Nanocomposite material as well as preparation method and application thereof
The nanocomposite materials were prepared by attaching iron-cobalt Prussian blue analogs to the inner core of molybdenum disulfide, and the problems of insufficient peroxidase activity and antibacterial performance of Prussian blue nanoparticles were solved, achieving efficient antibacterial effects.
Patent Information
- Application Number
- CN202510318477.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-18
- Publication Date
- 2025-07-11
AI Technical Summary
The existing Prussian blue nanoparticles have weak peroxidase activity and poor antibacterial performance, which cannot meet the requirements of antibacterial materials.
A nanocomposite material was prepared, including a core of molybdenum disulfide and an iron-cobalt Prussian blue analogue attached to its surface. The nanocomposite material was prepared by solvothermal method to improve its peroxidase mimic enzyme activity and antibacterial properties.
Nanocomposites show excellent peroxidase mimicking enzyme activity, and the reactive oxygen produced by catalysis has strong antibacterial effects, and are suitable for the preparation of antibacterial products.
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Figure CN120288800A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to nanozyme antibacterial technology, and specifically, to a nano composite material, a preparation method thereof, and an application thereof. Background Art
[0002] Bacteria are an important part of the human microbiome and exist in various tissues. Bacterial pathogenesis is caused by the disruption of the normal coexistence of bacteria and host cells in healthy individuals, leading to infections and even global pandemics. For example, Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) can cause severe intestinal diseases and inflammatory infections. However, traditional antibacterial drugs can develop drug resistance during long-term use, and some antibacterial materials also have problems such as potential toxicity and high cost. Therefore, the development of highly efficient antibacterial materials is a severe and urgent need.
[0003] Artificial mimetic enzymes are nanomaterials with enzymatic catalytic properties. Compared with natural enzymes, mimetic enzymes show great potential in various applications in multiple fields due to their mimetic activity, stability, ease of storage, and cost-effectiveness. For example, Prussian blue nanoparticles and their analogues exhibit peroxidase catalytic activity and have good manufacturing processes. However, the existing Prussian blue nanoparticles and their analogues have weak peroxidase activity and poor antibacterial properties, and cannot meet the requirements of antibacterial materials. Summary of the Invention
[0004] The purpose of the present invention is to overcome the problems of weak peroxidase activity and poor antibacterial properties of existing Prussian blue nanoparticles, and to provide a nano composite material, a preparation method thereof, and an application thereof. The nano composite material has more excellent peroxidase mimetic enzyme activity and strong antibacterial activity.
[0005] To achieve the above purpose, the first aspect of the present invention provides a nano composite material, which includes a core containing molybdenum disulfide and an iron-cobalt Prussian blue analogue attached to the surface of the core.
[0006] Preferably, the core has a block structure.
[0007] Preferably, the weight ratio of the iron-cobalt Prussian blue analogue to the molybdenum disulfide is 1-50:1, more preferably 10-46:1.
[0008] The second aspect of the present invention provides a preparation method of a nano composite material, which includes: reacting the iron-cobalt Prussian blue analogue with molybdate and thioamide to carry out Reaction I.
[0009] Preferably, the preparation process of the iron-cobalt Prussian blue analogue includes: reacting iron cyanide with a cobalt salt in the presence of a polybasic acid in Reaction II.
[0010] Preferably, the polybasic acid is selected from at least one of malic acid, citric acid, and oxalic acid, and more preferably citric acid.
[0011] Preferably, the iron cyanide is selected from at least one of potassium ferrocyanide, sodium ferrocyanide, magnesium ferrocyanide, and calcium ferrocyanide, and more preferably potassium ferrocyanide and / or sodium ferrocyanide.
[0012] Preferably, the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, and more preferably cobalt chloride.
[0013] Preferably, the process of mixing the iron cyanide with the cobalt salt includes: mixing the iron cyanide with a part of the polybasic acid to form Solution A, mixing the cobalt salt with another part of the polybasic acid to form Solution B, and then mixing Solution A and Solution B.
[0014] Preferably, the molar ratio of the iron cyanide to the cobalt salt is 0.8 - 1.2:1.
