A kind of nano particle and its preparation method and application
Technical field
The present invention relates to field of nanometer material technology, be specially one and there is unsymmetric structure nano particle and its preparation method and application.
Background technology
Silver is well-known antiseptic bacterium to resistant function, also for a long time far away by the history being directly used as medical antibacterial.When the size of silver is reduced to Nano grade, because it has skin effect, the bacteriostatic activity of Nano silver grain substantially increases.Nano silver grain slowly releases Ag
+, when it arrives electronegative microbial cell film, destroy cell membrane by their firm absorption of electrostatic interaction.Ag
+the functional group of organized enzyme through cell wall damage, inhibits the activity of enzyme to hinder further synthetic protein Protein and nucleic acid Nucleicacid, destroys bacterium housing construction and cause it dead rapidly.But Nano Silver (AgNPs) is very easily reunited, and under illumination easily oxidation cause antibacterial activity to decline, limit its extensive use in daily life greatly.
Chinese patent literature CN102430375A discloses a kind of silicon dioxide-silver nanometer composite microspheres, described complex microsphere take silica as core, polymer is shell, utilize silica polymer microsphere surface carboxyl to be adsorbed by silver ion the complexing of silver ion and ion exchange and be stabilized in SiO 2 composite microsphere surface, then prepare the little and Nano silver grain that decentralization is high of diameter by in-situ chemical reduction.Nano silver particles is carried on the larger silica core surface of volume by described complex microsphere, efficiently solves the problem that Nano Silver is very easily reunited.But because silica core is wherein the symmetrical structure of isotropic, Surface Physical Chemistry performance is evenly distributed state, this just means, described complex microsphere again other functional particles of load time, the performance of each load is very easily offset or weakens, and making it cannot effective efficiency.
Summary of the invention
For this reason, solved by the invention is that existing composite silver particle microballoon cannot the problem of effective efficiency, provides a kind of unsymmetric structure nano particle having several functions concurrently and its preparation method and application.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of nano particle of the present invention, comprises meso-porous titanium dioxide silicon rod, is embedded the magnetic particle in described silica bar one end, and load is in the silver particles on described silica bar surface; The length of described silica bar is 20 ~ 500nm, and the particle diameter of described magnetic particle is 50 ~ 150nm, and the particle diameter of described silver particles is 1 ~ 5nm, and described mesoporous aperture is 1 ~ 3nm.
Described magnetic particle is r-Fe
2o
3, MeFe
2o
3, Fe
3o
4, at least one in MnO, NiO, NiCoFe, FeCo, NiFe, wherein, Me is the one in Co, Mn, Ni.
The specific area of described nano particle is 800 ~ 1200m
2/ g, accumulation pore volume is not less than 0.5cm
3/ g; The magnetic response ability of described nano particle is not less than 58emu/g.
The preparation method of nano particle of the present invention, comprises the steps:
Prepare magnetic particle,
By the mixture of magnetic presoma, polyacrylic acid (PAA) and diethylene glycol (DEG) (DEG) under nitrogen protection room temperature 100 ~ 1000rpm stir 30 minutes; be heated to 240 ~ 280 DEG C of continuation 100 ~ 1000rpm afterwards and stir 30 minutes; obtained first reaction solution
In described first reaction solution, inject diethylene glycol (DEG) (DEG) solution of the NaOH of 60 ~ 75 DEG C, continuation 100 ~ 1000rpm stirs reaction in 1 hour and finally generates magnetic particle,
Described magnetic particle carried out be separated, wash, dry;
Described polyacrylic acid is 10:1 with the ratio of the amount of substance of described magnetic presoma, and the parts by volume of described diethylene glycol (DEG) is the volume of described diethylene glycol (DEG) and the ratio of the amount of substance of described magnetic presoma, and described parts by volume is 30 ~ 40ml/mmol;
Preparation is embedded with the meso-porous titanium dioxide silicon rod of described magnetic particle,
Be that the described magnetic particle aqueous solution of 8.6mg/ml joins in the aqueous solution of 5mg/ml cationic surfactant of 10ml by 1ml concentration, abundant dispersion, add 0.5ml ammoniacal liquor, stirring is continued 30 minutes after adding rapidly ethyl orthosilicate afterwards, wash away described cationic surfactant, the obtained meso-porous titanium dioxide silicon rod being embedded with described magnetic particle;
The surface treatment of described silica bar,
Be dispersed in alcoholic solution by described silica bar, stir after adding amino silicone, then add siloxanes hydrolytic reagent, agitating heating refluxes 24 hours, obtains it after cleaning;
Silver particles described in load,
Described silica bar after surface treatment is dispersed in alcoholic solution, adds containing silver salt solution, and stir process is carried out to described solution, stirring reaction is continued 0.5 ~ 1.5 hour after adding reducing agent, obtained described nano particle after washing, disperse in water, 4 DEG C keep in Dark Place.
