Modified nano-silver material as well as preparation method and application thereof

Abstract

The invention discloses a modified nano-silver material and a preparation method and application thereof, the preparation method comprises the following steps: S1, heating 3-(2 '-chloroethyl)-5, 5-dimethyl hydantoin and polyethyleneimine for reaction to obtain modified polyethyleneimine; s2, the modified polyethyleneimine and cysteine are subjected to a dehydration reaction, and cysteine modified polyethyleneimine is obtained; s3, reacting the cysteine modified polyethyleneimine with nano-silver to obtain a modified nano-silver material; the mass ratio of the polyethyleneimine to the cysteine is 1: (0.1-1.0). According to the modified nano-silver material disclosed by the invention, nano-silver is uniformly embedded into a three-dimensional structure of the modified nano-silver material, so that the structural stability of the modified nano-silver material is improved; and the synergistic antibacterial effect of the 3-(2 '-chloroethyl)-5, 5-dimethylhydantoin, the polyethyleneimine and the nano-silver is better played, so that the antibacterial material prepared from the modified nano-silver material has a very good antibacterial effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antibacterial materials, and more particularly to a modified nano-silver material and a preparation method and application thereof. BACKGROUND

[0002] In the face of bacteria invading the human body and parasitizing and breeding in the human body, and then causing diseases to prevail, adopting effective protective measures to block the contact between bacteria and the human body can play a good effect on the prevention and treatment of diseases. Medical instruments and supplies made of glass are indispensable in the prevention and treatment of diseases and are objects in close contact with the human body, so antibacterial treatment of medical instruments and supplies made of glass can effectively block the contact between bacteria and the human body.

[0003] At present, there are many methods for antibacterial treatment of medical instruments and supplies made of glass, one of which is to coat antibacterial materials on the surface of medical instruments and supplies made of glass. After the antibacterial materials adhere to the surface of medical instruments and supplies made of glass, they can inhibit the growth and reproduction of bacteria or kill bacteria for a long period of time, thereby playing a sustained antibacterial role.

[0004] Therefore, it is of great significance to develop a modified nano-silver material capable of improving the antibacterial effect of antibacterial materials for treating glass products. SUMMARY

[0005] The present application aims to solve the problems of the prior art and provide a modified nano-silver material and a preparation method and application thereof.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] In a first aspect, the present application provides a preparation method of a modified nano-silver material, comprising the following steps:

[0008] S1. Heating 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine to react to obtain modified polyethyleneimine;

[0009] S2. Dehydrating the modified polyethyleneimine with cysteine to obtain cysteine-modified polyethyleneimine;

[0010] S3. Reacting the cysteine-modified polyethyleneimine with nano-silver to obtain a modified nano-silver material;

[0011] The mass ratio of the polyethyleneimine and the cysteine is 1:(0.1-1.0).

[0012] The application prepares a modified nano-silver material by grafting cysteine-modified polyethylene imine synthesized by 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethylene imine and cysteine on the surface of nano-silver through Ag-S bond.

[0013] In the modified nano-silver material of the application, the long main chain of the cysteine-modified polyethylene imine synthesized by 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethylene imine and cysteine has abundant branched chain structure, can form a three-dimensional structure by bending and folding, and can uniformly inlay nano-silver therein, thereby improving the structural stability of the modified nano-silver material, making the modified nano-silver material continuously exert its antibacterial effect, and further better exerting the synergistic antibacterial effect of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethylene imine and nano-silver, and making the antibacterial material prepared by using the modified nano-silver material have good antibacterial effect.

[0014] It is worth noting that by adjusting the mass ratio of polyethylene imine and cysteine, sufficient nano-silver with antibacterial effect can be stably connected on the cysteine-modified polyethylene imine through Ag-S bond; at the same time, polyethylene imine can retain sufficient amino groups to maintain the antibacterial effect of polyethylene imine; thereby improving the antibacterial effect of the modified nano-silver material and the antibacterial material prepared by using the modified nano-silver material.

[0015] Preferably, the mass ratio of the polyethylene imine and the cysteine is 1:(0.3-0.8).

[0016] Preferably, in step S3, the particle size (or diameter) of the nano-silver is 15-100 nm.

