A bionic pine needle nano antibacterial material and its preparation method and application

Abstract

The present invention belongs to the field of synthetic nanomaterials, and in particular to a bionic pine needle nano antibacterial material and its preparation method and application. The particle size of the antibacterial material is uniform, and a single particle is a three-dimensional spike structure composed of 80-300 ZnO nano spikes. The preparation method comprises the following steps: weighing raw materials according to a preset ratio: anhydrous zinc acetate powder, a methanol-based organic solvent, and oleylamine, reacting at a preset temperature to prepare a ZnO bionic nano pine needle solution; purifying the ZnO bionic nano pine needle solution to obtain a ZnO bionic nano pine needle solid powder sample. The present invention prepares a nano antibacterial material with a unique three-dimensional spike structure, uniform size, good dispersibility, and excellent antibacterial performance, and explores its antibacterial application in multiple fields to meet the market demand for efficient, long-lasting, and safe antibacterial materials.

Description

Technical Field

[0001] The present invention belongs to the field of synthetic nanomaterials, and in particular relates to a bionic pine needle nano antibacterial material and a preparation method and application thereof. Background Art

[0002] Today, people's quality of life is constantly improving, and the concept of health is becoming more and more deeply rooted in people's minds. This trend has given rise to the booming antimicrobial materials market. This is especially true in the medical industry, where operating rooms and wards, where life is at stake, urgently need antimicrobial materials to build a safe environment. In the food packaging field, to protect the safety of food, there is a growing demand for antimicrobial and fresh-keeping packaging materials. The textile industry is no exception. Clothing and home textile products that are close to the skin are also in urgent need of antimicrobial materials to add health protection to daily wear and home life. Therefore, the market is in urgent need of highly effective, long-lasting, and safe antimicrobial materials, hoping to effectively inhibit the growth and spread of bacteria, and even effectively kill bacteria and block their growth.

[0003] Metal and metal oxide nanoantibacterial materials have been extensively researched in recent years. Among numerous metal elements, gold and silver, as inert metals with high biosafety, have long been a focus of biological research. Furthermore, the antibacterial properties of metal nanomaterials depend largely on their size, shape, and composition. To date, numerous methods have been developed to synthesize metal nanomaterials in various shapes, such as rods, clusters, cubes, spheres, and cages. The primary antibacterial mechanism of gold nanoantibacterial materials is to influence changes in bacterial membrane potential and reduce ATP levels, as well as to enter bacterial cells, generate reactive oxygen species, and interfere with bacterial DNA transcription and replication. Silver nanoparticle antibacterial materials can also release silver ions, which directly interact with cellular enzymes and proteins, affecting bacterial respiration and generating cytotoxicity through transmembrane transport, leading to bacterial death. However, these two precious metals are too expensive and expensive for everyday use.

[0004] Zinc oxide, with its environmentally friendly, biocompatible, widely available, and affordable properties, has found widespread application in daily life, particularly in antimicrobial and cosmetic applications. Zinc oxide (ZnO), a classic photoresponsive material, is a rare antimicrobial agent approved by the U.S. Food and Drug Administration (FDA). Its application in biosafety and medicine has a long history, dating back to the Common Era. Zinc oxide exhibits excellent inhibitory or bactericidal effects against a wide range of Gram-negative and Gram-positive bacteria. The photodynamic bactericidal activity of ZnO is primarily due to its wide bandgap (∼3.37 eV). However, traditional ZnO antimicrobial materials can only damage bacterial cell membranes and DNA through photocatalytic generation of reactive oxygen species (such as superoxide anions and hydroxyl radicals). Research and development of ZnO spike nanomaterials with a spiky structure that can directly bind to bacterial cell membranes and cause cell membrane rupture are urgently needed. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this paper innovatively develops a biomimetic pine needle nano-antimicrobial material, its preparation method, and its application. The resulting nano-antimicrobial material features a unique three-dimensional spike structure, uniform size, good dispersibility, and excellent antimicrobial properties. The material is being explored for antimicrobial applications in multiple fields to meet market demand for highly effective, long-lasting, and safe antimicrobial materials.

[0006] To achieve the above object, the present invention is implemented through the following technical solutions:

[0007] In a first aspect, the present invention provides a bionic pine needle nano antibacterial material, wherein the particles of the antibacterial material are uniform in size, and a single particle is a three-dimensional spike structure composed of 80-300 ZnO nano spikes.

