CN109276714A - A kind of Zn2+Adulterate the preparation method of ultra-small grain size prussian blue nano probe - Google Patents
A kind of Zn2+Adulterate the preparation method of ultra-small grain size prussian blue nano probe Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 91
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 27
- 239000013225 prussian blue Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 5
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
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- 238000009413 insulation Methods 0.000 claims abstract description 3
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- 238000010521 absorption reaction Methods 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- -1 Iron ion Chemical class 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
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- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
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Abstract
The invention belongs to nanosecond medical science fields, and in particular to a kind of Zn2+The preparation method for adulterating ultra-small grain size prussian blue nano probe, molysite is mixed in proportion with zinc salt and is dissolved in solvent, and magnetic agitation to the solution A for forming stable homogeneous is heated to 30~100 DEG C, keeps the temperature 10~60 min.Potassium ferrocyanide is mixed with organic acid and is dissolved in solvent, magnetic agitation to the solution B for forming stable homogeneous is heated to 30~100 DEG C, keeps the temperature 10~60 min；Solution A is mixed with solution B, is continuously stirred and heated to 30~100 DEG C, 10~60 min of insulation reaction.After the reaction was completed, reaction solution cooled to room temperature, then washed with a certain proportion of deionized water and dehydrated alcohol mixed liquor, be centrifuged 2 ~ 4 times, and saved at a certain temperature.The present invention prepares resulting USPBZn nano-probe water solubility, good biocompatibility, and bio-toxicity is low.Pass through Zn2+Doping significantly improves the photothermal conversion efficiency, relaxation rate and antioxygenic property of USPBZn, has broad application prospects in field of biomedicine.
Description
Technical field
The invention belongs to nanosecond medical science fields, and in particular to a kind of Zn2+Adulterate ultra-small grain size prussian blue nano probe
Preparation method.
Background technique
In recent years, cancer has become one of the major disease for seriously threatening human health and life.It is annual newly-increased in China
Suffer from cancer number and account for about the newly-increased half (about 8,000,000) for suffering from cancer number in the world, and this data is also being continuously increased.How cancer is improved
The therapeutic efficiency of disease and the survival rate for suffering from carninomatosis people are the hot spots that current oncology studies are explored.The common hand for the treatment of of cancer at present
Section is operation, chemotherapy and radiation, this three kinds of methods all have the limitation of its own.Tumour operation excision often will form compared with
Big wound area, the convalescence after Miles operation are long, have the danger recurred again；The targeting selectivity of chemotherapeutics used in chemotherapy is low,
Human autoimmune's system can be destroyed and form systemic toxic side effect；Radiotherapy then will appear the damage of radiation, and cannot be complete
Full kill cancer cell, therapeutic effect are poor.Therefore develop a kind of safe and efficient treatment means, be oncology studies field urgently
Critical issue to be solved.
Photo-thermal therapy (Photothermal Therapy, PTT) has toxic side effect low compared with traditional treatment means,
The advantages that wound area is small, safe and efficient is treated, has become a big research hotspot of tumour novel therapeutic at present.PTT technology is logical
Crossing near infrared light, (700-1100 nm, the blood and water of human normal tissue are very low to the light absorption of this wave band, therefore it can
Arrive at human body deep tissues) irradiation make optothermal material sharply heat production formed localized hyperthermia kill cancer cell to realize oncotherapy
Purpose.Therefore a kind of nanometer optothermal material with low bio-toxicity, high photothermal conversion efficiency and high photo and thermal stability is developed
It is the precondition for carrying out photo-thermal therapy.
It is Prussian blue be it is a kind of by Food and Drug Adminstration of the US (Food and Drug Administration,
FDA) the medicament that can be used for clinical radiation treatment of approval.It can be used as photo-thermal therapy some researches show that Prussian blue
Reagent be applied to the photo-thermal therapy of tumour, compared with other photo-thermal therapy agents, such as noble metal based nano-material, carbon-based receive
Rice material, the bio-toxicity of prussian blue nano particle is lower, water-soluble more preferable.Further, since prussian blue nano particle is same
Shi Hanyou Fe2+And Fe3+, thus it not only has the function of magnetic resonance imaging radiography, also has oxidation resistant function.