[0017] More preferably, in step S3, the particle size (or diameter) of the nano-silver is one of 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 80 nm, 100 nm or a range value of any two thereof.

[0018] Still more preferably, in step S3, the particle size of the nano-silver is 40-80 nm.

[0019] In the application, nano-silver with a suitable particle size can be more uniformly inlaid in the cysteine-modified polyethylene imine to form a three-dimensional structure, which can better improve the structural stability of the modified nano-silver material, thereby being conducive to better improving the antibacterial effect of the modified nano-silver material and the antibacterial material prepared by using the modified nano-silver material.

[0020] Preferably, the mass ratio of the polyethylene imine and the nano-silver is 1:(0.001-0.010).

[0021] More preferably, the mass ratio of the polyethyleneimine and the nano-silver is 1:(0.003-0.007).

[0022] Preferably, in the step S1, the polyethyleneimine is at least one of linearized polyethyleneimine and branched polyethyleneimine.

[0023] More preferably, the weight average molecular weight Mw of the linearized polyethyleneimine is 25000-40000.

[0024] More preferably, the weight average molecular weight Mw of the branched polyethyleneimine is 800-25000.

[0025] In the present application, compared with the linearized polyethyleneimine, the branched polyethyleneimine can provide more abundant branched structures for the modified polyethyleneimine and cysteine, and can further improve the structural stability of the modified nano-silver material, and ultimately better improve the antibacterial effect of the modified nano-silver material and the antibacterial material prepared by using the modified nano-silver material.

[0026] Preferably, in the step S1, the mass ratio of the 3-(2'-chloroethyl)-5,5-dimethylhydantoin and the polyethyleneimine is (0.1-1):1.

[0027] More preferably, in the step S1, the mass ratio of the 3-(2'-chloroethyl)-5,5-dimethylhydantoin and the polyethyleneimine is (0.3-0.8):1.

[0028] Preferably, in the step S1, the heating temperature is 60-85℃.

[0029] Preferably, in the step S1, the reaction time is 12-36h.

[0030] Preferably, in the step S1, the liquid environment of the reaction is water, and the solid-liquid ratio of the polyethyleneimine and water is 1g:(5-25)mL.

[0031] Preferably, in the step S1, the preparation method of the 3-(2'-chloroethyl)-5,5-dimethylhydantoin comprises the following steps:

[0032] (1) 5,5-dimethylhydantoin, strong base and 1-bromo-2-chloroethane are reacted at 75-90℃, distilled under reduced pressure, extracted with ethyl acetate and water as the extraction liquid, and the upper clear organic phase 1 is reserved;

[0033] (2) The upper clear organic phase 1 and the sodium bicarbonate aqueous solution are mixed and shaken, and the upper clear organic phase 2 is reserved;

[0034] (3) Anhydrous sodium sulfate is added to the upper clear organic phase 2, and the filtrate is collected by suction filtration;

[0035] (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground, pulverized, and dried to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

[0036] More preferably, in step (1), the molar ratio of 5,5-dimethylhydantoin, the strong base and 1-bromo-2-chloroethane is 1:1:(1-2).

[0037] More preferably, in step (1), the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0038] More preferably, in step (1), the reaction time is 8-24 hours.

[0039] More preferably, in step (1), the liquid environment of the reaction is anhydrous ethanol, and the solid-liquid ratio of 5,5-dimethylhydantoin to anhydrous ethanol is 1g:(3-8)mL.

[0040] More preferably, in step (1), the endpoint of the vacuum distillation is the appearance of a white or pale yellow viscous solid-liquid mixture.

[0041] More preferably, in step (1), the volume ratio of ethyl acetate to water is (1-2):1.

[0042] More preferably, in step (2), the mass fraction of the sodium bicarbonate aqueous solution is 4-8%.

[0043] More preferably, in step (4), the drying temperature is 35-45°C.

[0044] Preferably, in step S2, the temperature of the dehydration reaction is 10-50℃ and the time is 0.5-24h.

[0045] Preferably, in step S2, the catalyst for the dehydration reaction is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS).

[0046] More preferably, the molar ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) to N-hydroxysuccinimide (NHS) is 1:(0.5-3).

[0047] More preferably, the molar ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) to the mass ratio of polyethyleneimine is (2-6) mmol:1g.