[0008] As a further optimization solution of the present invention, the overall particle size of the single particles is 300-600 nm.

[0009] In a second aspect, the present invention provides a method for preparing the bionic pine needle nano antibacterial material as described above, comprising the following steps:

[0010] Weigh the raw materials: anhydrous zinc acetate powder, methanol organic solvent and oleylamine according to a preset ratio, react at a preset temperature to prepare a ZnO biomimetic nano-pine needle solution;

[0011] The ZnO bionic nano-pine needle solution is purified to obtain a ZnO bionic nano-pine needle solid powder sample.

[0012] As a further optimized solution of the present invention, the molar ratio of the anhydrous zinc acetate powder, the methanol organic solvent and oleylamine is 1: (10-15): (4-6).

[0013] As a further optimization scheme of the present invention, the methanol organic solvent is a mixed solvent of methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1.

[0014] As a further optimization solution of the present invention, the preset temperature is 130-160° C., and the reaction time is 10-14 hours.

[0015] As a further optimization scheme of the present invention, the purification step of the ZnO biomimetic nano pine needle solution includes: adding isopropanol and acetone to the ZnO biomimetic nano pine needle solution, mixing thoroughly and then centrifuging to separate the phases, discarding the upper clear layer, dissolving the lower precipitate with chloroform, then evaporating the solution to dryness, dispersing with isopropanol and acetone and centrifuging and precipitating, and finally dissolving the precipitated product in tert-butanol, freezing with liquid nitrogen and vacuum drying to obtain a ZnO biomimetic nano pine needle solid powder sample.

[0016] As a further optimization solution of the present invention, the volume of the added isopropanol and acetone is 4-6 times the volume of the ZnO bionic nano-pine needle solution.

[0017] The reaction mechanism for synthesizing ZnO bionic nano-pine needles is as follows:

[0018] 1. Raw materials react to form zinc oxide nuclei: Anhydrous zinc acetate serves as the zinc and oxygen sources. In an oil bath at 130-160°C, zinc acetate thermally decomposes zinc ions and oxygen ions, forming zinc oxide (ZnO) nuclei. Methanol, an organic solvent, regulates the reaction rate and controls the direction of crystal growth. As the reaction proceeds, more zinc oxide bonds to the nuclei, promoting their continued growth.

[0019] 2. Oleylamine's Regulation of Crystal Growth: Oleylamine acts as a ligand in the reaction. On the one hand, by coordinating with the zinc ion, it influences the zinc ion's reactivity and the surrounding electron cloud distribution, thereby controlling the growth rate and direction of the zinc oxide crystals. On the other hand, the steric hindrance of the oleylamine molecule restricts the growth of the zinc oxide crystals in certain directions, prompting them to develop a three-dimensional, spiky structure resembling pine needles. For example, oleylamine molecules may preferentially adsorb on certain crystal faces, hindering their growth, while other unadsorbed faces continue to grow, ultimately forming a distinctive, spiky morphology. The disappearance of the characteristic thiol peak at 2500-2600 in the Fourier transform infrared spectrum demonstrates that oleylamine, acting as a protective ligand, participates in the entire reaction process, playing a key role in the ultimate formation of the unique ZnO biomimetic nano-pine needle structure.

[0020] 3. Reaction conditions promote structure formation: An oil bath temperature of 130-160°C and a reaction time of 10-14 hours provide suitable kinetic conditions for the above reaction. The appropriate temperature allows the raw materials to fully react, resulting in vigorous molecular thermal motion, which is conducive to ionic bonding and crystal growth. A sufficiently long reaction time ensures that the crystal nuclei have ample time to grow and develop into ZnO biomimetic nano-pine needle structures with specific size and morphology. If the temperature is too low or the reaction time is too short, the reaction may be incomplete, preventing the formation of a complete pine needle-like three-dimensional spike structure, or the resulting particles may be small and unstable.

[0021] In a third aspect, the present invention provides an application of the bionic nano antibacterial material in the antibacterial field, which includes the medical industry, food packaging field, and textile industry.

[0022] As a further optimization solution of the present invention, the antibacterial material is applied to the environment or surface of the object to be antibacterial by spraying.

