CN114796485B - Sn nano-sheet and preparation of composite material thereof and application of Sn nano-sheet in sound power antibacterial - Google Patents

Sn nano-sheet and preparation of composite material thereof and application of Sn nano-sheet in sound power antibacterial Download PDF

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CN114796485B
CN114796485B CN202210179606.0A CN202210179606A CN114796485B CN 114796485 B CN114796485 B CN 114796485B CN 202210179606 A CN202210179606 A CN 202210179606A CN 114796485 B CN114796485 B CN 114796485B
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nano
antibacterial
hydrogel
sheet
cationic polymer
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CN114796485A (en
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刘丹
邓留
曾智麟
刘又年
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Central South University
Xiangya Hospital of Central South University
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Xiangya Hospital of Central South University
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Abstract

The invention belongs to the field of medical materials, and particularly relates to an application of Sn nano-sheets as sound-sensitive agents for preparing sound-powered antibacterial materials. In addition, the invention also provides a composite acoustic power antibacterial material containing Sn nano-sheets @ cationic polymer and composite hydrogel. The Sn nano-sheet and the composite material thereof have good sound power antibacterial performance.

Description

Sn nano-sheet and preparation of composite material thereof and application of Sn nano-sheet in sound power antibacterial
Technical Field
The invention belongs to the technical field of medicines, in particular to the field of acoustic power antibacterial materials.
Background
Microbial infection is a major factor in postoperative complications, an important source of infectious disease, and partial infectious disease has extremely high mortality. The current treatment method commonly used in clinic is antibiotic treatment, but improper selection and excessive use can lead to the appearance of drug-resistant bacteria and even multiple drug-resistant bacteria. As the threat to human health increases, the desire for new methods of treating bacterial infections becomes more urgent, scientists in various countries have also begun to search for new methods of combating microbial infections.
As an emerging disease treatment, sonodynamic antimicrobial therapy can stimulate sonosensitizers to produce reactive oxygen species by low frequency ultrasound, thereby killing bacteria. The acoustic power treatment has the advantages of high broad-spectrum bactericidal activity, no drug resistance induction, no wound, small side effect, simple operation and the like, and has potential clinical application value in the treatment of tumors, infectious diseases, atherosclerosis and the like. However, high performance sonosensitizers are still very scarce and limited ROS production efficiency makes them inadequate for timely and thorough cure of bacterial infections under current technical conditions. The development of new sonosensitizers with high sonosensitization activity is therefore an important challenge for the development of SDT technology.
In addition, the porous and highly flexible three-dimensional hydrophilic network of hydrogels can provide a suitable moist, tissue-like environment, and thus hydrogels become suitable biomaterials for biomedical applications. The hydrogel prepared by the method is used for preparing the injectable antibacterial hydrogel, and the method for preparing the injectable antibacterial hydrogel is used for preparing the injectable antibacterial hydrogel by using the antibacterial hydrogel is suitable for the wound dressing, and has the advantages of high safety, high flexibility, no toxic or side effect, no air permeability, high water permeability and the like.
Based on the current situation of medical dressing, there is a need for a hydrogel dressing with strong comprehensive properties of acoustic power antibacterial property and biocompatibility, which provides necessary mechanical support for wounds, meets the efficacy requirements of non-antibiotic antibacterial property and healing promotion of the medical dressing in the wound healing process, and realizes the treatment and management of easily infected wounds.
Disclosure of Invention
The invention aims at overcoming the defects of the research in the field and provides an application of Sn nano-sheets in sound power antibacterial.
The second object of the invention is to provide Sn nano-sheet@cationic polymer composite acoustic power antibacterial material (also referred to as composite material for short) and preparation and application thereof.
The third object of the invention is to provide Sn nano-sheet composite acoustic power antibacterial hydrogel (also simply called composite hydrogel in the invention) and preparation and application thereof.
The Sn nanometer sheet is used as sound sensitizer in preparing sound power antibacterial material.
The research of the invention discovers that the Sn nano-sheet has good sound sensitivity property, can effectively inhibit pathogenic bacteria under ultrasound, and can be used for preparing sound power antibacterial materials.