[0048] Preferably, in step S3, the reaction temperature is 15-40℃ and the time is 0.1-5h.

[0049] In a second aspect, the present invention provides a modified silver nanomaterial, which is prepared by the method for preparing modified silver nanomaterials as described in the first aspect.

[0050] Thirdly, the present invention provides an application of modified silver nanomaterials in antibacterial applications.

[0051] Fourthly, the present invention provides an antibacterial material comprising modified nano-silver material in a mass ratio of 1:(0.5-3) and a silane derivative of 5,5-dimethylhydantoin;

[0052] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows: 5,5-dimethylhydantoin, a strong base and 3-chloropropyltriethoxysilane are mixed and reacted to obtain the silane derivative of 5,5-dimethylhydantoin.

[0053] In this invention, the antibacterial material, due to containing a silane derivative of 5,5-dimethylhydantoin, is able to adhere better to the surface of glass products and has a stronger antibacterial effect.

[0054] Preferably, the mass ratio of the modified silver nanomaterial to the silane derivative of 5,5-dimethylhydantoin is 1:(1-2).

[0055] Preferably, the reaction temperature is 80-100℃ and the time is 3-6h.

[0056] Preferably, the molar ratio of 5,5-dimethylhydantoin, the strong base, and 3-chloropropyltriethoxysilane is 1:1:(1-1.5).

[0057] Preferably, the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0058] Preferably, the method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0059] a. Add 5,5-dimethylhydantoin and a strong base to ethanol and mix. Remove the ethanol by vacuum distillation to obtain sodium 5,5-dimethylhydantoin crystals.

[0060] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF) and react to obtain a silane derivative of 5,5-dimethylhydantoin.

[0061] More preferably, in step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:10-100mL.

[0062] More preferably, the solid-liquid ratio of 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1g:10-100mL.

[0063] In this invention, after reacting 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane, sodium chloride insoluble in N,N-dimethylformamide (DMF) can be removed by filtration.

[0064] Fifthly, the present invention provides a method for preparing an antibacterial material, comprising:

[0065] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0066] In a sixth aspect, the present invention provides an antibacterial glass article, comprising a glass article having an antibacterial material as described in the fifth aspect.

[0067] In a seventh aspect, the present invention provides a method for preparing an antibacterial glass article, comprising:

[0068] (1) Add modified nano-silver material and 5,5-dimethylhydantoin silane derivative to a solvent and mix to obtain mixture A;

[0069] (2) Apply or spray mixture A onto the surface of the glass product to obtain the antibacterial glass product.

[0070] Preferably, the solvent is at least one of N,N-dimethylformamide (DMF), ethanol, and methanol.

[0071] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0072] This invention prepares modified silver nanomaterials by grafting cysteine-modified polyethyleneimine containing 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethyleneimine, and cysteine ​​onto the surface of silver nanomaterials via Ag-S bonds.

[0073] In the modified silver nanomaterial of this invention, the long main chain of cysteine-modified polyethyleneimine, synthesized using 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethyleneimine, and cysteine, has abundant branched structures. It can be bent and folded to form a three-dimensional structure, allowing silver nanoparticles to be uniformly embedded within it. This improves the structural stability of the modified silver nanomaterial, enabling it to continuously exert its antibacterial effect. Furthermore, it better leverages the synergistic antibacterial effect of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethyleneimine, and silver nanoparticles, resulting in antibacterial materials prepared using the modified silver nanomaterial exhibiting excellent antibacterial properties.

[0074] It is worth noting that by adjusting the mass ratio of polyethyleneimine to cysteine, sufficient antibacterial silver nanoparticles can be stably linked to cysteine-modified polyethyleneimine via Ag-S bonds; at the same time, polyethyleneimine can retain enough amino groups to maintain its antibacterial effect; thereby improving the antibacterial effect of modified silver nanoparticles and antibacterial materials prepared using modified silver nanoparticles.

[0075] In this invention, nano-silver of suitable particle size can be more uniformly embedded in the three-dimensional structure formed by cysteine-modified polyethyleneimine, which can better improve the structural stability of the modified nano-silver material, thereby improving the antibacterial effect of the modified nano-silver material and the antibacterial material prepared using the modified nano-silver material.