[0023] As a further optimization scheme of the present invention, the preparation method of the spray containing the antibacterial material includes: dissolving the ZnO bionic nano pine needle solid powder sample obtained by vacuum drying in a mixed solvent of ultrapure water and ethanol, and ultrasonically obtaining the ZnO bionic nano pine needle spray.

[0024] As a further optimization scheme of the present invention, the volume ratio of ultrapure water to ethanol is 1: (5-10), and the ultrasonic time is 5-10 minutes.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] This invention utilizes a one-step hydrothermal method for the first time to prepare biomimetic ZnO nanoparticles with a three-dimensional, spiky structure resembling pine needles. Existing methods for synthesizing metal and metal oxide nanoantibacterial materials vary, but most often involve high synthesis temperatures, complex processes, or high costs. Synthesis of gold and silver nanoantibacterial materials often requires specialized equipment and complex processes. However, the present one-step hydrothermal method is relatively simple to operate, completing the conversion from raw materials to the target product within a single reaction system, eliminating intermediate steps and reducing both synthesis difficulty and production costs.

[0027] The raw materials used in the preparation process, such as anhydrous zinc acetate, methanol-based organic solvents, and oleylamine, are widely available and relatively environmentally friendly. Compared to some traditional antimicrobial material synthesis processes that use toxic, hazardous, or expensive raw materials, this invention is more in line with the concept of green chemistry, reducing negative environmental impacts and minimizing safety risks during production.

[0028] The ZnO biomimetic nano-pine needles produced by the present invention possess a three-dimensional spiky structure, a key feature that distinguishes them from traditional ZnO antibacterial materials. Traditional ZnO antibacterial materials primarily rely on photocatalysis to generate reactive oxygen species to destroy bacterial structures. However, the present material not only utilizes photocatalysis, but its spiky structure can also directly bind to bacterial cell membranes, physically puncturing them and leaking their contents, leading to bacterial death. Scanning electron microscopy images clearly show that incubation of the material with Escherichia coli and Staphylococcus aureus punctured the bacterial cell membranes. This multi-mechanism antibacterial approach significantly improves antibacterial efficiency.

[0029] The ZnO biomimetic nano-pine needle particles are uniform in size, consisting of 80-300 ZnO nanospikes with an overall particle size of 300-600nm. This uniform size distribution ensures the stability of the material's performance. In practical applications, there will be no uneven antibacterial effect due to differences in particle size. At the same time, the particles can be evenly and stably dispersed in ethanol or water and can be directly sprayed using a spray bottle, making them easy to use. In contrast, some traditional antibacterial materials have problems with dispersibility and are prone to agglomeration, which affects their antibacterial properties.

[0030] The material of the present invention exhibits highly effective, broad-spectrum antimicrobial properties against a variety of bacteria and fungi, with antimicrobial efficiencies exceeding 99.99%. MIC data and antimicrobial efficiency statistical charts show significant inhibitory effects against seven types of bacteria and fungi. Existing antimicrobial materials may only be effective against specific bacterial species and lack broad-spectrum antimicrobial properties, or their antimicrobial efficiencies are low, failing to meet practical needs.

[0031] With its excellent antimicrobial properties and good dispersibility, it has broad application prospects in various industries, including healthcare, food packaging, and textiles. In the healthcare industry, it can be used to disinfect operating rooms and hospital wards, reducing the risk of cross-infection; in food packaging, it can extend the shelf life of food and ensure food safety; and in the textile industry, it can impart antimicrobial properties to clothing and home textiles, improving quality of life. In contrast, some traditional antimicrobial materials face numerous limitations in their application due to safety and cost issues. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Schematic diagram of the synthesis process of ZnO bionic nano pine needles in Example 1 of the present invention.

[0033] Figure 2 This is a transmission electron microscope image (0.5 μm) of the ZnO bionic nano-pine needle according to Example 1 of the present invention.

[0034] Figure 3 This is a transmission electron microscope image (200 nm) of the ZnO bionic nano-pine needle according to Example 1 of the present invention.

[0035] Figure 4This is a transmission electron microscope image of the ZnO bionic nano-pine needle according to Example 1 of the present invention.

[0036] Figure 5 This is a scanning electron microscope image of the ZnO bionic nano-pine needle according to Example 1 of the present invention.