But photothermal conversion efficiency, relaxation rate and the antioxygenic property of prussian blue nano particle reported at present are all
It is relatively low, and larger (the ACS Nano 2016,10,11115-11126 of the partial size of prussian blue nano particle; ACS Appl.
Mater. Interfaces 2015, 7, 11575-11582;), so that it is there is very overall situation in the application of field of biomedicine
It is sex-limited.Existing research prove have small particle feature nano material can be reduced in tumor therapeutic procedure macrophage to its
Phagocytosis simultaneously extends intracorporal circulation time, in addition, can also pass through the high-permeability and retention effect of tumor tissues
The richness in tumor tissues of (Enhanced Permeability and Retention Effect, EPR) realization nano material
Collection and passive target treatment (Journal Of Controlled Release, 2013,172:782-794).Therefore, it develops
It is a kind of with ultra-small grain size, good water solubility, bio-toxicity is low, photothermal conversion efficiency is high and with excellent MR imaging contrast and anti-
The prussian blue nano probe of oxidation susceptibility has important scientific meaning and wide application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of Zn2+Adulterate ultra-small grain size prussian blue nano probe (Zn2+ doped
Ultra-Small Prussian Blue Nanoprobe, USPBZn) preparation method, to solve existing prussian blue nano
The deficiencies of particle technology of preparing is excessively complicated and partial size is bigger than normal, by changing Zn2+Doping concentration realizes prussian blue nano
On the basis of diameter of particle regulation, the MR imaging contrast performance and its photo-thermal/anti-oxidant of USPBZn nano-probe are further increased
The effect of synergistic treatment.
To achieve the above object, a kind of technical solution that the present invention specifically provides are as follows: Zn2+It is Prussian blue to adulterate ultra-small grain size
The preparation method of nano-probe, molysite is mixed in proportion with zinc salt and is dissolved in solvent, magnetic agitation to formation stable homogeneous
Solution A is heated to 30~100 DEG C, keeps the temperature 10~60 min.
Potassium ferrocyanide is mixed with organic acid and is dissolved in solvent, magnetic agitation to the solution B for forming stable homogeneous, heating
To 30~100 DEG C, 10~60 min are kept the temperature；
Solution A is mixed with solution B, is continuously stirred and heated to 30~100 DEG C, 10~60 min of insulation reaction.
A, B solution are mixed, persistently stirs and is cooled to room temperature, carries out centrifuge washing after cooling, with volume ratio be 1:1 ~
The deionized water and dehydrated alcohol mixed liquor of 1:5 is washed, and is saved at a certain temperature.
Further, the proportion of the solution A is 0.05~0.5 g/L of molysite, 0.05~0.5 g/L of zinc salt.
Further, the proportion of the solution B is 0.1~1 g/L of potassium ferrocyanide, 1~10 g/L of organic acid.
Further, in the synthetic technology, the centrifugal speed of the centrifuge washing of sample is the rpm of 10000 rpm ~ 50000.
Further, with deionized water and washes of absolute alcohol 2~4 times, 4 ~ 25 DEG C of preservations.
Preparation method of the present invention is simply controllable, can regulate and control USPBZn nanometers of spies by reaction temperature and the ratio of added solution
The pattern and doping ratio of needle, and the USPBZn nano-probe pattern as obtained by the technology is uniform, good water solubility can be water-soluble
Liquid, various buffers, long-term stable dispersion in serum.
The cubic phase that present invention preparation gained USPBZn nano-probe pattern is uniform, TEM characterization partial size is 5~150 nm is brilliant
Body.By changing Zn2+The size control of doping concentration realization USPBZn nano-probe.