[0015] Preferably, the conditions of Reaction II include: temperature of 10 - 30 °C and time of 40 - 80 min.
[0016] Preferably, the molybdate is selected from at least one of ammonium molybdate, potassium molybdate, and sodium molybdate, and preferably ammonium molybdate.
[0017] Preferably, the thioamide is selected from at least one of thioformamide, thioacetamide, thiopropionamide, and thiobutyramide, and more preferably thioacetamide.
[0018] Preferably, the conditions of Reaction I include: temperature of 150 - 200 °C and time of 20 - 30 h.
[0019] Preferably, Reaction I is carried out in a polyol solvent, and the polyol is selected from at least one of ethylene glycol, 1,3-propanediol, 1,2-propanediol, and 1,4-butanediol.
[0020] Preferably, the weight ratio of the iron-cobalt Prussian blue analogue, the thioamide, and the molybdate is 1 - 40:30 - 125:1, and more preferably 9 - 37.5:50 - 75:1.
[0021] Preferably, the method further includes: performing solid-liquid separation on the product of Reaction I to obtain a solid, and then washing and drying the solid.
[0022] The third aspect of the present invention provides a nanocomposite material prepared by the above preparation method.
[0023] The fourth aspect of the present invention provides the application of the above-mentioned nanocomposite as a mimic enzyme.
[0024] Preferably, the mimic enzyme is peroxidase, and more preferably catalase.
[0025] The fifth aspect of the present invention provides the application of the above-mentioned nanocomposite in the preparation of antibacterial products.
[0026] Preferably, the antibacterial product is a drug against Escherichia coli and / or Staphylococcus aureus.
[0027] Through the above technical solutions, the beneficial effects of the present invention are as follows:
[0028] The nanocomposite provided by the present invention exhibits excellent peroxidase mimic enzyme properties, and through the action of reactive oxygen species generated during the catalytic process on bacteria, it can exhibit strong antibacterial activity, expanding its application in the antibacterial field and providing a new direction for the development of antibacterial products. Description of the Drawings
[0029] The drawings are used to provide a further understanding of the present invention, and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention, but do not constitute a limitation to the present invention. In the drawings:
[0030] Figure 1 They are the scanning electron microscope (SEM) images, mapping images of the FeCoPBA / MoS2 composite material prepared in Example 1, and the SEM image of pure MoS2. Among them, (a) is the SEM image of the FeCoPBA / MoS2 composite material prepared in Example 1, with a scale bar of 5.00 μm; (b) is the SEM image of pure MoS2 prepared in Comparative Example 2, with a scale bar of 3.00 μm; (c) is the mapping image (in the order of Ch 1, C, N, O, Mo, S, Fe, Co) of the FeCoPBA / MoS2 composite material prepared in Example 1, with a scale bar of 4 μm.
[0031] Figure 2 They are the infrared spectra (IR) of the FeCoPBA / MoS2 composite material prepared in Example 1, pure FeCoPBA prepared in Comparative Example 1, and pure MoS2 prepared in Comparative Example 2.
[0032] Figure 3 They are the X-ray photoelectron spectroscopy (XPS) analysis images of the FeCoPBA / MoS2 composite material prepared in Example 1.
[0033] Figure 4UV absorption diagrams for comparing the peroxidase-mimicking enzyme properties of the FeCoPBA / MoS2 composite material prepared in Example 1, the individual FeCoPBA prepared in Comparative Example 1, and the individual MoS2 prepared in Comparative Example 2;
[0034] Figure 5 Growth curves of the FeCoPBA / MoS2 composite material prepared in Example 1 as a peroxidase mimic acting on Escherichia coli and Staphylococcus aureus. The FeCoPBA / MoS2 nanocomposite solution (concentration 0.2 mg / mL) or H2O2 solution (concentration 0.2 mM) prepared in Example 1 was added separately as a control group, and the bacterial solution without any reagent was used as a reference group. Detailed implementation manners
[0035] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0036] The first aspect of the present invention provides a nanocomposite material, which includes a core containing molybdenum disulfide (MoS2) and an iron-cobalt prussian blue analogue (FeCoPBA) attached to the surface of the core.