Described magnetic presoma is the one in molysite, manganese salt, nickel salt.
Described polyacrylic molecular weight is 1500 ~ 3000; The concentration of the diethylene glycol solution of described NaOH is 0.1g/mL; Described cationic surfactant is alkyl quaternary ammonium salts.
Described reducing agent is ammoniacal liquor and/or sodium borohydride.
Described ethyl orthosilicate with the ratio of the amount of substance of described magnetic particle is:
[TEOS×10
-7]/[Fe
3O
4]=4.9~7.6;
The concentration of described cationic surfactant is 10
-2~ 10
2mg/mL.
The application of described nano particle in antibacterial or bacteria distribution.
The application of described nano particle in sewage purification.
The application of described nano particle in biomedical imaging.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, a kind of nano particle of the present invention, comprises meso-porous titanium dioxide silicon rod, is embedded the magnetic particle in described silica bar one end, and load is at the Nano silver grain on described meso-porous titanium dioxide silicon rod surface; The length of described silica bar is 20 ~ 500nm, and the particle diameter of described magnetic particle is 50 ~ 150nm, and the particle diameter of described silver particles is 1 ~ 5nm, and described mesoporous aperture is 1 ~ 3nm; Because the two kind Nanocomposites of nano particle of the present invention by heterogeneity are formed, and be unsymmetric structure, there is anisotropy, it is the nano particle that Surface Physical Chemistry performance presents non-uniform Distribution, respective physicochemical properties do not disappear because of compound or weaken, both magnetic, bacteriostatic activity and biocompatibility, and dispersive property is good, can realize the application in antibacterial, sewage purification and biomedical imaging.
2, the preparation method of a kind of nano particle of the present invention, technique is simple, is applicable to large-scale industrial production.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the transmission electron microscope photo of the meso-porous titanium dioxide silicon rod being embedded with magnetic particle described in embodiment 1;
Fig. 2 a is the electromicroscopic photograph of nano particle described in embodiment 1;
Fig. 2 b is the electromicroscopic photograph of nano particle described in embodiment 1;
Fig. 3 a is colibacillary antibacterial growth curve under the effect of nano particle variable concentrations described in embodiment 1;
Fig. 3 b is the antibacterial growth curve of hay bacillus under the effect of nano particle variable concentrations described in embodiment 1;
Fig. 4 is the hemolytic experiment of nano particle described in embodiment 4.
In figure, Reference numeral is expressed as: 1-magnetic particle, 2-silica bar, 3-silver particles.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiments of the present invention are described in further detail.
The present invention can implement in many different forms, and should not be understood to be limited to embodiment set forth herein.On the contrary, provide these embodiments, make the disclosure to be thorough and complete, and design of the present invention fully will be conveyed to those skilled in the art, the present invention will only be limited by claim.
