CN109331182A - A kind of conducting polymer nano material and the preparation method and application thereof of poly-dopamine modification - Google Patents
A kind of conducting polymer nano material and the preparation method and application thereof of poly-dopamine modification Download PDFInfo
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- CN109331182A CN109331182A CN201811577916.8A CN201811577916A CN109331182A CN 109331182 A CN109331182 A CN 109331182A CN 201811577916 A CN201811577916 A CN 201811577916A CN 109331182 A CN109331182 A CN 109331182A
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Abstract
The invention discloses a kind of conducting polymer nano materials and its preparation method and application of poly-dopamine modification, the material is a kind of near-infrared conducting polymer to be prepared into conducting polymer nano particle first with reprecipitation method, then conducting polymer nano particle is added to what concussion in the Tris-HCl solution containing dopamine was formed.The scantling is uniform, with strong near infrared absorption and efficient light thermal property, the fluorescence of nano particle can be quenched, enhance the light thermal property and photoacoustic signal of nano particle, and good biocompatibility, there is functional group abundant on surface, convenient for modifying various functional ligands, there is the potentiality of applications well in terms of photo-thermal therapy.
Description
Technical field
The invention belongs to organic photoelectrics, technical field of biological materials.It is high more particularly to a kind of conduction of poly-dopamine modification
The preparation method of molecule nano material and its photo-thermal therapy field application.
Background technique
Tumour be it is a kind of seriously threaten health of human body and be difficult to the fatal disease captured, the traditional therapy master of tumour
It to be operative treatment, chemotherapy or radiotherapy；These therapeutic modalities are often along with the generation of toxic side effect, and therapeutic effect is not
It is good.With the continuous development of science and technology, researcher gradually develops various new therapeutic scheme, and wherein photo-thermal therapy is made
For a kind of extensive concern of the tolerable oncotherapy means by medical field of Noninvasive, the action principle of this method be by
Luminous energy is converted into thermal energy, using the heat for concentrating on tumor tissues position, enhances tumor locus blood circulation, improves the confession of oxygen
It gives, kills tumor tissues or cancer cell.Photo-thermal therapy has many advantages, such as small wound, few side effects and highly selective, the party
Method will become the main means of future therapeutic tumour, and how select suitable optothermal material by the direct work for determining this method
Use effect.
In recent years, the conjugatd polymers nano particle with good biocompatibility is absorbed with strong near-infrared (NIR)
Synthesis application become the research of the fields scientific research person such as bio-sensing, fluorescence imaging, photoacoustic imaging and photo-thermal therapy
Hot spot.But there are nano particle dissociation and structural stability differences etc. for most of existing conjugatd polymers nano particles
Problem, and their surface does not have the functional group for further bioconjugate, particle surface is not easy functionalization, these because
Element all limits such material further applying in therapeutic field of tumor.
Poly-dopamine is a kind of biopolymer materials, have unique coating quality and excellent biocompatibility, by
It is widely used in a variety of materials surface and forms thin surface adhesive.Conjugatd polymers nano grain surface is such as coated into poly- DOPA
Amine will make its surface have functional group abundant, be convenient for functionalization, this will be used for the organic total of photo-thermal therapy for further development
Conjugated polymer nano particle opens up new thinking.
Summary of the invention
It is asked for what conjugatd polymers nanoparticles stable difference existing in the prior art and surface difficulty were modified
Topic, the present invention provides a kind of conducting polymer nano materials of poly-dopamine modification, and conducting polymer nanometer may be implemented in it
The easy functionalization in the surface of particle, and can be used in the photo-thermal therapy of tumour, effective ablated tumor.
The technical solution of the present invention is as follows: a kind of conducting polymer nano material of poly-dopamine modification, the poly-dopamine are repaired
The conducting polymer nano material PSBTBT@PDA NPs of decorations is coated on the conducting polymer nano particle surface PSBTBT NPs
It is formed after dopamine, the particle size of PSBTBT@PDA NPs is uniform, and partial size is in 68-71 nm.
The preparation method of the conducting polymer nano material of the poly-dopamine modification, main preparation step are as follows:
1) conducting polymer PSBTBT is prepared into nano particle PSBTBT NPs using reprecipitation method；
2) PSBTBT NPs is added in the Tris-HCl buffer containing dopamine, shakes 8-10 h at room temperature；
3) with the product in ultrapure water cleaning step 2, centrifugal purification 3 times, obtained final product-poly-dopamine modification is led
Electric biopolymer nanoparticles PSBTBT@PDA NPs is dispersed in ultrapure water.