[0037] During the R & D process, the inventors of the present invention unexpectedly found that attaching an iron-cobalt prussian blue analogue to the surface of molybdenum disulfide to form a FeCoPBA / MoS2 composite nanomaterial can exhibit excellent peroxidase mimic enzyme activity, which is greatly improved compared to the activity of the iron-cobalt prussian blue analogue itself. And with the assistance of H2O2, by the reactive oxygen species generated during the catalytic process acting on bacteria, it can exhibit strong antibacterial effects, expanding its application in antibacterial aspects and providing a new direction for the development of antibacterial products.
[0038] According to the present invention, preferably, the core has a block structure.
[0039] According to the present invention, preferably, the weight ratio of the iron-cobalt prussian blue analogue to the molybdenum disulfide is 1 - 50:1, more preferably 10 - 46:1.
[0040] The second aspect of the present invention provides a method for preparing a nanocomposite material, which includes: reacting an iron-cobalt prussian blue analogue with a molybdate and a thioamide in Reaction I.
[0041] The nanocomposite material of the present invention is obtained by a solvothermal method. The preparation process is simple and convenient, easy to operate, and conducive to industrial development and application.
[0042] According to the present invention, preferably, the preparation process of the iron-cobalt Prussian blue analogue includes: reacting an iron cyanide with a cobalt salt in the presence of a polybasic acid to carry out Reaction II.
[0043] In the present invention, the polybasic acid can be any organic acid containing multiple carboxyl groups applicable to the reaction process of the iron cyanide and the cobalt salt. Preferably, the polybasic acid is selected from at least one of malic acid, citric acid, and oxalic acid, and more preferably citric acid. The inventors have found that in this preferred mode, it is beneficial to improve the peroxidase mimetic enzyme activity and antibacterial activity of the nanocomposite material.
[0044] In the present invention, the iron cyanide can be any iron cyanide capable of preparing an iron-cobalt Prussian blue analogue. Preferably, the iron cyanide is selected from at least one of potassium ferrocyanide, sodium ferrocyanide, magnesium ferrocyanide, and calcium ferrocyanide, and more preferably potassium ferrocyanide and / or sodium ferrocyanide.
[0045] In the present invention, the cobalt salt can be any cobalt salt capable of preparing an iron-cobalt Prussian blue analogue. Preferably, the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, and more preferably cobalt chloride.
[0046] The above-mentioned raw material substances can be obtained by commercial purchase or can be prepared by oneself using the methods in the prior art.
[0047] According to the present invention, preferably, the process of mixing the iron cyanide and the cobalt salt includes: mixing the iron cyanide with a part of the polybasic acid to form Solution A, mixing the cobalt salt with another part of the polybasic acid to form Solution B, and then mixing Solution A and Solution B. The inventors have found that in this preferred mode, it is beneficial to the contact between the iron cyanide and the cobalt salt and improve the yield of the iron-cobalt Prussian blue analogue.
[0048] According to the present invention, preferably, the molar ratio of the iron cyanide to the cobalt salt is 0.8 - 1.2:1, specifically, it can be 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, or any value between the above two values.
[0049] According to the present invention, preferably, the conditions of Reaction II include: the temperature is 10 - 30 °C, specifically it can be 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, or any value between the above two values; the time is 40 - 80 min, specifically it can be 40 min, 50 min, 60 min, 70 min, 80 min, or any value between the above two values. The inventors have found that in this preferred mode, it is beneficial to improve the yield of the iron-cobalt Prussian blue analogue.
[0050] In the present invention, the preparation process of the iron-cobalt Prussian blue analogue further includes: washing and drying the solid obtained after solid-liquid separation of the product of Reaction II to obtain the solid powder of the iron-cobalt Prussian blue analogue.
[0051] According to the present invention, preferably, the molybdate is selected from at least one of ammonium molybdate, potassium molybdate and sodium molybdate, and preferably ammonium molybdate.
[0052] According to the present invention, preferably, the thioamide is selected from at least one of thioformamide, thioacetamide, thiopropionamide and thiobutyramide, and more preferably thioacetamide.