The invention is preferably applied to preparing at least one of the acoustic power antibacterial polymer composite material and the composite hydrogel;
the invention is preferably applied to prepare the acoustic power antibacterial injectable composite hydrogel;
in the invention, the thickness of the Sn nano-sheet is 2-10 nm; the plane size is 80-200 nm.
Preferably, the Sn nano-sheet is obtained by ultrasonic stripping of tin powder in a solvent;
preferably, in the ultrasonic stripping process, the solvent is C1-C4 alcohol; such as at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol;
preferably, the power of the ultrasonic stripping stage is not particularly required, for example 300 to 700kw;
preferably, the time of ultrasonic stripping is not particularly required, and is, for example, 4 to 20 hours.
In the invention, the preparation process of the Sn nanometer sheet is as follows: dispersing large blocks of Sn powder in isopropanol solution, carrying out ultrasonic treatment for 4-20 hours under ice bath condition, then centrifuging at low speed (such as 2000-3000 rpm) to remove unpeeled Sn residues, and taking supernatant to obtain brown Sn nano-sheet transparent liquid. The obtained solution is stored in a refrigerator for standby, and is centrifuged at high speed (such as 10000-12000 rpm) before use, so as to obtain Sn nano-sheet precipitate, and the Sn nano-sheet precipitate is dispersed in the required solution by ultrasonic.
The invention also provides a Sn nano-sheet@cationic polymer composite acoustic power antibacterial material which comprises the Sn nano-sheet and a cationic polymer coating the Sn nano-sheet.
The Sn nano-sheet is an inorganic two-dimensional material, is easy to agglomerate, has poor adaptive binding capacity with organic materials, and is difficult to prepare an effective preparation. Coating with polymers can improve agglomeration and organic compounding effects to some extent, however, compounding of organic materials can affect its acoustic response efficiency to some extent. According to the technical problem, the invention discovers that the Sn nano-sheets are coated by the cationic polymer, so that the structural stability of the Sn nano-sheets can be effectively improved, and in addition, the acoustic sensitivity effect capability of the material is not lost, and the acoustic power antibacterial performance of the Sn nano-sheets is cooperatively improved to a certain extent.
In the invention, the combination and cooperation of the cationic polymer type and the Sn nano-sheet are key to solving the problem of coating sound sensitivity and synergistically improving the antibacterial performance. The cationic polymer mainly refers to a polymer containing primary ammonia, secondary ammonia and tertiary ammonia structures in the polymer chain, and is further preferably Polyethyleneimine (PEI).
Preferably, the weight ratio of the Sn nano-sheets to the cationic polymer is 1-5: 1 to 100; further preferably 1:1 to 10; still more preferably 1:4 to 10; most preferably 1:4 to 6.
The invention also provides a preparation method of the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material, which is characterized in that the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material is prepared by mixing and compounding the dispersion liquid dispersed with the Sn nano-sheet and the cationic polymer solution.
The cationic polymer solution is, for example, an aqueous solution of a cationic polymer.
Adding a cationic polymer aqueous solution (such as a polyethyleneimine solution) into an Sn nanosheet aqueous solution, and stirring the mixed solution for 10-100 minutes; and then, carrying out centrifugal treatment and washing with pure water to obtain the composite material.
The invention also provides an application of the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material, which is used for preparing the acoustic power antibacterial material; preferably, it is used to prepare an acoustic dynamic antibacterial hydrogel; preferably, the method is used for preparing the acoustic power antibacterial temperature-sensitive hydrogel; preferably, it is used in the preparation of a topical dressing for an photodynamic antibacterial hydrogel.
The invention also provides an Sn nano-sheet composite acoustic power antibacterial hydrogel, which comprises a hydrogel matrix and the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material dispersed in the hydrogel matrix.
The invention researches find that for Sn nano-sheet based acoustic dynamic hydrogel, the problems of structural stability of Sn and acoustic sensitivity response efficiency loss of a composite material to Sn nano-sheets are required to be solved, and in addition, the problems of degradation and damage of acoustic dynamic free radicals to a hydrogel structure are also required to be overcome. Based on the above, the invention researches and discovers that the Sn nano-sheets are creatively coated by adopting the cationic polymer and then are compounded in the hydrogel matrix, so that the problem of dispersion stability of Sn can be synergistically improved, the mechanical tolerance of free radicals of the hydrogel is synergistically improved, the sound sensitivity is improved, and the sound power antibacterial performance is synergistically improved.
