CN110038127A - Polypyrrole/gold composite hollow micro-sphere structure material preparation method and applications - Google Patents
Polypyrrole/gold composite hollow micro-sphere structure material preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of polypyrrole/gold composite hollow micro-sphere structure material preparation method, the step of method in contain: S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, silica/polypyrrole complex microsphere is obtained；S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, and golden shell is coated on the silica/polypyrrole complex microsphere surface, the silica in silica/polypyrrole complex microsphere of cladding golden shell is melted again, obtains polypyrrole/gold composite hollow micro-sphere structure material.The material of method preparation of the invention has good biocompatibility and biological metabolism, and imaging function is good, photothermal conversion efficiency is high, light and heat stability, has Drug loading capacity, and preparation method is simple to operation, and preparation efficiency is high.
Description
Technical field
The present invention relates to a kind of polypyrrole/gold composite hollow micro-sphere structure material preparation method and applications.
Background technique
Currently, cancer has become one of most serious disease, the conventional method for the treatment of cancer includes surgical operation, radiates and control
Treatment and chemotherapy etc., these therapies have common shortcoming, normal cell are also killed while killing cancer cell, to siberian crabapple
System has certain destruction, and adverse reaction is very big.Photo-thermal therapy technology is a kind of minimally invasive treatment technology, using with light absorption energy
The optothermal material of power converts thermal energy for near-infrared laser luminous energy to killing cancer cell, the side effect compared with classic chemotherapy radiotherapy
It is small, treatment specificity it is good.The key of photo-thermal therapy technology is exploitation bio-compatible, efficient, stable optical-thermal conversion material, at present
Studying more optical-thermal conversion material has noble metal optical-thermal conversion material, carbon base optic hot-cast socket material and semiconductor light hot material.
Wherein, noble metal optical-thermal conversion material is expensive, and after temperature raising, pattern easily changes, and influences its photo-thermal
The stability of energy；The absorption coefficient of light of carbon-based optical-thermal conversion material is lower, and carbon material preparation and functionalization condition compared with
Just to carve；Semiconductor light hot material contains heavy metal ion, and dissolution toxicity problem in vivo is difficult to be resolved.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of existing technologies, provide a kind of polypyrrole/gold it is compound in
The material of the preparation method of empty micro-sphere structure material, the method preparation has good biocompatibility and biological metabolism, at
As better function, photothermal conversion efficiency height, light and heat stability, there is Drug loading capacity, and preparation method is simple to operation, preparation
It is high-efficient.
In order to solve the above-mentioned technical problem, the technical scheme is that a kind of polypyrrole/gold composite hollow micro-sphere structure
Contain in the step of preparation method of material, method:
S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；
S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, it is multiple to obtain silica/polypyrrole
Close microballoon；
S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, and in the dioxy
SiClx/polypyrrole complex microsphere surface coats golden shell, then melts in the silica/polypyrrole complex microsphere for coating golden shell
Silica obtains polypyrrole/gold composite hollow micro-sphere structure material.
Further provide for a kind of preparation method of monodispersive silica microballoon, in step sl, monodispersity dioxy
The preparation step of SiClx microballoon is as follows:
The water, ammonium hydroxide and dehydrated alcohol of proper ratio are mixed and stirred for；
Appropriate ethyl orthosilicate is added and stirs；
Be centrifugated and clean, dry after obtain monodispersive silica microballoon.
Further, the water, ammonium hydroxide and dehydrated alcohol take 1 ~ 3mL, 3 ~ 10mL and 50 ~ 100mL respectively；And/or stirring
Mode is magnetic agitation, and when stirring is 20 ~ 60 minutes a length of, and stirring rate is 100 ~ 400 revs/min；And/or solution temperature is 25
~60℃；And/or be added ethyl orthosilicate be 1 ~ 5mL, be added ethyl orthosilicate after stir when it is 8 ~ 16 hours a length of.
A kind of specific method with polyvinyl pyrrolidon modified monodispersive silica microballoon is further provided for, in step
In rapid S1, with polyvinyl pyrrolidon modified monodispersive silica microballoon the step of is as follows:
Take appropriate monodispersive silica microballoon ultrasonic disperse into dehydrated alcohol；
Appropriate polyvinylpyrrolidone is added, is stirred after ultrasonic treatment；
Centrifuge separation, then washes and dries, obtains the monodispersive silica microballoon of modified.
Further, the monodispersive silica microballoon is 0.05 ~ 0.2g, and the dehydrated alcohol is 20mL；And/or add
The polyvinylpyrrolidone entered is 0.1 ~ 2g, and when 10 ~ 30 minutes a length of, the stirring being ultrasonically treated after polyvinylpyrrolidone is added
Shi Changwei 12 ~ 24 hours, solution temperature was 30 ~ 50 DEG C.
A kind of specific method by polypyrrole package to monodispersive silica microsphere surface is further provided for, in step
In S2, by polypyrrole package to monodispersive silica microsphere surface the step of is as follows:
It will be put into appropriate dehydrated alcohol by the monodispersive silica microballoon of polyvinyl pyrrolidon modified mistake and at ultrasound
Reason；
It is ultrasonically treated after appropriate pyrroles is added；
It is stirred after appropriate ammonium persulfate solution is added；
Then centrifuge separation cleans, is dry, obtaining silica/polypyrrole complex microsphere.
