Nanomaterials for interfering with electron chain transfer and high-efficiency anti-infection, as well as preparation methods and applications thereof

Abstract

The present invention discloses a nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection function, as well as its preparation method and application. The preparation method of the nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection function is to use an oxidizing etchant to etch a porous SnSe nanosheet structure with uniform nanoscale pores and intermediate valence Sn elements. 1‑X Se nanosheets, wherein 0.13≤X≤0.32, correspond to a molar ratio of Sn to Se of 0.68-0.87:1, and an average valence of Sn of 2.30-2.95. The nanomaterial for high-efficiency anti-infection by interfering with electron chain transfer can efficiently supply electrons to bacteria-rich areas, killing bacterial cells by interfering with bacterial electron chain transfer without interfering with the respiration of normal somatic cells. It can be used as a highly efficient and low-toxic biomedical nanomaterial for the treatment of bacterial infections.

Description

Technical Field

[0001] The present invention belongs to the technical field of inorganic nanomaterials, and specifically relates to a nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection effect, as well as a preparation method and application thereof. Background Art

[0002] Respiration is a basic process for the survival of cells and the living organisms composed of cells. The cellular respiratory chain is also called the electron chain. The respiratory chain of eukaryotic cells, represented by somatic cells, exists on the mitochondria inside the cells. The difference is that the respiratory chain of prokaryotic cells, represented by bacteria, is located on the cell membrane. During this process, bacteria use oxygen to decompose glucose into carbon dioxide and water, while generating energy for bacterial survival and proliferation. This provides an entry point for the design of antibacterial drugs or antibacterial functional nanomaterials, that is, to interfere with the electron chain transfer of bacteria to achieve safe and efficient antibacterial and anti-infection purposes. For example, in 2021, some scholars discovered that the nanoscale pore defects on the surface structure of nanomaterials cause atoms at the edge of the pores to easily gain and lose electrons due to quantum confinement and edge effects, and the infection microenvironment caused by bacteria is characterized by high oxidative stress. Therefore, when this type of porous nanomaterial is applied to the bacterial infection area, the porous nanomaterial and the biofilm formed by bacterial enrichment will act as electron donors and acceptors, respectively, and electron transfer will occur between the porous nanomaterial and the biofilm (Nat. Commun. 2021, 12, 493). The additional electron input brought about by this electron transfer process interferes with the electron chain transport process on the bacterial cell membrane, preventing bacterial respiration from proceeding normally. This new antibacterial strategy that interferes with the bacterial electron chain transport process can kill bacteria efficiently and broadly without causing toxicity to normal animal cells, avoiding the defects of antibiotics in promoting drug resistance and the shortcomings of traditional nanomaterials with single functions and limited antibacterial effects. However, the nanopores obtained by ultraviolet bombardment are uneven in size, and the overall structure of the material is easily destroyed, which hinders the improvement of its anti-infection efficiency and large-scale production.

[0003] Therefore, research on nanomaterials rich in pore defects for the treatment of bacterial infections is still in its infancy. For example, there are many problems in the method of pore formation (physical stimulation or chemical reaction pore formation, pore formation in response to the lesion microenvironment, etc.), the original nanomaterial morphology (zero-dimensional, two-dimensional, three-dimensional nanomaterials, etc.), and the selection of components. In terms of pore formation, if the material is slightly degraded into pores in vivo in response to characteristics of the bacterial infection microenvironment, such as weak acidity or high oxidative stress, the pore formation efficiency is too low, and the substances released by degradation may be cytotoxic. If the material is pore-formed in vitro through physical external fields such as laser bombardment, problems such as uneven pore size and easy destruction of the overall material structure are likely to occur. For example, in the selection of the original material, due to the inherent granular form of zero-dimensional or three-dimensional nanomaterials, the density of active sites in the material after pore formation is far less than that of two-dimensional nanomaterials. Summary of the Invention

[0004] To address the above-mentioned issues, the present invention aims to provide a nanomaterial for high-efficiency anti-infection by interfering with electron chain transport, as well as its preparation method and application. This nanomaterial can efficiently supply electrons to bacteria-rich areas, killing bacterial cells by disrupting bacterial electron chain transport without interfering with normal cell respiration. It can be used as a highly effective and low-toxic biomedical nanomaterial for the treatment of bacterial infections.