The research of the invention also discovers that in order to further improve the mechanical tolerance, the sound sensitivity, the water retention and other performances of the composite hydrogel to sound-sensitive free radicals, the proportion of the gel forming substances and materials is further controlled on the premise of coating the cationic polymer, the synergy can be further realized, the free radical tolerance strength of the hydrogel is further improved, the water retention and the bioavailability are improved, and the sound power antibacterial performance is synergistically improved.
Preferably, the gel forming substance of the hydrogel substrate is a temperature sensitive gel forming substance, preferably at least one of poly (N-isopropyl acrylamide), polylactic acid-polyethylene glycol-polylactic acid, and a block copolymer of poly (N-isopropyl acrylamide) and polyethylene glycol.
Preferably, in the composite acoustic power antibacterial hydrogel, the mass concentration of the Sn@ cationic polymer is 3-10mg/mL, and more preferably 4-6 mg/mL; the mass concentration of the gel-forming substance is 50.0 to 300.0mg/mL, more preferably 200 to 250mg/mL.
In the invention, the Sn nano-sheet composite acoustic power antibacterial hydrogel can be prepared based on the existing hydrogel composite mode, for example, the preparation process is as follows: and mixing the dispersion liquid of the Sn nano sheet@cationic polymer composite acoustic power antibacterial material and the aqueous solution of the hydrogel gel forming substance to form the composite acoustic power antibacterial hydrogel.
The invention relates to a preparation method of a preferable injectable temperature-controllable composite acoustic power antibacterial hydrogel, which comprises the following steps:
(1) Preparation of polylactic acid-polyethylene glycol-polylactic acid (PLEL) solution: the preparation is carried out by a low-temperature dissolution method; 2) Preparation of antibacterial substance solution: dispersing the Sn nano-sheets in deionized water through PEI encapsulation; 3) Preparation of hydrogels: and (3) fully and uniformly mixing the Sn@PEI nano-sheet solution and the PLEL solution at a low temperature, and performing water bath gelling to obtain the nano-sheet.
In a preferred step (1): a certain amount of PLEL is taken, PBS buffer solution is added, and stirring and dissolution are carried out at room temperature (20-25 ℃), thus obtaining PLEL solution; the mass concentration of the PLEL solution is not particularly limited, and may be, for example, 100.0 to 400.0mg/mL. In a preferred step (2): weighing a certain amount of Sn@PEI nano sheet, adding deionized water for full dispersion to obtain Sn@PEI dispersion liquid, wherein the concentration of Sn@PEI is not particularly required, for example, 5-15 mg/mL.
In a preferred step (3): fully and uniformly mixing the Sn@PEI dispersion liquid and the PLEL solution at a low temperature (for example, lower than 1-10 ℃), and then forming glue in a water bath (the glue forming temperature is for example, 34-40 ℃); the final concentration of each component is 3-10mg/mL Sn@PEI nano-sheet, and 50.0-300.0mg/mLPLEL.
The invention also provides application of the Sn nano-sheet composite acoustic power antibacterial hydrogel in preparing acoustic power antibacterial external hydrogel dressing.
Preferably, the composition is used for preparing the acoustic power antibacterial injectable external temperature-sensitive external hydrogel dressing.
According to the research of the invention, the Sn nano-sheet, the composite material and the hydrogel thereof generate active free radicals at an infection part under the ultrasonic action, and can effectively destroy the bacterial membrane structure, thereby killing pathogenic bacteria (such as bacteria, fungi and the like). Antibacterial activity tests and animal test results prove that the tin nano hydrogel-mediated acoustic power antibacterial hydrogel therapy can effectively inhibit the activity of staphylococcus aureus and drug-resistant staphylococcus aureus. The composite hydrogel not only has good antibacterial capability, but also has a moisturizing function, thereby promoting the regeneration and repair of the wound surface of a patient, shortening the healing time of the wound surface and achieving good treatment effect. Compared with the prior conventional antibacterial method, the antibacterial agent has higher effectiveness, safety and operability.