Further, the monodispersive silica microballoon is 0.05 ~ 0.2g, and the dehydrated alcohol is 150 mL, ultrasound
Processing when it is 10 ~ 30 minutes a length of；And/or be added pyrroles be 0.02 ~ 0.2mL, be added pyrroles after be ultrasonically treated when a length of 5
~ 10 minutes；And/or the ammonium persulfate solution being added is 2 ~ 10mL, mass-volume concentration 0.06g/mL, and ammonium persulfate is added
Stirred after solution when it is 8 ~ 24 hours a length of；And/or the temperature of solution is 15 ~ 30 DEG C.
Further, specific step is as follows by step S3:
By appropriate silica/polypyrrole complex microsphere and appropriate polyvinylpyrrolidone ultrasonic disperse in appropriate amount of deionized water
In；
Appropriate chlorauric acid solution is added and stirs；
The sodium borohydride solution of proper amount of fresh configuration and stirring is added, obtains dispersion liquid；
Appropriate above-mentioned dispersion liquid is taken, appropriate sodium hydroxide solution is added, is stood after oscillation treatment；
It is dried after centrifuge separation, obtains polypyrrole/gold composite hollow micro-sphere structure material.
Further, by silica/polypyrrole complex microsphere ultrasonic disperse in 50mL deionized water, in obtained solution
Silica/polypyrrole complex microsphere mass-volume concentration is 0.5 ~ 5mg/mL；The polyvinylpyrrolidone of addition be 20 ~
80mg；And/or the chlorauric acid solution being added is 0.5 ~ 3mL, molar concentration is 0.02 ~ 0.05mol/L, and chlorauric acid solution is added
It is 3 ~ 5 hours a length of when rear stirring；And/or the sodium borohydride solution being added is 5 ~ 9mL, molar concentration is 0.02 ~ 0.1
Mol/L, be added sodium borohydride solution after stir when it is 3 ~ 5 hours a length of；And/or take the dispersion liquid 30mL, the hydrogen-oxygen of addition
Change sodium solution is 10 ~ 30mL, and molar concentration is 0.5 ~ 2 mol/L, when 5 ~ 10 minutes a length of, the duration of standing of oscillation treatment
It is 4 ~ 10 hours；And/or the rate of centrifugal treating is 8000 revs/min, when a length of 5 min of centrifugal treating；And/or drying temperature
Degree is 40 ~ 60 DEG C.
The present invention also provides a kind of applications of polypyrrole/gold composite hollow micro-sphere structure material, by above-mentioned preparation method
The polypyrrole being prepared/gold composite hollow micro-sphere structure material is applied in photo-thermal therapy technology as optical-thermal conversion material.
After above-mentioned technical proposal, first with polyvinyl pyrrolidon modified monodispersive silica microballoon, then
By polypyrrole package to the surface of monodispersive silica microballoon, silica/polypyrrole complex microsphere is obtained, then with poly- second
Alkene pyrrolidone modifies the polypyrrole in the silica/polypyrrole complex microsphere, and multiple in the silica/polypyrrole
The surface for closing microballoon coats golden shell, then melts the silica in the silica/polypyrrole complex microsphere for coating golden shell, obtains
Polypyrrole/gold composite hollow micro-sphere structure material.Polypyrrole/gold composite hollow micro-sphere structure material of the method preparation has good
Good biocompatibility and biological metabolism, the structure that imaging function is good, light and heat stability, photothermal conversion efficiency are high, hollow
Drug loading capacity is made it have, photothermal conversion experiment shows using power density to be 0.5W/cm2980nm near infrared light exciter
Polypyrrole/gold composite hollow micro-sphere structure material dispersion liquid that mass-volume concentration is 0.15mg/mL is irradiated, it is molten after ten minutes
The temperature of liquid rises to 50.1 DEG C from 25.0 DEG C, and this preparation method is simple to operation, and preparation efficiency is high.
Detailed description of the invention
Fig. 1 is silica/polypyrrole microballoon grain size distribution；
Fig. 2 is silica/polypyrrole/gold microsphere grain size distribution；
Fig. 3 is polypyrrole/gold tiny balloon grain size distribution；
Fig. 4 is the ultraviolet-visible absorption spectroscopy that silica/polypyrrole and silica/polypyrrole/gold microsphere disperse solution；
Fig. 5 is temperature variation after the irradiation of various sample 980nm near infrared lights.
Specific embodiment
In order that the present invention can be more clearly and readily understood, right below according to specific embodiment and in conjunction with attached drawing
The present invention is described in further detail.
Embodiment one
Contain in a kind of the step of preparation method of polypyrrole/gold composite hollow micro-sphere structure material, method:
S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；To improve monodispersive silica microballoon
Hydrophily and biocompatibility；
S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, it is multiple to obtain silica/polypyrrole
Close microballoon；
S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, to prevent polypyrrole
Nano particle structure collapses, and coats golden shell on the silica/polypyrrole complex microsphere surface, then melt cladding golden shell
Silica/polypyrrole complex microsphere in silica, obtain polypyrrole/gold composite hollow micro-sphere structure material.
