CN118267508B - Metal-based composite antibacterial liquid and preparation method and application thereof - Google Patents

Abstract

The invention provides a metal-based composite antibacterial liquid, a preparation method and application thereof, wherein the metal-based composite antibacterial liquid is prepared from polymer-coated metal nanowire dispersion liquid, polymer-coated chitosan rare earth complex solution and a solvent, the content of metal nanowires in the metal-based composite antibacterial liquid is 3-30mg/L, and the concentration of chitosan rare earth complex in the metal-based composite antibacterial liquid is 0.00001-0.0005mol/L. The metal-based composite antibacterial liquid has excellent antibacterial performance, long-acting antibacterial performance and excellent ageing resistance.

Description

Metal-based composite antibacterial liquid and preparation method and application thereof

Technical Field

The invention belongs to the field of antibacterial materials, and particularly relates to a metal matrix composite antibacterial liquid, and a preparation method and application thereof.

Background

At present, the antibacterial liquid which can be directly sprayed on the surface of an object mostly adopts an organic antibacterial agent as an active ingredient, and the organic antibacterial agent has extremely high antibacterial and bacteriostatic efficiency, but has poor ageing resistance, and can realize sustainable antibacterial by a frequent spraying method, so that the use cost is indirectly increased; meanwhile, silver and copper nano-particles are used as antibacterial active ingredients, but the silver and copper nano-particles are easy to color and have higher cost.

According to the invention, the polymer-coated metal nanowire is adopted, the risk of color change of the metal nanowire can be avoided through polymer coating, an antibacterial network with a positive large surface can be formed through the mutual intersection of the nanowires, meanwhile, rare earth has excellent antibacterial performance, and the rare earth has extremely outstanding ageing resistance, high temperature resistance and long-acting property, so that the metal nanowire is matched with the rare earth complex to prepare the antibacterial liquid with low cost, environmental protection, low carbon, excellent antibacterial effect and excellent long-acting property.

Disclosure of Invention

In view of the above, the present invention aims to overcome the defects in the prior art, and provides a metal matrix composite antibacterial liquid, and a preparation method and application thereof.

In order to achieve the above purpose, the technical scheme of the invention is realized as follows:

In a first aspect, the invention provides a metal-based composite antibacterial solution, which is prepared from polymer-coated metal nanowire dispersion liquid, polymer-coated chitosan rare earth complex solution and a solvent, wherein the content of metal nanowires in the metal-based composite antibacterial solution is 3-30mg/L, and the concentration of chitosan rare earth complex in the metal-based composite antibacterial solution is 0.00001-0.0005mol/L.

Preferably, the polymer is one or a combination of at least two of polyvinylpyrrolidone (PVP), hydroxypropyl cellulose, sodium hydroxypropyl cellulose, polyvinylidene fluoride (PVDF), polyacrylic acid.

Preferably, the metal nanowire is one or a combination of at least two of silver nanowire, copper nanowire and zinc nanowire.

Preferably, the chitosan rare earth complex is synthesized by reacting rare earth salt with chitosan or chitosan quaternary ammonium salt.

Preferably, the cation of the rare earth salt comprises any one or a combination of at least two of cerium ion, lanthanum ion, yttrium ion, samarium ion, europium ion or neodymium ion.

Preferably, the anion of the rare earth salt is any one or a combination of at least two of nitrate ion, chloride ion, sulfate ion or acetate ion.

Preferably, the solvent is ethanol and/or water.

Preferably, the preparation method of the polymer-coated metal nanowire dispersion liquid comprises the following steps:

dissolving a polymer in water to obtain a polymer water solution A, adding the metal nanowire into the polymer water solution A, and stirring for 0.5-4h at the rotating speed of 50-500 rad/min to obtain a polymer coated metal nanowire dispersion.

Preferably, the concentration of the metal nanowires in the polymer-coated metal nanowire dispersion is 1-10g/L.

Preferably, the mass concentration of the polymer aqueous solution A is 0.5% -5%.