[0076] In this invention, branched polyethyleneimine, compared to linearized polyethyleneimine, can provide a richer branched structure for modified polyethyleneimine and cysteine, which can further improve the structural stability of modified silver nanomaterials and ultimately better enhance the antibacterial effect of modified silver nanomaterials and antibacterial materials prepared using modified silver nanomaterials. Detailed Implementation

[0077] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0078] The experimental methods in the following examples, comparative examples, application examples, and comparative application examples, unless otherwise specified, are generally performed under conventional conditions in the art or under conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market.

[0079] The use of reagents in the various embodiments, comparative examples, application examples, and comparative application examples of this invention is as follows:

[0080] Nano silver 1, nano silver with a particle size (or diameter) of 60 nm, is achieved by using Aladdin's 0.1 mg / mL nano silver particle dispersion S196431;

[0081] Nano silver 2, nano silver with a particle size (or diameter) of 80 nm, is achieved by using Aladdin's 0.1 mg / mL nano silver particle dispersion S196433;

[0082] Nano silver 3, nano silver with a particle size (or diameter) of 40 nm, is achieved by using Aladdin's 0.1 mg / mL nano silver particle dispersion S196429;

[0083] Nano silver 4, nano silver with a particle size (or diameter) of 15 nm, is achieved by using Aladdin's 0.1 mg / mL nano silver particle dispersion S196426;

[0084] Nano silver 5, nano silver with a particle size (or diameter) of 100nm, is achieved by using Aladdin's nano silver conductive ink (silver powder) N196406;

[0085] Ultrafine silver powder, silver powder with a particle size (or diameter) of 2μm (i.e. 2000nm), S871820, McLean;

[0086] Branched polyethyleneimine 1, weight-average molecular weight Mw = 25000, P766520, Maclean;

[0087] Branched polyethyleneimine 3, weight-average molecular weight Mw = 800, P871833, Maclean;

[0088] Linear polyethyleneimine 1, weight-average molecular weight Mw = 40000, P924174, McLean;

[0089] Linear polyethyleneimine 2, weight-average molecular weight Mw = 25000, P982589, McLean;

[0090] The preparation method of 3-(2'-chloroethyl)-5,5-dimethylhydantoin specifically includes the following steps:

[0091] (1) Add 5,5-dimethylhydantoin, sodium hydroxide and 1-bromo-2-chloroethane to anhydrous ethanol, heat to 80°C and reflux for 10 h, distill under reduced pressure until a white or pale yellow viscous solid-liquid mixture appears. Use ethyl acetate and water in a volume ratio of 1:1 as the extraction solution for extraction, and retain the organic phase 1 of the supernatant liquid.

[0092] (2) Mix the organic phase 1 of the supernatant with a 5% sodium bicarbonate aqueous solution, shake for 5 min, and retain the organic phase 2 of the supernatant.

[0093] (3) Add anhydrous sodium sulfate to the organic phase 2 of the upper clear liquid, shake for 5 min, filter, and collect the filtrate;

[0094] (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground and dried at 40°C to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

[0095] In step (1), the molar ratio of 5,5-dimethylhydantoin, sodium hydroxide and 1-bromo-2-chloroethane is 1:1:1.6, the solid-liquid ratio of 5,5-dimethylhydantoin to anhydrous ethanol is 1g:6mL, and the volume ratio of the extract to anhydrous ethanol is 1:1.

[0096] The volume ratio of the sodium bicarbonate aqueous solution to anhydrous ethanol is 1:1.

[0097] Example 1

[0098] This embodiment provides a modified silver nanomaterial, the preparation method of which includes the following steps:

[0099] S1. Add 5.0 g of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and 10.0 g of branched polyethyleneimine 1 (weight average molecular weight Mw = 25000) to 200 mL of water, heat to 75 °C and react for 24 h to obtain modified polyethyleneimine;

[0100] S2. Add 60 mmol of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), 60 mmol of N-hydroxysuccinimide (NHS) and 5.0 g of cysteine ​​to modified polyethyleneimine, and heat to 30 °C for 4 h to carry out dehydration reaction to obtain cysteine-modified polyethyleneimine.

