CN108785276A - A kind of purposes of radio therapy sensitization nano material - Google Patents
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- CN108785276A CN108785276A CN201811082334.2A CN201811082334A CN108785276A CN 108785276 A CN108785276 A CN 108785276A CN 201811082334 A CN201811082334 A CN 201811082334A CN 108785276 A CN108785276 A CN 108785276A
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Abstract
The invention discloses a kind of purposes of radio therapy sensitization nano material, which is to load the silica composite material of SODIUM PERCARBONATE and ferric oxide nano particles, is denoted as H-HMS-Fe, which can be used for radio therapy sensitization.H-HMS-Fe prepared by the present invention realizes the passive target to tumor tissues using the EPR effects of the nano material itself, later by generating oxygen around solid tumor tissue to improve tumor tissues oxygenation status, to reach radio therapy sensitization purpose, there is preferable application prospect.
Description
Technical field
The invention belongs to field of medical materials, and in particular to a kind of purposes of radio therapy sensitization nano material.
Background technology
Micro-environmental hypoxia is the important feature of entity tumor.Under anoxic conditions, tumour cell can secrete a variety of blood vessel lifes
The long factor is to promote the formation of abnormal vascular.While in order to find more preferably suitable soil, invasion and the transfer energy of tumour cell
Power can also be further improved.In addition, micro-environmental hypoxia makes the grade malignancy of tumour further increase, lead to tumour cell
It is insensitive to chemotherapeutics or radiotherapy.An important factor for micro-environmental hypoxia is tumour poor prognosis.In this microenvironment
Tumour growth, transfer and being obtained for the resistivity of drug and radiotherapy greatly improves.
Therefore, it is expected to become the new method for improving entity tumor curative effect by improving tumor hypoxia microenvironment.
Invention content
The object of the present invention is to provide a kind of purposes of radio therapy sensitization nano material, by being selectively enriched in tumour
Oxygen and living radical are discharged in the microenvironment of cell, are reached precisely attack tumour cell, are inhibited activity of tumor cells, carry
The purpose of high entity tumor curative effect.
In order to achieve the above object, the present invention provides a kind of purposes of radio therapy sensitization nano material, which receives
Rice material is the silica composite material for loading SODIUM PERCARBONATE and ferric oxide nano particles, is denoted as H-HMS-Fe, the H-HMS-Fe
It can be used for radio therapy sensitization.
Preferably, the H-HMS-Fe includes the HMS of hierarchy（Hollow meso-porous nano silicon ball, Hollow
mesoporous nanoparticles）, the HMS is with internal layer meso-hole structure and outer layer meso-hole structure, wherein the mesoporous knot of internal layer
Load has Na in structure2CO3•H2O2, in outer layer meso-hole structure load have ferric oxide nano particles.
Preferably, the aperture of the internal layer meso-hole structure is 2-4nm.
Preferably, the aperture of the outer layer meso-hole structure is 4-10nm.
Preferably, the preparation method of the H-HMS-Fe includes：
Step 1, H@HMS are prepared, it includes：
Step 1.1, by Na2CO3It is dissolved in deionized water, stabilizer is added, stirs evenly, adds HMS, stir so that HMS
It is uniformly dispersed；
Step 1.2, aminotrimethylene is added into aqueous hydrogen peroxide solution and pitches phosphonic acids（For providing weak acid environment）And it stirs
It mixes uniformly, is slow added into the finely dispersed solution of HMS that step 1.1 obtains, stir 1.5-3h, so that hydrogen peroxide is use up can
Entrance more than energy is mesoporous interior；Stand a period of time（Such as, 40min-60min）, it centrifuges, washes, it is dry, obtain load Na2CO3•
H2O2HMS powders, be denoted as H@HMS；
Step 2, H-HMS-Fe is prepared：Above-mentioned H@HMS are distributed in n-hexane, the hexane solution concentration of H@HMS is about
Ferric oxide nano particles are added in 1mg/mL-5mg/mL, and by mixed liquor magnetic agitation 12h-24h, through centrifugation, n-hexane is washed, obtained
The silica composite material for loading SODIUM PERCARBONATE and ferric oxide nano particles, is denoted as H-HMS-Fe.
