阅读说明：本技术 一种类普鲁士蓝纳米材料及其制备方法和应用 (Prussian-like blue nano material and preparation method and application thereof ) 是由 汪维云 丁晓远 尹晨阳 陈小庆 杨恩东 郭峰 孙冬冬 于 2020-11-16 设计创作，主要内容包括：本发明一种类普鲁士蓝纳米材料,包括类普鲁士蓝纳米颗粒Ru@PB,所述类普鲁士蓝纳米颗粒Ru@PB为将金属钌配合至普鲁士蓝纳米颗粒上所获得,所述类普鲁士蓝纳米颗粒Ru@PB的直径为50～100nm,还提供了一种上述类普鲁士蓝纳米材料在抗菌纳米材料领域中的应用。相比较现有技术,采用了纳米材料与金属钌进行合成,金属钌取代了普鲁士蓝纳米颗粒中的铁元素,与传统的普鲁士蓝纳米颗粒相比,金属钌本身就具有较强的抗菌能力,金属钌的加入使得普鲁士蓝纳米颗粒具有更强的抗菌能力,也使本身具有耐药性的细菌被抑制生长。(The invention relates to a Prussian blue-like nano material which comprises Prussian blue-like nano particles Ru @ PB, wherein the Prussian blue-like nano particles Ru @ PB are obtained by matching metal ruthenium to Prussian blue nano particles, and the diameter of the Prussian blue-like nano particles Ru @ PB is 50-100 nm. Compared with the prior art, the nano material and the metal ruthenium are adopted for synthesis, the metal ruthenium replaces an iron element in the Prussian blue nano particles, compared with the traditional Prussian blue nano particles, the metal ruthenium has stronger antibacterial capability, and the addition of the metal ruthenium enables the Prussian blue nano particles to have stronger antibacterial capability and also enables the bacteria with drug resistance to be inhibited from growing.)

1. The Prussian-blue-like nano material is characterized by comprising Prussian-blue-like nano particles Ru @ PB, wherein the Prussian-blue-like nano particles Ru @ PB are obtained by matching metal ruthenium to Prussian-blue nano particles, and the diameters of the Prussian-blue-like nano particles Ru @ PB are 50-100 nm.

2. The use of the prussian-like blue nanomaterial of claim 1 in the field of antibacterial nanomaterials.

3. A method for preparing the prussian-like blue nanomaterial as claimed in claim 1, comprising the steps of:

(1) adding polyvinylpyrrolidone PVP into water, dropwise adding HCl into the solution to make the pH of the solution acidic, and stirring at room temperature to form a uniform solution I.

(2) And (3) adding potassium ferricyanide into the solution I in the step (1) to form a mixed solution, and heating, preserving heat and cooling the mixed solution to obtain a blue solution II during reaction.

(3) And (3) adding acetone into the blue solution II in the step (2), uniformly mixing, centrifuging, removing a supernatant, washing, and performing vacuum drying on an obtained sample to obtain the material, namely the Prussian blue nano-particles.

(4) Adding polyvinylpyrrolidone PVP into water, stirring uniformly, and adding RuCl into the solution₃，RuCl₃And adding formaldehyde into the solution after dissolution, uniformly mixing, adding the material I into the solution, heating, preserving heat, and cooling to room temperature to obtain a solution III.

(5) And washing the solution III with acetone, alcohol and water for several times respectively to obtain a sample, and performing vacuum drying to obtain the Prussian-like blue nano particles Ru @ PB.

4. The method for preparing Prussian-like blue nano-materials according to claim 3, wherein the polyvinylpyrrolidone PVP in the step (1) and the step (4) is PVP-K30, and the molecular weight is 44000-54000.

5. The method for preparing Prussian-like blue nano-materials according to claim 3, wherein the pH of the solution in the step (1) is adjusted to 2-3.

6. The method for preparing Prussian-like blue nano-materials according to claim 3, wherein the reaction temperature of the mixed solution in the step (2) is 80-100 ℃.

7. The method for preparing Prussian-like blue nano-materials according to claim 3, wherein the volume ratio of acetone to the solution II added in the step (3) is 1: 1.

8. the method for preparing Prussian-like blue nano-materials according to claim 3, wherein the washing in the step (3) and the washing in the step (4) are centrifugal washing, the centrifugal rotating speed is 8000-10000 rpm, and the centrifugal time is 5-10 min.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a Prussian blue-like nano material as well as a preparation method and application thereof.