In step sl, the preparation step of monodispersive silica microballoon can be with are as follows:
The water, ammonium hydroxide and dehydrated alcohol of proper ratio are mixed and stirred for；
Appropriate ethyl orthosilicate is added and stirs；
Be centrifugated and clean, dry after obtain monodispersive silica microballoon.
Specifically, the water, ammonium hydroxide and dehydrated alcohol can take 1 ~ 3mL, 3 ~ 10mL and 50 ~ 100mL, solution temperature respectively
Can be 25 ~ 60 DEG C, the mode of stirring is magnetic agitation, and stirring duration can be 20 ~ 60 minutes, stirring rate can for 100 ~
400 revs/min；The ethyl orthosilicate of addition can be 1 ~ 5mL, and the duration stirred after ethyl orthosilicate is added can be small for 8 ~ 16
When, in the present embodiment, water, ammonium hydroxide and dehydrated alcohol take 2mL, 6mL and 75mL respectively, and solution temperature is 40 DEG C, stir duration
It is 40 minutes, stirring rate is 250 revs/min, and the ethyl orthosilicate of addition is 3mL, and stirring 12 is small after ethyl orthosilicate is added
When, the number of cleaning is 3 times.
In step sl, with can be with the step of polyvinyl pyrrolidon modified monodispersive silica microballoon are as follows:
Take appropriate monodispersive silica microballoon ultrasonic disperse into dehydrated alcohol；
Appropriate polyvinylpyrrolidone is added, is stirred after ultrasonic treatment；
Centrifuge separation, then washes and dries, obtains the monodispersive silica microballoon of modified.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be
20mL；The polyvinylpyrrolidone of addition can be 0.1 ~ 2g, and the duration that is ultrasonically treated is added after polyvinylpyrrolidone can be with
It is 10 ~ 30 minutes, stirring duration can be 12 ~ 24 hours, and solution temperature can be 30 ~ 50 DEG C.In the present embodiment, the list
Dispersed silica microballoon is 0.1g, and the polyvinylpyrrolidone of addition is 1g, after addition polyvinylpyrrolidone at ultrasound
Reason when it is 20 minutes a length of, when stirring, is 18 hours a length of, and solution temperature is 40 DEG C, when cleaning three times with washes of absolute alcohol.
In step s 2, the step of polypyrrole being wrapped up to monodispersive silica microsphere surface can be with are as follows:
It will be put into appropriate dehydrated alcohol by the monodispersive silica microballoon of polyvinyl pyrrolidon modified mistake and at ultrasound
Reason；
It is ultrasonically treated after appropriate pyrroles is added；
It is stirred after appropriate ammonium persulfate solution is added；
Then centrifuge separation cleans, is dry, obtaining silica/polypyrrole complex microsphere.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be 150
ML, the duration of ultrasonic treatment can be 10 ~ 30 minutes；The pyrroles of addition can be 0.02 ~ 0.2mL, after addition pyrroles at ultrasound
The duration of reason can be 5 ~ 10 minutes；The ammonium persulfate solution of addition can be 2 ~ 10mL, and mass-volume concentration can be
0.06g/mL, the duration stirred after ammonium persulfate solution, which is added, to be 8 ~ 24 hours, and the temperature of solution can be 15 ~ 30 DEG C,
It is cleaned multiple times when cleaning with dehydrated alcohol and water, is then transferred in air dry oven dry, the monodispersive silica
The partial size of microballoon can be 400nm or so.In the present embodiment, the monodispersive silica microballoon be 0.1g, ultrasound at
Reason when it is 20 minutes a length of, the pyrroles of addition is 0.1mL, be added after pyrroles be ultrasonically treated when it is 7 minutes a length of；The over cure of addition
Acid ammonium solution is 5mL, be added after ammonium persulfate solution stir when it is 18 hours a length of, the temperature of solution is 22 DEG C.
The specific steps of step S3 can be with are as follows:
By appropriate silica/polypyrrole complex microsphere and appropriate polyvinylpyrrolidone ultrasonic disperse in appropriate amount of deionized water
In；
Appropriate chlorauric acid solution is added and stirs；
The sodium borohydride solution of proper amount of fresh configuration and stirring is added, obtains dispersion liquid；
Appropriate above-mentioned dispersion liquid is taken, appropriate sodium hydroxide solution is added, is stood after oscillation treatment；
It is dried after centrifuge separation, obtains polypyrrole/gold composite hollow micro-sphere structure material.