[0101] S3. Add 0.05g of nano-silver 1 [particle size (or diameter) of 60nm] to cysteine-modified polyethyleneimine and react at 25℃ for 2h to obtain modified nano-silver material;

[0102] The mass ratio of polyethyleneimine to cysteine ​​is 1:0.5.

[0103] In step S1, the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is 0.5:1;

[0104] The mass ratio of polyethyleneimine to nano-silver is 1:0.005.

[0105] Examples 2-5 and Comparative Examples 1-2

[0106] Examples 2-5 and Comparative Examples 1-2 provide different modified silver nanomaterials. The difference between them and Example 1 is that the mass ratio of polyethyleneimine and cysteine ​​is different. All other aspects are the same as in Example 1, as shown in the table below:

[0107] Table 1. Mass ratio of polyethyleneimine and cysteine ​​in Examples 1-5 and Comparative Examples 1-2

[0108]

[0109] Examples 6-9 and Comparative Example 3

[0110] Examples 6-9 and Comparative Example 3 provide different modified silver nanomaterials, which differ from Example 1 in that the particle size (or diameter) of the silver nanomaterials is different. All other aspects are the same as in Example 1, as shown in the table below:

[0111] Table 2. Particle size (or diameter) of silver nanometers in Examples 1, 6-9 and Comparative Example 3.

[0112]

[0113] Examples 10-14 and Comparative Example 4

[0114] Examples 10-14 and Comparative Example 4 provide different modified silver nanomaterials, differing from Example 1 in the mass ratio of polyethyleneimine to silver nanomaterials. All other aspects are the same as in Example 1, as detailed in the table below:

[0115] Table 3. Mass ratio of polyethyleneimine and nanosilver in Examples 1, 10-14 and Comparative Example 4.

[0116]

[0117] Examples 15-17

[0118] Examples 15-17 provide different modified silver nanomaterials, which differ from Example 1 in that the type of polyethyleneimine is different; otherwise, they are the same as Example 1, as shown in the table below:

[0119] Table 4. Types of Polyethyleneimine in Examples 1, 15-17

[0120] Polyethyleneimine species Weight average molecular weight Mw Example 1 Branched polyethyleneimine 1 25000 Example 15 Branched polyethyleneimine 2 800 Example 16 Linear polyethyleneimine 1 40000 Example 17 Linear polyethyleneimine 2 25000

[0121] Examples 18-21

[0122] Examples 18-21 provide different modified silver nanomaterials, which differ from Example 1 in the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine. All other aspects are the same as in Example 1, as shown in the table below:

[0123] Table 5. Mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine in Examples 1, 18-21

[0124]

[0125] Application examples and comparative application examples

[0126] Application Example 1

[0127] This application example provides an antibacterial material comprising the modified nano-silver material of Example 1 in a mass ratio of 1:1.5 and a silane derivative of 5,5-dimethylhydantoin;

[0128] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0129] a. Add 5,5-dimethylhydantoin and sodium hydroxide to anhydrous ethanol and mix. Remove the ethanol by vacuum distillation to obtain 5,5-dimethylhydantoin sodium salt crystals.

[0130] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF), react at 90°C for 4 h, filter to remove sodium chloride that is insoluble in N,N-dimethylformamide (DMF), and obtain silane derivatives of 5,5-dimethylhydantoin.

[0131] The molar ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloropropyltriethoxysilane is 1:1:1.2.

[0132] In step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:20mL;

[0133] The solid-liquid ratio of the 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1 g: 20 mL.

[0134] The preparation method of the above-mentioned antibacterial material includes:

[0135] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0136] Application Example 2-21 and Comparison with Application Example 1-4

[0137] Application Examples 2-21 and Comparative Application Examples 1-4 provide different antibacterial materials. The difference between Application Examples 2-21 and Comparative Application Examples 1-4 is that the modified nano-silver materials of Examples 2-21 and 1-4, respectively, are used instead of the modified nano-silver materials of Example 1. All other aspects are the same as Application Example 1.

[0138] Application Example 22

[0139] This application example provides an antibacterial material comprising the modified nano-silver material of Example 1 in a mass ratio of 1:1 and a silane derivative of 5,5-dimethylhydantoin;

[0140] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0141] a. Add 5,5-dimethylhydantoin and sodium hydroxide to anhydrous ethanol and mix. Remove the ethanol by vacuum distillation to obtain 5,5-dimethylhydantoin sodium salt crystals.

