CN103936985B - A kind of preparation method and applications of Nano particles of polyaniline - Google Patents
A kind of preparation method and applications of Nano particles of polyaniline Download PDFInfo
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Abstract
The invention provides a kind of preparation method of Nano particles of polyaniline, comprise the following steps：In the presence of template and oxidant, aniline is carried out into oxidative polymerization, obtain Nano particles of polyaniline；The template includes one or more in polyvinyl alcohol, polyethylene glycol polypropylene glycol polyethylene glycol triblock polymer, polyethylene glycol b polyglutamic acids bi-block copolymer, poly- polysaccharide and protein.The present invention is using one or more in polyvinyl alcohol, polyethylene glycol polypropylene glycol polyethylene glycol triblock polymer, polyethylene glycol b polyglutamic acids, poly- polysaccharide and protein as template, obtained Nano particles of polyaniline has stronger absorption near infrared region, there is good imaging effect.Test result indicate that：The photoacoustic signal of the Nano particles of polyaniline that the preparation method that the present invention is provided is prepared is strong, and photoacoustic imaging contrast is high, image clearly.
Description
Technical field
The present invention relates to technical field of photoacoustic, more particularly to a kind of Nano particles of polyaniline preparation method and its should
With.
Background technology
Photoacoustic imaging is a kind of lossless medical imaging modalities for growing up recent years, and it is set up based on optoacoustic effect
Mixed mode imaging method, the high-contrast of pure optical imagery and the high-penetration of pure ultrasonic imaging are combined, by optoacoustic
Imaging, can obtain the imaging of tissue of high-resolution and high-contrast.Recent study confirms that it is new that photoacoustic imaging can be used for tumour
Many life and the medical science such as detection, blood oxygen saturation scanning, cerebral function imaging and the cutaneous melanoma detection of angiogenic
Field.
At present, in imaging field, what photoacoustic imaging was applied is thermal-elastic expansion mechanism.Light based on thermoelasticity mechanism
Acoustic imaging process refers to：A branch of short pulse (ns magnitudes) laser is irradiated into biological tissue, there is strong optical absorption in biological tissue
The absorber of characteristic is absorbed after light energy, and light energy causes absorber to rise mild inflation, and the expansion of absorber volume can be extruded
Tissue around absorber so as to produce local pressure ripple, the difference of absorber absorbent properties, for example HC is big
Small, the height of tissue oxygenation saturation degree can influence the light absorpting ability of absorber, so as to change the intensity of ultrasonic signal, lead to
The spatial distribution of detector detecting ultrasonic signal intensity is crossed, so as to reflect the pathological information of imaging object.
Inorganic carbon material of the prior art, such as Graphene, CNT, due to very big specific surface area, quilt
Being widely used as bio-carrier carries out biological detection, drug delivery etc..In addition, it also has optical solitons, used also as
Magnetic resonance imaging and photoacoustic imaging, but its as photoacoustic imaging contrast agent when it is weaker in the absorption of near infrared region, it is difficult to obtain
Good imaging effect.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method and applications of Nano particles of polyaniline, this
The Nano particles of polyaniline that the preparation method that invention is provided is prepared is stronger in the absorption of near infrared region, there is good imaging
Effect.
The invention provides a kind of preparation method of Nano particles of polyaniline, comprise the following steps：
In the presence of template and oxidant, aniline is carried out into oxidative polymerization in water, obtain polyaniline nano
Particle；
The template includes polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, poly- second two
One or more in alcohol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide and protein.
Preferably, the poly- polysaccharide includes one or more in glucan, shitosan and sodium carboxymethylcellulose.
Preferably, the number-average molecular weight of the poly- polysaccharide is 4kDa~90kDa.
Preferably, the protein includes bovine serum albumin(BSA), human serum albumins, transferrins, lactalbumin and molten
One or more in bacterium enzyme.
Preferably, the oxidant includes one or more in ferric ion, hydrogen peroxide and ammonium persulfate.
Preferably, the temperature of the oxidative polymerization is 15 DEG C~35 DEG C.
Preferably, the time of the oxidative polymerization is 12h~72h.
Preferably, the mass ratio of the template and aniline is 3~30:1.
Preferably, the mol ratio of the oxidant and aniline is 0.5~20:1.
The Nano particles of polyaniline prepared the invention provides preparation method described in above-mentioned technical proposal is used as optoacoustic
The application of image-forming contrast medium.
The invention provides a kind of preparation method of Nano particles of polyaniline, comprise the following steps：In template and oxidation
In the presence of agent, aniline is carried out into oxidative polymerization in water, obtain Nano particles of polyaniline；The template includes poly- second
Enol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol-b- polyglutamic acids bi-block copolymer,
One or more in poly- polysaccharide and protein.The present invention is embedding with polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol three
One or more in section polymer, polyethylene glycol-b- polyglutamic acids, poly- polysaccharide and protein is obtained poly- as template
Aniline nano particle has stronger absorption near infrared region, there is good imaging effect.Test result indicate that：The present invention is carried
The photoacoustic signal of the Nano particles of polyaniline that the preparation method of confession is prepared is strong, and photoacoustic imaging contrast is high, image clearly.
In addition, the Nano particles of polyaniline that the preparation method that the present invention is provided is prepared has good bio-compatible
Property, water dispersible and water solubility.
The preparation method that the present invention is provided in aqueous is carried out, it is to avoid organic solvent and other toxic solvents make
With reaction condition is gentle, and controllability is strong, is a kind of safe and reliable and efficient preparation method, it is easy to promote and amplify.
Brief description of the drawings
Fig. 1 is the uv absorption spectra of Nano particles of polyaniline prepared by the embodiment of the present invention 1；
Fig. 2 is the photoacoustce signal intensity-nanoparticle concentration result of Nano particles of polyaniline prepared by the embodiment of the present invention 1
Figure；
Fig. 3 is the photoacoustic signal figure of Nano particles of polyaniline prepared by the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of Nano particles of polyaniline prepared by the embodiment of the present invention 9；
Fig. 5 is Nano particles of polyaniline uv absorption spectra prepared by the embodiment of the present invention 9；
Fig. 6 is the photoacoustce signal intensity-nanoparticle concentration result of Nano particles of polyaniline prepared by the embodiment of the present invention 9
Figure；
Fig. 7 is the photoacoustic signal figure of Nano particles of polyaniline prepared by the embodiment of the present invention 9；
Fig. 8 is Nano particles of polyaniline uv absorption spectra prepared by the embodiment of the present invention 20；
Fig. 9 is the photoacoustic signal figure of Nano particles of polyaniline prepared by the embodiment of the present invention 20；
Figure 10 is that the photoacoustce signal intensity-nanoparticle concentration of Nano particles of polyaniline prepared by the embodiment of the present invention 20 is closed
System's figure；
Figure 11 is the photoacoustic signal pcolor in different wave length of Nano particles of polyaniline prepared by the embodiment of the present invention 20；
Figure 12 is the scanning electron microscope (SEM) photograph of Nano particles of polyaniline prepared by the embodiment of the present invention 24；
Figure 13 is Nano particles of polyaniline uv absorption spectra prepared by the embodiment of the present invention 24；
Figure 14 is the photoacoustce signal intensity-nanoparticle concentration knot of Nano particles of polyaniline prepared by the embodiment of the present invention 24
Fruit is schemed；
Figure 15 is the photoacoustic signal figure of Nano particles of polyaniline prepared by the embodiment of the present invention 24；
Figure 16 is the subcutaneous contrasting effects in Balb/C nude mices of Nano particles of polyaniline prepared by the embodiment of the present invention 24
Figure；
Figure 17 is the bowel radiography effect in Balb/C nude mices of Nano particles of polyaniline prepared by the embodiment of the present invention 24
Figure；
Figure 18 is to inject polyaniline nano grain prepared by the embodiment of the present invention 3, embodiment 9, embodiment 20 and embodiment 24
Influence curve figure of the son to Balb/C mouse body weight；
The ultra-violet absorption spectrum pair of the Nano particles of polyaniline that Figure 19 is prepared for the graphene oxide and embodiment 1 of comparative example
Than figure.