Background

Antibacterial substances are very important and essential in the treatment of infectious diseases caused by pathogenic bacteria. However, the widespread use of antibiotics has resulted in the development of increasingly greater resistance of pathogenic bacteria to commercially available antibacterial drugs, resulting in poor therapeutic efficacy and significant economic losses. In addition to the commonly used antibiotics, specific metals or metal-based materials have some specific physical and chemical properties and are effective bacteriostats. Metal elements such as copper, cobalt, nickel, zinc, and ruthenium (Ru) have been studied because of their small volume and relatively high nuclear charge, and thus have a strong ability to form a complex compound. The development of the metal ruthenium is a field of medical science, particularly a field of rapid development in the field of chemotherapy, and has the advantages of minimal side effect, strong drug resistance and the like.

The metal organic framework compounds (MOFs) are coordination polymers MOFs which are mixed between organic and inorganic phases, central metal cations (or metal clusters) are connected through organic ligands to form basic structural units, the basic structural units continuously and infinitely extend, and the metal organic framework compounds which are self-assembled on a molecular level to form a periodic network structure are taken as special novel porous materials.

The transition metal cyanide is a metal organic framework compound which has a simple structure, is simple and convenient to prepare, is low in price and has a long history, wherein Prussian blue is the earliest metal organic framework compound which can be traced back to the world, and is found to be used as an oil painting dye and glazing three hundred years ago. Nowadays, a large number of transition metal cyanides with similar structures to prussian blue, called prussian blue analogues or prussian-like blue (PBA), can be prepared by selecting appropriate transition metal ions to replace ferrous and ferric ions in prussian blue. The Prussian-like blue particles have the advantages of rich diversity, controllable pore channel structure, higher specific surface area and the like, and the application of the Prussian-like blue particles in various related fields is greatly widened.

The existing commonly used antibacterial drugs have poor effects on some bacteria with strong drug resistance, cannot be widely applied to some fields with high antibacterial requirements, although the existing antibacterial drugs can be modified to increase the antibacterial efficiency, the antibacterial performance is still poor, particularly the antibacterial effects on common bacteria such as escherichia coli and staphylococcus aureus are poor, and the nano material has the advantages of low toxicity, good antibacterial effect, easiness in modification and the like. Based on the above, a Prussian blue-like nano material, a preparation method and an application thereof are provided.

Disclosure of Invention

The invention aims to provide a Prussian-like blue nano material, a preparation method and application thereof, so as to solve the problems in the background technology.

The invention realizes the purpose through the following technical scheme:

the invention provides a Prussian-blue-like nano material which comprises Prussian-blue-like nano particles Ru @ PB, wherein the Prussian-blue-like nano particles Ru @ PB are obtained by matching metal ruthenium to Prussian-blue nano particles, and the diameters of the Prussian-blue-like nano particles Ru @ PB are 50-100 nm.

The invention also provides an application of the prussian-like blue nano material in the field of antibacterial nano materials.

The invention also provides a preparation method of the prussian-like blue nano material, which comprises the following steps:

(1) adding polyvinylpyrrolidone PVP into water, dropwise adding HCl into the solution to make the pH of the solution acidic, and stirring at room temperature to form a uniform solution I.

(2) And (3) adding potassium ferricyanide into the solution I in the step (1) to form a mixed solution, and heating, preserving heat and cooling the mixed solution to obtain a blue solution II during reaction.

(3) And (3) adding acetone into the blue solution II in the step (2), uniformly mixing, centrifuging, removing a supernatant, washing, and performing vacuum drying on an obtained sample to obtain the material, namely the Prussian blue nano-particles.

(4) Adding polyvinylpyrrolidone PVP into water, stirring uniformly, and adding RuCl into the solution₃，RuCl₃And adding formaldehyde into the solution after dissolution, uniformly mixing, adding the material I into the solution, heating, preserving heat, and cooling to room temperature to obtain a solution III.

(5) And washing the solution III with acetone, alcohol and water for several times respectively to obtain a sample, and performing vacuum drying to obtain the Prussian-like blue nano particles Ru @ PB.

As a further optimization scheme of the invention, the polyvinylpyrrolidone in the step (1) and the step (4) is PVP-K30, and the molecular weight is 44000-.

As a further optimization scheme of the invention, the pH of the solution in the step (1) is adjusted to be 2-3.