[0037] Figure 6 This is a secondary electron microscope image of the ZnO bionic nano-pine needle according to Example 1 of the present invention.

[0038] Figure 7 This is a high-angle annular dark-field image of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0039] Figure 8 This is the EDS mapping image of the zinc element of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0040] Figure 9 This is the oxygen element EDS mapping image of the ZnO bionic nano-pine needles according to Example 1 of the present invention.

[0041] Figure 10 This is a high-resolution transmission electron microscope image of the ZnO bionic nano-pine needle and its interplanar spacing measurement diagram of Example 1 of the present invention, wherein a is a high-resolution transmission electron microscope image and b is a interplanar spacing measurement diagram.

[0042] Figure 11 This is the UV-visible spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0043] Figure 12 This is the Fourier infrared spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0044] Figure 13 This is the X-ray diffraction pattern of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0045] Figure 14 This is the full X-ray photoelectron spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0046] Figure 15 This is the X-ray photoelectron spectroscopy zinc fine spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention.

[0047] Figure 16 This is the MIC graph of the ZnO bionic nanoparticles according to Example 1 of the present invention against seven types of bacteria and fungi.

[0048] Figure 17 This is a statistical chart of the antibacterial efficiency of ZnO bionic nano pine needles in Example 1 of the present invention.

[0049] Figure 18 This is a scanning electron microscope image of the ZnO bionic nano-pine needles and Escherichia coli after culture in Example 1 of the present invention.

[0050] Figure 19 This is a scanning electron microscope image of the ZnO bionic nano-pine needles and Staphylococcus aureus after cultivation according to Example 1 of the present invention.

[0051] Figure 20 This is a transmission electron microscope image of the ZnO bionic nano-pine needle of comparative example 1 of the present invention.

[0052] Figure 21 This is the MIC graph of ZnO bionic nanopine in comparative example 1 of the present invention against 7 kinds of bacteria and fungi.

[0053] Figure 22 This is a statistical chart of the antibacterial efficiency of ZnO bionic nano pine needles in comparative example 1 of the present invention.

[0054] Figure 23 This is a transmission electron microscope image of the ZnO bionic nano-pine needle of comparative example 2 of the present invention.

[0055] Figure 24 This is the MIC graph of ZnO bionic nanopine in comparative example 2 of the present invention against 7 kinds of bacteria and fungi.

[0056] Figure 25 This is a statistical chart of the antibacterial efficiency of ZnO bionic nano pine needles in comparative example 2 of the present invention. DETAILED DESCRIPTION

[0057] In order to enable those skilled in the art to better understand the technical solutions of the present invention, preferred embodiments of the present invention are described below in conjunction with specific examples. However, these examples are not to be construed as limiting the present invention and are merely examples.

[0058] Example 1

[0059] This embodiment provides a method for preparing a bionic pine needle nano antibacterial material, comprising the following steps:

[0060] Step 1: Synthesis of ZnO bionic nano-pine needles:

[0061] Anhydrous zinc acetate powder, methanol-based organic solvent (methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1) and oleylamine in a molar ratio of 1:12.5:5 were weighed and reacted in an oil bath at 145°C for 12 hours to obtain a ZnO biomimetic nano-pine needle solution.

[0062] Step 2: Purification of ZnO bionic nano-pine needles:

[0063] Purification of ZnO bionic nano-pine needles: add 5 times the volume of isopropanol and acetone to the ZnO bionic nano-pine needle solution in the above step 2, mix thoroughly and then centrifuge to separate the phases, discard the upper clear layer, dissolve the lower precipitate with chloroform, then evaporate the solution to dryness, disperse with isopropanol and acetone and centrifuge and precipitate, repeat three times, finally dissolve the precipitate in tert-butanol, freeze with liquid nitrogen and vacuum dry for 3 days to obtain a solid powder sample.

[0064] Step 3: Preparation of ZnO bionic nano pine needle spray:

[0065] The ZnO bionic nano-pine needle solid powder sample obtained by vacuum drying was dissolved in a mixed solvent of ultrapure water and ethanol in a volume ratio of 1:8, and ultrasonicated for 8 minutes to obtain a ZnO bionic nano-pine needle spray.