Specific embodiment
The invention provides a kind of preparation method of Nano particles of polyaniline, comprise the following steps：
In the presence of template and oxidant, aniline is carried out into oxidative polymerization in water, obtain polyaniline nano
Particle；
The template includes polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, poly- second two
One or more in alcohol-b- polyglutamic acids, poly- polysaccharide and protein.
The present invention is gathered with polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol-b-
One or more in glutamic acid bi-block copolymer, poly- polysaccharide and protein as template, obtained polyaniline nano grain
Son has stronger absorption near infrared region, there is good imaging effect.Test result indicate that：The preparation side that the present invention is provided
The photoacoustic imaging contrast of the Nano particles of polyaniline that method is prepared is high, image clearly.
Aniline is carried out oxidative polymerization by the present invention in the presence of template and oxidant in water, obtains polyphenyl
Amine nano-particle；The template includes polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, poly- second
One or more in glycol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide and protein.The present invention to the template,
The order by merging of oxidant, water and aniline is not particularly limited, and preferably first mixes the template and water, obtains template molten
Liquid, then the template solution is mixed with oxidant, the mixing of last and aniline.In the present invention, the template and water are mixed
The temperature of conjunction is preferably 25 DEG C~70 DEG C, more preferably 50 DEG C~65 DEG C；The time of the template and water mixing is preferably
10min~40min, more preferably 15min~35min, most preferably 20min~30min.In this present invention, the property of template
Matter is different, and the temperature when template mixes from water is different；Specifically, when the template is polyethylene glycol-b- polyglutamics
During sour bi-block copolymer, the temperature mixed with water is preferably 10 DEG C~45 DEG C, more preferably 25 DEG C~40 DEG C；Mix with water
Time is preferably 50min~70min, most preferably more preferably 50min~65min, 60min；The present invention is preferably by template
Solution is adjusted to pH value=7.4 using the sodium hydroxide solution of 0.1mol/L, then is mixed with oxidant and aniline.
When template is that the temperature mixed with water is preferably 15 DEG C~35 DEG C when being modified poly- polysaccharide, more preferably 20 DEG C~
25℃；The time mixed with water is preferably 50min~65min, more preferably 60min；The present invention preferably adjusts template solution
Section is to pH value=7~8, then mixes with oxidant and aniline.
When template is polyvinyl alcohol and/or polyethylene glycol propane diols-polyethylene glycol triblock polymer, with water
The temperature of mixing is preferably 50 DEG C~70 DEG C, more preferably 60 DEG C；The time mixed with water is preferably 20min~40min, more excellent
Elect 25min~35min as；The present invention does not preferably adjust the pH value of template solution, and the template solution that will be obtained is cooled to 10
DEG C~20 DEG C, then with oxidant and aniline reaction.
The present invention does not have special limitation to the mode that the template and water mix, and is carried out preferably under conditions of stirring
Mixing.In the present invention, the water preferably includes one or more in distilled water, deionized water and running water, more preferably
Deionized water；The quality of the template and the volume ratio of water are preferably (20~200) mg:1mL, more preferably (50~120)
mg:1mL。
In the present invention, carried out preferably under conditions of stirring when the template solution mixes with oxidant；The mould
Plate agent solution and the temperature of oxidant mixing are preferably 15 DEG C~30 DEG C, more preferably 20 DEG C~25 DEG C；The template solution
The time mixed with oxidant is preferably 20min~40min, most preferably more preferably 25min~305min, 30min.
In the present invention, the template includes that polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol three block are gathered
One or more in compound, polyethylene glycol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide and protein.In the present invention,
The poly- polysaccharide includes one or more in natural polysaccharide and modified poly- polysaccharide, preferably includes glucan, shitosan and carboxylic
One or more in sodium carboxymethylcellulose pyce, more preferably including glucan and/or sodium carboxymethylcellulose；The number of the poly- polysaccharide
Average molecular weight is preferably 4kDa~90kDa, most preferably more preferably 20kDa~80kDa, 10kDa~60kDa, the most preferably
It is 10kDa~40kDa；The protein preferably includes bovine serum albumin(BSA), human serum albumins, transferrins, lactalbumin
With one or more in lysozyme, more preferably including one or more in bovine serum albumin, human albumin and lysozyme.
In the present invention, the template increases the hydrophily of aniline, beneficial to the formation of Nano particles of polyaniline, and the stabilization in water
Dispersion.
The present invention originates without special limitation to the aniline, is using aniline well known to those skilled in the art
Can, such as can be using the commercial goods of aniline, it would however also be possible to employ the technical scheme for preparing aniline well known to those skilled in the art
Voluntarily prepare.
In the present invention, the oxidant preferably include one kind in ferric ion, hydrogen peroxide and ammonium persulfate or
It is various, more preferably hydrogen peroxide.The present invention does not have special limitation to the material for providing ferric ion, can be ferric iron
The water soluble salt compound of ion, can be such as iron chloride or ferric nitrate, in an embodiment of the present invention, can be specially six
Ferric Chloride Hydrated.In the present invention, when the oxidant is hydrogen peroxide, present invention preferably employs the water-soluble of hydrogen peroxide
Liquid, i.e. hydrogen peroxide, in the present invention, the mass fraction of the hydrogen peroxide is preferably 20%~40%, more preferably 25%~
35%, most preferably 30%.
In the present invention, the mass ratio of the template and aniline is preferably 3~30:1, more preferably 5~28:1, it is optimal
Elect 8~25 as:1；The mol ratio of the oxidant and aniline is preferably 0.5~20:1, more preferably 1.0~18:1, most preferably
It is 2.0~15:1.
Aniline is carried out oxidative polymerization by the present invention preferably under conditions of lucifuge, obtains Nano particles of polyaniline.This
Invention carries out oxidative polymerization preferably under conditions of stirring.In the present invention, the temperature of the oxidative polymerization is preferred
It is 15 DEG C~35 DEG C, more preferably 18 DEG C~33 DEG C, most preferably 20 DEG C~30 DEG C；The time of the oxidative polymerization is preferred
It is 12h~72h, more preferably 15h~70h, most preferably 20h~60h.