Specifically, by silica/polypyrrole complex microsphere ultrasonic disperse in 50mL deionized water, in obtained solution
Silica/polypyrrole complex microsphere mass-volume concentration can be 0.5 ~ 5mg/mL；The polyvinylpyrrolidone of addition can
Think 20 ~ 80mg；The chlorauric acid solution of addition can be 0.5 ~ 3mL, and molar concentration can be 0.02 ~ 0.05mol/L, be added
Stirring duration after chlorauric acid solution can be 3 ~ 5 hours；The sodium borohydride solution of addition can be 5 ~ 9mL, molar concentration
It can be 0.02 ~ 0.1 mol/L, the duration stirred after sodium borohydride solution, which is added, to be 3 ~ 5 hours；Take the dispersion liquid
30mL, the sodium hydroxide solution of addition can be 10 ~ 30mL, and molar concentration can be 0.5 ~ 2 mol/L, oscillation treatment when
Length can be 5 ~ 10 minutes, and the duration of standing can be 4 ~ 10 hours, and the rate of centrifugal treating can be 8000 revs/min, from
The duration of heart processing can be 5 min, and drying temperature can be 40 ~ 60 DEG C.In the present embodiment, by silica/polypyrrole
Complex microsphere ultrasonic disperse is in 50mL deionized water, silica/polypyrrole complex microsphere mass body in obtained solution
Product concentration is 2.5mg/mL；The polyvinylpyrrolidone of addition is 50mg；The chlorauric acid solution of addition is 1.5mL, mole dense
Degree is 0.03mol/L, is stirred 4 hours after chlorauric acid solution is added；The sodium borohydride solution of addition is 7.5mL, molar concentration
For 0.06 mol/L, stirred 4 hours after sodium borohydride solution is added；Take the dispersion liquid 30mL, the sodium hydroxide solution of addition
For 20mL, molar concentration is 1 mol/L, oscillation treatment 7 minutes, stands 6 hours, the rate of centrifugal treating is 8000 revs/min
Clock, when a length of 5 min of centrifugal treating, drying temperature are 50 DEG C.
Embodiment two
Contain in a kind of the step of preparation method of polypyrrole/gold composite hollow micro-sphere structure material, method:
S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；To improve monodispersive silica microballoon
Hydrophily and biocompatibility；
S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, it is multiple to obtain silica/polypyrrole
Close microballoon；
S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, to prevent polypyrrole
Nano particle structure collapses, and coats golden shell on the silica/polypyrrole complex microsphere surface, then melt cladding golden shell
Silica/polypyrrole complex microsphere in silica, obtain polypyrrole/gold composite hollow micro-sphere structure material.
In step sl, the preparation step of monodispersive silica microballoon can be with are as follows:
The water, ammonium hydroxide and dehydrated alcohol of proper ratio are mixed and stirred for；
Appropriate ethyl orthosilicate is added and stirs；
Be centrifugated and clean, dry after obtain monodispersive silica microballoon.
Specifically, the water, ammonium hydroxide and dehydrated alcohol can take 1 ~ 3mL, 3 ~ 10mL and 50 ~ 100mL, solution temperature respectively
Can be 25 ~ 60 DEG C, the mode of stirring is magnetic agitation, and stirring duration can be 20 ~ 60 minutes, stirring rate can for 100 ~
400 revs/min；The ethyl orthosilicate of addition can be 1 ~ 5mL, and the duration stirred after ethyl orthosilicate is added can be small for 8 ~ 16
When, in the present embodiment, water, ammonium hydroxide and dehydrated alcohol take 1mL, 3mL and 50mL respectively, and solution temperature is 25 DEG C, stir duration
It is 20 minutes, stirring rate is 100 revs/min, and the ethyl orthosilicate of addition is 1mL, and stirring 8 is small after ethyl orthosilicate is added
When, the number of cleaning is 3 times.
In step sl, with can be with the step of polyvinyl pyrrolidon modified monodispersive silica microballoon are as follows:
Take appropriate monodispersive silica microballoon ultrasonic disperse into dehydrated alcohol；
Appropriate polyvinylpyrrolidone is added, is stirred after ultrasonic treatment；
Centrifuge separation, then washes and dries, obtains the monodispersive silica microballoon of modified.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be
20mL；The polyvinylpyrrolidone of addition can be 0.1 ~ 2g, and the duration that is ultrasonically treated is added after polyvinylpyrrolidone can be with
It is 10 ~ 30 minutes, stirring duration can be 12 ~ 24 hours, and solution temperature can be 30 ~ 50 DEG C.In the present embodiment, the list
Dispersed silica microballoon is 0.05g, and the polyvinylpyrrolidone of addition is 0.2g, and ultrasound after polyvinylpyrrolidone is added
Processing when it is 10 minutes a length of, when stirring, is 12 hours a length of, and solution temperature is 30 DEG C, when cleaning three times with washes of absolute alcohol.