As a further optimization scheme of the invention, the reaction temperature of the mixed solution in the step (2) is 80-100 ℃.

As a further optimized scheme of the invention, the volume ratio of the acetone added in the step (3) to the solution II is 1: 1.

as a further optimization scheme of the invention, the washing in the step (3) and the washing in the step (4) are centrifugal washing, the centrifugal rotating speed is 8000-10000 rpm, and the centrifugal time is 5-10 min.

The invention has the beneficial effects that: the invention adopts the synthesis of the nano material and the metal ruthenium, the metal ruthenium replaces the iron element in the Prussian blue nano particles, compared with the traditional Prussian blue nano particles, the metal ruthenium has stronger antibacterial capability, and the addition of the metal ruthenium ensures that the Prussian blue nano particles have stronger antibacterial capability and also ensures that the bacteria with drug resistance are inhibited from growing; and the prussian blue-like nano particles are safe and harmless to human bodies, have strong near infrared absorption capacity, are good photosensitizers, have lower price and simpler synthesis compared with other noble metals, so that the material has the advantages of strong antibacterial capacity, low toxicity, low price and the like compared with the traditional antibacterial material, improves the application of the nano material in the medical field, and is a nano material which has wider application range and is more worthy of popularization.

Drawings

FIG. 1: (A) transmission electron microscopy of prussian-like blue nanoparticles of comparative example 1; (B) transmission electron microscopy of prussian blue nanoparticles of comparative example 2; (C) transmission electron microscopy of prussian-like blue nanoparticles in comparative example 3; (D) transmission electron microscopy images of prussian-like blue nanoparticles in example 1;

FIG. 2 is a transmission electron micrograph of Prussian-like blue nanoparticles in comparative example 4;

FIG. 3: (A) prussian blue nanoparticle PB; an ultraviolet-visible spectrum chart of the Prussian-like blue nanoparticle Ru @ PB. (B) Prussian blue nanoparticle PB; an X-ray diffraction pattern of the Prussian-like blue nanoparticle Ru @ PB. (C) Prussian blue nanoparticle PB; an infrared spectrogram of the Prussian-like blue nanoparticle Ru @ PB. (D) An X-ray photoelectron spectrum of the Prussian-like blue nanoparticle Ru @ PB;

FIG. 4 is a graph showing the effect of treatment of nanomaterial (30. mu.g/mL) with ampicillin (30. mu.g/mL) on colony forming units of E.coli in example 1 and comparative examples 1 to 3;

FIG. 5 is a graph showing the effect of treatment of nanomaterial (30. mu.g/mL) with ampicillin (30. mu.g/mL) in examples 1 and comparative examples 1 to 3 on colony forming units of Staphylococcus aureus.

Detailed Description

The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.

Example 1

A Prussian blue-like nano material is prepared by the following steps:

(1) adding 1.5g of polyvinylpyrrolidone (PVP) into 20mL of water, dropwise adding 6mol/L of HCL into the solution to ensure that the pH value of the solution is 2, and stirring at room temperature for 5-10min to form a uniform solution I;

(2) and adding 45mg of potassium ferricyanide into the first solution, and uniformly mixing. Adding the solution into a reaction kettle, placing the reaction kettle in an oven at 80 ℃ for 2 hours, taking out the reaction kettle, and cooling the reaction kettle at room temperature to obtain a solution II;

(3) adding acetone into the generated blue solution II, uniformly mixing, centrifuging, removing a supernatant, washing by respectively using 4ml of ethanol and water as solvents, and performing vacuum drying on the obtained sample at 60 ℃ for 10 hours to obtain a material I;

(4) weighing 200mg of polyvinylpyrrolidone PVP, adding 15mL of water, stirring uniformly, adding 4mg of RuCl₃Dissolving, adding 2mL of formaldehyde, uniformly mixing, adding 2mg of the first material, placing in a 150 ℃ oven for 6h, taking out, and cooling at room temperature to obtain a third solution;

(5) and (3) centrifuging and washing the solution III for a plurality of times by using acetone, alcohol and water respectively to obtain a sample, and drying the sample in vacuum at the temperature of 60 ℃ to obtain a product I.