Embodiment 1
The present embodiment provides a kind of nano particle, as depicted in figs. 1 and 2, comprises meso-porous titanium dioxide silicon rod 2, be embedded the magnetic particle 1 in described silica bar 2 one end, and load is in the silver particles 3 on described silica bar surface; The length of described silica bar 2 is 200 ~ 300nm, and the particle diameter of described magnetic particle 1 is 50 ~ 60nm, and the particle diameter of described silver particles 3 is 1 ~ 3nm, and the aperture of described meso-porous titanium dioxide silicon rod 2 intermediary hole is 1 ~ 3nm.
Described magnetic particle 1 is selected from but is not limited to r-Fe
2o
3, MeFe
2o
3, Fe
3o
4, at least one in MnO, NiO, NiCoFe, FeCo, NiFe, wherein, Me is the one in Co, Mn, Ni; The present embodiment is preferably Fe
3o
4.
The specific area of described nano particle is 838.8m
2/ g, accumulation pore volume is 0.6cm
3/ g; The magnetic response ability of described nano particle is 62emu/g.
The preparation method of described nano particle, comprises the steps:
(1) magnetic particle is prepared,
By the mixture of magnetic presoma, polyacrylic acid and diethylene glycol (DEG) under nitrogen protection room temperature 800rpm stir 30 minutes, be heated to 250 DEG C afterwards and continue 800rpm and stir 30 minutes, obtained first reaction solution.Described magnetic presoma is the one in molysite, manganese salt, nickel salt, and in the present embodiment, described magnetic presoma is ferric trichloride (FeCl
3).
In described first reaction solution, inject the diethylene glycol solution of the NaOH of 70 DEG C, continuation 800rpm stirs reaction in 1 hour and finally generates magnetic particle.
Described polyacrylic molecular weight is 1500 ~ 3000, and the present embodiment is preferably 1800.
Preferably, the concentration of the diethylene glycol solution of described NaOH is 0.1g/mL.
Described magnetic particle is carried out centrifugation, washing, drying;
Described polyacrylic acid is 10:1 with the ratio of the amount of substance of described magnetic presoma, the parts by volume of described diethylene glycol (DEG) is the volume of described diethylene glycol (DEG) and the ratio of the amount of substance of described magnetic presoma, described parts by volume is 30 ~ 40ml/mmol, and the present embodiment is preferably 35ml/mmol.
(2) preparation is embedded with the meso-porous titanium dioxide silicon rod of described magnetic particle,
Be that the described magnetic particle aqueous solution of 8.6mg/ml joins in the aqueous solution of 5mg/ml cationic surfactant of 10ml by 1ml concentration, abundant dispersion, add 0.5ml ammoniacal liquor, stirring is continued 30 minutes after adding rapidly ethyl orthosilicate afterwards, wash away described cationic surfactant, the obtained meso-porous titanium dioxide silicon rod being embedded with described magnetic particle.
Described ethyl orthosilicate with the ratio of the amount of substance of described magnetic particle is: [TEOS × 10
-7]/[Fe
3o
4]=4.9 ~ 7.6; The present embodiment is preferably 6.
Described cationic surfactant is alkyl quaternary ammonium salts C
xtAB (x=12 ~ 18), the concentration of described cationic surfactant is 10
?2~ 10
2mg/mL; The present embodiment is preferably cetyl ammonium bromide, and its concentration of aqueous solution is 10
2mg/mL.
(3) surface treatment of described silica bar,
Described silica bar is dispersed in alcoholic solution, stirs after adding amino silicone, then add siloxanes hydrolytic reagent, stir and 100 DEG C add hot reflux 24 hours, after ethanol purge it; Described amino silicone is selected from but is not limited to one or more the combination in 3-aminopropyl trimethoxysilane (APS), APTES (APTS), APTES (APTES), and the present embodiment is preferably APS.
(4) silver particles described in load,
Described silica bar after surface treatment is dispersed in ethanolic solution, adds containing silver salt solution, and stir process is carried out to described solution, stirring reaction is continued 1.5 hours after adding reducing agent, obtained described nano particle after washing, disperse in water, 4 DEG C keep in Dark Place.