Further, the concentration of PSBTBT NPs solution is 0.08 mg/mL in the step 2, in Tris-HCl buffer
Dopamine concentration is 0.5 mg/mL, and the concentration of Tris-HCl buffer is 10 mM, pH value 8.5.
Further, in the step 3, centrifugal rotational speed is 12000 rpm/min, and centrifugation time is 15-20 min.
Further, the preparation step of the PSBTBT NPs are as follows: prepare the tetrahydrofuran solution of PSBTBT first；Then
It by the tetrahydrofuran solution of PSBTBT in the state of ultrasound, is quickly driven into ultrapure water, ultrasonic 8-10 min；Last benefit
Tetrahydrofuran is removed with the method for revolving, is filtered with 0.22 μm of water phase filtering head, obtains PSBTBT NPs.
The conducting polymer nano material of the poly-dopamine modification can be applicable in the photo-thermal therapy of tumour.
The beneficial effects of the present invention are:
1. the conducting polymer preparation method of nano material of poly-dopamine modification disclosed by the invention is simple, mild condition, raw material
It is cheap and easy to get, and the size uniformity for the product prepared, good biocompatibility；
2. the more unmodified conducting polymer nanometer of the conducting polymer nano material of poly-dopamine modification disclosed by the invention
Not only biocompatibility is promoted for grain, and surface is covered with functional group abundant, convenient for modifying various functional ligands；
3. conducting polymer nano particle can be quenched in the conducting polymer nano material of poly-dopamine modification disclosed by the invention
Fluorescence, enhance conducting polymer nano particle light thermal property and photoacoustic signal；
4. the conducting polymer nano material of poly-dopamine modification disclosed by the invention can be used in the photo-thermal therapy of tumour,
Effective ablated tumor kills cancerous tumor cell.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of PSBTBT@PDA NPs in the embodiment of the present invention 1；
Fig. 2 is in the embodiment of the present invention 1, and the TEM of PSBTBT@PDA NPs schemes；
Fig. 3 is the UV absorption and fluorescence emission spectrum of PSBTBT NPs and PSBTBT@PDA NPs in the embodiment of the present invention 2
Figure；
Fig. 4 is the surface-functionalized infrared spectroscopy of PSBTBT@PDA NPs in the embodiment of the present invention 3；
Fig. 5 a is in the embodiment of the present invention 4, and photo-thermal of PSBTBT NPs and PSBTBT the@PDA NPs under laser irradiation heats up bent
Line chart；
Fig. 5 b is Photoa-counstic spectra of PSBTBT NPs and PSBTBT the@PDA NPs under laser irradiation in the embodiment of the present invention 4；
Fig. 6 is the cytotoxicity test figure of PSBTBT NPs and PSBTBT@PDA NPs in the embodiment of the present invention 5, wherein Fig. 6 a
For with the experimental result picture of the experimental group of laser illumination, Fig. 6 b is the experimental result picture of the control group of unused laser illumination；
Fig. 7 is in the embodiment of the present invention 6, and PSBTBT@PDA NPs is used for the mouse photo-thermal heating curve of tumor thermal therapy, small
Mouse gross tumor volume and changes of weight figure, wherein Fig. 7 a is photo-thermal heating curve figure, and Fig. 7 b is mouse tumor volume change figure, Fig. 7 c
For changes of weight figure.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Embodiment 1
Fig. 1 is the preparation route figure of the conducting polymer nano material of poly-dopamine modification, it is specific the preparation method is as follows:
(1) preparation of conducting polymer (PSBTBT) tetrahydrofuran solution: weighing 1 mg PSBTBT, and 12 mL tetrahydrofurans are added
Ultrasound makes it completely dissolved；
(2) in the state of ultrasound, the conducting polymer tetrahydrofuran solution of 2 mL is quickly driven into the ultrapure water of 10 mL
In, 8 min of ultrasound；
(3) tetrahydrofuran is removed using the method for revolving, is filtered with 0.22 μm of filtering head, obtains conducting polymer nanometer
Grain (PSBTBT NPs)；
(4) conducting polymer nanoparticles solution (0.08 mg/mL) is added to the Tris- containing dopamine (0.5 mg/mL)
In HCl buffer (10 mM, pH=8.5), 8 h are shaken at room temperature；
(5) product in (4) is cleaned with ultrapure water, centrifugal purification 3 times, obtained final product-poly-dopamine modification conduction
Biopolymer nanoparticles (PSBTBT@PDA NPs) are dispersed in ultrapure water.