[0066] Example 2

[0067] This embodiment provides a method for preparing a bionic pine needle nano antibacterial material, comprising the following steps:

[0068] Step 1: Synthesis of ZnO bionic nano-pine needles:

[0069] Anhydrous zinc acetate powder, methanol-based organic solvent (methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1) and oleylamine in a molar ratio of 1:10:4 were weighed and reacted in an oil bath at 130°C for 10 hours to obtain a ZnO biomimetic nano-pine needle solution.

[0070] Step 2: Purification of ZnO bionic nano-pine needles:

[0071] Purification of ZnO biomimetic nano-pine needles: add 4 times the volume of isopropanol and acetone to the ZnO biomimetic nano-pine needle solution in the above step 2, mix thoroughly and then centrifuge to separate the phases, discard the upper clear layer, dissolve the lower precipitate with chloroform, then evaporate the solution to dryness, disperse with isopropanol and acetone and centrifuge and precipitate, repeat three times, finally dissolve the precipitate in tert-butanol, freeze with liquid nitrogen and vacuum dry for 2 days to obtain a solid powder sample.

[0072] Step 3: Preparation of ZnO bionic nano pine needle spray:

[0073] The ZnO bionic nano-pine needle solid powder sample obtained by vacuum drying was dissolved in a mixed solvent of ultrapure water and ethanol in a volume ratio of 1:5, and ultrasonicated for 5 minutes to obtain a ZnO bionic nano-pine needle spray.

[0074] Example 3

[0075] This embodiment provides a method for preparing a bionic pine needle nano antibacterial material, comprising the following steps:

[0076] Step 1: Synthesis of ZnO bionic nano-pine needles:

[0077] Anhydrous zinc acetate powder, methanol-based organic solvent (methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1) and oleylamine in a molar ratio of 1:15:6 were weighed and reacted in an oil bath at 160°C for 14 hours to obtain a ZnO biomimetic nano-pine needle solution.

[0078] Step 2: Purification of ZnO bionic nano-pine needles:

[0079] Purification of ZnO biomimetic nano-pine needles: add 6 times the volume of isopropanol and acetone to the ZnO biomimetic nano-pine needle solution in the above step 2, mix thoroughly and then centrifuge to separate the phases, discard the upper clear layer, dissolve the lower precipitate with chloroform, then evaporate the solution to dryness, disperse with isopropanol and acetone and centrifuge and precipitate, repeat three times, finally dissolve the precipitated product in tert-butanol, freeze with liquid nitrogen and vacuum dry for 3 days to obtain a solid powder sample.

[0080] Step 3: Preparation of ZnO bionic nano pine needle spray:

[0081] The ZnO bionic nano-pine needle solid powder sample obtained by vacuum drying was dissolved in a mixed solvent of ultrapure water and ethanol in a volume ratio of 1:10, and ultrasonicated for 10 minutes to obtain a ZnO bionic nano-pine needle spray.

[0082] Comparative Example 1

[0083] The difference from Example 1 is that the anhydrous zinc acetate powder, methanol-based organic solvent (methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1) and oleylamine are selected in a molar ratio of 0.5:12.5:5. The other conditions are the same. The number of ZnO bionic nanopine needles obtained is reduced to 40-100, and the size is about 250 nm.

[0084] Comparative Example 2

[0085] The difference from Example 1 is that anhydrous zinc acetate powder, methanol-based organic solvent (methanol, methyl formate and benzyl alcohol in a volume ratio of 3:1:1) and oleylamine are weighed in a molar ratio of 1:12.5:5 and reacted in an oil bath at 145°C for 6 hours. The other conditions are the same. The number of ZnO bionic nanopine needles obtained is reduced to about 6, and the size is about 220 nm.

