An organic non-woven fabric based on silver ion zeolite and its antibacterial application

Abstract

The present invention belongs to the field of antibacterial organic non-woven fabrics, and discloses an organic non-woven fabric based on silver ion zeolite and its antibacterial application. It comprises silver ion zeolite and an organic polymer; the organic polymer is any one of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) and polyacrylic acid (PAA) composition, and polyvinylidene fluoride (PVDF). The antibacterial organic non-woven fabric based on silver ion zeolite is prepared by electrostatic spinning of a mixture of silver ion zeolite and organic matter. It is an organic non-woven fabric with high antibacterial properties and long-lasting effect. Experimental results show that the non-woven fabric prepared by spinning silver ion zeolite and certain organic substances still has good antibacterial activity and long-lasting effect, which expands the antibacterial application scenarios of silver ion zeolite.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial organic nonwoven fabrics, and particularly relates to an organic nonwoven fabric based on silver ion zeolite and its antibacterial application, and more particularly to an organic nanofiber nonwoven fabric based on silver ion nano Y-zeolite and its antibacterial application. Background Art

[0002] Silver ions are widely used in antimicrobial agents due to their high efficacy, broad spectrum, resistance to drug resistance, and safety. Furthermore, silver also inhibits the growth of fungi and viruses. Silver additives used in antimicrobial applications typically take the form of silver salts, nanosilver, and silver metal. Given the diverse applications, the methods for incorporating silver into these products vary widely, each with its own specificity for each application. However, the bactericidal properties of silver ions are dependent on many factors, including the carrier form and the environment in which they are used. Recent studies have shown that zeolites, with their microporous structure, are optimal carriers for silver ions. Due to their vast internal space and negatively charged framework, zeolites can store large quantities of silver ions. Furthermore, the silver ions within zeolites release silver ions in response to the ionic strength of the external environment, resulting in long-lasting bactericidal activity. Therefore, zeolites loaded with silver ions can reduce the amount of silver required in the antimicrobial agent while maintaining equivalent bactericidal activity, while also prolonging bactericidal activity and achieving long-term antimicrobial protection.

[0003] Although silver ion zeolite has a good bactericidal effect, it cannot be used directly in many applications. Instead, it needs to be embedded in organic fibers. When encapsulated in organic materials, most bactericidal materials cannot directly come into contact with bacteria, thus losing their bactericidal effect. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, the present invention provides an organic non-woven fabric based on silver ion zeolite and its antibacterial application, which is an organic non-woven fabric with high antibacterial properties and long-lasting effect.

[0005] The above-mentioned object of the present invention is achieved through the following technical solutions:

[0006] An antibacterial organic nonwoven fabric based on silver ion zeolite comprises the silver ion zeolite and an organic polymer; the organic polymer is any one of polymethyl methacrylate (PMMA), a combination of polyvinyl alcohol (PVA) and polyacrylic acid (PAA), and polyvinylidene fluoride (PVDF). The antibacterial organic nonwoven fabric based on silver ion zeolite is produced by electrospinning a mixture of the silver ion zeolite and an organic material.

[0007] The specific preparation method of the above non-woven fabric is:

[0008] (1) dissolving a certain amount of organic polymer in an organic mixed solvent and stirring to form a viscous organic solution;

[0009] The organic polymer is any one of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) and polyacrylic acid (PAA) composition, and polyvinylidene fluoride (PVDF);

[0010] The organic solutions were prepared in the following proportions: (a) 2 g PMMA was dissolved in 12 ml N,N-dimethylformamide (DMF); (b) 0.5 g PVA and 0.5 g PAA were mixed and added to 10 ml water and stirred at 80 °C; (c) 0.8 g PVDF was dissolved in 4.8 ml DMF and 3.2 ml acetone solution.

[0011] (2) adding the silver ion zeolite to the viscous organic solution prepared in step (1) and stirring and ultrasonicating the silver ion zeolite to uniformly disperse it in the organic solution.

[0012] The silver ion zeolite was added in the following proportions: (a) 0.2 g of silver ion zeolite was added to the PMMA solution; (b) 0.1 g of silver ion zeolite was added to the mixed solution of PVA and PAA; and (c) 0.08 g of silver ion zeolite was added to the PVDF solution.