After completing the oxidative polymerization of aniline, the product that the present invention will preferably be obtained is dialysed, is centrifuged and washed
Wash, obtain Nano particles of polyaniline.The present invention does not have special limitation to the method for the dialysis, using those skilled in the art
Well known dialysis scheme.In the present invention, the solvent of the dialysis is preferably deionized water；What the dialysis was used
The molecular cut off of dialysis membrane is preferably 3500Da~15000Da, more preferably 7000Da~10000Da；The temperature of the dialysis
Degree is preferably 15 DEG C~40 DEG C, more preferably 20 DEG C~35 DEG C, most preferably 25 DEG C~30 DEG C；The time of the dialysis is preferably
2.5 days~3.5 days, more preferably 3 days.In the present invention, the particle diameter of Nano particles of polyaniline is preferably 60nm~100nm.
The present invention to it is described centrifugation and washing method there is no special limitation, using it is well known to those skilled in the art from
The heart and the technical scheme of washing.In the present invention, the rotating speed of the centrifugation is preferably 10000rpm~20000rpm, more excellent
Elect 12000rpm~18000rpm, most preferably 15000rpm~16000rpm as；The time of the centrifugation be preferably 10min~
60min, more preferably 20min~40min.In the present invention, the solvent of the washing is preferably deionized water；The washing
Number of times is preferably 5 times~8 times.
After the product washed, product of the present invention preferably by the washing is dried.In the present invention
In, the drying is preferably using vacuum drying or freeze-drying.
The Nano particles of polyaniline that the present invention is obtained can disperse in an aqueous medium, to preserve in liquid form；The water
Property medium include the aqueous medium be distilled water, physiological saline, cushioning liquid, tissue culture medium and body fluid in one kind or many
Kind；The quality of the Nano particles of polyaniline and the volume of solvent are preferably (25~800) μ g:1mL；
The Nano particles of polyaniline that the present invention is obtained can also be preserved in solid form.
The Nano particles of polyaniline obtained the invention provides above-mentioned technical proposal as photoacoustic imaging contrast agent application.
In the present invention, the particle diameter of Nano particles of polyaniline is preferably 20nm~200nm.
In an embodiment of the present invention, the head subcutaneous part of the Nano particles of polyaniline injection experimentses animal that will can be obtained
Position, observes the photoacoustic imaging effect of the Nano particles of polyaniline for preparing；The Nano particles of polyaniline that will can also be obtained is by real
The oral way for testing animal enters into the internal of experimental animal, and the enteron aisle position to experimental animal carries out radiography, prepared by observation
The light sound effective value of Nano particles of polyaniline.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining.The present invention is to the polyaniline
The method that nano-particle carries out ultraviolet-visible spectrum test does not have special limitation, using purple well known to those skilled in the art
The technical scheme of outward-visible spectrum test.
Test result shows：The Nano particles of polyaniline for preparing of preparation method that the present invention is provided 600nm~
There is absorption in the range of 900nm.
The present invention is scanned electronic microscope photos to the Nano particles of polyaniline for obtaining.Analysis result shows：The present invention is provided
The Nano particles of polyaniline for preparing of preparation method it is spherical in shape be uniformly distributed, a diameter of 20nm of Nano particles of polyaniline~
200nm。
The present invention carries out photoacoustic signal spectrum test to the Nano particles of polyaniline for obtaining, and detailed process is as follows：
Nano particles of polyaniline is injected in agar prosthese, the agar prosthese containing Nano particles of polyaniline is placed in 34 DEG C
Constant temperature water tank in, selection wavelength be 680nm~900nm, wavelength interval carries out photoacoustic signal test for 5nm.
Test result shows：Nano particles of polyaniline prepared by the preparation method that the present invention is provided has light near infrared region
Acoustical signal, can analyze as photoacoustic imaging contrast agent for photoacoustic imaging.
The present invention is tested the concentration of Nano particles of polyaniline and the relation of photoacoustce signal intensity, and detailed process is such as
Under：
The Nano particles of polyaniline solution of series concentration is injected separately into agar prosthese, the various concentrations that will be obtained
The agar prosthese of Nano particles of polyaniline is placed in 34 DEG C of constant water bath box, and its phase is tested using multispectral photoacoustic imaging system
The photoacoustce signal intensity answered.
Test result shows：The present invention provide preparation method prepare Nano particles of polyaniline photoacoustce signal intensity and
Concentration is respectively provided with preferable linear relationship, and the quantitative analysis of photoacoustic imaging can be carried out according to its light sound intensity.
The photoacoustic imaging contrasting effects of Nano particles of polyaniline of the present invention to obtaining are tested, and detailed process is as follows：
The Nano particles of polyaniline of the μ g/mL of 0.1mL 100 is injected under the scalp of male Balb/C nude mices, then will be naked
Mouse is placed in 34 DEG C of constant water bath box after being coated with transparent plastic film, and the mixed gas for being continually fed into isoflurane and air are protected
Hold experimental animal and be in narcosis, multispectral tomoscan is carried out using multispectral photoacoustic imaging system；
The Nano particles of polyaniline of the μ g/mL of 0.2mL 100 is injected in the present invention gastric perfusion needle male for breaking off diet 12h
In Balb/C nude mouses, it is placed in 34 DEG C of constant water bath box after then nude mice is coated with transparent plastic film, is continually fed into
The mixed gas of isoflurane and air keep experimental animal to be in narcosis, and light more is carried out using multispectral photoacoustic imaging system
Spectrum tomoscan.
Test result shows：Nano particles of polyaniline prepared by the present invention has good contrasting effects, and image clearly is right
It is higher than degree, it is highly suitable for photoacoustic imaging visualization.
The invention provides a kind of preparation method of Nano particles of polyaniline, comprise the following steps：In template and oxidation
In the presence of agent, aniline is carried out into oxidative polymerization, obtain Nano particles of polyaniline；The template include polyvinyl alcohol,
Polyethylene glycol propane diols-polyethylene glycol triblock polymer, polyethylene glycol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide
With one or more in protein.The present invention is polymerized with polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol three block
Made as template for one or more in thing, polyethylene glycol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide and protein
The Nano particles of polyaniline for obtaining has stronger absorption near infrared region, there is good imaging effect.Test result indicate that：This
The photoacoustic signal for inventing the Nano particles of polyaniline that the preparation method for providing is prepared is strong, and photoacoustic imaging contrast is high, image
Clearly.
In order to further illustrate the present invention, a kind of Nano particles of polyaniline provided the present invention with reference to embodiment
Preparation method and the application in photoacoustic imaging radiography are described in detail, but can not be interpreted as them protecting the present invention
The restriction of scope.