Preferably, the preparation method of the polymer-coated chitosan rare earth complex solution comprises the following steps:

S1: dispersing chitosan or chitosan quaternary ammonium salt in pure water, heating to 50-80 ℃, and stirring for 0.1-2h at a rotating speed of 50-500rad/min to obtain chitosan solution;

s2: dissolving rare earth salt hydrate in pure water to prepare rare earth salt solution;

S3: dropwise adding the rare earth salt solution into the chitosan solution, and stirring for 0.5-4h at 50-80 ℃ under vacuum condition to obtain chitosan rare earth complex solution;

s4: and (3) dropwise adding the chitosan rare earth complex solution into the polymer aqueous solution B, and stirring for 10-60min at normal temperature to obtain the polymer-coated chitosan rare earth complex solution.

Preferably, the concentration of the chitosan solution prepared in the step S1 is 0.05-0.3mol/L.

Preferably, the concentration of the rare earth salt solution prepared in the step S2 is 0.3-0.8 mol/L.

Preferably, the concentration of the chitosan rare earth complex solution prepared in the step S3 is 0.4-1 mol/L.

Preferably, the mass concentration of the aqueous polymer solution B in the step S4 is 0.5% -5%.

Preferably, the concentration of the polymer coated chitosan rare earth complex solution prepared in the step S4 is 0.05-0.5mol/L.

Preferably, the preparation method of the metal-based composite antibacterial liquid comprises the following steps:

adding the polymer-coated rare earth complex solution and the polymer-coated metal nanowire dispersion into a solvent, and stirring for 10-60min to obtain the metal-based composite antibacterial solution.

In a second aspect, the invention also provides the metal-based composite antibacterial liquid prepared by the preparation method.

In a third aspect, the invention also provides application of the metal-based composite antibacterial liquid in preparation of wound dressing, antibacterial coating or antibacterial spray. For example, the wound dressing can be prepared into a dressing for long-acting sterilization and antibiosis of wounds, and surgical articles such as bandages, absorption pads and the like can be prepared; the long-acting antibacterial coating is coated or sprayed on the surface of the special medical instrument, is used for cleaning the surface of the high-value medical instrument, and plays roles in sterilization and antibiosis; the method is applied to scenes with high environmental requirements (such as for patients with immunity deficiency), and is used for cleaning and sterilizing the environment.

Compared with the prior art, the invention has the following advantages:

The prepared metal-based composite antibacterial liquid is coated on the metal nanowire together with the polymer through the chitosan rare earth complex coated by the polymer, so that the metal-based composite antibacterial liquid becomes a composite antibacterial agent. The metal nanowire can avoid the risk of color change through the coating of the polymer, is favorable for forming an antibacterial network in an antibacterial layer, can form a larger antibacterial effective area by adopting lower use amount compared with the metal nanowire, and simultaneously cooperates with the chitosan rare earth complex, so that the antibacterial composite has the advantages of low cost, excellent antibacterial performance, long-acting antibacterial performance, excellent ageing resistance and the like, has the antibacterial efficiency of over 95 percent for escherichia coli and staphylococcus aureus, and has the advantages of low cost, no toxicity and harm, excellent antibacterial persistence and capability of effectively reducing the propagation and infection risk of bacteria.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

Chitosan, purchased from henna Qianlu chemical products limited, has a deacetylation degree of >85% and a relative molecular mass of 1.8x10 ⁶. The present invention will be described in detail with reference to examples.

Example 1

(1) Preparing a polymer coated metal nanowire dispersion: 100mg of silver nanowires were added to 100mL of 1% PVP in water and stirred at a rate of 200rad/min for 0.5h to give PVP-coated silver nanowire dispersion.

(2) Preparing chitosan solution: dispersing chitosan in pure water, heating to 60deg.C in water bath or oil bath, and magnetically stirring at 200rad/min for 10min to obtain chitosan solution with concentration of 0.1 mol/L.

(3) Preparing rare earth salt solution: cerium nitrate hydrate was dissolved in pure water to prepare a cerium nitrate solution of 0.6 mol/L.

(4) Preparing a chitosan rare earth complex solution: adding cerium nitrate solution into chitosan solution, vacuumizing (-0.1 MPa) and stirring for 1h at 60 ℃ to obtain chitosan rare earth complex solution with the concentration of 0.4 mol/L.