[0053] The above raw material substances can be obtained by commercial purchase or can be prepared by the methods in the prior art.
[0054] According to the present invention, preferably, the conditions of Reaction I include: the temperature is 150 - 200 °C, specifically it can be 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, or any value between the above two values; the time is 20 - 30 h, specifically it can be 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, or any value between the above two values. The inventors have found that in this preferred mode, it is beneficial to the attachment effect of the iron-cobalt Prussian blue analogue on the surface of molybdenum disulfide, and improve the peroxidase mimetic enzyme activity and antibacterial activity of the nanocomposite.
[0055] According to the present invention, preferably, Reaction I is carried out in a polyol solvent, and the polyol is selected from at least one of ethylene glycol, 1,3-propanediol, 1,2-propanediol and 1,4-butanediol, and more preferably ethylene glycol.
[0056] According to the present invention, preferably, the weight ratio of the iron-cobalt Prussian blue analogue, the thioamide to the molybdate is 1 - 40:30 - 125:1; more preferably 9 - 37.5:50 - 75:1.
[0057] According to the present invention, preferably, the method further includes: performing solid-liquid separation on the product of Reaction I to obtain a solid, and then washing and drying the solid.
[0058] In the present invention, the solid-liquid separation method can be centrifugation, filtration, etc., and preferably centrifugation is adopted.
[0059] The third aspect of the present invention provides the nanocomposite prepared by the above preparation method.
[0060] The fourth aspect of the present invention provides the application of the above nanocomposite as a mimetic enzyme. Preferably, the mimetic enzyme is peroxidase, and more preferably catalase. The nanocomposite provided by the present invention can catalyze hydrogen peroxide (H2O2) to generate a large amount of reactive oxygen species (ROS), act on the cell membrane, and has good antibacterial and bactericidal effects.
[0061] The fifth aspect of the present invention provides the application of the above nanocomposite in the preparation of antibacterial products.
[0062] According to the present invention, preferably, the antibacterial product is a drug against Escherichia coli and / or Staphylococcus aureus.
[0063] The antibacterial product provided by the present invention may contain the above nanocomposite, may also contain hydrogen peroxide (H2O2) as an auxiliary, and in addition, may also contain other suitable excipients.
[0064] According to a particularly preferred embodiment of the present invention, the preparation method of the nanocomposite includes:
[0065] S1. Mix a part of the polybasic acid with the ferrocyanide to form solution A, mix another part of the polybasic acid with the cobalt salt to form solution B, then mix solution A and solution B, and react at a temperature of 10 - 30 °C for 40 - 80 min to obtain product I; the polybasic acid is selected from at least one of malic acid, citric acid, and oxalic acid, the ferrocyanide is selected from at least one of potassium ferrocyanide, sodium ferrocyanide, magnesium ferrocyanide, and calcium ferrocyanide, the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, and the molar ratio of the ferrocyanide to the cobalt salt is 0.8 - 1.2:1;
[0066] Wash and dry the solid obtained after solid-liquid separation of product I to obtain a solid powder of iron-cobalt Prussian blue analogue.
[0067] S2. After mixing the iron-cobalt Prussian blue analogue with molybdate and thioamide in a polyol solvent, react at a temperature of 150 - 200 °C for 20 - 30 h to obtain product II; the molybdate is selected from at least one of ammonium molybdate, potassium molybdate, and sodium molybdate, the thioamide is selected from at least one of thioformamide, thioacetamide, thiopropionamide, and thiobutyramide, the polyol is selected from at least one of ethylene glycol, 1,3-propanediol, 1,2-propanediol, and 1,4-butanediol, and the weight ratio of the iron-cobalt Prussian blue analogue to the molybdate is 1 - 40:1;
[0068] The solid is obtained by performing solid-liquid separation on the product II, and then the solid is washed and dried.
[0069] The present invention will be described in detail below through examples.
[0070] In the following examples, the formula of the liquid medium is 0.5 g of tryptone, 0.25 g of yeast extract powder, 0.5 g of sodium chloride plus 50 mL of water.