[0005] In the first aspect, the present invention provides a method for preparing a nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection properties, wherein an oxidizing etchant (an etchant capable of oxidizing divalent Sn) is used to etch a porous Sn having uniform nanoscale pores and intermediate valence Sn elements on a two-dimensional SnSe nanosheet structure. 1-X Se nanosheets, wherein 0.13≤X≤0.32, corresponding to a molar ratio of Sn to Se elements of 0.68-0.87:1, and an average valence of the Sn element of 2.30-2.95.

[0006] Inspired by the specificity of the infection microenvironment, this invention designs a self-pore-forming nanomaterial and its preparation method that can mimic endogenous biological responses, addressing the shortcomings of existing pore-forming methods. Specifically, by simulating the high oxidative stress state of the bacterial infection microenvironment in vitro, an oxidative etchant is used to efficiently etch uniform nanopores on the surface of the two-dimensional nanomaterial. This material is then applied to the field of interfering with electron chain transport to treat bacterial infections.

[0007] Sn of the present invention 1-X Se combines the strong electron-donating properties of the Sn element in an unstable intermediate valence state produced after pore engraving with the huge reaction specific surface area brought by the abundant pores. The former provides the core bactericidal mechanism, and the latter ensures the high efficiency of sterilization. That is, the realization of the technical effect of the present invention requires not only the generation of pores, but also the appearance of Sn elements in the intermediate valence state. Based on the gradual progression of the mechanism of action, the use of acidic buffer to promote the degradation of two-dimensional SnSe into pores or increase the specific surface area cannot bring about changes in the Sn valence state, and therefore cannot achieve the present invention.

[0008] Preferably, the preparation method comprises: dispersing the two-dimensional SnSe nanosheets and the oxidative etchant in an aqueous solution system, mixing them evenly, and reacting them at 4-40° C. for 3-24 hours.

[0009] Preferably, the oxidizing etchant is H2O2; preferably, the feed ratio of the two-dimensional SnSe nanosheets and H2O2 is 1-100 μmol of H2O2 per mg of two-dimensional SnSe nanosheets.

[0010] Preferably, the two-dimensional SnSe nanosheets are obtained by ultrasonically fragmenting nanoflowers grown from SnSe single crystals exhibiting a 0kl space group.

[0011] Preferably, two-dimensional SnSe or SnSe nanoflowers are synthesized by a one-step method using a solution containing a tin source, a selenium source, a shape regulator and an organic solvent, and then ultrasonically crushed to obtain two-dimensional SnSe nanosheets; preferably, the tin source, selenium source and shape regulator are dissolved in an organic solvent and stirred evenly, stirred and reacted at 115-125°C in a N2 atmosphere for 10-15 minutes, then heated to 250-270°C and kept warm for 30-45 minutes to obtain SnSe nanoflowers, which are then ultrasonically crushed to obtain two-dimensional SnSe nanosheets; more preferably, the concentrations of the tin source, selenium source and shape regulator are independently 5-10 mmol / L.

[0012] Preferably, the tin source is one or more of tin tetrachloride, stannous chloride and hydrates thereof; the selenium source is one or more of tin dioxide and sodium selenate pentahydrate; the organic solvent is one or more of oleylamine and ethylene glycol; and the shape regulator is 1,10-phenanthroline.

[0013] Preferably, the diameter of the nanoscale pores is 40-70 nm.

[0014] Preferably, the porous Sn 1-X The diameter of the Se nanosheets is 120-700 nm and the thickness is 1.0-1.5 nm.