In step s 2, the step of polypyrrole being wrapped up to monodispersive silica microsphere surface can be with are as follows:
It will be put into appropriate dehydrated alcohol by the monodispersive silica microballoon of polyvinyl pyrrolidon modified mistake and at ultrasound
Reason；
It is ultrasonically treated after appropriate pyrroles is added；
It is stirred after appropriate ammonium persulfate solution is added；
Then centrifuge separation cleans, is dry, obtaining silica/polypyrrole complex microsphere.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be 150
ML, the duration of ultrasonic treatment can be 10 ~ 30 minutes；The pyrroles of addition can be 0.02 ~ 0.2mL, after addition pyrroles at ultrasound
The duration of reason can be 5 ~ 10 minutes；The ammonium persulfate solution of addition can be 2 ~ 10mL, and mass-volume concentration can be
0.06g/mL, the duration stirred after ammonium persulfate solution, which is added, to be 8 ~ 24 hours, and the temperature of solution can be 15 ~ 30 DEG C,
It is cleaned multiple times when cleaning with dehydrated alcohol and water, is then transferred in air dry oven dry, the monodispersive silica
The partial size of microballoon can be 400nm or so.In the present embodiment, the monodispersive silica microballoon be 0.05g, ultrasound at
Reason when it is 10 minutes a length of, the pyrroles of addition is 0.02mL, be added after pyrroles be ultrasonically treated when it is 5 minutes a length of；The mistake of addition
Ammonium sulfate is 2mL, be added after ammonium persulfate solution stir when it is 8 hours a length of, the temperature of solution is 15 DEG C.
The specific steps of step S3 can be with are as follows:
By appropriate silica/polypyrrole complex microsphere and appropriate polyvinylpyrrolidone ultrasonic disperse in appropriate amount of deionized water
In；
Appropriate chlorauric acid solution is added and stirs；
The sodium borohydride solution of proper amount of fresh configuration and stirring is added, obtains dispersion liquid；
Appropriate above-mentioned dispersion liquid is taken, appropriate sodium hydroxide solution is added, is stood after oscillation treatment；
It is dried after centrifuge separation, obtains polypyrrole/gold composite hollow micro-sphere structure material.
Specifically, by silica/polypyrrole complex microsphere ultrasonic disperse in 50mL deionized water, in obtained solution
Silica/polypyrrole complex microsphere mass-volume concentration can be 0.5 ~ 5mg/mL；The polyvinylpyrrolidone of addition can
Think 20 ~ 80mg；The chlorauric acid solution of addition can be 0.5 ~ 3mL, and molar concentration can be 0.02 ~ 0.05mol/L, be added
Stirring duration after chlorauric acid solution can be 3 ~ 5 hours；The sodium borohydride solution of addition can be 5 ~ 9mL, molar concentration
It can be 0.02 ~ 0.1 mol/L, the duration stirred after sodium borohydride solution, which is added, to be 3 ~ 5 hours；Take the dispersion liquid
30mL, the sodium hydroxide solution of addition can be 10 ~ 30mL, and molar concentration can be 0.5 ~ 2 mol/L, oscillation treatment when
Length can be 5 ~ 10 minutes, and the duration of standing can be 4 ~ 10 hours, and the rate of centrifugal treating can be 8000 revs/min, from
The duration of heart processing can be 5 min, and drying temperature can be 40 ~ 60 DEG C.In the present embodiment, by silica/polypyrrole
Complex microsphere ultrasonic disperse is in 50mL deionized water, silica/polypyrrole complex microsphere mass body in obtained solution
Product concentration is 0.5mg/mL；The polyvinylpyrrolidone of addition is 20mg；The chlorauric acid solution of addition is 0.5mL, mole dense
Degree is 0.02mol/L, is stirred 3 hours after chlorauric acid solution is added；The sodium borohydride solution of addition is 5mL, and molar concentration is
0.02 mol/L is stirred 3 hours after sodium borohydride solution is added；The dispersion liquid 30mL is taken, the sodium hydroxide solution of addition is
10mL, molar concentration are 0.5 mol/L, oscillation treatment 5 minutes, stand 4 hours, the rate of centrifugal treating is 8000 revs/min
Clock, when a length of 5 min of centrifugal treating, drying temperature are 40 DEG C.
Embodiment three
Contain in a kind of the step of preparation method of polypyrrole/gold composite hollow micro-sphere structure material, method:
S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；To improve monodispersive silica microballoon
Hydrophily and biocompatibility；
S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, it is multiple to obtain silica/polypyrrole
Close microballoon；
S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, to prevent polypyrrole
Nano particle structure collapses, and coats golden shell on the silica/polypyrrole complex microsphere surface, then melt cladding golden shell
Silica/polypyrrole complex microsphere in silica, obtain polypyrrole/gold composite hollow micro-sphere structure material.
In step sl, the preparation step of monodispersive silica microballoon can be with are as follows:
The water, ammonium hydroxide and dehydrated alcohol of proper ratio are mixed and stirred for；
Appropriate ethyl orthosilicate is added and stirs；
Be centrifugated and clean, dry after obtain monodispersive silica microballoon.
Specifically, the water, ammonium hydroxide and dehydrated alcohol can take 1 ~ 3mL, 3 ~ 10mL and 50 ~ 100mL, solution temperature respectively
Can be 25 ~ 60 DEG C, the mode of stirring is magnetic agitation, and stirring duration can be 20 ~ 60 minutes, stirring rate can for 100 ~
400 revs/min；The ethyl orthosilicate of addition can be 1 ~ 5mL, and the duration stirred after ethyl orthosilicate is added can be small for 8 ~ 16
When, in the present embodiment, water, ammonium hydroxide and dehydrated alcohol take 3mL, 10mL and 100mL respectively, and solution temperature is 60 DEG C, when stirring
A length of 60 minutes, stirring rate was 400 revs/min, and the ethyl orthosilicate of addition is 5mL, stirred 16 after ethyl orthosilicate is added
Hour, the number of cleaning is 3 times.