[0071] Unless otherwise specified, the raw materials and reagents used are all conventional commercially available products.
[0072] Example 1
[0073] S1. Accurately weigh 0.0856 g of K3[Fe(CN)6] and 0.9605 g of citric acid and mix and stir them into solution A. Accurately weigh 0.0565 g of CoCl2·6H2O and 0.9605 g of citric acid and mix and stir them into solution B. Add solution A to solution B, and stir and react at room temperature (about 25 °C) for 1 h to obtain product I. After centrifuging product I, the solid is washed and dried to obtain a solid powder of iron-cobalt Prussian blue analogue (FeCoPBA) for standby;
[0074] S2. Accurately weigh 0.18 g of FeCoPBA, 0.0048 g of (NH4)2MoO4, 0.3 g of thioacetamide C2H5NS, and 15 mL of ethylene glycol solution, mix them evenly, and transfer them to a reaction kettle to react at 180 °C for 24 h to obtain product II. The solid obtained by centrifuging product II is washed and dried to obtain a nanocomposite.
[0075] Example 2
[0076] S1. Accurately weigh 0.0626 g of K3[Fe(CN)6] and 0.9605 g of citric acid and mix and stir them into solution A. Accurately weigh 0.0565 g of CoCl2·6H2O and 0.9605 g of citric acid and mix and stir them into solution B. Add solution A to solution B, and stir and react at 10 °C for 80 min to obtain product I. After centrifuging product I, the solid is washed and dried to obtain a solid powder of iron-cobalt Prussian blue analogue (FeCoPBA) for standby;
[0077] S2. Accurately weigh 0.09 g of FeCoPBA, 0.0048 g of (NH4)2MoO4, 0.24 g of thioacetamide C2H5NS, and 15 mL of ethylene glycol solution, mix them evenly, and transfer them to a reaction kettle to react at 150 °C for 30 h to obtain product II. The solid obtained by centrifuging product II is washed and dried to obtain a nanocomposite.
[0078] Example 3
[0079] S1. Accurately weigh 0.0938 g of K3[Fe(CN)6] and 0.9605 g of malic acid, mix and stir to form solution A. Accurately weigh 0.0565 g of CoCl2·6H2O and 0.9605 g of citric acid, mix and stir to form solution B. Add solution A to solution B, stir and react at 30 °C for 40 min to obtain product I. After centrifuging product I, wash and dry the solid to obtain the solid powder of iron-cobalt Prussian blue analogue (FeCoPBA) for standby;
[0080] S2. Accurately weigh 0.045 g of FeCoPBA, 0.0048 g of (NH4)2MoO4, 0.36 g of thioacetamide C3H7NS, and 15 mL of ethylene glycol solution, mix and stir evenly, then transfer to a reaction kettle and react at 200 °C for 20 h to obtain product II. Wash and dry the solid obtained by centrifuging product II to obtain the nanocomposite.
[0081] Example 4
[0082] Prepare the nanocomposite according to the method of Example 1, except that the mass of FeCoPBA in step S2 is replaced with 0.023 g.
[0083] Example 5
[0084] Prepare the nanocomposite according to the method of Example 1, except that the mass of FeCoPBA in step S2 is replaced with 0.015 g.
[0085] Example 6
[0086] Prepare the nanocomposite according to the method of Example 1, except that the mass of FeCoPBA in step S2 is replaced with 0.0075 g.
[0087] Example 7
[0088] Prepare the nanocomposite according to the method of Example 1, except that the mass of FeCoPBA in step S2 is replaced with 0.18 g and the mass of thioacetamide C2H5NS is replaced with 0.6 g.
[0089] Example 8
[0090] Prepare the nanocomposite according to the method of Example 1, except that the mass of FeCoPBA in step S2 is replaced with 0.18 g and the mass of (NH4)2MoO4 is replaced with 0.0096 g.
[0091] Example 9
[0092] Prepare the nanocomposite according to the method of Example 3, except that step S2 is replaced with:
[0093] S2. Accurately weigh 0.045 g of FeCoPBA, 0.0048 g of (NH4)2MoO4, 0.36 g of thioacetamide C3H7NS, and mix them with 15 mL of ethylene glycol solution. After stirring evenly, transfer them to a reaction kettle and react at 210 °C for 20 h to obtain Product II. Wash and dry the solid obtained by centrifuging Product II to obtain the nanocomposite.