In the invention, the ultrasonic power in the acoustic power treatment stage is 0.5-50W cm -2 。
The invention has the advantages that:
1. the Sn nano-sheet has the sound-sensitive effect for the first time, can effectively release free radicals under ultrasound, and can effectively resist bacteria based on the free radicals.
2. The Sn nanosheets are coated by the cationic polymer, so that the structural stability can be improved, the sound sensitivity performance can be synergistically improved, and the antibacterial performance can be improved;
3. sn is coated by a cationic polymer and then is compounded in the hydrogel, so that the acoustic power antibacterial hydrogel with good acoustic sensitivity can be obtained. On the basis, the proportion of the glue substance and the components is further controlled, so that the sound power antibacterial performance can be further improved by further synergism.
4. The preparation method of the hydrogel is simple and convenient to operate, the prepared hydrogel has good antibacterial performance, can quickly pass through temperature response to form gel, and the injectability of the hydrogel can meet the biomedical dressing requirements of irregular and deep wounds, so that an idea and a method are provided for preparing the injectable acoustic power antibacterial hydrogel, the development and the utilization of the acoustic power hydrogel material are facilitated, and the hydrogel material can be conveniently applied to the fields of biological materials, tissue engineering and the like.
Drawings
FIG. 1 is a TEM image of Sn nanosheets obtained in example 1 (scale bar=100 nm)
Fig. 2 is a Sn 3d X ray photoelectron spectroscopy (XPS) chart of the Sn nanoplatelets prepared in example 1.
FIG. 3 shows the change in free radical release versus UV absorption under ultrasonic irradiation of Sn@PEI prepared in example 1.
FIG. 4 shows the change in fluorescence of superoxide anions under ultrasonic irradiation of Sn@PEI prepared in example 1.
FIG. 5 shows the results of experiments in which the different experimental groups of example 1 were tested for their bacteriostatic properties against resistant Staphylococcus aureus, staphylococcus aureus and Escherichia coli.
FIG. 6 is a graph showing the measurement of the properties of Sn@PLEL hydrogels prepared in example 2; wherein a is a temperature dependent modulus of 25 ℃ to 70 ℃; b is the shear rate dependent viscosity at 25 ℃.
FIG. 7 is a graph showing the effect of Sn@PLEL hydrogels provided in example 2 on wound healing.
FIG. 8 is a graph showing the Sn@PLEL hydrogel of example 2 as a mouse bacterium for an anti-infective nanocomposite hydrogel skin repair test.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the attached drawings: it should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation. Various changes or modifications to the invention based on the principles of the invention will also fall within the scope of the appended claims after reading the description of the invention.
Example 1
Step (1): and stripping the Sn powder sample by an ultrasonic stripping method to prepare the ultrathin nano sheet. The preparation method comprises dispersing bulk Sn powder in isopropanol, performing ultrasonic treatment (power 500-600 kw) under ice bath condition for 12 hr, centrifuging at low speed (3000 rpm, for example) to remove unpeeled Sn residues, and collecting supernatant to obtain brown Sn nanosheet transparent liquid. The obtained solution is stored in a refrigerator at 4 ℃ for standby, and is centrifuged at a high speed (e.g. 12000 rpm) before use to obtain Sn nano-sheet precipitate (TEM and XPS are shown in figures 1 and 2), and the Sn nano-sheet precipitate is dispersed in water by ultrasonic to obtain a suspension with the concentration of 200mg/mL for standby.
Step 2Sn@PEI nanosheets
Adding a polyethyleneimine solution (the concentration is 10mg/mL, the mass ratio of the Sn nanosheets to the polyethyleneimine is 1:5) into the aqueous solution of the Sn nanosheets prepared in the step (1), stirring the mixed solution for 30 minutes, centrifuging for 3 minutes at 11000 r, and washing for 3-4 times by pure water to prepare the SnNSs@PEI (also called Sn@PEI).