Containing silver salt described in the present embodiment is silver nitrate; Described silver nitrate concentration is 0.03mol/L.Described reducing agent is ammoniacal liquor, and the addition of ammoniacal liquor is 1:40 with the volume ratio of the described silica bar solution adding silver nitrate.
Embodiment 2
The present embodiment provides a kind of nano particle, comprises meso-porous titanium dioxide silicon rod, is embedded the magnetic particle in described silica bar one end, and load is in the silver particles on described silica bar surface; The length of described silica bar is 400 ~ 500nm, and the particle diameter of described magnetic particle is 60 ~ 100nm, and the particle diameter of described silver particles is 2 ~ 4nm, and the aperture of described meso-porous titanium dioxide silicon rod intermediary hole is 1 ~ 3nm.
Described magnetic particle is selected from but is not limited to r-Fe
2o
3, MeFe
2o
3, Fe
3o
4, at least one in MnO, NiO, NiCoFe, FeCo, NiFe, wherein, Me is the one in Co, Mn, Ni; The present embodiment is preferably Fe
3o
4.
The specific area of described nano particle is 1080.8m
2/ g, accumulation pore volume is 0.6cm
3/ g; The magnetic response ability of described nano particle is 69emu/g.
The preparation method of described nano particle, comprises the steps:
(1) magnetic particle is prepared,
By the mixture of magnetic presoma, polyacrylic acid and diethylene glycol (DEG) under nitrogen protection room temperature 100rpm stir 30 minutes, be heated to 240 DEG C afterwards and continue 100rpm and stir 30 minutes, obtained first reaction solution.Described magnetic presoma is the one in molysite, manganese salt, nickel salt, and in the present embodiment, described magnetic presoma is ferric trichloride (FeCl
3).
In described first reaction solution, inject the diethylene glycol solution of the NaOH of 75 DEG C, continuation 100rpm stirs reaction in 1 hour and finally generates magnetic particle.
Described polyacrylic molecular weight is 1500 ~ 3000, and the present embodiment is preferably 3000.
Preferably, the concentration of the diethylene glycol solution of described NaOH is 0.1g/mL.
Described magnetic particle is carried out centrifugation, washing, drying;
Described polyacrylic acid is 10:1 with the ratio of the amount of substance of described magnetic presoma, and the parts by volume of described diethylene glycol (DEG) is the volume of described diethylene glycol (DEG) and the ratio of the amount of substance of described magnetic presoma, and described parts by volume is 40ml/mmol.
(2) preparation is embedded with the meso-porous titanium dioxide silicon rod of described magnetic particle,
Be that the described magnetic particle aqueous solution of 8.6mg/ml joins in the aqueous solution of 5mg/ml cationic surfactant of 10ml by 1ml concentration, abundant dispersion, add 0.5ml ammoniacal liquor, stirring is continued 30 minutes after adding rapidly ethyl orthosilicate afterwards, wash away described cationic surfactant, the obtained meso-porous titanium dioxide silicon rod being embedded with described magnetic particle.
Described ethyl orthosilicate with the ratio of the amount of substance of described magnetic particle is: [TEOS × 10
-7]/[Fe
3o
4]=4.9 ~ 7.6; The present embodiment is preferably 4.9.
Described cationic surfactant is alkyl quaternary ammonium salts C
xtAB (x=12 ~ 18), the concentration of described cationic surfactant is 10
?2~ 10
2mg/mL; The present embodiment is preferably cetyl ammonium bromide, and its concentration of aqueous solution is 1mg/mL.
(3) surface treatment of described silica bar,
Described silica bar is dispersed in alcoholic solution, stirs after adding amino silicone, then add siloxanes hydrolytic reagent, stir and 100 DEG C add hot reflux 24 hours, after ethanol purge it; Described amino silicone is selected from but is not limited to one or more the combination in 3-aminopropyl trimethoxysilane (APS), APTES (APTS), APTES (APTES), and the present embodiment is preferably APS.