In step sl, with can be with the step of polyvinyl pyrrolidon modified monodispersive silica microballoon are as follows:
Take appropriate monodispersive silica microballoon ultrasonic disperse into dehydrated alcohol；
Appropriate polyvinylpyrrolidone is added, is stirred after ultrasonic treatment；
Centrifuge separation, then washes and dries, obtains the monodispersive silica microballoon of modified.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be
20mL；The polyvinylpyrrolidone of addition can be 0.1 ~ 2g, and the duration that is ultrasonically treated is added after polyvinylpyrrolidone can be with
It is 10 ~ 30 minutes, stirring duration can be 12 ~ 24 hours, and solution temperature can be 30 ~ 50 DEG C.In the present embodiment, the list
Dispersed silica microballoon is 0.2g, and the polyvinylpyrrolidone of addition is 2g, after addition polyvinylpyrrolidone at ultrasound
Reason when it is 30 minutes a length of, when stirring, is 24 hours a length of, and solution temperature is 50 DEG C, when cleaning three times with washes of absolute alcohol.
In step s 2, the step of polypyrrole being wrapped up to monodispersive silica microsphere surface can be with are as follows:
It will be put into appropriate dehydrated alcohol by the monodispersive silica microballoon of polyvinyl pyrrolidon modified mistake and at ultrasound
Reason；
It is ultrasonically treated after appropriate pyrroles is added；
It is stirred after appropriate ammonium persulfate solution is added；
Then centrifuge separation cleans, is dry, obtaining silica/polypyrrole complex microsphere.
Specifically, the monodispersive silica microballoon can be 0.05 ~ 0.2g, the dehydrated alcohol can be 150
ML, the duration of ultrasonic treatment can be 10 ~ 30 minutes；The pyrroles of addition can be 0.02 ~ 0.2mL, after addition pyrroles at ultrasound
The duration of reason can be 5 ~ 10 minutes；The ammonium persulfate solution of addition can be 2 ~ 10mL, and mass-volume concentration can be
0.06g/mL, the duration stirred after ammonium persulfate solution, which is added, to be 8 ~ 24 hours, and the temperature of solution can be 15 ~ 30 DEG C,
It is cleaned multiple times when cleaning with dehydrated alcohol and water, is then transferred in air dry oven dry, the monodispersive silica
The partial size of microballoon can be 400nm or so.In the present embodiment, the monodispersive silica microballoon be 0.2g, ultrasound at
Reason when it is 30 minutes a length of, the pyrroles of addition is 0.2mL, be added after pyrroles be ultrasonically treated when it is 10 minutes a length of；The mistake of addition
Ammonium sulfate is 10mL, be added after ammonium persulfate solution stir when it is 24 hours a length of, the temperature of solution is 30 DEG C.
The specific steps of step S3 can be with are as follows:
By appropriate silica/polypyrrole complex microsphere and appropriate polyvinylpyrrolidone ultrasonic disperse in appropriate amount of deionized water
In；
Appropriate chlorauric acid solution is added and stirs；
The sodium borohydride solution of proper amount of fresh configuration and stirring is added, obtains dispersion liquid；
Appropriate above-mentioned dispersion liquid is taken, appropriate sodium hydroxide solution is added, is stood after oscillation treatment；
It is dried after centrifuge separation, obtains polypyrrole/gold composite hollow micro-sphere structure material.
Specifically, by silica/polypyrrole complex microsphere ultrasonic disperse in 50mL deionized water, in obtained solution
Silica/polypyrrole complex microsphere mass-volume concentration can be 0.5 ~ 5mg/mL；The polyvinylpyrrolidone of addition can
Think 20 ~ 80mg；The chlorauric acid solution of addition can be 0.5 ~ 3mL, and molar concentration can be 0.02 ~ 0.05mol/L, be added
Stirring duration after chlorauric acid solution can be 3 ~ 5 hours；The sodium borohydride solution of addition can be 5 ~ 9mL, molar concentration
It can be 0.02 ~ 0.1 mol/L, the duration stirred after sodium borohydride solution, which is added, to be 3 ~ 5 hours；Take the dispersion liquid
30mL, the sodium hydroxide solution of addition can be 10 ~ 30mL, and molar concentration can be 0.5 ~ 2 mol/L, oscillation treatment when
Length can be 5 ~ 10 minutes, and the duration of standing can be 4 ~ 10 hours, and the rate of centrifugal treating can be 8000 revs/min, from
The duration of heart processing can be 5 min, and drying temperature can be 40 ~ 60 DEG C.In the present embodiment, by silica/polypyrrole
Complex microsphere ultrasonic disperse is in 50mL deionized water, silica/polypyrrole complex microsphere mass body in obtained solution
Product concentration is 5mg/mL；The polyvinylpyrrolidone of addition is 75mg；The chlorauric acid solution of addition is 3mL, and molar concentration is
0.05mol/L is stirred 5 hours after chlorauric acid solution is added；The sodium borohydride solution of addition is 9mL, molar concentration 0.1
Mol/L is stirred 5 hours after sodium borohydride solution is added；The dispersion liquid 30mL is taken, the sodium hydroxide solution of addition is 30mL,
Its molar concentration is 2 mol/L, oscillation treatment 10 minutes, stands 10 hours, and the rate of centrifugal treating is 8000 revs/min, from
When a length of 5 min of heart processing, drying temperature are 60 DEG C.
