, gradually increase the proportion of ethyl acetate, and divide each 50 mL fraction into 5 fractions. Combine the fractions containing the same components into 5 components by thin-layer chromatography, dry them, and the antibacterial component of traditional Chinese medicine is obtained. Preparation of S2 cotton cellulose solution: Cotton or waste cotton products are used as raw materials. After being shredded, the raw materials are first soaked in deionized water, centrifuged, and the deionized water is squeezed out. Then, N,N-dimethylacetamide is added to immerse the raw materials. After centrifugation, the raw materials are soaked repeatedly 2-3 times. Finally, N,N-dimethylacetamide and LiCl are added, heated to 50-70℃ and stirred until LiCl is completely dissolved. The mixture is filtered while hot, and the filter residue is squeezed. A LiCl N,N-dimethylacetamide solution is added, and the mixture is stirred at 50-70℃ until the raw materials are dissolved. The mixture is then filtered to obtain cotton cellulose solution. Loading of antibacterial components of traditional Chinese medicine in S3: The cotton cellulose solution prepared in S2 was mixed with the N,N-dimethylacetamide solution of antibacterial components of traditional Chinese medicine, and then placed in a mold to solidify. The mixture was then soaked in water to allow N,N-dimethylacetamide and LiCl to dissolve completely. Finally, it was quick-frozen under liquid nitrogen conditions to obtain antibacterial cotton cellulose aerogel. Alternatively, the cotton cellulose solution obtained in S2 can be mixed with the antibacterial components of traditional Chinese medicine and then wet-spun to obtain cotton fibers containing antibacterial agents.

3. The preparation method according to claim 2, characterized in that, In S1, the volume ratio of petroleum ether to ethyl acetate is 10:1 to 0:

1.

4. The preparation method according to claim 2, characterized in that, In S2, the heating temperature is 60°C.

5. The preparation method according to claim 2, characterized in that, In S3, the coagulation process involves placing the mixture at room temperature in the dark for 12-36 hours, immersing the formed gel in water for 48 hours, changing the water every 12 hours, and using liquid nitrogen for quick freezing at a temperature of -120 to -40°C.

6. The preparation method according to claim 2, characterized in that, In S3, the volume ratio of the cotton cellulose solution to the N,N-dimethylacetamide solution containing the antibacterial component of traditional Chinese medicine is 3~5:1, the concentration of the cotton cellulose solution is 1%~1.5%, and the concentration of the antibacterial component of traditional Chinese medicine in the N,N-dimethylacetamide solution is 8~15 mg / mL.

7. The application of the antibacterial cotton cellulose material as described in claim 1 in the preparation of antibacterial products.

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