[0015] In a second aspect, the present invention provides a nanomaterial for high-efficiency anti-infective electron chain transport interference, obtained by any of the aforementioned methods. This nanomaterial can efficiently deliver electrons to bacterial-rich areas in an aqueous environment, killing them by disrupting their electron chain transport. This material exhibits an electron chain interference therapeutic approach tailored to the respiratory characteristics of bacteria, ensuring safety.

[0016] In a third aspect, the present invention provides the application of the above-mentioned nanomaterials for interfering with electron chain transfer and having high efficiency in anti-infection as medical nanomaterials for anti-bacterial infection.

[0017] Beneficial effects:

[0018] According to the present invention, the porous Sn2O2 obtained by etching the two-dimensional SnSe is 1-XSe nanosheets exhibit excellent anti-bacterial infection properties due to the strong electron-donating properties of the Sn element at the edge of the hole due to its own intermediate valence state and the influence of quantum confinement and edge effect, as well as the huge reaction specific surface area brought by the abundant holes. Due to the universality of the bacterial respiratory chain mechanism among bacterial species and its huge difference from the normal somatic cell respiratory mechanism, the material of the present invention has the advantages that traditional antibiotic bactericidal drugs do not have, such as broad spectrum, non-toxicity, and no induction of drug resistance, in addition to high efficiency. In addition, compared with other responsive anti-infection nanomaterials that rely on external field stimuli such as light, sound, electricity, heat and magnetism, the material of the present invention has the advantages of low cost, non-invasiveness, no reliance on external fields, and no need for external equipment. Finally, the present invention can also respond to the high oxidative stress characteristics commonly found in bacteria-enriched microenvironments to obtain a higher electron supply capacity, thereby further improving the bactericidal ability, with internal field responsiveness and a wider range of applications.

[0019] In addition, the above-mentioned preparation method of the present invention is simple, easy and low-cost. The diameter and thickness of the obtained nanomaterial system are controllable, and it has good stability in organic solvents such as ethanol and cyclohexane and in water. At the same time, it has high electron donating capacity and bacterial killing effect, and is one of the bacterial infection treatment options with great application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a flow chart for preparing nanomaterials for interfering with electron chain transport and having high efficiency and anti-infection properties according to an embodiment of the present invention;

[0021] Figure 2 TEM image (A) of the two-dimensional SnSe material synthesized in Example 1 and TEM image (B) of the nanomaterial for interfering with electron chain transfer and high efficiency anti-infection formed after H2O2 etching;

[0022] Figure 3 The UV absorption spectra (A) and macroscopic color (B) of two-dimensional SnSe after different treatment conditions are shown, as well as the changes in the molar ratio of Sn and Se elements in two-dimensional SnSe after different treatments measured by ICP-OES and the average valence of Sn elements calculated based on this (C);

[0023] Figure 4 The figures are atomic force microscope images of the two-dimensional SnSe (A) and the nanomaterial for interfering with electron chain transport and high efficiency anti-infection (B) synthesized in Example 1 and the corresponding thickness analysis curves;

[0024] Figure 5 1 is a graph showing the animal safety evaluation results of the nanomaterial for interfering with electron chain transport and high-efficiency anti-infection in Example 1: (A) shows the weight changes of mice treated with different methods over 14 days, and (B) shows the corresponding blood routine indicators of the mice;

[0025] Figure 6 1 and 2. The figures are the growth status test results of the bacterial colonies of the control group 1, the experimental group 1 and the experimental group 2 in Example 1 and Example 2 (A) and the corresponding bacterial survival rate statistical graph (B). DETAILED DESCRIPTION

[0026] The present invention is further described below with reference to the accompanying drawings and the following embodiments. It should be understood that the accompanying drawings and the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0027] The following combination Figure 1 The preparation method of the nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection effect is described. The method is based on the original two-dimensional SnSe and uses an oxidative etchant to etch abundant nanoscale pores on its nanosheet structure. According to this etching method, SnSe with abundant nanoscale pores and maintaining the two-dimensional nanosheet structure can be obtained. 1-X Se (0.13≤X≤0.32), the etched holes are evenly distributed on the nanosheet. After reaching the bacteria-rich area, Sn 1-X Se can kill bacteria by donating electrons, making it a good functional drug.