Test of acoustic dynamic Performance
FIG. 3 is the UV absorption of 1, 3-diphenylisobenzofuran in the blank (Control group), ultrasound group (US group), sn@PEI group (SnNSs@PEI) and Sn@PEI plus ultrasound group (SnNSs@PEI+US); FIG. 4 is a graph of fluorescence emission of terephthalic acid in a blank (Control group), an ultrasound group (US group), a Sn@PEI group (SnNSs@PEI), a Sn@PEI plus ultrasound group (SnNSs@PEI+US); by ultrasonic irradiation (1.75W cm) -2 10 min), the free radical and the superoxide radical are obviously increased, which proves that the Sn@PEI has good sound power effect and moderate ultrasonic intensity; meanwhile, the ultrasonic antibacterial effect is proved to be derived from the sound power effect of Sn@PEI.
Test of antibacterial Effect
100 μl of SnNSs@PEI (1 mg/mL) is dispersed in a buffer solution, and added into a culture medium for culturing escherichia coli, staphylococcus aureus and methicillin-resistant staphylococcus aureus respectively, and after culturing, 12 5mL centrifuge tubes with caps are taken and divided into a blank group (I; control group), an ultrasonic group (II; US group), a Sn@PEI group (III; snNSs@PEI) and a Sn@PEI plus ultrasonic group (IV; snNSs@PEI+US group), and three samples are taken in each group. Ultrasound group was sonicated for 10 minutes at 1.75W cm ultrasound power -2 The method comprises the steps of carrying out a first treatment on the surface of the The non-sonicated set was placed in the dark at 20 ℃. After the ultrasonic treatment, respectively taking 100 mu L of ultrasonic solution and non-ultrasonic solution, placing into a conical flask filled with 9.9mL of sterile physiological saline, shaking uniformly, respectively taking 100 mu L of diluted solution on the surface of a solid culture medium, uniformly coating with a glass rake, marking, and then transferring into a conical flaskThe incubator was incubated upside down for 24 hours, after which colony counts were performed and the antibacterial rate was calculated. The experimental results are shown in FIG. 5. As can be seen from fig. 5, the number of bacteria in the blank control group is the greatest, and the number of bacteria in the experimental group is obviously smaller than that in the control group, which indicates that snnss@pei has a better antibacterial effect, wherein the antibacterial effect snnss@pei+ ultrasonic group is the best. After being combined with ultrasonic irradiation, the Sn@PEI has 99.95% and 99.82% of bacteriostasis rate on staphylococcus aureus and methicillin-resistant staphylococcus aureus respectively.
Example 2
Preparation of injectable hydrogels
Stirring 500 mu l of an aqueous solution (with the concentration of 10 mg/mL) of SnNSs@PEI nano-sheets (prepared in example 1) and 500 mu l of an aqueous solution (with the concentration of 400 mg/mL) of polylactic acid-polyethylene glycol-polylactic acid (PLEL) for 12 hours (30-40 ℃) to obtain a temperature-sensitive hydrogel, wherein the concentration of the SnNSs@PEI nano-sheets is 5mg/mL; the concentration of PLEL was 200 mg/mL. In the step, the polylactic acid-polyethylene glycol-polylactic acid has temperature-sensitive property, namely, the polylactic acid-polyethylene glycol-polylactic acid is in a solution state at room temperature (20-25 ℃), a gel structure is formed at the temperature of more than 36 ℃, and the prepared hydrogel is marked as Sn@PLEL hydrogel.
Characterization of injectable hydrogels the rheological properties of sn@ple were measured by rheometer. First, as can be seen from fig. 6b, the injectability of sn@ple at 25 ℃ was investigated by shear rate dependent viscosity. When the shear rate increases from 0.01 to 10s -1 The viscosity of Sn@PLEL was reduced from-500 Pa s to-10 Pa s, and when the shear rate was reduced from 10 to 0.01s-1, the viscosity of Sn@PLEL was restored to substantially the original state. The Sn@PLEL has been demonstrated to have good injectability. FIG. 6a is a graph of the thixotropic properties of Sn@PLEL, recording the changes in G 'and G' at different temperatures. From 36℃to 42℃G 'is higher than G', and Sn@PLEL is in a gel state in this temperature range. When the strain exceeds below 36 ℃ and above 42 ℃, G' becomes lower than G ", indicating that sn@ple is in solution, which means that sn@ple has good temperature responsiveness.