[0013] (3) The mixed solution obtained in step (2) is poured into a syringe, and a non-woven fabric containing silver ion zeolite and organic mixed fibers is prepared on an electrospinning instrument according to certain parameters. The electrospinning voltages of the mixed solutions are as follows: the spinning voltage of the mixed solution of PMMA and zeolite is 15 kV, the spinning voltage of the mixed solution of PVA and PAA and zeolite is 23 kV, and the spinning voltage of the mixed solution of PVDF and zeolite is 25 kV.

[0014] The non-woven fabric prepared above is used in antibacterial applications, specifically: antibacterial application of the non-woven fabric against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300; the organic non-woven fabric containing silver ion zeolite has a good inhibitory effect on both Staphylococcus aureus and Escherichia coli.

[0015] The beneficial effects of the present invention compared with the prior art are:

[0016] The preparation method of this invention encapsulates silver ion zeolite within nanofibers, allowing the silver ions in the zeolite to be slowly released from the organic fibers, achieving a bactericidal effect and imparting bactericidal properties to organic nonwoven fabrics. Experimental results demonstrate that nonwoven fabrics prepared by spinning silver ion zeolite with certain organic materials still exhibit good and long-lasting antimicrobial activity, expanding the antimicrobial application of silver ion zeolite. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The figure is the XRD pattern of the silver ion zeolite used in the present invention.

[0018] Figure 2 This is a TEM image of the silver ion zeolite used in the present invention.

[0019] Figure 3 This is the SEM image of PMMA nanofibers obtained by electrospinning in the present invention.

[0020] Figure 4 This is the SEM image of nanofibers obtained by electrospinning a mixture of PMMA and silver ion zeolite according to the present invention.

[0021] Figure 5 This is the SEM image of PVA+PAA nanofibers obtained by electrospinning in the present invention.

[0022] Figure 6 This is the SEM image of nanofibers obtained by electrospinning a mixture of PVA+PAA and silver ion zeolite of the present invention.

[0023] Figure 7 This is the SEM image of PVDF nanofibers obtained by electrospinning in the present invention.

[0024] Figure 8 This is a SEM image of nanofibers obtained by electrospinning a mixture of PVDF and silver ion zeolite of the present invention.

[0025] Figure 9 The graph shows the antibacterial effects of the nonwoven fabrics prepared in Examples 1-3 of the present invention on Escherichia coli. The graphs include: PVA+PAA: a nonwoven fabric blended with PVA and PAA; PVA+PAA (100°C): a nonwoven fabric blended with PVA and PAA and then heated; PVA+PAA+zeolite: an electrospun nonwoven fabric blended with PVA and PAA and zeolite; PVDF; PMMA; PVA: electrospun nonwovens made from organic materials alone; PVDF+zeolite; PMMA+zeolite; PVA+zeolite: electrospun nonwovens blended with organic materials and zeolite; and PVDF+zeolite (immersion): a PVDF nonwoven fabric immersed in a zeolite suspension.

[0026] Figure 10 The graph shows the antibacterial effects of nonwoven fabrics prepared in Examples 1-3 of the present invention on Staphylococcus aureus. The graphs include: PVA+PAA: a nonwoven fabric blended with PVA and PAA; PVA+PAA (100°C): a nonwoven fabric blended with PVA and PAA and then heated; PVA+PAA+zeolite: an electrospun nonwoven fabric blended with PVA and PAA and zeolite; PVDF; PMMA; PVA: electrospun nonwovens made from organic materials alone; PVDF+zeolite; PMMA+zeolite; PVA+zeolite: electrospun nonwovens blended with organic materials and zeolite; and PVDF+zeolite (immersion): a PVDF nonwoven fabric immersed in a zeolite suspension.

[0027] Figure 11 This is a graph showing the antibacterial test results of the non-woven fabric prepared in Example 4 of the present invention against Staphylococcus aureus at different times. DETAILED DESCRIPTION

[0028] The present invention is described in detail below through specific examples, but the scope of protection of the present invention is not limited. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be obtained from commercial channels. The synthesis method of silver ion zeolite is as follows: the molar composition of the zeolite synthesis solution: 9Na2O: 0.7Al2O3: 10SiO2: 160H2O. The initial reactants are mixed to prepare two initial solutions, namely A and B. Solution A is prepared by dissolving 2g NaOH in 4g distilled water, and then slowly adding 0.189g aluminum powder. Solution B is mixed with 10g colloidal silica (Ludox-HS 30, 30wt.% SiO 2, Solution B was then incubated at 100°C for 6 minutes. Solution A was added dropwise to solution B with vigorous stirring and maintained at room temperature for 24 hours. Finally, the mixture was heated at 50°C for 45 hours. The resulting zeolite was then placed in a 0.5 mol silver nitrate solution for 24 hours for ion exchange, yielding a silver ion zeolite.