[0086] Antibacterial testing

[0087] MIC determination:

[0088] Inoculate the strain to be tested onto the corresponding solid culture plate in advance and culture overnight in a 37°C bacterial incubator. According to the experimental requirements, dilute the stock solution to the highest concentration of the drug to be tested using LB liquid medium. Take a sterile 96-well plate and dilute the drug in a biosafety cabinet. The specific operation is as follows: add 200μL of the highest concentration of the drug to be tested to the first well (A1), add 100μL of LB liquid medium to wells A2 to A12, then aspirate 100μL from well A1 and add it to well A2. After mixing, aspirate 100μL from well A2 and add it to well A3. Repeat the gradient dilution to well A12, and discard the last 100μL of diluted liquid. ; Add 1 mL of PBS to a transparent plastic test tube; place it on a turbidity meter and adjust it to zero, then pick the strain to be tested and fully dissolve it in physiological saline, shake and mix, adjust the turbidity to between 0.4 and 0.6, and continue to dilute it 20 times with PBS for later use; add 10 μL of the diluted bacterial suspension to each concentration of drug well (A1~A12) in turn; place the 96-well plate in a 37°C bacterial incubator and culture it for 16~18 hours; read the lowest drug concentration at which no bacteria grows, which is the minimum inhibitory concentration of bionic nanopine against the bacteria.

[0089] Calculation of antibacterial rate:

[0090] The antibacterial activity of biomimetic nanopine needles was studied using the colony-forming unit (CFU) method on Luria-Bertani (LB) agar plates, using Escherichia coli (Gram-negative bacteria), Staphylococcus aureus (Gram-positive bacteria), and methicillin-resistant Staphylococcus aureus as representative bacteria. Escherichia coli, Staphylococcus aureus, or methicillin-resistant Staphylococcus aureus were cultured in LB medium. The original bacterial suspension was incubated in a shaking incubator at 37°C overnight. The bacterial suspension was then diluted with PBS (pH 7.4) and Escherichia coli, Staphylococcus aureus, or methicillin-resistant Staphylococcus aureus (1×10 7 CFUmL -1 ) bacterial suspensions were incubated with control (PBS) or biomimetic nanopine needles at 37°C for 24 hours. For colony count experiments, the bacterial suspensions were spread on agar plates and incubated for another 24 hours to evaluate their antibacterial activity. The bacterial lethality was calculated using the following formula:

[0091] .

[0092] The present invention takes the products prepared in Example 1, Comparative Example 1 and Comparative Example 2 as examples to illustrate their synthesis results and performance characterizations:

[0093] Figure 1 This is a schematic diagram of the synthesis process of ZnO biomimetic nano-pine needles according to Example 1 of the present invention. This diagram shows the preparation process of ZnO biomimetic nano-pine needle particles. The entire reaction process system is single, and the synthesis process is simple, green, and efficient.

[0094] Figure 2 This is a transmission electron microscope image of the ZnO bionic nano pine needles of Example 1 of the present invention. The image is an overall display of the synthesized ZnO bionic nano pine needle particles, indicating that the synthesized ZnO bionic nano pine needle particles have good dispersion and uniform size, with an overall particle size of 300-600nm.

[0095] Figure 3 This is a transmission electron microscope image of the ZnO bionic nano pine needle of Example 1 of the present invention. The image is a front view of a single ZnO bionic nano pine needle particle, indicating that the synthesized ZnO bionic nano pine needle is composed of 80-300 ZnO nano spikes with an overall particle size of 300-600nm.

[0096] Figure 4 This is a transmission electron microscope image of the ZnO bionic nano-pine needle of Example 1 of the present invention. The image is a top view of a single ZnO bionic nano-pine needle particle. The image shows that the synthesized ZnO bionic nano-pine needle has a three-dimensional spike structure similar to that of a pine needle.

[0097] Figure 5 This is a scanning electron microscope image of the ZnO bionic nano-pine needle of Example 1 of the present invention. Figure 2 It also shows that the synthesized ZnO bionic nano pine needle particles are uniform in size, with an overall particle size of 300-600nm.

[0098] Figure 6 This is a secondary electron microscope image of the ZnO bionic nano-pine needles of Example 1 of the present invention. The image shows that the synthesized ZnO bionic nano-pine needles have a three-dimensional spike structure.

[0099] Figure 7 This is a high-angle annular dark field image of the ZnO bionic nano-pine needles of Example 1 of the present invention. The image shows that the synthesized ZnO bionic nano-pine needle particles are uniform in size, with an overall particle size of 300-600nm.

[0100] Figure 8 This is an EDS mapping image of zinc elements in the ZnO bionic nano-pine needles of Example 1 of the present invention. The image shows that the synthesized ZnO bionic nano-pine needle particles contain zinc elements.