Embodiment 1
0.6145g polyvinyl alcohol and 8mL deionized waters are placed in 25mL reaction bulbs, 60 DEG C are heated to, stirring 30min makes
Polyvinyl alcohol is completely dissolved, and obtains poly-vinyl alcohol solution；After poly-vinyl alcohol solution is cooled to room temperature, it is added thereto to
0.4110g ferric chloride hexahydrates, add 0.0615g aniline, lucifuge, the mixed solution that will be obtained to exist after 30min is stirred at room temperature
Stirred at 30 DEG C, carry out oxidative polymerization 24h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is through going
Ionized water is dialysed three days, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The Nano particles of polyaniline that the present invention is obtained carries out ultraviolet-visible spectrum test, its ultra-violet absorption spectrum such as Fig. 1 institutes
Show, Fig. 1 is the uv absorption spectra of Nano particles of polyaniline prepared by the embodiment of the present invention 1.As seen from Figure 1, this hair
The Nano particles of polyaniline that bright embodiment 1 is obtained has absorption in the range of 600nm~900nm.
By 50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 300 μ g/mL, 400 μ g/mL, 500 μ g/mL and 600 μ g/mL polyphenyl
Amine nano-particle is injected separately into different agar prostheses, according to above-mentioned technical proposal by the agar containing Nano particles of polyaniline
Prosthese carries out photoacoustce signal intensity test test result as shown in Fig. 2 Fig. 2 is the polyaniline nano that the embodiment of the present invention 1 is obtained
The photoacoustce signal intensity of particle-concentration relationship figure.As seen from Figure 2, the optoacoustic letter of the Nano particles of polyaniline of different-grain diameter
Number intensity and concentration are respectively provided with preferable linear relationship, and linear equation is y=35.55x+907.16, R2=0.9978.Therefore,
Light sound intensity according to Nano particles of polyaniline, can carry out the quantitative analysis of photoacoustic imaging.
The Nano particles of polyaniline that the present invention will be obtained carries out photoacoustic signal spectrum test, test knot according to above-mentioned technical proposal
Fruit is as shown in figure 3, Fig. 3 is the photoacoustic signal spectrogram of the Nano particles of polyaniline that the embodiment of the present invention 1 is obtained.Can be seen by Fig. 3
Go out, Nano particles of polyaniline prepared by the embodiment of the present invention has photoacoustic signal near infrared region, can be used as photoacoustic imaging radiography
Agent is analyzed for photoacoustic imaging.
Embodiment 2
1.0275g polyvinyl alcohol and 10mL deionized waters are placed in 25mL reaction bulbs, being heated to 60 DEG C of stirring 30min makes
Be completely dissolved；After poly-vinyl alcohol solution to be obtained is cooled to room temperature, the hydrogen peroxide that 0.18mL mass fractions are 30% is added,
Add 0.0514g aniline, lucifuge, the mixed solution that will be obtained to be stirred at 20 DEG C after stirring 30min at room temperature, carry out oxidation poly-
Reaction 60h is closed, reaction system color is gradually deepened, eventually become black, products therefrom is dialysed three days through deionized water, repeatedly high
Nano particles of polyaniline is obtained after speed centrifugation, deionized water washing.
The Nano particles of polyaniline that the present invention is obtained carries out ultraviolet-visible spectrum test, and test result shows：It is of the invention real
Apply the Nano particles of polyaniline that example 2 obtains has absorption in the range of 600nm~900nm.
Embodiment 3
1.6245g polyvinyl alcohol and 10mL deionized waters are placed in 25mL reaction bulbs, 60 DEG C are heated to, 30min is stirred
Polyvinyl alcohol is completely dissolved, poly-vinyl alcohol solution is obtained；After poly-vinyl alcohol solution is cooled to room temperature, to poly-vinyl alcohol solution
Middle addition 0.4712g ferric chloride hexahydrates, at room temperature stir 30min after add 0.0541g aniline, at 15 DEG C lucifuge stir into
Row oxidative polymerization 72h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is through deionized water dialysis three
My god, obtain Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 3 is obtained has absorption in the range of 600nm~900nm.
Embodiment 4
By polyethylene glycol propane diols-embedding polymer of polyethylene glycol three and 8mL that 1.5351g number-average molecular weights are 14600
Deionized water is placed in 25mL reaction bulbs, and being heated to 60 DEG C of stirring 30min makes polyethylene glycol propane diols-polyethylene glycol three embedding
Polymer is completely dissolved；After the embedding polymer solution of polyethylene glycol propane diols-polyethylene glycol three is cooled to room temperature, add
0.4521g ammonium persulfates, the mixed solution that will be obtained adds 0.0613g aniline, lucifuge, 25 after 30min is stirred at room temperature
Stirred at DEG C, carry out oxidative polymerization 36h, reaction system color is gradually deepened, eventually become black, products therefrom through go from
Sub- water is dialysed three days, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 4 is obtained has absorption in the range of 600nm~900nm.
Embodiment 5
By polyethylene glycol propane diols-embedding polymer of polyethylene glycol three and 14mL that 1.3562g number-average molecular weights are 8400
Deionized water is placed in 25mL reaction bulbs, and being heated to 60 DEG C of stirring 30min makes polyethylene glycol propane diols-polyethylene glycol three embedding
Polymer is completely dissolved；After the embedding polymer solution of polyethylene glycol propane diols-polyethylene glycol three is cooled to room temperature, add
0.41mL mass fractions are 30% hydrogen peroxide, and the mixed solution that will be obtained adds 0.0678g benzene after 30min is stirred at room temperature
Amine, lucifuge is stirred under the conditions of 20 DEG C, carries out oxidative polymerization 48h, and reaction system color is gradually deepened, and is eventually become black
Color, products therefrom is dialysed three days through deionized water, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 5 is obtained has absorption in the range of 600nm~900nm.
Embodiment 6
By polyethylene glycol propane diols-embedding polymer of polyethylene glycol three and 9mL that 0.4261g number-average molecular weights are 5800
Deionized water is placed in 25mL reaction bulbs, and being heated to 60 DEG C of stirring 30min makes polyethylene glycol propane diols-polyethylene glycol three embedding
Polymer is completely dissolved；After the embedding polymer solution of polyethylene glycol propane diols-polyethylene glycol three is cooled to room temperature, add
0.31mL mass fractions are 30% hydrogen peroxide, and 0.0852g aniline, lucifuge, by what is obtained are added after 30min is stirred at room temperature
Mixed solution is stirred at 30 DEG C, carries out oxidative polymerization 24h, and reaction system color is gradually deepened, and eventually becomes black, institute
Obtain product to be dialysed three days through deionized water, obtain Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 6 is obtained has absorption in the range of 600nm~900nm.
Embodiment 7
0.5136g polyethylene glycol glutamic acid bi-block copolymers, the block of polyethylene glycol glutamic acid two are gathered
The degree of polymerization of polyethylene glycol section and polyglutamic acid section is respectively 113 and 45 in compound, and 17mL deionized waters are placed in 25mL reactions
In bottle, pH value is adjusted to 7.4 with the NaOH of 0.1mol/L, 0.5581g six is added after bi-block copolymer fully dissolves
Ferric Chloride Hydrated, room temperature adds 0.0641g aniline after being sufficiently stirred for 30min, and lucifuge is stirred under the conditions of 25 DEG C, aoxidized
Polymerisation 24h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly
Nano particles of polyaniline is obtained after high speed centrifugation, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 7 is obtained has absorption in the range of 600nm~900nm.