PSBTBT@PDA NPs obtained is observed using transmission electron microscope (TEM).PSBTBT@PDA NPs is water-soluble
Drop is added on the copper mesh for being coated with carbon, and using transmission electron microscope observation after being dried at room temperature for, as a result as shown in Fig. 2,
As can be seen from Figure 2 the size uniformity of PSBTBT@PDA NPs, partial size are about 70 nm.
Embodiment 2, the UV absorption of PSBTBT@PDA NPs and fluorescent emission test:
Prepare embodiment 1 in PSBTBT NPs and PSBTBT@PDA NPs solution (15 μ g/mL), test they absorption and
As a result as shown in figure 3, test data shows that poly-dopamine successfully coats, and PSBTBT has successfully been quenched in emission spectrum
The fluorescence of NPs.
Embodiment 3, PSBTBT@PDA NPs surface multifunctional examination of infrared spectrum:
The PSBTBT@PDA NPs solution in embodiment 1 is prepared, with the difference in Tris-HCl buffer (10 mM, pH 8.5)
Ligand (PEG-SH, cRGD and FA) mixing, is stirred at room temperature 12 h, centrifugal purification three times after (12000 rpm/min, 20
Min), with ultrapure water dispersion product, after product is mixed drying with potassium bromide, the infrared spectroscopy of product is tested in tabletting, as a result such as
Shown in Fig. 4, test data shows that the surface PSBTBT@PDA NPs can successfully modify different ligands, shows the easy functionalization in its surface
The advantages of.
Embodiment 4, the external photo-thermal of PSBTBT@PDA NPs and optoacoustic test:
PSBTBT NPs and PSBTBT@PDA the NPs solution (100 μ g/mL) in embodiment 1 is prepared, and using ultrapure water as sky
White control.Above-mentioned prepared solution is put in centrifuge tube, the laser for the use of wavelength being then 635 nm, power density is
0.5 W/cm2Irradiate 5 min.As a result as shown in Figure 5 a, test data shows that PSBTBT@PDA NPs is raised within 5 min
Temperature is apparently higher than the conducting polymer nano particle for not coating poly-dopamine.
PSBTBT NPs and PSBTBT@PDA the NPs solution (100 μ g/mL) in embodiment 1 is prepared, optoacoustic spectroscopy passes through
The pulse laser of 680 to 975 nm measures.As shown in Figure 5 b, test data shows that the photoacoustic signal of PSBTBT@PDA NPs is obvious
Higher than the conducting polymer nano particle of no cladding poly-dopamine.This example demonstrates that poly-dopamine enhances nano particle
Light thermal property and photoacoustic signal.
The cytotoxicity test of embodiment 5, PSBTBT@PDA NPs:
PSBTBT NPs and PSBTBT the@PDA NPs solution of 0,10,25,50,100 μ g/mL is prepared respectively.First by HeLa cell
It is seeded on 96 orifice plates, is incubated for 24 h, culture solution in hole is then abandoned it, the material of various concentration is added, continues incubation 24
H in power density is 0.5 W/cm with the laser of 635 nm of wavelength25 min are irradiated under intensity, and MTT reagent is added to incubate again later
Educate 4 h.The difference of control group and experimental group is not having to laser illumination.It can be seen that all samples in no laser from Fig. 6 b
Display is almost without toxicity when irradiation.It can be seen that from Fig. 6 a in the case where laser irradiation, PSBTBT@PDA NPs is in high concentration
When, excellent light thermal property is shown, most cell is killed.This example demonstrates that PSBTBT@PDA NPs tool obtained
There is preferable biocompatibility, and after illumination, has good lethal effect to cancer cell by photo-thermal effect.