[0029] Example 1

[0030] (1) 2 g of PMMA was dissolved in 12 ml of N,N-dimethylformamide (DMF) and stirred for 2 hours.

[0031] (2) Add 0.2 g of silver ion zeolite to the PMMA solution prepared in step (1), and stir and ultrasonicate to make it uniformly mixed.

[0032] (3) The mixed solution obtained in step (2) was poured into a syringe, and the spinning voltage of the solution after the mixture of PMMA and zeolite was 15 kV on an electrospinning instrument to prepare a non-woven fabric containing silver ion zeolite and organic mixed fiber.

[0033] The prepared nonwoven fabric is used in antibacterial applications. The antibacterial properties against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC25922 were tested according to standard procedures. The antibacterial test process is as follows:

[0034] Single colonies of Escherichia coli and Staphylococcus aureus were picked and cultured overnight in LB and MH2 medium, respectively. 1% of the colonies were then transferred to fresh medium and cultured to the mid-logarithmic phase. The bacterial concentration was assessed using a spectrophotometer and adjusted to a final concentration of 1 × 10 5 -1×10 6 CFU / ml.

[0035] Place approximately 4-6 mg of nonwoven fabric in a sterile EP tube.

[0036] 200-300ul bacterial suspension (1×10 5-1×10 6 CFU / ml) was added to the fiber sample in the EP tube, and the bacterial solution was pipetted to evenly distribute on the fiber. The EP tube was incubated at 37°C with shaking for 120 minutes.

[0037] After 120 minutes, 450-600 μl of 0.5 wt% thioglycolic acid was added, ultrasonicated for 2 minutes, and the supernatant culture fluid was diluted and plated for counting. Figure 9 and 10 shown.

[0038] Example 2

[0039] (1) 0.5 g of PVA and 0.5 g of PAA were mixed and added to 10 ml of water, and stirred at 80°C for 4 hours.

[0040] (2) 0.1 g of silver ion zeolite was added to the mixed solution of PVA and PAA prepared in step (1), and stirred and ultrasonicated to make it uniformly mixed.

[0041] (3) The mixed solution obtained in step (2) was poured into a syringe, and a non-woven fabric containing silver ion zeolite and organic mixed fibers was prepared on an electrospinning instrument. The spinning voltage of the solution after PVA and PAA were mixed with zeolite was 23 kV.

[0042] The prepared nonwoven fabric is used in antibacterial applications. The antibacterial properties against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300 were tested according to standard procedures. Figure 9 and 10 The test method is the same as that in Example 1.

[0043] Example 3

[0044] (1) 0.8 g of PVDF was dissolved in 4.8 ml of DMF and 3.2 ml of acetone solution and stirred for 2 hours.

[0045] (2) 0.1 g of silver ion zeolite was added to the PVDF solution prepared in step (1), and stirred and ultrasonicated to make it uniformly mixed.

[0046] (3) The mixed solution obtained in step (2) was poured into a syringe, and a non-woven fabric containing silver ion zeolite and organic mixed fiber was prepared on an electrospinning instrument, wherein the spinning voltage of the solution after the PVDF and zeolite were mixed was 25 kV.

[0047] The prepared nonwoven fabric is used in antibacterial applications. The antibacterial properties against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300 were tested according to standard procedures. Figure 9 and 10 The test method is the same as that in Example 1.

[0048] Example 4

[0049] Antibacterial test of organic non-woven fabric containing silver ion zeolite on Staphylococcus aureus at different time periods.

[0050] (1) A certain amount of organic polymer is dissolved in an organic mixed solvent and stirred to form a viscous organic solution.

[0051] The organic polymer is any one of polymethyl methacrylate (PMMA), a mixed solution of polyvinyl alcohol (PVA) and polyacrylic acid (PAA), and polyvinylidene fluoride (PVDF).