(5) Preparing a polymer coated chitosan rare earth complex solution: 12.5mL of the chitosan rare earth complex solution is dripped into 87.5mL of 1% PVP water solution, and stirring is carried out for 20min, thus obtaining 100mLPVP coated chitosan rare earth complex solution.

(6) Preparing a metal-based composite antibacterial solution: 3mL of PVP coated silver nanowire dispersion liquid and 0.2mLPVP coated chitosan rare earth complex solution are added into ethanol to be fixed to 1L and stirred for 20min, so as to prepare the cerium-silver based composite antibacterial liquid.

Example 2

(1) Preparing a polymer coated metal nanowire dispersion: 500mg of copper nanowires were added to 100mL of a 1.5% PVDF aqueous solution and stirred at 300rad/min for 1 hour to give a PVDF-coated copper nanowire dispersion.

(2) Preparing chitosan quaternary ammonium salt solution: dispersing chitosan quaternary ammonium salt in 50mL of pure water, heating to 70 ℃ in water bath or oil bath, and magnetically stirring at a speed of 200rad/min for 10min to prepare the chitosan quaternary ammonium salt solution with the concentration of 0.15 mol/L.

(3) Preparing rare earth salt solution: yttrium nitrate hydrate was dissolved in pure water to prepare a 0.75mol/L yttrium nitrate solution.

(4) Preparing a chitosan quaternary ammonium salt rare earth complex solution: adding yttrium nitrate solution into the aqueous solution dispersed with chitosan quaternary ammonium salt, and vacuumizing (-0.1 MPa) and stirring for 1.5h at 60 ℃ to obtain the solution of the chitosan quaternary ammonium salt rare earth complex with the concentration of 0.5 mol/L.

(5) Preparing a polymer coated chitosan rare earth complex solution: 20mL of chitosan quaternary ammonium salt rare earth complex solution is dripped into 80mL of 1.5% PVDF aqueous solution, and stirring is carried out for 35min, thus obtaining 100mL of PVDF coated chitosan rare earth complex solution.

(6) Preparing a metal-based composite antibacterial solution: adding 2mLPVDF of copper nanowire dispersion liquid coated with the coating and 1mLPVDF of chitosan quaternary ammonium salt rare earth complex solution into ethanol to fix the volume to 1L, and stirring for 30min to prepare yttrium-copper-based composite antibacterial liquid.

Example 3

(1) Preparing a polymer coated metal nanowire dispersion: 600mg of zinc nanowires were added to 100mL of an aqueous solution with 5% PVDF and stirred at 300rad/min for 1 hour to give a PVDF-coated copper nanowire dispersion.

(2) Preparing chitosan solution: dispersing chitosan quaternary ammonium salt in 100mL of pure water, heating to 70 ℃ in water bath or oil bath, and magnetically stirring at a speed of 200rad/min for 10min to prepare 0.2mol/L chitosan quaternary ammonium salt solution.

(3) Preparing rare earth salt solution: the samarium nitrate hydrate was dissolved in 50mL of pure water to prepare a 0.6mol/L samarium nitrate solution.

(4) Preparing a chitosan quaternary ammonium salt rare earth complex solution: adding samarium nitrate solution into aqueous solution dispersed with chitosan quaternary ammonium salt, vacuumizing (-0.1 MPa) and stirring for 1.5h at 60 ℃ to obtain 0.6mol/L chitosan quaternary ammonium salt rare earth complex solution.

(5) Preparing a polymer-coated chitosan quaternary ammonium salt rare earth complex solution: and (3) dropwise adding 50mL of the chitosan quaternary ammonium salt rare earth complex solution into 50mL of 1.5% PVDF aqueous solution, and stirring for 35min to obtain 100mL of PVDF-coated chitosan quaternary ammonium salt rare earth complex solution.

(6) Preparing a metal-based composite antibacterial solution: adding 3mLPVDF coated zinc nanowire dispersion liquid and 1mLPVDF coated chitosan quaternary ammonium salt rare earth complex solution into ethanol to fix the volume to 1L, and stirring for 30min to prepare the samarium-zinc-based composite antibacterial liquid.