Example IV
A kind of application of polypyrrole/gold composite hollow micro-sphere structure material, preparation method described in embodiment one is prepared
Polypyrrole/gold composite hollow micro-sphere structure material as optical-thermal conversion material be applied to photo-thermal therapy technology in, to absorb
The luminous energy of near-infrared laser is converted into thermal energy to kill cancer cell.
Working principle of the present invention is as follows:
First with polyvinyl pyrrolidon modified monodispersive silica microballoon, then polypyrrole is wrapped up to monodispersity dioxy
The surface of SiClx microballoon, obtains silica/polypyrrole complex microsphere, then with the polyvinyl pyrrolidon modified titanium dioxide
Polypyrrole in silicon/polypyrrole complex microsphere, and golden shell is coated on the silica/polypyrrole complex microsphere surface, then
Silica in silica/polypyrrole complex microsphere of ablation cladding golden shell, obtains polypyrrole/gold composite hollow microballoon knot
Structure material.Polypyrrole/gold composite hollow micro-sphere structure material of the method preparation has good biocompatibility and biological generation
Xie Xing, imaging function is good, light and heat stability, photothermal conversion efficiency are high, and hollow structure makes it have Drug loading capacity, and photo-thermal turns
Experiment is changed to show using power density to be 0.5W/cm2980nm near infrared light exciter irradiation mass-volume concentration be
The polypyrrole of 0.15mg/mL/gold composite hollow micro-sphere structure material dispersion liquid, the temperature of solution is from 25.0 DEG C after ten minutes
50.1 DEG C are raised to, and this preparation method is simple to operation, preparation efficiency is high.
Particular embodiments described above, pair present invention solves the technical problem that, technical scheme and beneficial effects carry out
It is further described, it should be understood that the above is only a specific embodiment of the present invention, is not limited to this
Invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in this hair
Within bright protection scope.
In the description of the present invention, it is to be understood that, indicating position or the term of positional relationship are based on shown in attached drawing
Orientation or positional relationship, be merely for convenience of description of the present invention and simplification of the description, rather than the equipment of indication or suggestion meaning
Or element must have a particular orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements.It for the ordinary skill in the art, can be according to specific feelings
Condition understands the concrete meaning of above-mentioned term in the present invention.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, or be somebody's turn to do
Invention product using when the orientation or positional relationship usually put, be merely for convenience of description of the present invention and simplification of the description, without
It is that the device of indication or suggestion meaning or element must have a particular orientation, be constructed and operated in a specific orientation, therefore not
It can be interpreted as limitation of the present invention.In addition, term " first ", " second ", " third " etc. are only used for distinguishing description, and cannot manage
Solution is indication or suggestion relative importance.
In addition, the terms such as term "horizontal", "vertical", " pendency " are not offered as requiring component abswolute level or pendency, and
It is that can be slightly tilted.It is not to indicate the structure if "horizontal" only refers to that its direction is more horizontal with respect to for "vertical"
It has to fully horizontally, but can be slightly tilted.
In the present invention unless specifically defined or limited otherwise, fisrt feature can be on or below second feature
Directly contacted including the first and second features, also may include the first and second features be not direct contact but by them it
Between other characterisation contact.Moreover, fisrt feature is on second feature, top and above include fisrt feature second spy
Right above sign and oblique upper, or first feature horizontal height is merely representative of higher than second feature.Fisrt feature second feature it
Under, lower section and fisrt feature included below be directly below and diagonally below the second feature, or be merely representative of first feature horizontal height
Less than second feature.
Claims (10)
1. a kind of polypyrrole/gold composite hollow micro-sphere structure material preparation method, it is characterised in that contain in the step of method:
S1: with polyvinyl pyrrolidon modified monodispersive silica microballoon；
S2: polypyrrole is wrapped up to the surface of the monodispersive silica microballoon after modification, it is multiple to obtain silica/polypyrrole
Close microballoon；
S3: with the polypyrrole in the polyvinyl pyrrolidon modified silica/polypyrrole complex microsphere, and in the dioxy
SiClx/polypyrrole complex microsphere surface coats golden shell, then melts in the silica/polypyrrole complex microsphere for coating golden shell
Silica obtains polypyrrole/gold composite hollow micro-sphere structure material.