[0052] The organic solutions are prepared as follows:

[0053] (a) 2 g of PMMA was dissolved in 12 ml of N,N-dimethylformamide (DMF);

[0054] (b) 0.5 g of PVA and 0.5 g of PAA were mixed and added to 10 ml of water and stirred at 80 °C;

[0055] (c) 0.8 g of PVDF was dissolved in 4.8 ml of DMF and 3.2 ml of acetone solution.

[0056] (2) adding the silver ion zeolite to the organic solution prepared in step (1) and stirring and ultrasonicating the silver ion zeolite to uniformly disperse it in the organic solution.

[0057] The silver ion zeolite addition ratios are:

[0058] (a) 0.2 g of silver ion zeolite was added to the PMMA solution;

[0059] (b) 0.1 g of silver ion zeolite was added to the mixed solution of PVA and PAA;

[0060] (c) 0.08 g of silver ion zeolite was added to the PVDF solution.

[0061] (3) Pour the mixed solution obtained in step (2) into a syringe, and prepare a non-woven fabric containing silver ion zeolite and organic mixed fibers on an electrospinning instrument.

[0062] The electrospinning voltages of the solutions were as follows: 15 kV for the mixed solution of PMMA and zeolite, 23 kV for the mixed solution of PVA and PAA and zeolite, and 25 kV for the mixed solution of PVDF and zeolite.

[0063] The application of the prepared nonwoven fabric in antibacterial. The antibacterial results of the nonwoven fabric after 6 hours and 24 hours in Staphylococcus aureus were tested according to the standard procedure. Figure 11 The test method is the same as that in Example 1.

[0064] Example 5

[0065] (1) 0.5 g of PVA and 0.5 g of PAA were mixed and added to 10 ml of water, and stirred at 80°C for 4 hours.

[0066] (2) 0.1 g of silver ion zeolite was added to the mixed solution of PVA and PAA prepared in step (1), and stirred and ultrasonicated to make it uniformly mixed.

[0067] (3) The mixed solution obtained in step (2) was poured into a syringe, and a non-woven fabric containing silver ion zeolite and organic mixed fibers was prepared on an electrospinning instrument. The spinning voltage of the solution after PVA and PAA were mixed with zeolite was 23 kV.

[0068] (4) The prepared nonwoven fabric was heated at 100°C for 1 hour to increase its hydrophobicity.

[0069] The prepared nonwoven fabric is used in antibacterial applications. The antibacterial properties against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300 were tested according to standard procedures. Figure 9 and 10 The test method is the same as that in Example 1.

[0070] Example 6

[0071] (1) 0.8 g of PVDF was dissolved in 4.8 ml of DMF and 3.2 ml of acetone solution and stirred for 2 hours.

[0072] (2) The mixed solution obtained in step (1) was poured into a syringe, and a non-woven fabric of organic fibers was prepared on an electrospinning instrument, wherein the spinning voltage of the PVDF solution was 25 kV.

[0073] (3) The non-woven fabric prepared in step (2) was immersed in a zeolite suspension containing 3% silver ions for 1 hour, and then dried at 50° C. for 1 hour.

[0074] The prepared nonwoven fabric is used in antibacterial applications. The antibacterial properties against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300 were tested according to standard procedures. Figure 9 and 10 The test method is the same as that in Example 1.

[0075] Comparative Example

[0076] A non-woven fabric without silver ion zeolite was prepared as a comparative example of antibacterial performance.

[0077] (1) A certain amount of organic polymer is dissolved in an organic mixed solvent and stirred to form a viscous organic solution.

[0078] The organic polymer is any one of polymethyl methacrylate (PMMA), a mixed solution of polyvinyl alcohol (PVA) and polyacrylic acid (PAA), and polyvinylidene fluoride (PVDF).

[0079] The organic solutions are prepared as follows:

[0080] (a) 2 g of PMMA was dissolved in 12 ml of N,N-dimethylformamide (DMF);

[0081] (b) 0.5 g of PVA and 0.5 g of PAA were mixed and added to 10 ml of water and stirred at 80 °C;

[0082] (c) 0.8 g of PVDF was dissolved in 4.8 ml of DMF and 3.2 ml of acetone solution.

[0083] (2) Pour the mixed solution obtained in step (1) into a syringe, and prepare a non-woven fabric of organic fibers on an electrospinning instrument.

