CN102669158B - Stannous salt complex antibacterial material and preparation method thereof - Google Patents
Stannous salt complex antibacterial material and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010099 solid forming Methods 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to a stannous salt complex antibacterial material and a preparation method of the material. The invention adopts a one-step method to synthesize the stannous salt/ polyaniline complex antibacterial material containing stannous chloride, stannous sulfate and the like; the polyaniline exists in a form of nanofiber and has the diameter of 50-300nm; and stannous salt coordinates with nitrogen atoms on the molecular chain of the polyaniline, so that stable complex can be formed. The stannous salt complex antibacterial material provided by the invention has excellent inhibitory action for different strains such as yeast, escherichia coli, staphylococcus aureus and the like. The stannous salt complex antibacterial material provided by the invention is low in raw material cost, simple in preparation technology and good in heat stability, overcomes the defect of high cost of silver-series antibacterial material in the existing market, has good biocompatibility, is free from toxicity and harmness for human body, can easily realize industrialization and has high economical and social value.
Description
Technical field
The present invention relates to a kind of tin salt complex anti-biotic material and preparation method thereof, belong to anti-biotic material technical field.
Technical background
Bacterium is ubiquitous, all-pervasive, their propagation and spread the health that the mankind in serious threat.Along with a large amount of uses of the chemicalses such as antibiotic, disinfectant and bactericide, the bacterial dissociation population being caused by drug resistance is more and more, and the global bacterium Disaster Event causing thus occurs again and again.For suppressing the generation of this bacterioid disaster, research and development and application novel antibacterial material are imperative.Anti-biotic material is mainly divided into inorganic antibacterial material, organic anti-bacterial material, organic and inorganic composite antibacterial material at present.Inorganic antibacterial material has safe, and warm tolerance and persistence are good, and the advantage such as be difficult for developing immunity to drugs, and obtained exploitation and application successively, but the biocompatibility of most inorganic antibacterial materials is poor since the eighties in 20th century.Organic anti-bacterial Biocompatibility is better, but stability is not good enough.Studying at present and apply more is inorganic-organic composite antibiotic material.
Metallic tin is rich in gloss, nontoxic, easy oxidation discoloration not, has good sterilization, purification, fresh-keeping effectiveness.In life, be usually used in the corrosion prevention film of food fresh keeping, can internal layer etc.As far back as the ancient times, people just find and use tin.In some ancient tombs of China, just normal excavation arrived some tinpots, tin candlestick and so on tinware.Since early 1980s finds that organotin complex has stronger active anticancer, it is synthesized domestic and international chemist and bioactive research is extraordinarily paid attention to.Research show very eurypalynous organo-tin compound have stronger antibiotic, active anticancer (Li Juan, etc. synthetic chemistry, 2007,15 (2): 176-180), but organo-tin compound complicated process of preparation, cost is higher.The inorganic tin salt such as stannous chloride, stannous sulfate, stannous methanesulfonate is widely used in the industry such as dyestuff, spices, mirror processed, plating, super-pressure lubricating oil, bleaching, and as reductant, mordant, decolorizer and analytical reagent, the aspects such as mensuration for silver, arsenic, molybdenum, mercury, its preparation cost is lower, and synthesis technique is simple.Inorganic tin salt has good biocompatibility, but its anti-microbial property so far there are no relevant report.Unstable due to pure stannous chloride, stannous sulfate, stannous methanesulfonate, itself and macromolecule are carried out to coordination, can improve its stability.
Polyaniline is widely used in electrode material, antistatic material, and electromagnetic shielding material, anticorrosive paint, anti-fouling material, electric driven color-changing part, selectivity sees through film, microwave absorption, the welding of plastics, luminous two machine pipe, optics and device for non-linear optical.The report of the current complex about polyaniline and tin salt is less, and the research for anti-microbial property simultaneously has no report.
Summary of the invention
The object of the present invention is to provide a kind of tin salt complex anti-biotic material, this material be take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and the imido grpup coordination on tin salt and polyaniline molecule chain forms complex; In anti-biotic material, polyaniline diameter is 50～300 nm.