Test of antibacterial Effect
The prepared mice full-thickness skin injury model is characterized in that drug-resistant staphylococcus aureus is respectively dripped into each wound surfaceThe bacterial liquid is 50 mu L and is divided into five groups, namely a blank group (I), an ultrasonic group (II), sn@PLEL (III) Sn@PLEL+ultrasonic (IV). Groups of mice were anesthetized by intraperitoneal injection after 14 days, and bandages and wound coverings were removed. Adding wound tissue into 5mL physiological saline, mixing, diluting with 100 μl, and diluting for 10 4 The cells were spread gently and uniformly by dropping 50. Mu.L of the cells onto a solid agar plate, and after culturing in a incubator at 37℃for 24 hours, plate colony counts were performed. Colony growth for each set of samples is shown in FIG. 8. As can be seen from FIG. 8, the blank control group has the greatest number of bacteria, and the experimental group has significantly fewer bacteria than the control group, which indicates that the Sn@PLEL hydrogel+ultrasound has a better antibacterial effect. The healing effect is shown in fig. 7, and the hydrogel has good acoustic power antibacterial healing effect.
The foregoing description is only illustrative of the preferred embodiments of the present invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. The Sn nano sheet@cationic polymer composite acoustic power antibacterial material is characterized by comprising Sn nano sheets and a cationic polymer coating the Sn nano sheets;
the cationic polymer is polyethyleneimine;
the weight ratio of the Sn nano-sheets to the cationic polymer is 1-5: 1-100 parts;
the thickness of the Sn nano sheet is 2-10 nm; the plane size is 80-200 nm;
the Sn nano-sheet is obtained by ultrasonic stripping of tin powder in a solvent;
in the ultrasonic stripping process, the solvent is C1-C4 alcohol;
the power of the ultrasonic stripping stage is 300-700 kw;
the ultrasonic stripping time is 4-20 h.
2. The preparation method of the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material is characterized by mixing and compounding a dispersion liquid in which the Sn nano-sheet is dispersed and a cationic polymer solution to prepare the Sn nano-sheet@cationic polymer composite acoustic power antibacterial material.
3. Use of the Sn nanoplatelets @ cationic polymer composite acoustic power antibacterial material of claim 1 for the preparation of acoustic power antibacterial materials.
4. Use according to claim 3, for the preparation of an photodynamic antibacterial hydrogel.
5. The use according to claim 4 for the preparation of an photodynamic antibacterial temperature sensitive hydrogel.
6. The use according to claim 5, for the preparation of a dressing for external use of an photodynamic antibacterial hydrogel.
7. A Sn-nanosheet composite acoustic-dynamic antibacterial hydrogel, comprising a hydrogel matrix and the Sn-nanosheet @ cationic polymer composite acoustic-dynamic antibacterial material of claim 1 dispersed therein;
the gel forming substance of the hydrogel matrix is at least one of poly (N-isopropyl acrylamide), polylactic acid-polyethylene glycol-polylactic acid, and a segmented copolymer of poly (N-isopropyl acrylamide) and polyethylene glycol;
in the composite acoustic power antibacterial hydrogel, the mass concentration of the Sn@ cationic polymer is 3-10 mg/mL; the mass concentration of the gel forming substance is 50.0-300.0 mg/mL.
8. A method of preparing the Sn-nanosheet composite acoustic dynamic antibacterial hydrogel of claim 7, wherein the dispersion of the Sn-nanosheet @ cationic polymer composite acoustic dynamic antibacterial material and the aqueous solution of the gel-forming substance of the hydrogel matrix are mixed to form the composite acoustic dynamic antibacterial hydrogel.
9. Use of the Sn-nanosheet composite acoustic power antibacterial hydrogel according to claim 7 for preparing an acoustic power antibacterial external hydrogel dressing.
10. The use of the Sn-nanosheet composite acoustic power antibacterial hydrogel according to claim 9 for preparing an acoustic power antibacterial injectable temperature-sensitive external hydrogel dressing.
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