[0084] The electrospinning voltages of the solutions were: 15 kV for PMMA solution, 23 kV for PVA and PAA mixed solution, and 25 kV for PVDF solution.

[0085] The application of the prepared nonwoven fabric in antibacterial. The antibacterial results of the nonwoven fabric in Staphylococcus aureus and Escherichia coli were tested according to standard procedures. Figure 9 , 10, 11. The test method is the same as that in Example 1.

[0086] The antibacterial test results of the non-woven fabrics prepared in the above examples and comparative examples are as follows: Figure 9 and Figure 10 The figures show the antibacterial effects of nonwoven fabrics against Escherichia coli and Staphylococcus aureus. The results show that nonwoven fabrics containing silver ion zeolite exhibit superior antibacterial efficacy compared to the control sample. PMMA, PVA, PAA, and PVDF containing silver ion zeolite exhibit significant bactericidal effects against E. coli. The PMMA nonwoven fabric containing silver ion zeolite virtually eliminated all E. coli within 2 hours. Only the PVA and PAA nonwoven fabrics containing silver ion zeolite showed some effectiveness against Staphylococcus aureus.

[0087] Figure 11The nonwoven fabrics demonstrated a long-lasting bactericidal effect against Staphylococcus aureus. PVA and PAA nonwovens containing silver ion zeolite, PMMA nonwovens containing silver ion zeolite, and PVDF nonwovens containing silver ion zeolite all demonstrated good bactericidal effects against Staphylococcus aureus over time. Among them, PMMA containing silver ion zeolite showed the most significant bactericidal effect against Staphylococcus aureus over a long period of time, essentially killing all Staphylococcus aureus within 6 hours.

[0088] The bactericidal effects of silver ion zeolites coated with different organic matter are different, which is related to the characteristics of the organic matter itself and needs further study.

[0089] The above-described embodiments are only preferred embodiments of the present invention, and are not intended to be all feasible embodiments of the present invention. Any obvious modifications made by a person skilled in the art without departing from the principles and spirit of the present invention should be considered to be included within the scope of protection of the claims of the present invention.

Claims

1. An antibacterial organic nonwoven fabric based on silver ion zeolite, characterized in that: The invention comprises silver ion zeolite and an organic polymer; the organic polymer is any one of polymethyl methacrylate, polyvinyl alcohol and polyacrylic acid composition, and polyvinylidene fluoride; the antibacterial organic non-woven fabric based on silver ion zeolite is prepared by mixing silver ion zeolite and organic matter and performing electrostatic spinning, and is specifically prepared by the following steps: (1) dissolving a certain amount of organic polymer in an organic mixed solvent and stirring to form a viscous organic solution; The organic polymer is any one of PMMA, PVA, PAA, and PVDF; The organic solutions were prepared in the following proportions: (a) 2 g PMMA was dissolved in 12 ml N,N-dimethylformamide; (b) 0.5 g PVA and 0.5 g PAA were mixed and added to 10 ml water and stirred at 80 °C; (c) 0.8 g PVDF was dissolved in 4.8 ml DMF and 3.2 ml acetone solution; (2) adding the silver ion zeolite to the viscous organic solution prepared in step (1) and stirring and ultrasonicating the silver ion zeolite to uniformly disperse it in the organic solution; The silver ion zeolite was added in the following proportions: (a) 0.2 g of silver ion zeolite was added to the PMMA solution; (b) 0.1 g of silver ion zeolite was added to the PVA and PAA mixed solution; (c) 0.08 g of silver ion zeolite was added to the PVDF solution; (3) The mixed solution obtained in step (2) is poured into a syringe, and a non-woven fabric containing silver ion zeolite and organic mixed fiber is prepared on an electrospinning instrument according to certain parameters; the electrospinning voltage of each mixed solution is: the spinning voltage of the mixed solution of PMMA and zeolite is 15 kV, the spinning voltage of the mixed solution of PVA and PAA and zeolite is 23 kV, and the spinning voltage of the mixed solution of PVDF and zeolite is 25 kV.

2. The use of an antibacterial organic nonwoven fabric based on silver ion zeolite in antibacterial applications as claimed in claim 1, characterized in that: Antibacterial application of nonwoven fabrics against Staphylococcus aureus ATCC43300 and Escherichia coli ATCC43300.

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