[0101] Figure 9 This is an EDS mapping image of oxygen elements of the ZnO bionic nano-pine needles of Example 1 of the present invention. The image shows that the synthesized ZnO bionic nano-pine needle particles contain oxygen elements.

[0102] Figure 7 、 Figure 8 and Figure 9It is proved that the composition of the ZnO bionic nano pine needle in Example 1 of the present invention is zinc oxide.

[0103] Figure 10 This is a high-resolution transmission electron microscope image of the ZnO bionic nano-pine needles of Example 1 of the present invention and a crystal plane spacing measurement diagram thereof. The image shows that the crystal plane of the synthesized ZnO bionic nano-pine needle particles is (002).

[0104] Figure 11 This is the UV-visible spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention. The image shows that the synthesized ZnO bionic nano-pine needle particles have a zinc oxide characteristic peak of 360nm, proving that zinc oxide is included in the composition of the bionic nano-pine needle particles.

[0105] Figure 12 This is a Fourier transform infrared spectrum of the ZnO biomimetic nano-pine needles of Example 1 of the present invention. The image shows that the characteristic peak of the thiol group of the synthesized ZnO biomimetic nano-pine needle particles at 2500-2600 disappears, proving that oleylamine acts as a ligand to protect the biomimetic nano-pine needle particles.

[0106] Figure 13 This is the X-ray diffraction pattern of the ZnO bionic nano-pine needles of Example 1 of the present invention. The characteristic peaks of the ZnO bionic nano-pine needles and the ZnO standard card #79-2205 correspond one to one, proving that its crystal structure is the same as the hexagonal wurtzite structure of the ZnO standard card #79-2205.

[0107] Figure 14 This is the full X-ray photoelectron spectrum of the ZnO bionic nano-pine needles of Example 1 of the present invention, proving that it contains elements such as zinc, oxygen, carbon, and nitrogen.

[0108] Figure 15 This is the zinc fine spectrum of the X-ray photoelectron spectrum of the ZnO bionic nano-pine needles in Example 1 of the present invention, proving that the zinc in the synthesized ZnO bionic nano-pine needles is positive divalent.

[0109] Figure 16 This is the MIC graph of the ZnO bionic nanopine in Example 1 of the present invention against 7 kinds of bacteria and fungi. Among them, it has strong antibacterial properties against Pseudomonas fluorescens and Candida albicans, with a MIC of only 2μg / mL, the MIC against Bacillus cereus is 4μg / mL, and the MIC against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis is 16μg / mL, proving that it has high-efficiency and broad-spectrum antibacterial properties.

[0110] Figure 17This is a statistical chart of the antibacterial efficiency of 16 μg / mL ZnO biomimetic nanopine against Escherichia coli, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus in Example 1 of the present invention; it proves that it has good antibacterial performance against a variety of bacteria, all higher than 99.99%.

[0111] Figure 18 This is a scanning electron microscope image of the ZnO bionic nano-pine needles and Escherichia coli after culture in Example 1 of the present invention; it can be clearly seen that the ZnO bionic nano-pine needles have obvious contact with the bacterial wall, and the bacterial wall has obvious shrinkage and rupture, proving that it can physically puncture the bacteria and achieve a bactericidal effect.

[0112] Figure 19 This is a scanning electron microscope image of the ZnO bionic nano-pine needles and Staphylococcus aureus after culture in Example 1 of the present invention; it can be clearly seen that the ZnO bionic nano-pine needles have obvious contact with the bacterial wall, and the bacterial wall has obvious shrinkage and rupture, proving that it can physically puncture the bacteria and achieve a bactericidal effect.

[0113] Figure 20 This is a transmission electron microscope image of the ZnO bionic nano pine needles of comparative example 1 of the present invention. The image shows that the number of ZnO rods in the ZnO bionic nano pine needles synthesized by reducing the proportion of anhydrous zinc acetate is reduced to 40-200, and the overall particle size is reduced to about 250nm, indicating that reducing the zinc source will cause the synthesized ZnO bionic nano pine needles to become smaller and have no obvious pine needle three-dimensional structure.

[0114] Figure 21 This is the MIC diagram of the ZnO bionic nanopine needles of comparative example 1 of the present invention against 7 kinds of bacteria and fungi. The MIC for Pseudomonas fluorescens and Bacillus cereus is 16 μg / mL, the MIC for Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis is 16 μg / mL, and the MIC for Candida albicans is 128 μg / mL, which proves that the antibacterial performance is worse than that of the ZnO bionic nanopine needles in Example 1 of the invention.