[0028] Preparation of precursor material: 2D SnSe nanosheets. 2D SnSe is a typical 2D nanomaterial, possessing inherent advantages such as high specific surface area, abundant surface active sites, and high biochemical reactivity. Furthermore, the Sn element in its composition has a variable valence state and a high ability to gain or lose electrons.

[0029] The size of the two-dimensional SnSe nanosheet can be selected according to actual needs. As an example, the diameter of the two-dimensional SnSe nanosheet can be 120-700 nm and the thickness can be about 1.5-2.0 nm.

[0030] The preparation method of two-dimensional SnSe nanosheets is not limited. In some embodiments, the two-dimensional SnSe nanosheets can be obtained by ultrasonically fragmenting nanoflowers grown from SnSe single crystals exhibiting the 0kl space group. As an example, the particle size of the SnSe nanoflowers is approximately 1.5-3 μm, for example, 2 μm.

[0031] In some embodiments, SnSe nanoflowers are synthesized in a one-step process using a solution containing a tin source, a selenium source, a shape modifier, and an organic solvent, which is then ultrasonically fragmented to obtain two-dimensional SnSe nanosheets. For example, SnSe nanoflowers can be synthesized in a one-step process using a tin salt such as SnCl4·5H2O or SnCl2·2H2O as a source of Sn, a selenium-containing compound such as SeO2 or Na2SeO3·5H2O as a source of Se, 1,10-phenanthroline (1,10-phenanthroline) as a shape modifier, and an organic solvent with a high boiling point and strong thermal stability such as oleylamine or ethylene glycol, followed by ultrasonic fragmentation to obtain two-dimensional SnSe. In a specific embodiment, SnCl4·5H2O, 1,10-phenanthroline, and SeO2 are dissolved in oleylamine and stirred until uniformly dissolved. The mixture is then transferred to a round-bottom flask and stirred at 115-125°C under a nitrogen atmosphere for 10-15 minutes. The temperature is then raised to 250-270°C at a rate of 10°C / min and maintained for 30-45 minutes to produce SnSe nanoflowers, which are then ultrasonically fragmented to produce two-dimensional SnSe nanosheets. The molar ratio of SnCl4·5H2O, 1,10-phenanthroline, and SeO2 can be 1:1:1. In some technical solutions, the concentrations of SnCl4·5H2O (tin source), 1,10-phenanthroline, and SeO2 (selenium source) in the two-dimensional SnSe preparation system are each independently 5-10 mmol / L.

[0032] Using H2O2 to etch two-dimensional SnSe nanosheets to form Sn 1-X Se. Two-dimensional SnSe powder and H2O2 stock solution can be co-dispersed in ultrapure water for etching. Two-dimensional SnSe has good dispersion in water, does not agglomerate after 24 hours, and can react with H2O2 in aqueous solution.

[0033] During the etching process, the addition ratio of 2D SnSe and H2O2 can be 1-100 μmol H2O2 per mg of 2D SnSe material, and the two are dispersed in 1 mL of water. This is conducive to the formation of SnSe with rich pores and complete nanosheet structure. 1-X Se. For example, 1 μmol, 10 μmol, or 100 μmol of H₂O₂ can be added per milligram of two-dimensional SnSe powder, preferably 10 μmol. The reaction temperature can be 4-40°C, preferably 37°C. The reaction environment can be a constant temperature shaker with an oscillation frequency of 200 rpm. The reaction time can be 3-24 hours, preferably 24 hours.