Embodiment 8
1.0145g polyethylene glycol glutamic acid bi-block copolymers, the block of polyethylene glycol glutamic acid two are gathered
The degree of polymerization of polyethylene glycol section and polyglutamic acid section is respectively 113 and 30 in compound, and 20mL deionized waters are placed in 25mL reactions
In bottle, pH value is adjusted to 7.4 with 0.1mol/L NaOH, the water of 0.3918g six is added after bi-block copolymer fully dissolves
Iron chloride is closed, adds 0.0675g aniline, lucifuge, the mixed solution that will be obtained to be stirred under the conditions of 30 DEG C after 30min is stirred at room temperature
Mix, carry out oxidative polymerization 24h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is saturating through deionized water
Analysis three days, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 8 is obtained has absorption in the range of 600nm~900nm.
Embodiment 9
By the embedding disconnected polymer of 0.9534g polyethylene glycols glutamic acid two, the polyethylene glycol glutamic acid two is embedding disconnected poly-
The degree of polymerization of polyethylene glycol section and polyglutamic acid section is respectively 113 and 20 in compound, and 10mL deionized waters are placed in 25mL reactions
In bottle, pH value is adjusted to 7.4 with 0.1mol/L NaOH, the water of 0.5763g six is added after bi-block copolymer fully dissolves
Iron chloride is closed, 0.0795g aniline is added after 30min is stirred at room temperature, lucifuge is stirred at 35 DEG C, carries out oxidative polymerization
20h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly at a high speed from
Nano particles of polyaniline is obtained after the heart, deionized water washing.
The present invention is scanned electronic microscope photos, analysis result as shown in figure 4, Fig. 4 is to the Nano particles of polyaniline for obtaining
The scanning electron microscope (SEM) photograph of the Nano particles of polyaniline that the embodiment of the present invention 9 is obtained.The embodiment of the present invention 9 is can be seen that by such as Fig. 4 to make
Nano particles of polyaniline it is spherical in shape be uniformly distributed, diameter is between 60nm~100nm.
The Nano particles of polyaniline that the present invention is obtained carries out ultraviolet-visible spectrum test, its uv absorption spectra such as Fig. 5
Shown, Fig. 5 is the uv absorption spectra of Nano particles of polyaniline prepared by the embodiment of the present invention 9.As seen from Figure 5, originally
The Nano particles of polyaniline that inventive embodiments 9 are obtained has absorption in the range of 600nm~900nm.
By 100 μ g/mL, 150 μ g/mL, 200 μ g/mL, 250 μ g/mL, 300 μ g/mL, 350 μ g/mL, 400 μ g/mL and 450
μ g/mL Nano particles of polyaniline is injected separately into different agar prostheses, and the agar prosthese containing Nano particles of polyaniline is pressed
Photoacoustce signal intensity test test result is carried out according to above-mentioned technical proposal as shown in fig. 6, Fig. 6 is what the embodiment of the present invention 9 was obtained
The photoacoustce signal intensity of Nano particles of polyaniline-concentration relationship figure.As seen from Figure 6, the polyaniline nano grain of different-grain diameter
The photoacoustce signal intensity and concentration of son are respectively provided with preferable linear relationship, and linear equation is y=30.65x+1819.36, R2=
0.9975.Therefore, the light sound intensity according to Nano particles of polyaniline, can carry out the quantitative analysis of photoacoustic imaging.
The Nano particles of polyaniline that the present invention will be obtained carries out photoacoustic signal spectrum test, test knot according to above-mentioned technical proposal
Fruit is as shown in fig. 7, Fig. 7 is the photoacoustic signal spectrogram of the Nano particles of polyaniline that the embodiment of the present invention 9 is obtained.Can be seen by Fig. 7
Go out, Nano particles of polyaniline prepared by the embodiment of the present invention has photoacoustic signal near infrared region, can be used as photoacoustic imaging radiography
Agent is analyzed for photoacoustic imaging.
Embodiment 10
By 1.0253g molecular weight for the glucan and 10mL deionized waters of 20000Da are placed in 25mL reaction bulbs, it is heated to
50 DEG C of stirring 60min are completely dissolved glucan；After dextran solution is cooled to room temperature, 0.3771g ammonium persulfates, room are added
0.0513g aniline is added after the lower stirring 30min of temperature, lucifuge is stirred at 30 DEG C, carries out oxidative polymerization 48h, reaction system
Color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, deionization washing
Nano particles of polyaniline is obtained after washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 10 is obtained has absorption in the range of 600nm~900nm.
Embodiment 11
By 0.8514g molecular weight for the glucan and 9mL deionized waters of 20kDa are placed in 25mL reaction bulbs, 50 are heated to
DEG C stirring 60min be completely dissolved glucan；After dextran solution is cooled to room temperature, it is 30% to add 0.20g mass fractions
Hydrogen peroxide, at room temperature stir 30min after add 0.0852g aniline, lucifuge, at 25 DEG C stir, carry out oxidative polymerization
24h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly at a high speed from
Nano particles of polyaniline is obtained after the heart, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 11 is obtained has absorption in the range of 600nm~900nm.
Embodiment 12
By 0.3528g molecular weight for the glucan and 7mL deionized waters of 40000Da are placed in 25mL reaction bulbs, it is heated to
50 DEG C of stirring 60min are completely dissolved glucan；After dextran solution is cooled to room temperature, the chloride hydrates of 0.6149g six are added
Iron, room temperature adds 0.0706g aniline after being sufficiently stirred for 30min, and lucifuge is stirred at 20 DEG C, carries out oxidative polymerization 60h,
Reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, go
Nano particles of polyaniline is obtained after ion water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 12 is obtained has absorption in the range of 600nm~900nm.
Embodiment 13
By 1.5261g molecular weight for the shitosan and 10mL deionized waters of 4000Da are placed in the reaction bulb of 25mL, dilute salt
To 3.0,60min is stirred at room temperature is completely dissolved shitosan to acid for adjusting pH value, adds 0.3738g ammonium persulfates, stirs at room temperature
0.0763g aniline is added after 30min, lucifuge is stirred at 15 DEG C, carries out oxidative polymerization 72h, and reaction system color is gradually
Deepen, eventually become black, products therefrom is dialysed three days through deionized water, obtained after high speed centrifugation, deionized water washing repeatedly
Nano particles of polyaniline.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 13 is obtained has absorption in the range of 600nm~900nm.
Embodiment 14
Shitosan that 0.6547g molecular weight is 8000 and 13mL deionized waters are placed in 25mL reaction bulbs, watery hydrochloric acid is adjusted
To 3.0,60min is stirred at room temperature is completely dissolved shitosan to section pH value, adds the hydrogen peroxide that 0.24mL mass fractions are 30%, room
0.0655g aniline is added after the lower stirring 30min of temperature, lucifuge is stirred at 25 DEG C, carries out oxidative polymerization 36h, reaction system
Color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, deionization washing
Nano particles of polyaniline is obtained after washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 14 is obtained has absorption in the range of 600nm~900nm.