[0094] Example 10
[0095] Prepare the nanocomposite according to the method of Example 3, except that step S1 is replaced with:
[0096] S1. Accurately weigh 0.0938 g of K3[Fe(CN)6] and 0.9605 g of citric acid and mix them into solution A by stirring. Accurately weigh 0.0565 g of CoCl2·6H2O and 0.9605 g of citric acid and mix them into solution B by stirring. Add solution A to solution B and stir and react at 50 °C for 40 min to obtain Product I. Wash and dry the solid after centrifuging Product I to obtain the solid powder of iron cobalt Prussian blue analogue (FeCoPBA) for standby.
[0097] Comparative Example 1
[0098] Accurately weigh 0.0856 g of K3[Fe(CN)6] and 0.9605 g of citric acid and mix them into solution A by stirring. Accurately weigh 0.0565 g of CoCl2·6H2O and 0.9605 g of citric acid and mix them into solution B by stirring. Add solution A to solution B and stir and react at room temperature for 1 h to obtain Product I. Wash and dry the solid after centrifuging Product I to obtain the solid powder of iron cobalt Prussian blue analogue (FeCoPBA).
[0099] Comparative Example 2
[0100] Accurately weigh 0.0048 g of (NH4)2MoO4, 0.3 g of thioacetamide C2H5NS, and mix them with 15 mL of ethylene glycol solution. After stirring evenly, transfer them to a reaction kettle and react at 180 °C for 24 h to obtain the product. Wash and dry the solid obtained by centrifuging the product to obtain MoS2.
[0101] Comparative Example 3
[0102] S1. Disperse 118.7 mg of MnCl2·4H2O, 0.25 g of Na3C6H5O7·2H2O and 0.3 g of PVP-K30 in 30 mL of deionized water to form solution A; disperse 66.0 mg of K3[Fe(CN)6] in 20 mL of deionized water to form solution B; add solution B to solution A and stir at room temperature for 10 min, then let it stand at normal temperature for 24 h. Wash the obtained precipitate with deionized water by centrifugation 3 times and then dry it in vacuum at 60 °C to obtain a manganese-iron Prussian blue analogue (denoted as MnFePBA).
[0103] S2. Accurately weigh 0.045 g of MnFePBA, mix it with 0.0048 g of (NH4)2MoO4, 0.3 g of thioacetamide C2H5NS and 15 mL of ethylene glycol solution, stir evenly and transfer it to a reaction kettle to react at 180 °C for 20 h to obtain product II. Wash and dry the solid obtained by centrifuging product II to obtain the MnFePBA / MoS2 nanocomposite.
[0104] Test Example 1
[0105] The electron microscope scanning results of the FeCoPBA / MoS2 nanocomposite prepared in Example 1 and MoS2 prepared in Comparative Example 2 are as Figure 1 shown. As can be seen from Figure 1 (b) therein, MoS2 presents a block structure. As can be seen from Figure 1 (a) therein, FeCoPBA in the nanocomposite adheres to the surface of MoS2; the mapping diagram of FeCoPBA / MoS2 is as Figure 1 (c) therein, and the elemental distribution on the FeCoPBA / MoS2 composite can be seen. From the infrared spectrum diagram (see Figure 2 ) and X-ray photoelectron spectroscopy analysis (see Figure 3 ) of the FeCoPBA / MoS2 nanocomposite prepared in Example 1, it can be seen that the FeCoPBA / MoS2 composite is successfully prepared.
[0106] Test Example 2 Determination of the peroxidase-mimicking enzyme activity of the FeCoPBA / MoS2 composite
[0107] Using 3,3',5,5'-tetramethylbenzidine (TMB) as a substrate, the characteristic absorption peak of TMB is at 652 nm. Under the action of H2O2, TMB is oxidized to o-TMB, and an absorption peak appears at 652 nm, showing the properties of a peroxidase mimic. To prove that FeCoPBA / MoS2 has excellent peroxidase mimic properties, the absorbances at 652 nm of the FeCoPBA / MoS2 nanocomposites prepared in Examples 1 - 10, FeCoPBA prepared in Comparative Example 1, MoS2 prepared in Comparative Example 2, before and after reacting with 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2 were measured respectively.