Example 4

(1) Preparing a polymer coated metal nanowire dispersion: 800mg of silver nanowires were added to 100mL of an aqueous solution with 5% PVDF and stirred at a rate of 300rad/min for 1 hour to give a PVDF-coated silver nanowire dispersion.

(2) Preparing chitosan quaternary ammonium salt solution: dispersing chitosan quaternary ammonium salt in 30mL of pure water, heating to 70 ℃ in water bath or oil bath, and magnetically stirring at a speed of 200rad/min for 10min to prepare 0.25mol/L chitosan quaternary ammonium salt solution.

(3) Preparing rare earth salt solution: europium nitrate hydrate was dissolved in 20mL of pure water to prepare a europium nitrate solution of 0.7 mol/L.

(4) Preparing a chitosan quaternary ammonium salt rare earth complex solution: adding europium nitrate solution into aqueous solution dispersed with chitosan quaternary ammonium salt, and vacuumizing (-0.1 MPa) and stirring for 1.5h at 60 ℃ to obtain 0.8mol/L solution of chitosan quaternary ammonium salt rare earth complex.

(5) Preparing a polymer-coated chitosan quaternary ammonium salt rare earth complex solution: and (3) dropwise adding 50mL of the chitosan quaternary ammonium salt rare earth complex solution into 50mL of the 5% PVDF aqueous solution, and stirring for 35min to obtain 100mL of PVDF-coated chitosan quaternary ammonium salt rare earth complex solution.

(6) Preparing a metal-based composite antibacterial solution: adding 3mLPVDF of silver nanowire dispersion liquid coated with the coating and 1mLPVDF of chitosan quaternary ammonium salt rare earth complex solution into 1.5kg of ethanol, and stirring for 30min to prepare europium-silver matrix composite antibacterial liquid.

Example 5

(1) Preparing a polymer coated metal nanowire dispersion: 1000mg of silver nanowires were added to 100mL of an aqueous solution with 0.5% PVDF and stirred at a rate of 300rad/min for 1 hour to give a PVDF-coated silver nanowire dispersion.

(2) Preparing chitosan solution: dispersing chitosan quaternary ammonium salt in 200mL of pure water, heating to 70 ℃ in water bath or oil bath, and magnetically stirring at a speed of 200rad/min for 10min to prepare 0.3mol/L chitosan quaternary ammonium salt solution.

(3) Preparing rare earth salt solution: neodymium nitrate hydrate was dissolved in 100mL of pure water to prepare a neodymium nitrate solution of 0.8 mol/L.

(4) Preparing a chitosan quaternary ammonium salt rare earth complex solution: adding neodymium nitrate solution into the aqueous solution dispersed with chitosan quaternary ammonium salt, and vacuumizing (-0.1 MPa) and stirring for 1.5 hours at 60 ℃ to obtain 1mol/L chitosan quaternary ammonium salt rare earth complex solution.

(5) Preparing a polymer-coated chitosan quaternary ammonium salt rare earth complex solution: and (3) dropwise adding 50mL of the chitosan quaternary ammonium salt rare earth complex solution into 50mL of 0.5% PVDF aqueous solution, and stirring for 35min to obtain 100mL of PVDF-coated chitosan quaternary ammonium salt rare earth complex solution.

(6) Preparing a metal-based composite antibacterial solution: adding 3mLPVDF of silver nanowire dispersion liquid coated with the silver nanowire and 1mLPVDF of chitosan quaternary ammonium salt rare earth complex solution coated with the silver nanowire dispersion liquid into ethanol to fix the volume to 1L, and stirring for 30min to prepare neodymium-silver based composite antibacterial liquid.

Comparative example 1

(1) Preparing chitosan solution: dispersing chitosan in pure water, heating to 60deg.C in water bath or oil bath, and magnetically stirring at 200rad/min for 10min to obtain 0.1mol/L chitosan solution.

(2) Preparing rare earth salt solution: cerium nitrate hydrate was dissolved in 10mL of pure water to prepare a cerium nitrate solution of 0.6 mol/L.