Another object of the present invention is to provide a kind of preparation method of tin salt complex anti-biotic material, the special coordination that the method utilizes polyaniline to have, by tin salts such as one-step method and stannous chloride, stannous sulfates, carry out coordination, obtain a kind of have anti-microbial property excellence, Heat stability is good, the good novel tin salt/polyaniline complex anti-biotic material of biocompatibility.
The inventive method comprises the following steps:
1) preparation molar concentration is the acid solution of 0.1～1.0 mol/L, and be divided into two equal portions, in a acid solution, add a certain amount of aniline monomer and tin salt, at room temperature stir, form A liquid, wherein aniline molar concentration is 0.5～2.0 mol/L, the molar concentration of stannous ion is 0.01～0.4mol/L, then in another part of acid solution, add ammonium persulfate, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 12～24 hours;
2) utilize filtration under diminished pressure separating step 1) the middle solid forming, and successively with distilled water, acetone washing, until the PH=7 of filtrate;
3) by step 2) vacuum drying 12 hours at 40～80 ℃ of the solid that obtains, obtain tin salt/polyaniline complex anti-biotic material.
In the present invention, the mol ratio of aniline and ammonium persulfate is 20:1～5:1.
In the present invention, acid solution is a kind of in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, toluenesulfonic acid.
In the present invention, tin salt is a kind of in stannous chloride, stannous sulfate, stannous methanesulfonate.
Gained tin salt/polyaniline complex anti-biotic material of the present invention, wherein polyaniline used exists with the form of nanofiber, and its diameter is between 50～300 nm, and the nitrogen-atoms coordination on tin salt and polyaniline molecule chain, forms stable complex; This complex reaches as high as 99.99% to the bacteriostasis rate of the different strains such as saccharomycete, Escherichia coli, staphylococcus aureus.
Compared with the existing technology, the present invention has the following advantages or good effect:
1, anti-biotic material cost of material provided by the invention is low, preparation technology simple, Heat stability is good, having overcome silver on existing market is the shortcoming that anti-biotic material cost is high, and expanded the application of tin salt, polyaniline, developed the preparation method of organic and inorganic composite antibacterial material.
2, in tin salt/polyaniline complex anti-biotic material, become nanometer fibrous polyaniline to there is larger specific surface, and polyaniline have good biocompatibility, nontoxic, harmless to human body, be easy to industrialization, there is very high economy and social value.
3, in tin salt/polyaniline complex anti-biotic material, polyaniline directly forms complex by the imido grpup on its strand and tin salt, due to tin salt and this special interaction of polyaniline, provide a kind of novel tin salt/polyaniline complex anti-biotic material to there is spectrum antibiotic property and long-acting bactericidal effect.
Embodiment
Below by embodiment, the invention will be further described, but protection domain of the present invention is not limited to described content.
embodiment 1:the preparation method of polyaniline anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 0.1 mol/L, and be divided into two equal portions, and in a hydrochloric acid solution, add aniline monomer, wherein aniline molar concentration is 0.5 mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.025mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 12 hours.Then utilize the solid forming in filtration under diminished pressure separating reaction system, and successively with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 80 ℃, obtain polyaniline antibacterial agent, the diameter of the polyaniline fiber that this method obtains is about 80 nm, and antibacterial experiment result shows: polyaniline antibacterial agent is 82.71%, colibacillary bacteriostasis rate is 85.02%, to the bacteriostasis rate of staphylococcus aureus, is 97.01% saccharomycetic bacteriostasis rate.
embodiment 2:the preparation method of this stannous chloride/polyaniline complex anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 0.1 mol/L, and be divided into two equal portions, in a hydrochloric acid solution, add aniline monomer and stannous chloride, in solution, the molar concentration of aniline monomer is that the molar concentration of 0.5 mol/L, stannous chloride is 0.01mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.025mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 12 hours.Then utilize filtration under diminished pressure separating reaction system, and successively with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 70 ℃, obtain stannous chloride/polyaniline complex anti-biotic material, wherein the diameter of polyaniline fiber is about 70 nm, and antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 93.77%, colibacillary bacteriostasis rate is 96.26%, to the bacteriostasis rate of staphylococcus aureus, is 97.99% saccharomycetic bacteriostasis rate.
Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 70 nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 3:the preparation method of this stannous chloride/polyaniline complex anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 0.1 mol/L, and be divided into two equal portions, in a hydrochloric acid solution, be added in and in a hydrochloric acid solution, add aniline monomer and stannous chloride, in solution, the molar concentration of aniline monomer is 0.5 mol/L, the molar concentration of stannous chloride is 0.05mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.025mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast, then at room temperature standing 24 hours.Then utilize filtration under diminished pressure separating reaction system, and with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 40 ℃, obtain nanometer stannous chloride/polyaniline complex anti-biotic material, wherein the diameter of polyaniline fiber is about 50 nm, and antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 99.99%, colibacillary bacteriostasis rate is 99.99%, to the bacteriostasis rate of staphylococcus aureus, is 99.99% saccharomycetic bacteriostasis rate.
Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 50nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 4:the preparation method of this stannous chloride/polyaniline complex anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 0.5 mol/L, and be divided into two equal portions, in a hydrochloric acid solution, be added in and in a hydrochloric acid solution, add aniline monomer and stannous chloride, in solution, the molar concentration of aniline monomer is 0.5 mol/L, the molar concentration of stannous chloride is 0.05mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.025mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast, then at room temperature standing 24 hours.Then utilize filtration under diminished pressure separating reaction system, and with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 40 ℃, obtain nanometer stannous chloride/polyaniline complex anti-biotic material, wherein the diameter of polyaniline fiber is about 50 nm, and antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 99.99%, colibacillary bacteriostasis rate is 99.99%, to the bacteriostasis rate of staphylococcus aureus, is 99.99% saccharomycetic bacteriostasis rate.
Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 50nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 5:the preparation method of this stannous chloride/polyaniline complex anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 0.5 mol/L, and be divided into two equal portions, in a hydrochloric acid solution, add aniline monomer and stannous chloride, in solution, the molar concentration of aniline monomer is that the molar concentration of 2.0 mol/L, stannous chloride is 0.4mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.2mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 20 hours.Then utilize filtration under diminished pressure separating reaction system, and with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 60 ℃, obtain nanometer stannous chloride/polyaniline complex anti-biotic material, wherein the diameter of polyaniline fiber is about 300 nm, and antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 99.99%, colibacillary bacteriostasis rate is 99.99%, to the bacteriostasis rate of staphylococcus aureus, is 97.32% saccharomycetic bacteriostasis rate.
Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 300nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 6:the preparation method of this stannous chloride/polyaniline complex anti-biotic material, concrete operations are as follows:
First preparing molar concentration is hydrochloric acid solution 300 ml of 1.0mol/L, and be divided into two equal portions, in a hydrochloric acid solution, add aniline monomer and stannous chloride, in solution, the molar concentration of aniline monomer is that the molar concentration of 1.5 mol/L, stannous chloride is 0.2mol/L, at room temperature stir, form A liquid, in another part of hydrochloric acid solution, add ammonium persulfate, in solution, ammonium persulfate molar concentration is 0.3mol/L, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 15 hours.Then utilize filtration under diminished pressure separating reaction system, and successively with distilled water, acetone washing, until the pH=7 of filtrate.Finally by the solid obtaining vacuum drying 12 hours at 50 ℃, obtain nanometer stannous chloride/polyaniline complex anti-biotic material, wherein the diameter of polyaniline fiber is about 250 nm, and antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 98.02%, colibacillary bacteriostasis rate is 94.09%, to the bacteriostasis rate of staphylococcus aureus, is 99.99% saccharomycetic bacteriostasis rate.
Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 250nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 7:the preparation method of this anti-biotic material is substantially the same manner as Example 4, be acid used be nitric acid.Gained nanometer stannous chloride/polyaniline complex anti-biotic material, antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 92.21%, colibacillary bacteriostasis rate is 87.41%, to the bacteriostasis rate of staphylococcus aureus, is 86.01% saccharomycetic bacteriostasis rate.Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 150nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 8:the preparation method of this anti-biotic material is identical with embodiment 4, be acid used be sulfuric acid, gained nanometer stannous chloride/polyaniline complex anti-biotic material, antibacterial experiment result shows: nanometer stannous chloride/polyaniline complex anti-biotic material is 94.71%, colibacillary bacteriostasis rate is 90.51%, to the bacteriostasis rate of staphylococcus aureus, is 90.07% saccharomycetic bacteriostasis rate.Stannous chloride/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 100nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 9:the preparation method of this anti-biotic material is substantially the same manner as Example 8, be tin salt used be stannous sulfate, gained nanometer stannous sulfate/polyaniline complex anti-biotic material, antibacterial experiment result shows: nanometer stannous sulfate/polyaniline complex anti-biotic material is 96.61%, colibacillary bacteriostasis rate is 94.31%, to the bacteriostasis rate of staphylococcus aureus, is 93.00% saccharomycetic bacteriostasis rate.Stannous sulfate/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 100 nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
embodiment 10:the preparation method of this anti-biotic material is substantially the same manner as Example 4, be acid used be toluene sulfonic acide, tin salt used is stannous methanesulfonate, gained nanometer stannous methanesulfonate/polyaniline complex anti-biotic material, antibacterial experiment result shows: nanometer stannous methanesulfonate/polyaniline complex anti-biotic material is 99.99%, colibacillary bacteriostasis rate is 99.99%, to the bacteriostasis rate of staphylococcus aureus, is 99.99% saccharomycetic bacteriostasis rate.Stannous sulfate/polyaniline complex the anti-biotic material making by above-mentioned preparation method, take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and wherein the diameter of polyaniline fiber is about 50 nm, imido grpup coordination on tin salt and polyaniline molecule chain, forms complex.
In sum, although the present invention be have been described in detail by specific embodiment.Persons skilled in the art should be understood that; above-described embodiment is only to the preparation method of the prepared a kind of sub-tin complex anti-biotic material of the present invention and the description of step; but not limiting the scope of the invention; the variation that persons skilled in the art can be expected easily in the disclosed technical scope of the present invention; if acid used can be other organic acids or inorganic acid; tin salt can be other tin salts such as stannous octoate; other forms such as polyaniline can be spherical, nano particle, all within protection scope of the present invention.
Claims (3)
1. a tin salt complex anti-biotic material, is characterized in that: it is to take polyaniline as carrier, and polyaniline exists with the form of nanofiber, and the imido grpup coordination on tin salt and polyaniline molecule chain forms complex;
The preparation method of wherein said tin salt complex anti-biotic material is as follows:
1) by molar concentration, be that the acid solution of 0.1～1.0 mol/L is divided into two equal portions, in a acid solution, add aniline monomer and tin salt, at room temperature stir, form A liquid, wherein aniline molar concentration is 0.5～2.0 mol/L, the molar concentration of stannous ion is 0.01～0.4mol/L, then in another part of acid solution, add ammonium persulfate, and stir, form B liquid, B liquid is at room temperature poured in A liquid fast into then at room temperature standing 12～24 hours;
2) utilize filtration under diminished pressure separating step 1) the middle solid forming, and use successively distilled water, acetone washing, until the pH=7 of filtrate;
3) by step 2) vacuum drying 12 hours at 40～80 ℃ of the solid that obtains, obtain tin salt/polyaniline complex anti-biotic material;
Wherein said acid solution is a kind of in hydrochloric acid, sulfuric acid, acetic acid, toluenesulfonic acid;
Described tin salt is a kind of in stannous chloride, stannous sulfate, stannous methanesulfonate.
2. tin salt complex anti-biotic material according to claim 1, is characterized in that: in anti-biotic material, polyaniline diameter is 50～300 nm.
3. tin salt complex anti-biotic material according to claim 1, is characterized in that: the mol ratio of aniline and ammonium persulfate is 20:1～5:1.
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