[0108] The specific operation is as follows: Take 100 μL of TMB solution (concentration 0.5 mM) in 2 mL of deionized water, and then add 100 μL of the FeCoPBA / MoS2 nanocomposites prepared in Examples 1 - 10, FeCoPBA prepared in Comparative Example 1, MoS2 prepared in Comparative Example 2, MnFePBA / MoS2 nanocomposites prepared in Comparative Example 3 (concentrations are all 1.4 mg / mL), 100 μL of H2O2 (10 mM) respectively. Finally, add Hac-NaAc buffer solution with pH = 4, react at 30 °C for 10 min, and monitor the change in absorbance at 652 nm before and after the reaction with a UV-visible spectrophotometer. The results are shown in Table 1; The absorbance changes of the FeCoPBA / MoS2 nanocomposites prepared in Example 1, FeCoPBA prepared in Comparative Example 1, and MoS2 prepared in Comparative Example 2 are as Figure 4 shown.
[0109] Table 1
[0110] Number Absorbance change value at 652 nm Example 1 0.486 Example 2 0.460 Example 3 0.450 Example 4 0.436 Example 5 0.420 Example 6 0.353 Example 7 0.411 Example 8 0.442 Example 9 0.432 Example 10 0.437 Comparative Example 1 0.248 Comparative Example 2 0.189 Comparative Example 3 0.287
[0111] Application of the FeCoPBA / MoS2 composite material in antibacterial
[0112] Using Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) as the research objects, the reactive oxygen species generated by the peroxidase mimic properties of the FeCoPBA / MoS2 nanocomposite act on the cell membrane, thereby achieving the purpose of killing bacteria.
[0113] The specific operation is as follows: Take 50 μL of Escherichia coli bacterial solution or Staphylococcus aureus bacterial solution in 5 mL of liquid medium, culture overnight at a temperature of 37 °C and a rotation speed of 180 rpm, and then dilute the bacteria to 10 -4 times.
[0114] For Escherichia coli, take 100 μL of the diluted Escherichia coli and place it in a 96-well plate. Then, add 50 μL of the FeCoPBA / MoS2 nanocomposite solution prepared in Examples 1 - 10, or FeCoPBA prepared in Comparative Example 1, or MoS2 prepared in Comparative Example 2, or the MnFePBA / MoS2 nanocomposite prepared in Comparative Example 3 (all at a concentration of 0.3 mg / mL), and 50 μL of the H2O2 solution (at a concentration of 0.2 mM). Separately, add the FeCoPBA / MoS2 nanocomposite solution prepared in Example 1 (at a concentration of 0.3 mg / mL) or the H2O2 solution (at a concentration of 0.2 mM) alone as the control group, and use Escherichia coli without adding reagents as the reference group. Incubate at 37 °C for 12 h, and measure the OD of the bacterial growth in each group every two hours. 600 values. For the FeCoPBA / MoS2 nanocomposite + H2O2 solution prepared in Example 1, the FeCoPBA / MoS2 nanocomposite prepared in Example 1 alone, the H2O2 solution alone, and Escherichia coli without adding reagents, the OD 600 changes with time as shown in Figure 5 (a); The OD 600 values of the bacterial growth in each group at 12 h of incubation are shown in Table 2.