[0034] H2O2 can be used in the form of H2O2 stock solution. The feed ratio of two-dimensional SnSe and H2O2 stock solution (10mol / L) can be selected according to the degree of mass loss after etching, the effect of hole generation and the integrity of the nanosheet morphology. In some technical solutions, Sn 1-X The concentration of two-dimensional SnSe powder in the Se preparation reaction system is 0.1 mg / mL, and the concentration of H2O2 in the mixed system is 10 mmol / L.

[0035] The above preparation method obtains a functionalized two-dimensional porous nanosheet material. The functionalized two-dimensional porous nanosheet material is specifically Sn nanomaterial with high efficiency and anti-infection function that interferes with electron chain transmission. 1-X Se (0.13≤X≤0.32). 1-X Se can efficiently supply electrons to bacteria-rich areas in an aqueous environment and kill bacterial cells by interfering with the bacterial electron chain transfer. 1-X Se combines electron transport with the bacterial respiratory chain, efficiently supplying electrons to areas rich in bacteria, and killing them by disrupting electron chain transport across the bacterial cell membrane. Furthermore, the present invention provides a simple, robust method for synthesizing a novel nanomaterial system with a porous two-dimensional nanosheet morphology, controllable pore size and nanosheet size, and uniform physical and chemical properties. Furthermore, the disclosed preparation method features a simple, feasible synthesis process, and precisely controlled reaction conditions.

[0036] The Sn 1-X Se has a two-dimensional nanosheet structure. In some technical solutions, the nanomaterial Sn 1-X The diameter of Se is about 120-700nm and the thickness is about 1.0-1.5nm. 1-X The pore diameter of the Se-rich nanopores is approximately 40–70 nm.

[0037] As a specific example, the preparation method of nanomaterials for interfering with electron chain transfer and high efficiency anti-infection includes: dissolving SnCl4·5H2O, 1,10-phenanthroline (o-phenanthroline|1,10-Phenanthroline) and SeO2 in oleylamine at room temperature and stirring for 5 minutes. The above solution is then transferred to a round-bottom flask and stirred for 10 minutes at 120°C under N2 atmosphere. The temperature is then raised to 260°C at a rate of 10°C / min and kept warm for 30 minutes. After cooling to room temperature, it is washed with cyclohexane, water and ethanol, and ultrasonically crushed for 6 hours to obtain a two-dimensional SnSe with an average diameter of about 300nm and an average thickness of about 2nm. The above two-dimensional SnSe is dispersed in an aqueous hydrogen peroxide solution, and the system is placed in a constant temperature shaker at 37°C, shaken at a frequency of 200rpm for 3-24 hours, and then centrifuged to collect the precipitate to obtain the nanomaterial Sn for interfering with electron chain transfer and high efficiency anti-infection. 1-X Se(0.13≤X≤0.32).

[0038] In a specific embodiment of the present invention, by 1-XSe was analyzed and found that the two-dimensional SnSe and the Sn 1-X The molar ratios of Sn and Se in Se (X = 0.32 / 0.26) are 1.10 and 0.68 / 0.74, respectively; the corresponding average valences of Sn are 1.82 and 2.95 / 2.71, respectively. The etched holes are approximately 60 nm in diameter. This indicates that etching causes Sn loss and raises the average valence of the remaining Sn to an unstable intermediate state, which is more conducive to the material's electron supply to the bacterial electron chain. The abundant holes created by etching also increase the material's specific surface area and active site density, thereby more effectively interfering with the bacterial respiratory chain and promoting apoptosis.

[0039] In summary, the nanomaterials for interfering with electron chain transfer and effectively preventing infection introduce a new concept for treating bacterial infection. 1-X Se can simultaneously avoid the drawbacks of clinical treatment options represented by antibiotics, such as toxic side effects and the development of drug resistance, as well as the shortcomings of traditional nanomaterials with single functions and limited antibacterial effects. It kills bacterial cells by interfering with bacterial electron chain transfer, thus achieving a safe and efficient bacterial infection treatment strategy. Compared with other functional nanomaterials that rely on external field stimulation, Sn 1-X Se circumvents the potential damage to normal tissues caused by external fields such as light, sound, heat, and magnetism, as well as the limitations of its application due to equipment issues. Instead, it spontaneously kills bacteria by responding to the internal field characteristics of the bacterial infection microenvironment. This new functional nanomaterial has great potential for safe and effective treatment of bacterial infections.