Comparative example 1

A Prussian blue-like nano material is prepared by the following steps:

(1) adding 1.5g of polyvinylpyrrolidone (PVP) into 20mL of water, dropwise adding 6mol/L of HCL into the solution to ensure that the pH value of the solution is 2, and stirring at room temperature for 5-10min to form a uniform solution I;

(2) adding 45mg of potassium ferricyanide into the solution I, uniformly mixing, adding the solution into a reaction kettle, placing the reaction kettle in a 100 ℃ oven for 2 hours, taking out the reaction kettle, and cooling the reaction kettle at room temperature to obtain a solution II;

(3) adding acetone into the generated blue solution II, uniformly mixing, centrifuging, removing a supernatant, washing by respectively using 4ml of ethanol and water as solvents, and performing vacuum drying on the obtained sample at 60 ℃ for 10 hours to obtain a material I;

(4) weighing 200mg of polyvinylpyrrolidone PVP, adding 15mL of water, stirring uniformly, adding 4mg of RuCl₃Dissolving, adding 2mL formaldehyde, mixing, adding 2mg materialPlacing the material I in an oven at 150 ℃ for 6h, taking out the material I, and cooling the material I at room temperature to obtain a solution III;

(5) and (3) centrifuging and washing the solution III for a plurality of times by using acetone, alcohol and water respectively to obtain a sample, and drying the sample in vacuum at the temperature of 60 ℃ to obtain a product II.

Comparative example 2

(1) Adding 1.5g of polyvinylpyrrolidone (PVP) into 20mL of water, dropwise adding 6mol/L of HCL into the solution to ensure that the pH value of the solution is 2, and stirring at room temperature for 5-10min to form a uniform solution I;

(2) adding 45mg of potassium ferricyanide into the solution I, uniformly mixing, adding the solution into a reaction kettle, placing the reaction kettle in an oven at the temperature of 80 ℃ for 2 hours, taking out the reaction kettle, and cooling the reaction kettle at room temperature to obtain a solution II;

(3) adding acetone into the generated blue solution II, uniformly mixing, centrifuging, removing a supernatant, washing by respectively using 4ml of ethanol and water as solvents, and performing vacuum drying on the obtained sample at 60 ℃ for 10 hours to obtain a material I;

(4) weighing 200mg of polyvinylpyrrolidone PVP, adding 15mL of water, dissolving, adding 2mL of formaldehyde, uniformly mixing, adding 2mg of material I, placing in an oven at 150 ℃ for 6 hours, taking out, and cooling at room temperature to obtain solution III;

(5) and (3) centrifuging and washing the solution III for a plurality of times by using acetone, alcohol and water respectively to obtain a sample, and drying the sample in vacuum at the temperature of 60 ℃ to obtain a product III.

Comparative example 3

(1) Dropwise adding 6mol/L HCL into 20mL of water to ensure that the pH value of the solution is 2, and stirring for 5-10min at room temperature to form a solution I;

(2) adding 45mg of potassium ferricyanide into the solution I, uniformly mixing, adding the solution into a reaction kettle, placing the reaction kettle in an oven at the temperature of 80 ℃ for 2 hours, taking out the reaction kettle, and cooling the reaction kettle at room temperature to obtain a solution II;

(3) adding acetone into the generated blue solution II, uniformly mixing, centrifuging, removing a supernatant, washing by respectively using 4ml of ethanol and water as solvents, and performing vacuum drying on the obtained sample at 60 ℃ for 10 hours to obtain a material I;

(4) 15mL of water was added to 4mgRuCl₃After being stirred uniformly, 2mL of formaldehyde is added and mixed uniformlyThen adding 2mg of the first material, placing the mixture in an oven at 150 ℃ for 6h, taking out the mixture, and cooling the mixture at room temperature to obtain a third solution;

(5) and (3) centrifuging and washing the solution III for a plurality of times by using acetone, alcohol and water respectively to obtain a sample, and drying the sample in vacuum at the temperature of 60 ℃ to obtain a product IV.

Comparative example 4

A Prussian blue-like nano material is prepared by the following steps:

(1) adding 20mL of water into 1.5g of Sodium Dodecyl Benzene Sulfonate (SDBS), dropwise adding 6mol/L of HCL into the solution to ensure that the pH value of the solution is 2, and stirring for 5-10min at room temperature to form a uniform solution I;

(2) adding 45mg of potassium ferricyanide into the solution I, uniformly mixing, adding the solution into a reaction kettle, placing the reaction kettle in an oven at the temperature of 80 ℃ for 2 hours, taking out the reaction kettle, and cooling the reaction kettle at room temperature to obtain a solution II;