(3) Preparing a chitosan rare earth complex solution: 10mL of cerium nitrate solution is added into 60mL of chitosan aqueous solution, and the mixture is vacuumized (-0.1 MPa) and stirred for 1 hour at 60 ℃ to obtain 70mL of 0.4mol/L chitosan rare earth complex solution.

(4) Preparing a polymer coated chitosan rare earth complex solution: 12.5mL of the chitosan rare earth complex solution is dripped into 97.5mL of 1% PVP water solution, and stirring is carried out for 20min, thus obtaining 100mLPVP coated chitosan rare earth complex solution.

(5) Preparing a metal-based composite antibacterial solution: adding 3mLPVP of silver nanowire dispersion liquid coated with the coating and 0.2mLPVP of chitosan rare earth complex solution into ethanol, fixing the volume to 1L, and stirring for 20min to prepare Cheng Shiji composite antibacterial liquid.

Comparative example 2

(1) Preparing a polymer coated metal nanowire dispersion: 100mg of silver nanowires were added to 100mL of 1% PVP in water and stirred at a rate of 200rad/min for 0.5h to give 100mL of PVP-coated silver nanowire dispersion having a concentration of 1 g/L.

(2) Adding the silver nanowire dispersion liquid coated by 2mLPVP into 1kg of ethanol, and stirring for 20min to prepare the composite antibacterial liquid.

Comparative example 3

The cerium-silver-based composite antibacterial solution in this comparative example is different from the preparation method of example 1 in that the same amount of silver nanoparticles is used instead of silver nanowires, and other parameters, ratios and processes are the same.

Comparative example 4

The cerium-silver-based composite antibacterial solution in this comparative example is different from the preparation method of example 1 in that the addition amount of the PVP coated silver nanowire dispersion solution is 31mL, and other proportions and parameters are the same.

Comparative example 5

The cerium-silver-based composite antibacterial solution in this comparative example is different from the preparation method of example 1 in that the PVP-coated silver nanowire dispersion in step (6) is added in an amount of 2mL, and the other ratios and parameters are the same.

Comparative example 6

The cerium-silver-based composite antibacterial solution in the comparative example is different from the preparation method of example 1 in that the PVP coated chitosan rare earth complex solution in the step (6) is added in an amount of 0.18mL, and other proportions and parameters are the same.

Comparative example 7

The cerium-silver-based composite antibacterial solution in the comparative example is different from the preparation method of the example 1 in that the PVP coated chitosan rare earth complex solution in the step (6) is added in an amount of 11mL, and other proportions and parameters are the same.

Bacteriostasis test:

And (3) dropwise adding 100 mu L of the prepared bacterial suspension into each test tube of the tested sample liquid and the test tube of the control sample liquid respectively by using 4 tubes of the antibacterial liquid and the control sample liquid prepared in the examples 1-5 and the comparative examples 1-7, uniformly mixing, taking the reaction time of 2min, 5min, 10min and 20min, then taking 0.5mL of the sample liquid, putting into the test tube containing 5mLPBS, fully mixing, properly diluting, pouring into a plate, culturing, and counting viable bacterial colonies.

The calculation formula of the bacteriostasis rate is as follows:

The test results are shown in the following table:

table 1 results of bacteriostasis rates of examples 1 to 5

TABLE 2 results of comparative examples 1-7 antibacterial rate

Remarks: the negative control group had no bacterial growth.

As can be seen from the table, the antibacterial performance of the antibacterial liquid is obviously superior to that of the chitosan rare earth complex alone, the metal nanowire alone, the metal nanoparticle and the content of the metal nanowire in the antibacterial liquid are lower than or higher than 3-30mg/L, and the concentration of the chitosan rare earth complex is lower than or higher than 0.00001-0.0005mol/L, because the chitosan rare earth complex is coated on the metal nanowire, the composite antibacterial agent is formed, the functions and advantages of the composite antibacterial agent are complementarily enhanced, and the relatively excellent antibacterial performance and the excellent long-acting antibacterial and aging-resistant performances are realized. If the content of the metal nano wire is too high, agglomeration phenomenon can be generated, a uniform antibacterial network can not be formed, so that the antibacterial effect is seriously affected, and meanwhile, the cost is greatly increased; too low a metal nanowire content does not form an antibacterial network. If the content of the chitosan rare earth complex is too high, the release of the antibacterial property of the metal nanowire can be greatly slowed down, and if the content is too low, the antibacterial effect of the slow-release metal nanowire can not be achieved, the antibacterial time of the antibacterial liquid can not be prolonged, and the aging resistance can be reduced.