2. polypyrrole according to claim 1/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
In step sl, the preparation step of monodispersive silica microballoon is as follows:
The water, ammonium hydroxide and dehydrated alcohol of proper ratio are mixed and stirred for；
Appropriate ethyl orthosilicate is added and stirs；
Be centrifugated and clean, dry after obtain monodispersive silica microballoon.
3. polypyrrole according to claim 2/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
The water, ammonium hydroxide and dehydrated alcohol take 1 ~ 3mL, 3 ~ 10mL and 50 ~ 100mL respectively；And/or the mode of stirring is magnetic agitation,
A length of 20 ~ 60 minutes when stirring, stirring rate is 100 ~ 400 revs/min；And/or solution temperature is 25 ~ 60 DEG C；And/or it is added
Ethyl orthosilicate be 1 ~ 5mL, be added ethyl orthosilicate after stir when it is 8 ~ 16 hours a length of.
4. polypyrrole according to claim 1/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
In step sl, with polyvinyl pyrrolidon modified monodispersive silica microballoon the step of, is as follows:
Take appropriate monodispersive silica microballoon ultrasonic disperse into dehydrated alcohol；
Appropriate polyvinylpyrrolidone is added, is stirred after ultrasonic treatment；
Centrifuge separation, then washes and dries, obtains the monodispersive silica microballoon of modified.
5. polypyrrole according to claim 4/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
The monodispersive silica microballoon is 0.05 ~ 0.2g, and the dehydrated alcohol is 20mL；And/or the polyvinyl pyrrole being added
Alkanone is 0.1 ~ 2g, be added after polyvinylpyrrolidone be ultrasonically treated when it is 10 ~ 30 minutes a length of, a length of 12 ~ 24 is small when stirring
When, solution temperature is 30 ~ 50 DEG C.
6. polypyrrole according to claim 1/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
In step s 2, the step of polypyrrole being wrapped up to monodispersive silica microsphere surface is as follows:
It will be put into appropriate dehydrated alcohol by the monodispersive silica microballoon of polyvinyl pyrrolidon modified mistake and at ultrasound
Reason；
It is ultrasonically treated after appropriate pyrroles is added；
It is stirred after appropriate ammonium persulfate solution is added；
Then centrifuge separation cleans, is dry, obtaining silica/polypyrrole complex microsphere.
7. polypyrrole according to claim 6/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
The monodispersive silica microballoon is 0.05 ~ 0.2g, and the dehydrated alcohol is 150 mL, ultrasonic treatment when it is a length of 10 ~
30 minutes；And/or be added pyrroles be 0.02 ~ 0.2mL, be added pyrroles after be ultrasonically treated when it is 5 ~ 10 minutes a length of；And/or add
The ammonium persulfate solution entered be 2 ~ 10mL, mass-volume concentration 0.06g/mL, addition ammonium persulfate solution after stir when
A length of 8 ~ 24 hours；And/or the temperature of solution is 15 ~ 30 DEG C.
8. polypyrrole according to claim 1/gold composite hollow micro-sphere structure material preparation method, which is characterized in that
Specific step is as follows by step S3:
By appropriate silica/polypyrrole complex microsphere and appropriate polyvinylpyrrolidone ultrasonic disperse in appropriate amount of deionized water
In；
Appropriate chlorauric acid solution is added and stirs；
The sodium borohydride solution of proper amount of fresh configuration and stirring is added, obtains dispersion liquid；
Appropriate above-mentioned dispersion liquid is taken, appropriate sodium hydroxide solution is added, is stood after oscillation treatment；
It is dried after centrifuge separation, obtains polypyrrole/gold composite hollow micro-sphere structure material.
9. polypyrrole according to claim 8/gold composite hollow micro-sphere structure material preparation method, it is characterised in that:
By silica/polypyrrole complex microsphere ultrasonic disperse in 50mL deionized water, silica/polypyrrole in obtained solution
The mass-volume concentration of complex microsphere is 0.5 ~ 5mg/mL；The polyvinylpyrrolidone of addition is 20 ~ 80mg；And/or be added
Chlorauric acid solution is 0.5 ~ 3mL, and molar concentration is 0.02 ~ 0.05mol/L, when stirring after chlorauric acid solution is added is a length of 3 ~
5 hours；And/or the sodium borohydride solution being added is 5 ~ 9mL, molar concentration is 0.02 ~ 0.1 mol/L, and sodium borohydride is added
Stirred after solution when it is 3 ~ 5 hours a length of；And/or the dispersion liquid 30mL is taken, the sodium hydroxide solution of addition is 10 ~ 30mL,
Its molar concentration be 0.5 ~ 2 mol/L, oscillation treatment when it is 5 ~ 10 minutes a length of, standing when it is 4 ~ 10 hours a length of；And/or from
The rate of heart processing is 8000 revs/min, when a length of 5 min of centrifugal treating；And/or drying temperature is 40 ~ 60 DEG C.
10. a kind of application of polypyrrole/gold composite hollow micro-sphere structure material, it is characterised in that: will be as in claim 1 to 9
The polypyrrole that described in any item preparation methods are prepared/gold composite hollow micro-sphere structure material is answered as optical-thermal conversion material
For in photo-thermal therapy technology.
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