[0115] Figure 22 This is a statistical chart of the antibacterial efficiency of 64 μg / mL ZnO bionic nanopine needles in comparative example 1 of the present invention against Escherichia coli, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus; it proves that its antibacterial performance is worse than that of the ZnO bionic nanopine needles in Example 1 of the invention.

[0116] Figure 23 This is a transmission electron microscope image of the ZnO bionic nano pine needles of comparative example 2 of the present invention. The image shows that the number of ZnO rods in the ZnO bionic nano pine needles synthesized by reducing the reaction time is reduced to about 6, and the overall particle size is reduced to about 220 nm, indicating that reducing the reaction time will cause the synthesized ZnO bionic nano pine needles to become smaller and have no obvious pine needle three-dimensional structure.

[0117] Figure 24 This is the MIC graph of the ZnO bionic nanopine needles of comparative example 2 of the present invention against 7 kinds of bacteria and fungi. The MIC for Pseudomonas fluorescens and Bacillus cereus is 128 μg / mL, the MIC for Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis is 256 μg / mL, and the MIC for Candida albicans is 512 μg / mL, which proves that the antibacterial performance is worse than that of the ZnO bionic nanopine needles in Example 1 of the invention.

[0118] Figure 25 This is a statistical chart of the antibacterial efficiency of 512 μg / mL ZnO bionic nanopine needles against Escherichia coli, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus in Comparative Example 2 of the present invention; it proves that its antibacterial performance is worse than that of the ZnO bionic nanopine needles in Example 1 of the invention.

[0119] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be construed as limiting the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. Persons skilled in the art will appreciate that improvements and modifications may be made without departing from the spirit and scope of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A bionic pine needle nano antibacterial material, characterized in that: The antibacterial material has uniform particle size, and a single particle is a three-dimensional spike structure composed of 80-300 ZnO nanospikes; The preparation method of the antibacterial material comprises the following steps: Weigh the raw materials: anhydrous zinc acetate powder, methanol organic solvent and oleylamine according to a preset ratio, react at a preset temperature to prepare a ZnO biomimetic nano-pine needle solution; Purifying the ZnO biomimetic nano-pine needle solution to obtain a ZnO biomimetic nano-pine needle solid powder sample; The molar ratio of the anhydrous zinc acetate powder, the methanol organic solvent, and oleylamine is 1: (10-15): (4-6); the preset temperature is 130-160° C., and the reaction time is 10-14 hours.

2. The bionic pine needle nano antibacterial material according to claim 1, characterized in that: The overall particle size of the individual particles is 300-600 nm.

3. The bionic pine needle nano antibacterial material according to claim 1, characterized in that: The purification step of the ZnO biomimetic nano pine needle solution includes: adding isopropanol and acetone to the ZnO biomimetic nano pine needle solution, fully mixing and then centrifuging to separate the phases, discarding the upper clear layer, dissolving the lower precipitate with chloroform, then evaporating the solution to dryness, dispersing with isopropanol and acetone and centrifuging and precipitating, and finally dissolving the precipitate in tert-butanol, freezing with liquid nitrogen and vacuum drying to obtain a ZnO biomimetic nano pine needle solid powder sample.

4. The bionic pine needle nano antibacterial material according to claim 3, characterized in that: The volume of the added isopropanol and acetone is 4-6 times the volume of the ZnO bionic nano-pine needle solution.

5. An application of the bionic nano antibacterial material according to claim 1 or 2 in the antibacterial field, characterized in that: The antibacterial field includes the medical industry, food packaging field, and textile industry, and the application is for non-disease diagnosis and treatment purposes.

6. The use according to claim 5, characterized in that The antibacterial material is applied to the environment or the surface of the object to be antibacterial by spraying.

7. The use according to claim 5 or 6, characterized in that The preparation method of the spray containing the antibacterial material comprises: dissolving a ZnO bionic nano-pine needle solid powder sample obtained by vacuum drying in a mixed solvent of ultrapure water and ethanol, and ultrasonically obtaining the ZnO bionic nano-pine needle spray.

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