[0142] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF), react at 90°C for 4 h, filter to remove sodium chloride that is insoluble in N,N-dimethylformamide (DMF), and obtain silane derivatives of 5,5-dimethylhydantoin.

[0143] The molar ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloropropyltriethoxysilane is 1:1:1.2.

[0144] In step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:20mL;

[0145] The solid-liquid ratio of the 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1 g: 20 mL.

[0146] The preparation method of the above-mentioned antibacterial material includes:

[0147] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0148] Application Example 23

[0149] This application example provides an antibacterial material comprising the modified nano-silver material of Example 1 in a mass ratio of 1:2 and a silane derivative of 5,5-dimethylhydantoin;

[0150] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0151] a. Add 5,5-dimethylhydantoin and sodium hydroxide to anhydrous ethanol and mix. Remove the ethanol by vacuum distillation to obtain 5,5-dimethylhydantoin sodium salt crystals.

[0152] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF), react at 90°C for 4 h, filter to remove sodium chloride that is insoluble in N,N-dimethylformamide (DMF), and obtain silane derivatives of 5,5-dimethylhydantoin.

[0153] The molar ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloropropyltriethoxysilane is 1:1:1.2.

[0154] In step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:20mL;

[0155] The solid-liquid ratio of the 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1 g: 20 mL.

[0156] The preparation method of the above-mentioned antibacterial material includes:

[0157] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0158] Application Example 24

[0159] This application example provides an antibacterial material comprising the modified nano-silver material of Example 1 in a mass ratio of 1:0.5 and a silane derivative of 5,5-dimethylhydantoin;

[0160] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0161] a. Add 5,5-dimethylhydantoin and sodium hydroxide to anhydrous ethanol and mix. Remove the ethanol by vacuum distillation to obtain 5,5-dimethylhydantoin sodium salt crystals.

[0162] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF), react at 90°C for 4 h, filter to remove sodium chloride that is insoluble in N,N-dimethylformamide (DMF), and obtain silane derivatives of 5,5-dimethylhydantoin.

[0163] The molar ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloropropyltriethoxysilane is 1:1:1.2.

[0164] In step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:20mL;

[0165] The solid-liquid ratio of the 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1 g: 20 mL.

[0166] The preparation method of the above-mentioned antibacterial material includes:

[0167] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0168] Application Example 25

[0169] This application example provides an antibacterial material comprising the modified nano-silver material of Example 1 in a mass ratio of 1:3 and a silane derivative of 5,5-dimethylhydantoin;

[0170] The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows:

[0171] a. Add 5,5-dimethylhydantoin and sodium hydroxide to anhydrous ethanol and mix. Remove the ethanol by vacuum distillation to obtain 5,5-dimethylhydantoin sodium salt crystals.

[0172] b. Add 5,5-dimethylhydantoin sodium salt crystals and 3-chloropropyltriethoxysilane to N,N-dimethylformamide (DMF), react at 90°C for 4 h, filter to remove sodium chloride that is insoluble in N,N-dimethylformamide (DMF), and obtain silane derivatives of 5,5-dimethylhydantoin.

[0173] The molar ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloropropyltriethoxysilane is 1:1:1.2.

[0174] In step a, the solid-liquid ratio of 5,5-dimethylhydantoin and ethanol is 1g:20mL;

[0175] The solid-liquid ratio of the 5,5-dimethylhydantoin and N,N-dimethylformamide (DMF) is 1 g: 20 mL.

[0176] The preparation method of the above-mentioned antibacterial material includes:

[0177] Antibacterial materials are obtained by mixing modified nano-silver materials and silane derivatives of 5,5-dimethylhydantoin.

[0178] Performance testing

[0179] Antimicrobial tests were performed on the antimicrobial materials in each application example and the comparative application example:

[0180] 1. Antibacterial test against Escherichia coli:

[0181] (1) Preparation of antibacterial glass 6-well plate (antibacterial glass product):

[0182] A. Add 1.0 g of the antibacterial material from each application example or comparative application example to 20 mL of N,N-dimethylformamide (DMF) and mix to obtain mixture A;

[0183] B. Apply mixture A to the bottom surface of a 6-well plate (glass product) made of 30206 confocal glass at a rate of 0.7 mL per well to obtain an antibacterial 6-well glass plate (antibacterial glass product).