Embodiment 15
By 0.3482g molecular weight for the shitosan and 11mL deionized waters of 12000Da are placed in 25mL reaction bulbs, watery hydrochloric acid
To 3.0,60min is stirred at room temperature is completely dissolved shitosan to regulation pH value, adds 0.5059g ferric chloride hexahydrates, at room temperature
0.0697g aniline is added after stirring 30min, lucifuge is stirred at 35 DEG C, carries out oxidative polymerization 24h, reaction system color
Gradually deepen, eventually become black, products therefrom is dialysed three days through deionized water, repeatedly after high speed centrifugation, deionized water washing
Obtain Nano particles of polyaniline.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 15 is obtained has absorption in the range of 600nm~900nm.
Embodiment 16
0.7) and 15mL deionized waters by 1.2564g sodium carboxymethylcelluloses, (molecular weight is 90000, and carboxyl substitution value is for
It is placed in the reaction bulb of 25mL, regulation pH value to 8.0,60min is stirred at room temperature is completely dissolved sodium carboxymethylcellulose, adds
0.4380g ferric chloride hexahydrates, 0.0503g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 25 DEG C, carries out oxygen
Change polymerisation 36h, reaction system color is gradually deepened, eventually become black, products therefrom is dialysed three days through deionization, repeatedly
Nano particles of polyaniline is obtained after high speed centrifugation, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 16 is obtained has absorption in the range of 600nm~900nm.
Embodiment 17
By 1.0234g sodium carboxymethylcelluloses, (molecule is 90000, and carboxyl substitution value is 0.7) to be put with 12mL deionized waters
In 25mL reaction bulbs, regulation pH value to 8.0,60min is stirred at room temperature is completely dissolved sodium carboxymethylcellulose；Again to carboxylic first
0.5941g ferric chloride hexahydrates are added in base sodium cellulosate solution, 0.0682g aniline is added after 30min is stirred at room temperature, kept away
Light, is stirred at 25 DEG C, carries out oxidative polymerization 36h, and reaction system color is gradually deepened, and eventually becomes black, and gained is produced
Thing is dialysed three days through deionized water, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 17 is obtained has absorption in the range of 600~900nm.
Embodiment 18
By 0.3358g sodium carboxymethylcelluloses, (molecular weight is 90000, and carboxyl substitution value is 0.7) to be put with 8mL deionized waters
In 25mL reaction bulbs, regulation pH value to 8.0,60min is stirred at room temperature is completely dissolved sodium carboxymethylcellulose, adds thereto
Enter the hydrogen peroxide that 0.23mL mass fractions are 30%, room temperature adds 0.0472g aniline, lucifuge, at 35 DEG C after being sufficiently stirred for 30min
Lower stirring, carries out oxidative polymerization 24h, and reaction system color is gradually deepened, and eventually becomes black, and products therefrom is through deionization
Water is dialysed three days, obtains Nano particles of polyaniline after high speed centrifugation, deionized water washing repeatedly.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 18 is obtained has absorption in the range of 600nm~900nm.
Embodiment 19
0.3541g bovine serum albumin(BSA)s and 12mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room
The lower stirring 30min of temperature is completely dissolved bovine serum albumin(BSA)；To addition 0.5183g ammonium persulfates in bovine serum albumin solution,
0.0705g aniline is added after stirring 30min at room temperature, lucifuge is stirred at 20 DEG C, carries out oxidative polymerization 60h, reactant
It is that color is gradually deepened, eventually becomes black, products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, deionized water
Nano particles of polyaniline is obtained after washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 19 is obtained has absorption in the range of 600nm~900nm.
Embodiment 20
0.8573g bovine serum albumin(BSA)s and 11mL deionized waters are placed in the reaction bulb of 25mL, pH value is adjusted to 7.4,
Stirring 30min is completely dissolved bovine serum albumin(BSA) at room temperature；To addition 0.42mL matter in the bovine serum albumin solution for obtaining
Amount fraction is 30% hydrogen peroxide, and 0.0857g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 30 DEG C, carried out
Oxidative polymerization 36h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water,
Repeatedly Nano particles of polyaniline is obtained after high speed centrifugation, deionized water washing.
The Nano particles of polyaniline that the present invention is obtained carries out ultraviolet-visible spectrum test, its ultra-violet absorption spectrum such as Fig. 8 institutes
Show, Fig. 8 is the uv absorption spectra of Nano particles of polyaniline prepared by the embodiment of the present invention 20.As seen from Figure 8, this hair
The Nano particles of polyaniline that bright embodiment 20 is obtained has absorption in the range of 600nm~900nm.
The Nano particles of polyaniline that the present invention will be obtained carries out photoacoustic signal spectrum test, test knot according to above-mentioned technical proposal
Fruit is as shown in figure 9, Fig. 9 is the photoacoustic signal figure of the Nano particles of polyaniline that the embodiment of the present invention 20 is obtained.Can be seen by Fig. 9
Go out, Nano particles of polyaniline prepared by the embodiment of the present invention 20 has photoacoustic signal near infrared region, can be made as photoacoustic imaging
Shadow agent is analyzed for photoacoustic imaging.
By 100 μ g/mL, 200 μ g/mL, 300 μ g/mL, 400 μ g/mL, 500 μ g/mL, 600 μ g/mL, 700 μ g/mL and 800
μ g/mL Nano particles of polyaniline is injected separately into different agar prostheses, and the present invention will obtain containing Nano particles of polyaniline
Agar prosthese carries out photoacoustce signal intensity test test result as shown in Figure 10 according to above-mentioned technical proposal, and Figure 10 is real for the present invention
Apply the photoacoustce signal intensity-concentration relationship figure of the Nano particles of polyaniline that example 20 is obtained.As seen from Figure 10, different-grain diameter
The photoacoustce signal intensity and concentration of Nano particles of polyaniline are respectively provided with preferable linear relationship, and linear equation is y=37.69x+
1647.39, R2=0.9987.Therefore, the light sound intensity according to Nano particles of polyaniline, can carry out quantitative point of photoacoustic imaging
Analysis.
The present invention carries out the test of the signal intensity of different wave length to the Nano particles of polyaniline for obtaining, and test result is as schemed
Shown in 11, Figure 11 is the pcolor of the signal intensity of the different wave length of the Nano particles of polyaniline that the embodiment of the present invention 20 is obtained.
As seen from Figure 11, the Nano particles of polyaniline that the embodiment of the present invention 20 is obtained in 680nm~900nm wave-length coverages, light
Acoustical signal is presented the trend for gradually weakening, and is consistent with the quantitative result of Fig. 9.
Embodiment 21
0.9871g bovine serum albumin(BSA)s and 16mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room
The lower stirring 30min of temperature is completely dissolved bovine serum albumin(BSA), to the addition water of 0.5002g six in the bovine serum albumin solution for obtaining
Iron chloride is closed, 0.0493g aniline monomers are added after 30min is stirred at room temperature, lucifuge is stirred at 25 DEG C, carries out oxidation polymerization
Reaction 48h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly at a high speed
Nano particles of polyaniline is obtained after centrifugation, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 21 is obtained has absorption in the range of 600nm~900nm.