The photo-thermal therapy test of embodiment 6, PSBTBT@PDA NPs:
By in the PSBTBT@PDA NPs tail vein injection to Mice Body of 200 μ L, 175 μ g/mL, 635 nm of wavelength is used after 4 h
Laser power density be 0.8 W/cm25 min, Fig. 7 a reflection are irradiated under intensity, mouse temperature can be raised to 65 °C or so；
Gross tumor volume and mouse weight are every other day measured, Fig. 7 b reflection injected the mouse tumor of PSBTBT@PDA NPs at second day
It when test, just melts completely, and in the later period also without there is phenomenon long again；Fig. 7 c reflect mouse weight almost without
Variation, shows that material almost without toxicity, can effectively melt mouse tumor.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (6)
1. a kind of conducting polymer nano material of poly-dopamine modification, which is characterized in that material PSBTBT@PDA NPs is
It is formed after the conducting polymer nano particle surface PSBTBT NPs coats dopamine, the particle size of PSBTBT@PDA NPs
Uniform, partial size is in 68-71 nm.
2. the preparation method of the conducting polymer nano material of poly-dopamine modification as described in claim 1, which is characterized in that
Main preparation step are as follows:
1) conducting polymer PSBTBT is prepared into nano particle PSBTBT NPs using reprecipitation method；
2) PSBTBT NPs is added in the Tris-HCl buffer containing dopamine, shakes 8-10 h at room temperature；
3) with the product in ultrapure water cleaning step 2, centrifugal purification 3 times, obtained final product PSBTBT@PDA NPs is dispersed in
In ultrapure water.
3. the preparation method of the conducting polymer nano material of poly-dopamine modification as claimed in claim 2, feature exist
In the concentration of PSBTBT NPs solution is 0.08 mg/mL in the step 2, and dopamine concentration is in Tris-HCl buffer
The concentration of 0.5 mg/mL, Tris-HCl buffer is 10 mM, pH value 8.5.
4. the preparation method of the conducting polymer nano material of poly-dopamine modification as claimed in claim 2, feature exist
In the centrifugal rotational speed in the step 3 is 12000 rpm/min, and centrifugation time is 15-20 min.
5. the preparation method of the conducting polymer nano material of poly-dopamine modification as claimed in claim 2, feature exist
In the preparation step of the PSBTBT NPs are as follows: prepare the tetrahydrofuran solution of PSBTBT first；Then by the tetrahydro of PSBTBT
Tetrahydrofuran solution is quickly driven into ultrapure water in the state of ultrasound, ultrasonic 8-10 min；Finally gone using the method for revolving
Except tetrahydrofuran, is filtered with 0.22 μm of water phase filtering head, obtain PSBTBT NPs.
6. the conducting polymer nano material of poly-dopamine modification according to any one of claims 1 to 5 is in the light of tumour
Application in heat cure, which is characterized in that PSBTBT@PDA NPs can photo-thermal ablated tumor.
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Cited By (3)
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| CN110623941A (en) * | 2019-09-12 | 2019-12-31 | 东华大学 | Mn-doped steel wire2+Polydopamine nano-carrier and preparation method thereof |
| CN111671898A (en) * | 2020-05-29 | 2020-09-18 | 南京邮电大学 | Nano gold/organic semiconductor composite nano particle, preparation and application |
| CN113368077A (en) * | 2021-04-27 | 2021-09-10 | 山东师范大学 | Polydopamine-modified nano covalent organic framework and preparation method and application thereof |
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Cited By (4)
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|---|---|---|---|---|
| CN110623941A (en) * | 2019-09-12 | 2019-12-31 | 东华大学 | Mn-doped steel wire2+Polydopamine nano-carrier and preparation method thereof |
| CN111671898A (en) * | 2020-05-29 | 2020-09-18 | 南京邮电大学 | Nano gold/organic semiconductor composite nano particle, preparation and application |
| CN113368077A (en) * | 2021-04-27 | 2021-09-10 | 山东师范大学 | Polydopamine-modified nano covalent organic framework and preparation method and application thereof |
| CN113368077B (en) * | 2021-04-27 | 2022-06-21 | 山东师范大学 | Polydopamine-modified nano covalent organic framework and preparation method and application thereof |
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Application publication date: 20190215 Assignee: Jiangsu Nanyou October Science Park Management Co.,Ltd. Assignor: NANJING University OF POSTS AND TELECOMMUNICATIONS Contract record no.: X2022980007683 Denomination of invention: A kind of conducting polymer nano material modified by polydopamine and its preparation method and Application Granted publication date: 20210528 License type: Common License Record date: 20220613 |
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