[0040] The following examples are further listed to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values exemplified below.

[0041] Example 1

[0042] (1) Preparation of two-dimensional SnSe. 35 mg of SnCl4·5H2O, 20 mg of 1,10-phenanthroline and 11 mg of SeO2 were added to 10 mL of oleylamine in sequence and stirred for 5 min. The reaction system was transferred to a round-bottom flask and stirred at 120°C under N2 atmosphere for 10 min. The temperature was then raised to 260°C at a rate of 10°C / min and kept warm for 30 min. The mixture was then cooled naturally to room temperature and washed twice by centrifugation with cyclohexane, water and ethanol. Finally, the material was dispersed in ethanol and ultrasonically crushed for 6 hours (ultrasonic power of 600 W, single ultrasonic duration of 3 seconds, ultrasonic interval of 3 seconds), collected by centrifugation and freeze-dried to obtain black two-dimensional SnSe powder.

[0043] (2) Preparation of Sn 1-X Se. Disperse 1 mg of two-dimensional SnSe in 10 mL of H2O2 aqueous solution (H2O2 concentration is 10 mmol / L), place it in a constant temperature shaker at 37°C, shake it at a frequency of 200 rpm for 12 hours, then collect the precipitate after the reaction by centrifugation and dry it to obtain red SnSe. 1-X Se powder (X=0.26).

[0044] Figure 2 The two-dimensional SnSe synthesized in this embodiment and the Sn obtained by etching 1-X TEM images of Se show that the nanosheets before and after etching can maintain a regular sheet morphology and uniform particle size, and abundant holes appear on the nanosheets after etching.

[0045] Figure 3 The following are the changes in the ultraviolet absorption spectrum (A) and macroscopic color (B) of two-dimensional SnSe after treatment under different conditions, as well as the changes in the mass ratio and molar ratio of Sn and Se elements in the two-dimensional SnSe with different treatments measured by ICP-OES and the average valence of the Sn element calculated based on this (C). It can be seen that in this embodiment, H2O2 etching causes the ultraviolet absorption intensity of two-dimensional SnSe to decrease, and the decrease is greater in the longer wavelength range, causing the color of the material to change from black to red, proving that material loss and chemical property changes have occurred. According to the ICP-OES results, it can be seen that it is specifically the loss of Sn element and the increase in the average valence, that is, the two-dimensional SnSe and Sn 1-X The molar ratios of Sn and Se in Se are 1.10 and 0.74, respectively; the corresponding average valences of Sn are 1.82 and 2.71, respectively. This indicates that etching causes Sn loss and increases its average valence to an unstable intermediate state, which contributes to the material's enhanced electron-donating ability.

[0046] Figure 4 In this embodiment, two-dimensional SnSe and Sn 1-XAtomic force microscope image of Se and corresponding thickness analysis curve. It can be analyzed that: Sn 1-X Se maintains a complete two-dimensional nanosheet morphology, with only a certain decrease in thickness, with an average thickness of about 1.5nm; the diameter of the pores rich in the surface is about 60nm, which is beneficial to increasing the specific surface area and active site concentration of the material, and obtaining higher anti-infection efficiency.

[0047] Tested for animal safety.

[0048] The animal safety test of the sample was conducted on adult female Balb / c mice with an average weight of about 22g. First, the hair on the back of the mouse was shaved, and 50μL of 100μg / mL Sn solution was applied to the back. 1-X Se (experimental group) or no treatment (control group), and the body weight of mice was monitored for 14 days, and blood was collected on the 14th day for routine blood tests. Figure 5 The following is a graph showing the animal safety evaluation results of the nanomaterials for interfering with electron chain transfer and high efficiency anti-infection in this embodiment, wherein (A) shows the weight changes of mice treated with different treatments within 14 days, and (B) shows the corresponding blood routine indicators of the mice. It can be seen that there was no significant change in the weight of the mice within 14 days after applying the material, and the blood routine indicators on the 14th day were not significantly different from those of the control group, and were all within the normal range. The above results show that Sn 1-X Se has good animal safety.