[0184] (2) Using the dilution plating method, 2.3 mL of LB liquid culture medium was added to each well of the antibacterial glass 6-well plate from step (1), followed by 500 μL of 10% LB liquid culture medium. 6 A CFU / mL suspension of Escherichia coli (8099, CICC10899) was incubated at 37°C for 4 h. Then, 100 μL was diluted 1000 times with LB liquid medium, and 100 μL was spread on Luria-Bertani (LB) agar medium. After incubation at 37°C for 20 h, the colony count was calculated.

[0185] (3) The antibacterial rate of the antimicrobial materials in each application example and the comparative application example was calculated using the following formula:

[0186] The inhibition rate (%) of antibacterial material against Escherichia coli = (number of colonies in the blank control group - number of colonies in the experimental group) / number of colonies in the blank control group × 100%;

[0187] 2. Antibacterial test against Staphylococcus aureus:

[0188] (1) Preparation of antibacterial glass 6-well plate (antibacterial glass product):

[0189] A. Add 1.0 g of the antibacterial material from each application example or comparative application example to 20 mL of N,N-dimethylformamide (DMF) and mix to obtain mixture A;

[0190] B. Apply mixture A to the bottom surface of a 6-well plate (glass product) made of 30206 confocal glass at a rate of 0.7 mL per well to obtain an antibacterial 6-well glass plate (antibacterial glass product).

[0191] (2) Using the dilution plating method, 2.3 mL of LB liquid culture medium was added to each well of the antibacterial glass 6-well plate from step (1), followed by 500 μL of 10% LB liquid culture medium. 6 A CFU / mL suspension of Staphylococcus aureus (Escherichia coli 8099, CICC10899) was incubated at 37°C for 4 h. Then, 100 μL was diluted 1000 times with LB liquid medium, and 100 μL was spread on Luria-Bertani (LB) agar medium. After incubation at 37°C for 20 h, the colony count was calculated.

[0192] (3) The antibacterial rate of the antimicrobial materials in each application example and the comparative application example was calculated using the following formula:

[0193] The inhibition rate (%) of antibacterial material against Staphylococcus aureus = (number of colonies in the blank control group - number of colonies in the experimental group) / number of colonies in the blank control group × 100%;

[0194] The experimental results are shown in the table below:

[0195] Table 6. Antibacterial effects of antibacterial materials in various application examples and comparative application examples.

[0196]

[0197]

[0198] As shown in Table 6, in the modified silver nanomaterial of the present invention, the long main chain of cysteine-modified polyethyleneimine synthesized using 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethyleneimine, and cysteine ​​has a rich branched structure. It can be bent and folded to form a three-dimensional structure, and the silver nanoparticles are uniformly embedded in it, thereby improving the structural stability of the modified silver nanomaterial. This allows the modified silver nanomaterial to continuously exert its antibacterial effect, and further enhances the synergistic antibacterial effect of 3-(2'-chloroethyl)-5,5-dimethylhydantoin, polyethyleneimine, and silver nanoparticles. As a result, the antibacterial material prepared using the modified silver nanomaterial has a very good antibacterial effect.

[0199] It is worth noting that by adjusting the mass ratio of polyethyleneimine to cysteine, sufficient antibacterial silver nanoparticles can be stably linked to cysteine-modified polyethyleneimine via Ag-S bonds; at the same time, polyethyleneimine can retain enough amino groups to maintain its antibacterial effect; thereby improving the antibacterial effect of modified silver nanoparticles and antibacterial materials prepared using modified silver nanoparticles.

[0200] As can be seen from Application Examples 1, 6-9 and Comparative Application Example 3, in this invention, nano-silver of suitable particle size can be more uniformly embedded in the three-dimensional structure formed by cysteine-modified polyethyleneimine, which can better improve the structural stability of the modified nano-silver material, thereby improving the antibacterial effect of the modified nano-silver material and the antibacterial material prepared using the modified nano-silver material.