The present invention, which prepares resulting USPBZn nano-probe, has strong light absorption phenomenon in 500 ~ 1100 nm wave bands,
Thus photothermal conversion efficiency with higher and good photo and thermal stability, have broad application prospects in photo-thermal therapy.Separately
Outside, the good light thermal property of USPBZn nano-probe can be applied to photoacoustic imaging.
The present invention, which is prepared in resulting USPBZn nano-probe, contains Fe2+And Fe3+, relaxation rate with higher and good
MR imaging contrast performance, can be applied to the contrast imaging of MR.
The present invention, which is prepared in resulting USPBZn nano-probe, contains Fe2+And Fe3+, in different redox environments,
Iron ion be can be realized in+transformation between divalent and+trivalent.In addition, the ultra-small grain size of USPBZn nano-probe has its surface
There are more iron ions.Therefore, with traditional prussian blue nano particle phase ratio, USPBZn, can with better antioxygenic property
Antioxidation Treatment applied to diseases such as tumour, Alzheimer's diseases.
The present invention prepares resulting USPBZn nano-probe water solubility, good biocompatibility, and bio-toxicity is low, cures in biology
Field has broad application prospects.
Zn proposed by the present invention2+The preparation method of ultra-small grain size prussian blue nano probe is adulterated, it is easy to operate, it is at low cost
It is honest and clean；Resulting nano-probe is prepared with excellent light thermal property, light strong to near-infrared absorption according to this synthetic technology
Thermal conversion efficiency height, light and heat stability；Pass through Zn2+Doping is easy to regulate and control the partial size of prussian blue nano probe, greatly extends
Application field of the USPBZn nano-probe in field of biomedicine.The structure of USPBZn nano-probe and possessed function are shown
It is intended to as shown in Figure 1.In addition, USPBZn nano-probe has the function of MR imaging contrast performance and oxidation resistant, it is a kind of tool
There are the magnetic resonance contrast agent, photo-thermal therapy and Antioxidation Treatment drug of broad prospect of application.
Detailed description of the invention
Fig. 1 show structure and possessed functional schematic using the USPBZn nano-probe of the invention synthesized；
Fig. 2 show prussian blue nano probe (a) and USPBZn(40% in embodiment 2) nano-probe in the embodiment of the present invention 1
(b) transmission electron microscope picture；
Fig. 3 show the Visible-to-Near InfaRed absorption spectrum of USPBZn (10%) nano-probe using the technology of the present invention preparation；
Fig. 4 show the temperature rise curve of various concentration USPBZn (20%) nano-probe in the embodiment of the present invention 3；
Fig. 5 show the photothermal conversion efficiency and photo and thermal stability of USPBZn (20%) nano-probe in the embodiment of the present invention 3；
Fig. 6 show the r of various concentration USPBZn (30%) nano-probe using the technology of the present invention preparation1、r2Relaxation rate fitting
And MR image as a result；
Fig. 7 show the 4T1 cytotoxicity MTT of various concentration USPBZn (50%) nano-probe using the technology of the present invention preparation
Method testing result.
Fig. 8 show the 4T1 cell photo-thermal therapy effect of USPBZn (40%) nano-probe in the embodiment of the present invention 2.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawings and detailed description
The present invention is described in further detail.
Embodiment 1 undopes Zn2+The synthesis of prussian blue nano probe
It weighs 3.2 mg iron chloride to be dissolved in 20 mL deionized waters, magnetic agitation is simultaneously heated to 60 DEG C, 5 min of heating to solution
For clear, pale yellowish liquid, this liquid is denoted as solution A.It weighs 8 mg potassium ferrocyanides and 105 mg citric acids is dissolved in 20 mL
In deionized water, magnetic agitation is simultaneously heated to 60 DEG C, and 5 min of heating to solution are clarified, this solution is denoted as solution B.By solution B
It is slowly added dropwise in solution A, and continuing magnetic force is stirred and heated, keeping temperature is 60 DEG C, reacts 10 min.To fully reacting
Afterwards, cooling solution.12000 rpm are centrifuged 50 min, make to be washed with deionized 2 times, obtain prussian blue nano probe.Pu Lu
The Electronic Speculum characterization result of scholar's indigo plant nano-probe is as shown in Figure 2 (a).