[0115] Table 2
[0116]
[0117]
[0118] For Staphylococcus aureus, take 100 μL of the diluted Staphylococcus aureus and place it in a 96-well plate. Then, add 50 μL of the FeCoPBA / MoS2 nanocomposite solution prepared in Examples 1 - 10, or FeCoPBA prepared in Comparative Example 1, or MoS2 prepared in Comparative Example 2, or the MnFePBA / MoS2 nanocomposite prepared in Comparative Example 3 (all at a concentration of 0.2 mg / mL), and 50 μL of the H2O2 solution (at a concentration of 0.2 mM). Separately, add the FeCoPBA / MoS2 nanocomposite solution prepared in Example 1 (at a concentration of 0.2 mg / mL) or the H2O2 solution (at a concentration of 0.2 mM) alone as the control group, and use Staphylococcus aureus without adding reagents as the reference group. Incubate at 37 °C for 12 h, and measure the OD of the bacterial growth in each group every two hours. 600 values. For the FeCoPBA / MoS2 nanocomposite + H2O2 solution prepared in Example 1, the FeCoPBA / MoS2 nanocomposite prepared in Example 1 alone, the H2O2 solution alone, and Staphylococcus aureus without adding reagents, the OD 600 changes with time as shown in Figure 5as shown in (b); the OD of the growth of bacteria in each group at 12 h of culture 600 values are shown in Table 3.
[0119] Table 3
[0120]
[0121]
[0122] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.
Claims
1. A nanocomposite material, characterized in that, The nano-composite material comprises a core containing molybdenum disulfide and an iron-cobalt Prussian blue analogue attached to the surface of the core.
2. The nanocomposite material according to claim 1, wherein, The core has a massive structure; Preferably, the weight ratio of the iron-cobalt Prussian blue analogue to the molybdenum disulfide is 1-50:1, more preferably 10-46:
1.
3. A method for preparing a nanocomposite material, characterized in that, The method comprises: reacting the iron-cobalt Prussian blue analogue with molybdate and thioamide to carry out Reaction I.
4. The preparation method according to claim 3, wherein The preparation process of the iron-cobalt Prussian blue analogue comprises: mixing iron cyanide with a cobalt salt in the presence of a polybasic acid to carry out Reaction II; Preferably, the polybasic acid is selected from at least one of malic acid, citric acid and oxalic acid, more preferably citric acid; Preferably, the iron cyanide is selected from at least one of potassium ferrocyanide, sodium ferrocyanide, magnesium ferrocyanide and calcium ferrocyanide, more preferably potassium ferrocyanide and / or sodium ferrocyanide; Preferably, the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate and cobalt nitrate, more preferably cobalt chloride.
5. The preparation method according to claim 4, characterized in that, The process of mixing the iron cyanide with the cobalt salt comprises: mixing the iron cyanide with a part of the polybasic acid to form Solution A, mixing the cobalt salt with another part of the polybasic acid to form Solution B, and then mixing Solution A and Solution B; Preferably, the molar ratio of the iron cyanide to the cobalt salt is 0.8-1.2:1; Preferably, the conditions of Reaction II include: temperature is 10-30 °C, time is 40-80 min.
6. The preparation method according to any one of claims 3 to 5, characterized in that, The molybdate is selected from at least one of ammonium molybdate, potassium molybdate and sodium molybdate, preferably ammonium molybdate; Preferably, the thioamide is selected from at least one of thioformamide, thioacetamide, thiopropionamide and thiobutyramide, more preferably thioacetamide; Preferably, the conditions of Reaction I include: temperature is 150-200 °C, time is 20-30 h; Preferably, the weight ratio of the iron-cobalt Prussian blue analogue, the thioamide to the molybdate is 1-40:30-125:1, more preferably 9-37.5:50-75:1; Preferably, Reaction I is carried out in a polyol solvent, and the polyol is selected from at least one of ethylene glycol, 1,3-propanediol, 1,2-propanediol and 1,4-butanediol.
7. The preparation method according to any one of claims 3 to 5, characterized in that, The method further comprises: carrying out solid-liquid separation on the product of Reaction I to obtain a solid, and then washing and drying the solid.
8. A nano-composite material prepared by the preparation method according to any one of claims 3 to 7.
9. Application of the nano-composite material according to any one of claims 1, 2 and 8 as a mimetic enzyme; Preferably, the mimetic enzyme is a peroxidase, more preferably a catalase.
10. Application of the nano-composite material according to any one of claims 1, 2 and 8 in the preparation of an antibacterial product; Preferably, the antibacterial product is a drug against Escherichia coli and / or Staphylococcus aureus.