(4) silver particles described in load,
By the described silica bar dispersion after surface treatment in ethanol, add silver chlorate, in the solution formed, described silver chlorate concentration is 0.03mol/L; And stir process is carried out to described mixed solution, continue stirring reaction after adding sodium borohydride aqueous solution 0.5 hour, after washing, obtained described nano particle, disperses 4 DEG C and keeps in Dark Place in water.The concentration of described sodium borohydride aqueous solution is 6 × 10
-4g/ml, described sodium borohydride aqueous solution addition is 1/40 of described silica bar aqueous solution volume.
Embodiment 3
The present embodiment provides a kind of nano particle, comprises meso-porous titanium dioxide silicon rod, is embedded the magnetic particle in described silica bar one end, and load is in the silver particles on described silica bar surface; The length of described silica bar is 20 ~ 200nm, and the particle diameter of described magnetic particle 1 is 100 ~ 150nm, and the particle diameter of described silver particles 3 is 3 ~ 5nm, and the aperture of described meso-porous titanium dioxide silicon rod intermediary hole is 1 ~ 3nm.
Described magnetic particle is selected from but is not limited to r-Fe
2o
3, MeFe
2o
3, Fe
3o
4, at least one in MnO, NiO, NiCoFe, FeCo, NiFe, wherein, Me is the one in Co, Mn, Ni; The present embodiment is preferably Fe
3o
4.
The specific area of described nano particle is 1208.8m
2/ g, accumulation pore volume is 0.7cm
3/ g; The magnetic response ability of described nano particle is 62emu/g.
The preparation method of described nano particle, comprises the steps:
(1) magnetic particle is prepared,
By the mixture of magnetic presoma, polyacrylic acid and diethylene glycol (DEG) under nitrogen protection room temperature 1000rpm stir 30 minutes, be heated to 280 DEG C afterwards and continue 1000rpm and stir 30 minutes, obtained first reaction solution.Described magnetic presoma is the one in molysite, manganese salt, nickel salt, and in the present embodiment, described magnetic presoma is ferric trichloride (FeCl
3).
In described first reaction solution, inject the diethylene glycol solution of the NaOH of 60 DEG C, continuation 1000rpm stirs reaction in 1 hour and finally generates magnetic particle.
Described polyacrylic molecular weight is 1500 ~ 3000, and the present embodiment is preferably 1500.
Preferably, the concentration of the diethylene glycol solution of described NaOH is 0.1g/mL.
Described magnetic particle is carried out centrifugation, washing, drying;
Described polyacrylic acid is 10:1 with the ratio of the amount of substance of described magnetic presoma, the parts by volume of described diethylene glycol (DEG) is the volume of described diethylene glycol (DEG) and the ratio of the amount of substance of described magnetic presoma, described parts by volume is 30 ~ 40ml/mmol, the preferred 30ml/mmol of the present embodiment.
(2) preparation is embedded with the meso-porous titanium dioxide silicon rod of described magnetic particle,
Be that the described magnetic particle aqueous solution of 8.6mg/ml joins in the aqueous solution of 5mg/ml cationic surfactant of 10ml by 1ml concentration, abundant dispersion, add 0.5ml ammoniacal liquor, stirring is continued 30 minutes after adding rapidly ethyl orthosilicate afterwards, wash away described cationic surfactant, the obtained meso-porous titanium dioxide silicon rod being embedded with described magnetic particle.
Described ethyl orthosilicate with the ratio of the amount of substance of described magnetic particle is: [TEOS × 10
-7]/[Fe
3o
4]=4.9 ~ 7.6; The present embodiment is preferably 7.6.
Described cationic surfactant is alkyl quaternary ammonium salts C
xtAB (x=12 ~ 18), the concentration of described cationic surfactant is 10
?2~ 10
2mg/mL; The present embodiment is preferably cetyl ammonium bromide, and its concentration of aqueous solution is 10
?2mg/mL.