The synthesis of embodiment 2 USPBZn (40%) nano-probe
It weighs 1.9 mg iron chloride and 1.1 mg zinc chloride is dissolved in 20 mL deionized waters, magnetic agitation is simultaneously heated to 60 DEG C, adds
5 min of heat are clear, pale yellowish liquid to solution, this liquid is denoted as solution A.Weigh 8 mg potassium ferrocyanides and 105 mg lemons
Lemon acid is dissolved in 20 mL deionized waters, and magnetic agitation is simultaneously heated to 60 DEG C, and 5 min of heating to solution are clarified, this solution is denoted as
Solution B.Solution B is slowly added dropwise in solution A, and continuing magnetic force is stirred and heated, keeping temperature is 60 DEG C, reaction 10
min.After complete reaction, cooling solution.12000 rpm are centrifuged 50 min, make to be washed with deionized 2 times, preparation gained
USPBZn (40%) nano-probe.The Electronic Speculum characterization result of USPBZn (40%) nano-probe is as shown in Fig. 2 (b).
The synthesis of embodiment 3 USPBZn (20%) nano-probe
It weighs 2.6 mg iron chloride and 0.8 mg zinc nitrate is dissolved in 20 mL deionized waters, magnetic agitation is simultaneously heated to 60 DEG C, adds
5 min of heat are clear, pale yellowish liquid to solution, this liquid is denoted as solution A.Weigh 8 mg potassium ferrocyanides and 105 mg lemons
Lemon acid is dissolved in 20 mL deionized waters, and magnetic agitation is simultaneously heated to 60 DEG C, and 5 min of heating to solution are clarified, this solution is denoted as
Solution B.Solution B is slowly added dropwise in solution A, and continuing magnetic force is stirred and heated, keeping temperature is 60 DEG C, reaction 10
min.After complete reaction, cooling solution.12000 rpm are centrifuged 50 min, make to be washed with deionized 2 times, preparation gained
USPBZn (20%) nano-probe.
The Visible-to-Near InfaRed absorption spectrum of nano-probe
Technology prepares USPBZn (10%) nano-probe and is scattered in deionized water according to the present invention, utilizes ultraviolet-visible
Sub-ray spectrometer scanning obtains it in the absorption spectrum of 500~1000 nm wave bands, can obtain it according to Fig. 3 and have near infrared light wave band
There is stronger absorption, and absorption is the strongest at 710 nm.In addition, at 808 nm wavelength USPBZn (10%) still have compared with
Strong absorption.Since 808 nm wavelength have better biological tissue's penetrability, mostly using the close of 808 nm in photo-thermal therapy
Infrared light is as treatment light source.Therefore, USPBZn (10%) can be used as photo-thermal therapy agent.
The temperature rise curve of nano-probe
The dispersion of PB obtained in embodiment 3 (Zn=20%) nano-probe material is dissolved in deionized water, sample concentration point is prepared
Not Wei 0,186 μ g/mL, 279 μ g/mL, 372 μ g/mL, 558 μ g/mL, 744 μ g/mL, six samples of 930 μ g/mL it is each
1.5 mL are placed in quartz colorimetric utensil, and application power is 6 W/cm2808 nm wavelength 5 min of laser irradiation.Record it
Temperature in different time points.As can be seen from FIG. 4, with the increase of USPBZn (20%) nano-probe concentration, the temperature rise of sample is imitated
Fruit is more obvious.In 6 W/cm2Under 808 nm laser irradiations of power, the sample solution that concentration is 930 μ g/mL heats up 24 DEG C, by
USPBZn (20%) nano-probe has good photothermal conversion performance known to this.