Embodiment 22
0.5214g human serum albumins and 10mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room
The lower stirring 30min of temperature is completely dissolved human serum albumins, to addition 0.7667g over cures in the human serum albumin solution for obtaining
Sour ammonium, 0.1043g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 15 DEG C, carries out oxidative polymerization 72h,
Reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, go
Nano particles of polyaniline is obtained after ion water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 22 is obtained has absorption in the range of 600nm~900nm.
Embodiment 23
0.6719g human serum albumins and 8mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room temperature
Lower stirring 30min is completely dissolved human serum albumins, divides to 0.33mL mass is added in the human serum albumin solution for obtaining
Number is 30% hydrogen peroxide, and 0.0672g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 35 DEG C, aoxidized
Polymerisation 48h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly
Nano particles of polyaniline is obtained after high speed centrifugation, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 23 is obtained has absorption in the range of 600nm~900nm.
Embodiment 24
0.8639g human serum albumins and 9mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room temperature
Lower stirring 30min is completely dissolved human serum albumins, to the addition hydrations of 0.5016g six in the human serum albumin solution for obtaining
Iron chloride, 0.0576g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 25 DEG C, carries out oxidative polymerization
48h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly at a high speed from
Nano particles of polyaniline is obtained after the heart, deionized water washing.
The present invention is scanned electronic microscope photos to the Nano particles of polyaniline for obtaining, and analysis result is as shown in figure 12, Figure 12
It is the scanning electron microscope (SEM) photograph of the Nano particles of polyaniline that the embodiment of the present invention 24 is obtained.Implementation of the present invention can be seen that by such as Figure 12
Nano particles of polyaniline obtained in example 24 is spherical in shape to be uniformly distributed, and diameter is between 35nm~70nm.
The Nano particles of polyaniline that the present invention is obtained carries out ultraviolet-visible spectrum test, its ultra-violet absorption spectrum such as Figure 13
Shown, Figure 13 is the uv absorption spectra of Nano particles of polyaniline prepared by the embodiment of the present invention 24.As seen from Figure 13,
The Nano particles of polyaniline that the embodiment of the present invention 24 is obtained has absorption in the range of 600~900nm.
The present invention is by 25 μ g/mL, 50 μ g/mL, 100 μ g/mL, 150 μ g/mL, 200 μ g/mL, 250 μ g/mL and 300 μ g/mL
Nano particles of polyaniline be injected separately into agar prosthese, by the agar prosthese containing Nano particles of polyaniline according to above-mentioned technology
Scheme carries out photoacoustce signal intensity test test result as shown in figure 14, and Figure 14 is that the polyaniline that the embodiment of the present invention 24 is obtained is received
The photoacoustce signal intensity of rice corpuscles-concentration relationship figure.As seen from Figure 14, the optoacoustic of the Nano particles of polyaniline of different-grain diameter
Signal intensity and concentration are respectively provided with preferable linear relationship, and linear equation is y=55.63x+1738.62, R2=0.9964.Cause
This, the light sound intensity according to Nano particles of polyaniline can carry out the quantitative analysis of photoacoustic imaging.
The Nano particles of polyaniline that the present invention will be obtained carries out photoacoustic signal spectrum test, test knot according to above-mentioned technical proposal
As shown in figure 15, Figure 15 is the photoacoustic signal spectrogram of the Nano particles of polyaniline that the embodiment of the present invention 24 is obtained to fruit.Can by Figure 15
To find out, Nano particles of polyaniline prepared by the embodiment of the present invention has photoacoustic signal near infrared region, can be used as photoacoustic imaging
Contrast agent is analyzed for photoacoustic imaging.
The Nano particles of polyaniline that the present invention will be obtained carries out optoacoustic contrasting effects test according to above-mentioned technical proposal, tests
As shown in figure 16, Figure 16 is the head of the Nano particles of polyaniline in male Balb/C nude mices of the preparation of the embodiment of the present invention 24 to result
Subcutaneous optoacoustic contrasting effects figure, wherein, solid line is the tomoscan profile of animal, and the signified dotted line inside of arrow is polyaniline
The photoacoustic imaging radiography figure of nano-particle.As seen from Figure 16, the present invention implements 24 Nano particles of polyaniline for preparing has
Good contrasting effects, image clearly, contrast is high, is highly suitable for photoacoustic imaging visualization.
The Nano particles of polyaniline that the present invention will be obtained carries out optoacoustic contrasting effects test according to above-mentioned technical proposal, tests
As shown in figure 17, Figure 17 is the enteron aisle of the Nano particles of polyaniline in male Balb/C nude mices of the preparation of the embodiment of the present invention 24 to result
Optoacoustic contrasting effects figure, wherein, solid line is the tomoscan profile of animal, and the signified dotted line inside of arrow is polyaniline nano
Photoacoustic imaging radiography figure of the particle at mouse intestinal position.As seen from Figure 16, the polyanilines that prepared by present invention implementation 24 are received
Rice corpuscles has good contrasting effects to digestion stage property, and image clearly, contrast is high, is highly suitable for photoacoustic imaging visualization
Embodiment 25
0.3258g lysozymes and 10mL deionized waters are placed in 25mL reaction bulbs, regulation pH value is stirred at room temperature to 7.4
Mixing 30min is completely dissolved lysozyme, to 0.4793g ammonium persulfates are added in the lysozyme soln for obtaining, stirs at room temperature
0.0652g aniline is added after 30min, lucifuge is stirred at 15 DEG C, carries out oxidative polymerization 72h, and reaction system color is gradually
Deepen, eventually become black, products therefrom is dialysed three days through deionized water, obtained after high speed centrifugation, deionized water washing repeatedly
Nano particles of polyaniline.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 25 is obtained has absorption in the range of 600nm~900nm.
Embodiment 26
0.5938g lysozymes and 11mL deionized waters are placed in 25mL reaction bulbs, regulation pH value is stirred at room temperature to 7.4
Mixing 30min is completely dissolved lysozyme；To the hydrogen peroxide that addition 0.22mL mass fractions in the lysozyme soln for obtaining are 30%,
0.0594g aniline is added after stirring 30min at room temperature, lucifuge is stirred at 25 DEG C, carries out oxidative polymerization 60h, reactant
It is that color is gradually deepened, eventually becomes black, products therefrom is dialysed three days through deionized water, repeatedly high speed centrifugation, deionized water
Nano particles of polyaniline is obtained after washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 26 is obtained has absorption in the range of 600nm~900nm.
Embodiment 27
0.9756g human serum albumins and 9mL deionized waters are placed in 25mL reaction bulbs, regulation pH value to 7.4, room temperature
Lower stirring 30min is completely dissolved human serum albumins, to the addition hydrations of 0.3549g six in the human serum albumin solution for obtaining
Iron chloride, 0.0489g aniline is added after 30min is stirred at room temperature, and lucifuge is stirred at 35 DEG C, carries out oxidative polymerization
24h, reaction system color is gradually deepened, and eventually becomes black, and products therefrom is dialysed three days through deionized water, repeatedly at a high speed from
Nano particles of polyaniline is obtained after the heart, deionized water washing.