The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A metal-based composite antibacterial solution is characterized in that: the metal-based composite antibacterial liquid is prepared from polymer-coated metal nanowire dispersion liquid, polymer-coated chitosan rare earth complex solution and a solvent, wherein the content of the metal nanowire in the metal-based composite antibacterial liquid is 3-30mg/L, and the concentration of the chitosan rare earth complex in the metal-based composite antibacterial liquid is 0.00001-0.0005mol/L;

The metal nanowire is one or a combination of at least two of a silver nanowire, a copper nanowire and a zinc nanowire;

The polymer is one or the combination of at least two of polyvinylpyrrolidone, hydroxypropyl cellulose, sodium hydroxypropyl cellulose, polyvinylidene fluoride and polyacrylic acid;

the chitosan rare earth complex is synthesized by reacting rare earth salt with chitosan or chitosan quaternary ammonium salt;

The cation of the rare earth salt comprises any one or a combination of at least two of cerium ions, lanthanum ions, yttrium ions, samarium ions, europium ions and neodymium ions; the anions of the rare earth salt are any one or a combination of at least two of nitrate ions, chloride ions, sulfate ions and acetate ions.

2. The metal-based composite antibacterial liquid according to claim 1, wherein: the preparation method of the polymer-coated metal nanowire dispersion liquid comprises the following steps:

Dissolving a polymer in water to obtain a polymer water solution A, adding the metal nanowire into the polymer water solution A, and stirring for 0.5-4h at the rotating speed of 50-500rad/min to obtain a polymer coated metal nanowire dispersion.

3. The metal-based composite antibacterial liquid according to claim 2, wherein: the concentration of the metal nanowires in the polymer coated metal nanowire dispersion liquid is 1-10g/L; the mass concentration of the polymer aqueous solution A is 0.5% -5%.

4. The metal-based composite antibacterial liquid according to claim 1, wherein: the preparation method of the polymer-coated chitosan rare earth complex solution comprises the following steps:

S1: dispersing chitosan or chitosan quaternary ammonium salt in pure water, heating to 50-80 ℃, and stirring for 0.1-2h at a rotating speed of 50-500rad/min to obtain chitosan solution;

s2: dissolving rare earth salt hydrate in pure water to prepare rare earth salt solution;

S3: dropwise adding the rare earth salt solution into the chitosan solution, and stirring for 0.5-4h at 50-80 ℃ under vacuum condition to obtain a chitosan rare earth complex solution;

s4: and (3) dropwise adding the chitosan rare earth complex solution into the polymer aqueous solution B, and stirring for 10-60min at normal temperature to obtain the polymer-coated chitosan rare earth complex solution.

5. The metal-based composite antibacterial liquid according to claim 4, wherein:

the concentration of the chitosan solution prepared in the step S1 is 0.05-0.3mol/L;

the concentration of the rare earth salt solution prepared in the step S2 is 0.3-0.8mol/L;

The concentration of the chitosan rare earth complex solution prepared in the step S3 is 0.4-1mol/L;

the mass concentration of the polymer aqueous solution B in the step S4 is 0.5% -5%;

The concentration of the polymer coated chitosan rare earth complex solution prepared in the step S4 is 0.05-0.5mol/L.

6. The metal-based composite antibacterial liquid according to claim 1, wherein: the preparation method of the antibacterial liquid comprises the following steps:

adding the polymer-coated rare earth complex solution and the polymer-coated metal nanowire dispersion into a solvent, and stirring for 10-60min to obtain the metal-based composite antibacterial solution.

7. Use of a metal matrix composite antiseptic solution according to any one of claims 1-6 for the preparation of a wound dressing, an antiseptic coating or an antiseptic spray.