The photothermal conversion efficiency and photo and thermal stability of nano-probe
Embodiment 3 is prepared resulting USPBZn (20%) nano-probe to be scattered in deionized water, takes 1.5 mL in quartz cuvette
It the use of power is 5 W/cm in ware2808 nm laser irradiation, 5 min, then be naturally cooling to room temperature；It is carried out again under the same terms
Laser irradiation and Temperature fall, are repeated 5 times, and calculate the photothermal conversion efficiency for obtaining sample.USPBZn can be obtained according to Fig. 5
(20%) photothermal conversion efficiency (Fig. 5 (a)) with higher and good photo and thermal stability (Fig. 5 (b)).
The relaxation rate and MR of nano-probe are imaged
Technology prepares resulting USPBZn (30%) nano-probe sample dispersion in deionized water according to the present invention, and configuration 5 is not
With the sample of concentration, 1.4 mL is taken to be placed in 1.5 mL centrifuge tubes.Utilize MesoMR23-060H-I MRI analysis instrument
Measure the T of sample1、T2Relaxation time, by 1/T1、1/T2Linear fit is carried out with sample concentration, obtains the horizontal and vertical of sample
Relaxation rate.Suitable MR imaging parameters are set simultaneously, Magnetic resonance imaging is carried out to sample.It is illustrated in figure 6 various concentration
The r of USPBZn (30%) nano-probe1、r2Relaxation rate fitting result and MR image.
The cytotoxicity of nano-probe
Technology prepares resulting USPBZn (50%) nano-probe sample and carries out disinfection sterilizing according to the present invention, and uses culture solution
It is configured as 0,12.5 μ g/mL, 25 μ g/mL, 50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 300 μ g/mL, 400 μ
The material of g/mL concentration.Using mtt assay measurement various concentration sample to the toxic effect of 4T1 cell.It is illustrated in figure 7 different dense
Sample is spent to the mtt assay toxicity evaluation result of 4T1 cell.MTT as the result is shown gained USPBZn (50%) nano-probe cell toxicant
Property is low.
The cell photo-thermal therapy of nano-probe
USPBZn obtained in embodiment 2 (40%) nano-probe sample is carried out disinfection sterilizing, and is configured using culture solution
For 0,12.5 μ g/mL, 25 μ g/mL, 50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 300 μ g/mL, 400 μ g/mL concentration
Material.It is acted on using photo-thermal therapy of the mtt assay measurement various concentration sample to cell.By 1 × 105 A/mL 4T1 cell connects
Kind into 96 orifice plates, every 100 μ L of hole, at 37 DEG C, 5% CO2Under conditions of cultivate 24 h, then various concentration is added in every hole
100 μ L of sample, cultivate 4 h after, using power be 1.5 W/cm2808 nm laser irradiation, 5 min, be further cultured for 20 h, often
10 μ L MTT are added in hole, after cultivating 4 h, remove solution in hole, then 150 μ L DMSO solutions are added to every hole, use microplate reader
The absorbance value in every hole under 490 nm wavelength is measured, and indicates the photo-thermal therapy effect of different samples with cell viability percentage
Fruit.Fig. 8 shows the increase with USPBZn (40%) nano-probe concentration, and significant decrease trend is presented in the survival rate of 4T1 cell.
Nano-probe is applied to the detection of uric acid in clinical serum sample
1 mL clinical serum sample is taken, 0.1 mL uricase is added to it, manufactured mixed liquor is placed in 37 DEG C, reaction 30
Min generates H2O2；It adds in the embodiment 2 of color developing agent (such as TMB) and 0.2 mL, 0.2 mg/mL and prepares resulting USPBZn
(40%) nano-probe is placed at 37 DEG C and is incubated for 30 min；USPBZn (40%) is catalyzed H2O2Generate hydroxyl radical free radical, hydroxyl free
Base is catalyzed the aobvious blue of TMB again.Using absorbance value of the UV-vis spectroscopy spectrometer measurement reaction solution at 650 nm, according to
The concentration of uric acid in sample is calculated in standard curve.