[0049] Antibacterial experiment.

[0050] Staphylococcus aureus was grown on an agar plate at 37°C overnight. A single colony of the strain was picked and cultured in 5 mL of LB broth at 37°C until the absorbance of the suspension at 600 nm was 0.5. The suspension was centrifuged and the supernatant removed. The precipitate, i.e., bacterial cytoplasm, was resuspended in the same volume of PBS. This suspension was mixed with PBS, a 2D SnSe dispersion in PBS, and SnSe in a volume ratio of 1:9. 1-X Se PBS dispersion system was mixed and used as control group, experimental group 1 and experimental group 2, respectively, and the concentration of the material in the final system of the latter two groups was 100 μg / mL. Antibacterial activity test was carried out by spread plate colony counting method. Figure 6 The antibacterial test results showed that the survival rate of bacteria in experimental group 2 was much lower than that in experimental group 1, indicating that the high-efficiency anti-infection nanomaterial for interfering with electron chain transfer of the present invention can effectively kill bacterial colonies, and its bactericidal efficiency is much higher than that of two-dimensional SnSe.

[0051] Example 2

[0052] (1) Preparation of two-dimensional SnSe, same as in Example 1.

[0053] (2) Preparation of Sn 1-XSe. Disperse 1 mg of two-dimensional SnSe in 10 mL of H2O2 aqueous solution (H2O2 concentration is 10 mmol / L), place it in a constant temperature shaker at 37°C, shake it at a frequency of 200 rpm for 24 hours, then collect the precipitate after the reaction by centrifugation and dry it to obtain red SnSe. 1-X Se powder (X=0.32).

[0054] Figure 3 The following are the changes in the UV absorption spectrum (A) and macroscopic color (B) of two-dimensional SnSe after different treatment conditions, as well as the changes in the mass ratio and molar ratio of Sn and Se elements in the two-dimensional SnSe with different treatments measured by ICP-OES and the average valence of Sn elements calculated based on this (C). It can be seen that in this embodiment, Sn 1-X The molar ratio of Sn to Se in Se is 0.68, corresponding to an average valence of Sn of 2.95. This indicates that increasing etching time significantly increases the loss of Sn and the increase in average valence.

[0055] Antibacterial test. Except for the Sn 1-X Se (X in this embodiment is 0.32, while that in Example 1 is 0.26) is different from Example 1, and other operations are the same. Figure 6 The antibacterial test results show that the Sn 1-X The survival rate of bacteria after Se treatment was lower than that in Example 1, indicating that within a certain range, the deeper the average valence of Sn element increases, the stronger its electron-donating ability and anti-infection ability are.

[0056] Comparative Example 1

[0057] (1) Preparation of two-dimensional SnSe, same as in Example 1.

[0058] (2) Etching two-dimensional SnSe using an acidic buffer solution. Disperse 1 mg of two-dimensional SnSe in 10 mL of PBS (pH 6.0, phosphate concentration 20 mmol / L), place in a 37°C constant temperature shaker, and shake at 200 rpm for 24 h. The precipitate after the reaction is collected by centrifugation and dried to obtain a black etched powder.