[0201] As can be seen from Application Examples 1 and 15-17, in this invention, branched polyethyleneimine, compared with linearized polyethyleneimine, can provide a richer branched structure for modified polyethyleneimine and cysteine, which can further improve the structural stability of modified silver nanomaterials and ultimately better improve the antibacterial effect of modified silver nanomaterials and antibacterial materials prepared using modified silver nanomaterials.

[0202] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing modified silver nanomaterials, characterized in that, Includes the following steps: S1. 3-(2'-chloroethyl)-5,5-dimethylhydantoin and polyethyleneimine were reacted by heating to obtain modified polyethyleneimine; S2. Modified polyethyleneimine is reacted with cysteine ​​to undergo a dehydration reaction to obtain cysteine-modified polyethyleneimine; S3. Cysteine-modified polyethyleneimine was reacted with nano-silver to obtain modified nano-silver materials; The mass ratio of polyethyleneimine to cysteine ​​is 1:(0.1-1.0).

2. The method for preparing the modified silver nanomaterial as described in claim 1, characterized in that, The mass ratio of polyethyleneimine to cysteine ​​is 1:(0.3-0.8).

3. The method for preparing the modified silver nanomaterial as described in claim 1, characterized in that, Includes at least one of the following (1)-(4): (1) In step S3, the particle size of the nano-silver is 15-100nm; (2) The mass ratio of the polyethyleneimine to the nano-silver is 1:(0.001-0.010); (3) In step S1, the polyethyleneimine is at least one of linearized polyethyleneimine and branched polyethyleneimine; (4) In step S1, the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is (0.1-1):

1.

4. The method for preparing the modified silver nanomaterial as described in claim 3, characterized in that, Includes at least one of the following (1)-(5): (1) In step S3, the particle size of the nano-silver is 40-80 nm; (2) The mass ratio of the polyethyleneimine to the nano-silver is 1:(0.003-0.007); (3) The weight-average molecular weight Mw of the linearized polyethyleneimine is 25,000-40,000; (4) The weight-average molecular weight Mw of the branched polyethyleneimine is 800-25000; (5) In step S1, the mass ratio of 3-(2'-chloroethyl)-5,5-dimethylhydantoin to polyethyleneimine is (0.3-0.8):

1.

5. The method for preparing the modified silver nanomaterial as described in claim 1, characterized in that, In step S1, the preparation method of 3-(2'-chloroethyl)-5,5-dimethylhydantoin includes the following steps: (1) 5,5-Dimethylhydantoin, a strong base and 1-bromo-2-chloroethane were reacted at 75-90℃, and the mixture was distilled under reduced pressure. Ethyl acetate and water were used as the extraction solution to extract the organic phase 1 of the supernatant. (2) Mix the organic phase 1 of the supernatant liquid with the sodium bicarbonate aqueous solution, shake, and retain the organic phase 2 of the supernatant liquid. (3) Add anhydrous sodium sulfate to the organic phase 2 of the upper clear liquid, filter, and collect the filtrate; (4) The filtrate was concentrated and distilled under reduced pressure to obtain crystals, which were then ground, pulverized, and dried to obtain 3-(2'-chloroethyl)-5,5-dimethylhydantoin.

6. A modified silver nanomaterial, characterized in that, It was prepared using the preparation method of the modified silver nanomaterial as described in any one of claims 1-5.

7. The application of the modified silver nanomaterial as described in claim 6 in antibacterial applications.

8. An antibacterial material, characterized in that, The modified silver nanomaterial of claim 6 and a silane derivative of 5,5-dimethylhydantoin are included in a mass ratio of 1:(0.5-3). The method for preparing the silane derivative of 5,5-dimethylhydantoin is as follows: 5,5-dimethylhydantoin, a strong base and 3-chloropropyltriethoxysilane are mixed and reacted to obtain the silane derivative of 5,5-dimethylhydantoin.

9. The antibacterial material as described in claim 8, characterized in that, The mass ratio of the modified silver nanomaterial to the silane derivative of 5,5-dimethylhydantoin is 1:(1-2).

10. An antibacterial glass product, characterized in that, Includes glass articles, wherein the glass articles are provided with the antibacterial material as described in any one of claims 8-9.

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