(3) adding acetone into the generated blue solution II, uniformly mixing, centrifuging, removing a supernatant, washing by respectively using 4ml of ethanol and water as solvents, and performing vacuum drying on the obtained sample at 60 ℃ for 10 hours to obtain a material I;

(4) weighing 200mg SDBS, adding 15mL water, stirring well, adding 4mg RuCl₃Dissolving, adding 2mL of formaldehyde, uniformly mixing, adding 2mg of the first material, placing in a 150 ℃ oven for 6h, taking out, and cooling at room temperature to obtain a third solution;

(5) and (4) centrifuging and washing the solution III for a plurality of times by using acetone, alcohol and water respectively to obtain a sample, and drying the sample in vacuum at the temperature of 60 ℃ to obtain a product V.

From A in FIG. 1, it can be seen that the Prussian-like blue nanoparticles are cubic, uniform in shape and between 50-100nm in size; b in FIG. 1 the nanoparticles of comparative example 1 due to the lack of RuCl₃The presence of ruthenium nanoparticles is not seen in the figure; fig. 1, C is an electron microscope image of the prussian blue-like nanoparticle of comparative example 2, which shows that the prussian blue-like nanoparticle becomes loose in morphology due to the absence of polyvinylpyrrolidone PVP, and cannot present a better tetragonal morphology; FIG. 1, D is a transmission electron micrograph of the Prussian-like blue nanoparticles of example 1, in which the size shapes can be seenThe state was uniform and smaller ruthenium nanoparticles were overlaid on top of the nanoparticles, demonstrating that ruthenium was successfully synthesized on the nanoparticles. Fig. 2 is a transmission electron microscope image of prussian blue-like nanoparticles prepared by adding a stabilizer of sodium dodecyl benzene sulfonate SDBS, and the nanoparticles are loose in shape and cannot present a good appearance.

As shown in fig. 3A, ultraviolet absorption peaks at 215nm and 256nm were observed in the spectrum of prussian blue PB, and ultraviolet absorption peaks at about 226nm and 260nm were observed in the spectrum of Ru @ PB, which was red-shifted from PB in relation to that of Ru @ PB in which ruthenium element was added and bound to PB, and the ultraviolet maximum absorption peak was changed due to the binding of ruthenium element; the X-ray diffraction (XRD) pattern of the diagram B shows that the PB has the same peak value and the same structure compared with a standard card, and the peak value of the PB is changed along with the addition of Ru, which indicates that the crystal structure of Ru @ PB is changed; the infrared spectrum of FIG. C shows that 3500cm can be seen from the graph^-1The nearby peak is from water in the sample, at 2075cm^-1The absorption peak at (A) is derived from the C.ident.N vibrational peak in PB, and 1650cm^-1The absorption peak is C ═ N vibration peak, and the red shift of Ru @ PB spectrogram shows that the structure of the nano particles is changed; the X-ray photoelectron spectroscopy (XPS) of the graph D shows that with the addition of ruthenium element in Ru @ PB, the 3P orbital peak of Ru is found in the nanoparticle, and from the above data, it can be demonstrated that Ru is added on the PB surface, resulting in Ru @ PB nanoparticles.

FIG. 4 is a graph showing the effect of treatment of nanomaterial (30. mu.g/mL) and ampicillin (30. mu.g/mL) in examples 1 and comparative examples 1 to 3 on colony forming units of E.coli, using ampicillin, which is a commonly used antibiotic, as a control, and showing that comparative example 2 has poor antibacterial ability due to the lack of addition of Ru as a result of CFU in the graph; comparative example 3 lacks the addition of a PVP stabilizer, the antibacterial ability is also affected; comparative example 1 compared with example 1, the antibacterial ability was not much different but the inhibitory ability against E.coli of example 1 was the most excellent, with the reaction temperature being changed.

FIG. 5 is a graph showing the effect of treatment of nanomaterial (30. mu.g/mL) with ampicillin (30. mu.g/mL) in examples 1 and comparative examples 1 to 3 on colony forming units of Staphylococcus aureus, and it can be seen that the results are similar to those in FIG. three, and comparative example 2 has poor antibacterial ability due to lack of addition of Ru; comparative example 3 lacks the addition of a PVP stabilizer, the antibacterial ability is also affected; compared with the example, the reaction temperature is changed, the antibacterial capacity is not greatly different, the inhibiting effect of the example 1 on staphylococcus aureus is the best, and the inhibiting effect is better than that of ampicillin.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.