[0059] Figure 3The following are the changes in the ultraviolet absorption spectrum (A) and macroscopic color (B) of two-dimensional SnSe after treatment under different conditions, as well as the changes in the mass ratio and molar ratio of Sn and Se elements in the two-dimensional SnSe with different treatments measured by ICP-OES and the average valence of the Sn element (C) calculated based on this. It can be seen that in this comparative example, the dispersion system of the etched material only shows a uniform decrease in ultraviolet absorption intensity compared to the untreated material and a lighter color of the dispersion system, without a more obvious decrease in the absorption spectrum in the long wavelength region and a reddish macroscopic color. At the same time, the molar ratio of the two elements Sn and Se is 1.16; the corresponding average valence of the Sn element is 1.72, which has no significant change compared to the untreated or after oscillation in water for 24 hours. It can be seen that using acidic buffer to promote the degradation of two-dimensional SnSe into pores or increase the specific surface area can only cause the loss of material substances, and cannot bring about changes in the valence of Sn, so the present invention cannot be realized.

[0060] In summary, the nanomaterial for interfering with electron chain transfer and having high efficiency in anti-infection of the present invention can fully adhere to the bacterial surface at the site of bacterial infection, and efficiently supply electrons to the bacterial cell body, killing it by interfering with its electron chain transmission, and does not interfere with the respiration of somatic cells. It can be used as a high-efficiency and low-toxic biomedical nanomaterial for related applications in treating bacterial infections.

Claims

1. A method for preparing a nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection properties, characterized in that: Using an oxidative etchant, porous Sn with uniform nanoscale pores and intermediate valence Sn elements was etched on the two-dimensional SnSe nanosheet structure. 1-X Se nanosheets, wherein 0.13≤X≤0.32, corresponding to a molar ratio of Sn to Se elements of 0.68-0.87:1, and an average valence of the Sn element of 2.30-2.

95.

2. The preparation method according to claim 1, wherein The preparation method comprises: dispersing two-dimensional SnSe nanosheets and an oxidative etchant in an aqueous solution system, mixing them evenly, and reacting them at 4-40° C. for 3-24 hours.

3. The preparation method according to claim 1 or 2, characterized in that The oxidizing etchant is H2O2.

4. The preparation method according to claim 3, wherein The feed ratio of two-dimensional SnSe nanosheets and H2O2 is 1-100 μmol of H2O2 per mg of two-dimensional SnSe nanosheets.

5. The preparation method according to claim 1, characterized in that Two-dimensional SnSe nanosheets are presented 0kl Nanoflowers grown from SnSe single crystals of the space group were obtained by ultrasonic crushing.

6. The preparation method according to claim 1, characterized in that Two-dimensional SnSe or SnSe nanoflowers are synthesized in a one-step method using a solution containing a tin source, a selenium source, a shape regulator and an organic solvent, and then ultrasonically crushed to obtain two-dimensional SnSe nanosheets.

7. The preparation method according to claim 6, wherein The tin source, selenium source and shape regulator are dissolved in an organic solvent and stirred evenly. The mixture is stirred and reacted at 115-125 °C in a N2 atmosphere for 10-15 min. The temperature is then raised to 250-270 °C and kept warm for 30-45 min to obtain SnSe nanoflowers. Subsequently, two-dimensional SnSe nanosheets are obtained by ultrasonic crushing.

8. The preparation method according to claim 6, wherein The concentrations of the tin source, selenium source, and shape-modifying agent are independently 5-10 mmol / L.

9. The preparation method according to claim 6, characterized in that The tin source is one or more of tin tetrachloride, stannous chloride and hydrates thereof; the selenium source is one or more of tin dioxide and sodium selenate pentahydrate; the organic solvent is one or more of oleylamine and ethylene glycol; and the shape regulator is 1,10-phenanthroline.

10. The preparation method according to claim 1, wherein The diameter of the nanoscale pores is 40-70 nm.

11. The preparation method according to claim 1, wherein The porous Sn 1-X The diameter of Se nanosheets is 120-700 nm and the thickness is 1.0-1.5 nm.

12. A nanomaterial for interfering with electron chain transfer and having high efficiency and anti-infection properties obtained by the preparation method according to any one of claims 1 to 11.

13. Use of the highly efficient anti-infective nanomaterial for interfering with electron chain transfer according to claim 12 in medical nanomaterials for anti-bacterial infection.

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