The MR that nano-probe is applied to mouse is imaged
By USPBZn obtained in embodiment 2 (40%) nano-probe sample dispersion in PBS, being configured to mass concentration is 20
The dispersion liquid of mg/mL takes 0.1 mL through in tail vein injection to Mice Body.Different time points are taken, MesoMR23-060H-I is utilized
MRI analysis instrument carries out magnetic resonance imaging to mouse.USPBZn (40%) nano-probe have good magnetic resonance at
As contrasting effects.
Nano-probe is applied to the photo-thermal therapy of mouse breast cancer model
2 X 10 are subcutaneously injected into mouse armpit6A 4T1 cell will be prepared resulting after tumour molding using the technology of the present invention
USPBZn (30%) nano-probe sample is configured to the material of 20 mg/mL concentration, takes 100 μ L samples to enter through tail vein injection small
In mouse body.Or the sample of 2 mg/mL of configuration, take 50 μ L to be injected directly into inside mouse tumor；Injection uses after a certain period of time
Power is 2 W/cm2808 nm laser irradiation tumor locus, 5 min.After the completion of implementing photo-thermal therapy, when continuing one section of raising
Between, mouse tumor volume and weight are measured between feeding period every other day.Experimental result explanation of the tumor mouse model through photo-thermal therapy
USPBZn (30%) nano-probe has good photo-thermal therapy effect.
Design parameter value is a citing within the scope of suitable parameters of the present invention in embodiment, can not be not understood as
Defining and limiting to enforceable range of the present invention.Based on the embodiments of the present invention, those skilled in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
The English of all english abbreviations, Chinese name list in this patent:
Claims (5)
1. a kind of Zn2+Adulterate the preparation method of ultra-small grain size prussian blue nano probe, it is characterised in that: press molysite and zinc salt
Ratio mixing is dissolved in solvent, and magnetic agitation to the solution A for forming stable homogeneous is heated to 30~100 DEG C, heat preservation 10~60
min；
Potassium ferrocyanide is mixed with organic acid and is dissolved in solvent, magnetic agitation is heated to 30 to the solution B for forming stable homogeneous
~100 DEG C, keep the temperature 10~60 min；
Solution A is mixed with solution B, is continuously stirred and heated to 30~100 DEG C, 10~60 min of insulation reaction；
A, B solution are mixed, lasting stirring and cooled to room temperature carry out centrifuge washing after cooling, gone with a certain proportion of
Ionized water and the washing of dehydrated alcohol mixed liquor, and save at a certain temperature.
2. a kind of Zn according to claim 12+Adulterate the preparation method of ultra-small grain size prussian blue nano probe, feature
Be: the proportion of the solution A is 0.05~0.5 g/L of molysite, 0.05~0.5 g/L of zinc salt.
3. a kind of Zn according to claim 12+Adulterate the preparation method of ultra-small grain size prussian blue nano probe, feature
Be: the proportion of the solution B is 0.1~1 g/L of potassium ferrocyanide, 1~10 g/L of organic acid.
4. a kind of Zn according to claim 12+Adulterate the preparation method of ultra-small grain size prussian blue nano probe, feature
Be: the centrifugal speed of the centrifuge washing is the rpm of 10000 rpm ~ 50000.
5. a kind of Zn according to claim 12+Adulterate the preparation method of ultra-small grain size prussian blue nano probe, feature
It is: is washed 2~4 times with a certain proportion of deionized water and dehydrated alcohol mixed liquor, prepares 4 ~ 25 DEG C of products therefrom preservations.
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| CN113104863A (en) * | 2021-03-29 | 2021-07-13 | 三峡大学 | Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material |
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