(3) surface treatment of described silica bar,
Described silica bar is dispersed in alcoholic solution, stirs after adding amino silicone, then add siloxanes hydrolytic reagent, stir and 100 DEG C add hot reflux 24 hours, after ethanol purge it; Described amino silicone is selected from but is not limited to one or more the combination in 3-aminopropyl trimethoxysilane (APS), APTES (APTS), APTES (APTES), and the present embodiment is preferably APTS.
(4) silver particles described in load,
By the described silica bar dispersion after surface treatment in ethanol, add silver nitrate aqueous solution, described silver nitrate concentration is 0.03mol/L; And stir process is carried out to described mixed solution, continue stirring reaction after adding ammoniacal liquor 1.0 hours, obtained described nano particle after washing, dispersion in water 4 DEG C keep in Dark Place.
The addition of ammoniacal liquor described in the present embodiment is 1/40 of described silica bar aqueous solution volume.
Experimental example 1
Escherichia coli and Bacillus subtilis is used to test the bacteriostasis property of described nano particle.
Experimental procedure is:
(1) configure LB culture medium, each flat board is containing 0.2gNaCl, 0.2g peptone, and 0.1g yeast extract, 0.3g agar, 20ml water, regulates PH to 7.0,120 DEG C of autoclaving 30min with 5mol/LNaOH.Take out and cultivate based on appropriateness cooling in super-clean bench, add ammonia benzyl antibiotic by 1:1000.
(2) the described nano particle prepared by embodiment 1 is mixed with culture medium by different dilution ratio, then pour in the culture dish after sterilizing.
(3) cultivate Gram-negative bacteria (Escherichia coli) and gram-positive bacteria (hay bacillus), picking proper amount of strains is in liquid LB medium, and in 37 DEG C of incubators, concussion overnight is cultured to exponential phase; After dilution, dull and stereotyped by being coated with after culture medium solidifying.Finally seal up with sealed membrane, put into 37 DEG C of incubator incubated overnight.
The antibacterial activity of described nano particle is by bacterial growth dynamic assessment, and optical density is at the spectrophotometer measurement and detection Growth of Cells of 600nm.Fig. 3 a is colibacillary antibacterial growth curve under the effect of nano particle variable concentrations described in embodiment 1, and Fig. 3 b is the antibacterial growth curve of hay bacillus under the effect of nano particle variable concentrations described in embodiment 1; As can be seen from Fig. 3 a and Fig. 3 b, the antibacterial action of described nano particle is typical dependent dose type, low concentration particle had a large deadtime before 15th hour, and due to the existence of high concentrations of particles, Escherichia coli and hay bacillus are completely suppressed in the culture period of 24 hours.
Experimental example 2
Defibrinated rabbit blood is used to test red blood cell to the compatibility of described nano particle.
Test procedure is:
(1) rabbit is carried on the back position and be fixed on rabbit platform, be separated arteria carotis communis intubate and get blood in centrifuge tube, blood is stirred gently except defibrinating with glass bar, except defibrinated blood physiological saline shakes up, supernatant is removed in centrifugal hypsokinesis, so three times repeatedly, measure the red blood cell suspension that red blood cell is diluted to 2% and be for experiment.
(2) by (nano particle described in the embodiment 1 containing variable concentrations of mixed solution in each test tube, not containing described nano particle in No.6 and No.7) shake up gently, put in 37 DEG C of water-baths, observe respectively and record the result of half an hour, 1 hour, observe with or without haemolysis and hemagglutination, and place 24 hours with room temperature, continue to observe with or without haemolysis and RCA generation.After in Fig. 4, test tube leaves standstill one hour there is haemolysis in the 3rd pipe and the later each pipe of the 3rd pipe, part haemolysis or Coagulation test, illustrate that the described nano-particle solution being not suitable for of corresponding concentration is done used for intravenous injection, 1, the described nano particle of the low concentration in 2 test tubes can be used for doing intravenous injection, on the red blood cell in blood without impact.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among protection scope of the present invention.