The present invention carries out ultraviolet-visible spectrum test to the Nano particles of polyaniline for obtaining, and test result shows：The present invention
The Nano particles of polyaniline that embodiment 27 is obtained has absorption in the range of 600nm~900nm.
Embodiment 28
By 50 normal male Balb/C mouses (body weight 18g~20g) raised, 5 groups are randomly divided into, every group 10, divided
Wei not be injected intravenously physiological saline, embodiment 3 prepare Nano particles of polyaniline, embodiment 9 prepare Nano particles of polyaniline,
Nano particles of polyaniline prepared by Nano particles of polyaniline and embodiment 24 prepared by embodiment 20, on the basis of rabbit body weight,
Injection volume is 5mg kg-1, the continuous two weeks body weight of monitoring experimental animal.
Experimental result is confirmed, without animal dead in two weeks；After 14 days, every group randomly select 3 carry out the heart, liver, spleen, lung,
The pathology slice analysis of kidney, brain, as a result, it was confirmed that compared with control group (injecting normal saline), injection embodiment 3 is not observed
Nano particles of polyaniline, the Nano particles of polyaniline of the preparation of embodiment 20 prepared by the Nano particles of polyaniline of preparation, embodiment 9
The organ of the mouse of the Nano particles of polyaniline prepared with embodiment 24 has obvious pathology to damage.
Figure 18 is polyaniline nano prepared by injecting normal saline, embodiment 3, embodiment 9, embodiment 20 and embodiment 24
The body weight versus time curve figure of the mouse of particle, wherein, curve A, curve B, curve C, curve D and curve E are followed successively by
Nano particles of polyaniline, Nano particles of polyaniline, the embodiment 20 of the preparation of embodiment 9 prepared by injecting normal saline, embodiment 3
The changes of weight of the mouse of Nano particles of polyaniline prepared by the Nano particles of polyaniline of preparation, embodiment 24.Can be with by Figure 18
Find out, without obvious changes of weight, obtained Nano particles of polyaniline has good the mouse of all experimental groups to mouse
Biocompatibility, can be as a kind of safe photoacoustic imaging contrast agent.
Comparative example
The present invention uses 10ugmL-1Graphene oxide carries out ultra-violet absorption spectrum test, and test result is shown in Figure 19, Figure 19
For 10ugmL prepared by the graphene oxide and embodiment 1 of comparative example-1The ultra-violet absorption spectrum contrast of Nano particles of polyaniline
Figure, wherein, curve A is the uv absorption spectra of Nano particles of polyaniline prepared by embodiment 1, and curve B is the oxygen of comparative example
The uv absorption spectra of graphite alkene.
As seen from Figure 19, the Nano particles of polyaniline that prepared by the present invention has stronger UV absorption.
As seen from the above embodiment, the invention provides a kind of preparation method of Nano particles of polyaniline, including following step
Suddenly：In the presence of template and oxidant, aniline is carried out into oxidative polymerization in water, obtain Nano particles of polyaniline；
The template includes polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer, the poly- paddy of polyethylene glycol-b-
One or more in propylhomoserin bi-block copolymer, poly- polysaccharide and protein.The present invention is with polyvinyl alcohol, polyethylene glycol third
In glycol-polyethylene glycol triblock polymer, polyethylene glycol-b- polyglutamic acids bi-block copolymer, poly- polysaccharide and protein
There is stronger absorption near infrared region, there is good as template, obtained Nano particles of polyaniline for one or more
Imaging effect.Test result indicate that：The photoacoustic signal of the Nano particles of polyaniline that the preparation method that the present invention is provided is prepared
By force, photoacoustic imaging contrast is high, image clearly.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of Nano particles of polyaniline, comprises the following steps：
In the presence of template and oxidant, aniline is carried out into oxidative polymerization in water, obtain Nano particles of polyaniline；
The template include polyvinyl alcohol, polyethylene glycol propane diols-polyethylene glycol triblock polymer and polyethylene glycol-
One or more in polyglutamic acid bi-block copolymer；
The template and water are first mixed, template solution is obtained；
When the template is polyvinyl alcohol or polyethylene glycol propane diols-polyethylene glycol triblock polymer, not adjusting template
The pH of agent solution；
When the template is polyethylene glycol glutamic acid bi-block copolymer, template solution 0.1mol/L NaOH
Solution is adjusted to pH value=7.4.
2. preparation method according to claim 1, it is characterised in that the oxidant includes ferric ion, peroxidating
One or more in hydrogen and ammonium persulfate.
3. preparation method according to claim 1, it is characterised in that the temperature of the oxidative polymerization is 15 DEG C ~ 35
℃。
4. preparation method according to claim 1, it is characterised in that the time of the oxidative polymerization is 12 h ~ 72
h。
5. preparation method according to claim 1, it is characterised in that the mass ratio of the template and aniline is 3 ~ 30:
1。
6. preparation method according to claim 1, it is characterised in that the mol ratio of the oxidant and aniline is 0.5 ~
20:1。
7. the Nano particles of polyaniline that preparation method described in claim 1 ~ 6 any one is prepared is used as photoacoustic imaging radiography
The application of agent.
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| CN201410177564.2A CN103936985B (en) | 2014-04-29 | 2014-04-29 | A kind of preparation method and applications of Nano particles of polyaniline |
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| CN105535973B (en) * | 2016-01-25 | 2018-10-19 | 天津大学 | For the phosphatide of photoacoustic imaging and/or photo-thermal therapy-polyaniline nano grain and preparation method |
| CN105561952A (en) * | 2016-01-29 | 2016-05-11 | 南京理工大学 | Multifunctional material PANI-CMC-Fe3O4And application in treatment of printing and dyeing wastewater |
| CN105561953A (en) * | 2016-01-29 | 2016-05-11 | 南京理工大学 | Composite adsorbent PANI-CMC and application thereof in dye wastewater treatment |
| CN107674202B (en) * | 2017-10-14 | 2020-04-28 | 郑州炜盛电子科技有限公司 | Protonic acid doped polyaniline material, room-temperature ammonia gas sensor and preparation method thereof |
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| US6429259B1 (en) * | 2000-04-03 | 2002-08-06 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Water soluble polymeric complex comprising a conducting polymer and a biopolymer |
| JP2006241334A (en) * | 2005-03-04 | 2006-09-14 | Japan Science & Technology Agency | Spiral electroconductive polymer nano wire/polysaccharide composite |
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| JPH02240139A (en) * | 1989-03-13 | 1990-09-25 | Fuji Photo Film Co Ltd | Production of aqueous polyaniline dispersion and conductive polymer material prepared by using same |
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| US4898921A (en) * | 1987-06-03 | 1990-02-06 | Montclair State College | Conducting polymer films, method of manufacture and applications therefor |
| US6429259B1 (en) * | 2000-04-03 | 2002-08-06 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Water soluble polymeric complex comprising a conducting polymer and a biopolymer |
| JP2006241334A (en) * | 2005-03-04 | 2006-09-14 | Japan Science & Technology Agency | Spiral electroconductive polymer nano wire/polysaccharide composite |
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