Preferably, the stabilizer is used as improving the stability of SODIUM PERCARBONATE, it is made of magnesium sulfate and sodium metasilicate,
In, magnesium sulfate：Sodium metasilicate is 5 by quality ratio:1-10:1.
Preferably, in step 1.1, the concentration range of sodium carbonate is 1mg/mL-5mg/mL, the mass ratio of sodium carbonate and HMS
Example is 2% ~ 20%.
Preferably, in step 1.2, the molar ratio of hydrogen peroxide and sodium carbonate is 0.5:1~2:1.
Preferably, in step 2, the molar ratio of H@HMS and ferric oxide nano particles is 10:1~20:1.
The present invention is carrier using organic meso pore silicon oxide material, by being loaded respectively in support material internal and surface
The method of sodium carbonate and magnetic ferric oxide nano particles, using SODIUM PERCARBONATE under the catalytic action of ferric oxide nano particles（pH
7.4）The effect for generating oxygen, to build the nanometer transmission material of release oxygen.
The present invention discharges the nano material of oxygen by structure, utilizes the EPR effects of nano material itself（That is solid tumor
High-permeability and retention effect, enhanced permeability and retention effect）It realizes to tumor tissues
Passive target, later by around solid tumor tissue generate oxygen to reach improve tumor tissues oxygenation status, and
Its radiotherapy effect is improved, there is preferable application prospect.
Description of the drawings
Fig. 1 is the H-HMS-Fe composite material preparation process schematic diagrames of the present invention.
Fig. 2 is nanocomposite provided by the invention（H-HMS-Fe）Release in vitro oxygen curve figure, wherein with H-
The PBS solution of HMS（pH 7.4）For control group, the PBS solution of H-HMS-Fe（pH 7.4）For experimental group.
Fig. 3 is the pass of clone cell survival rate and roentgen dose X during the radio therapy sensitization performance study of nanocomposite is tested
It is curve graph.
Specific implementation mode
Below in conjunction with drawings and examples, the following further describes the technical solution of the present invention.
Embodiment 1
A kind of Na provided by the invention2CO3•H2O2@HMS-Fe3O4The preparation method of composite material is as follows：
1. preparing composite mesopore silicon oxide nanoparticle（HMS）：
2g hexadecyltrimethylammonium chlorides and 0.08g triethanolamines are dissolved in 20 mL deionized waters, heating stirring to 95
℃.1g ethyl orthosilicates are added dropwise in above-mentioned solution later, and continue to stir 1h.1g is being added just into above-mentioned solution later
Silester and 2g be bis--mixed solution of [3- (triethoxysilicane) propyl]-tetrasulfide, and continue stirring 4h.Pass through later
Centrifugation, washing, alcohol are washed, and are used in combination acid ethanol solution to remove the surfactant in mesoporous, you can to obtain composite mesopore silica
Nano-particle HMS.
The present invention, as surfactant, is self-assembly of first with hexadecyltrimethylammonium chloride CTAC using CTAC
Micella, ethyl orthosilicate TEOS are hydrolyzed in alkaline aqueous solution, and internal layer meso-hole structure is formed by template assemblies of micella（Aperture is
2-4nm）.As expanding agent, which continues to be self-assembly of [3- (triethoxysilicane) propyl]-tetrasulfide for addition pair-
Micella, teos hydrolysis product can form outer layer meso-hole structure by template assemblies of the micella（Aperture is 4-10nm）.
2. preparing magnetic ferric oxide nano particles（Fe3O4NPs）
By 2mmol Fe (acac)3, 10mmol1,2- hexadecane diols, 6mmol oleic acid, 6mmol oleyl amines, the mixing of 20mL diphenyl ether
Uniformly, and under nitrogen protection magnetic agitation 1h.Solution temperature is slowly raised to 200 DEG C, and is reacted at this temperature
Solution temperature is increased to 265 DEG C by 30min later, and the reaction was continued 30min.After reaction room temperature is down to through temperature, and to
Be added 40mL ethanol solutions in above-mentioned solution, reactant be distributed to after centrifugation oleic acid containing 0.05mL and 0.05mL oleyl amines just oneself
In alkane solution, it is centrifuged off unreacted residual substance, obtained magnetic ferric oxide nano particles are distributed to n-hexane later
In.
3. preparing H-HMS-Fe, as shown in Figure 1：
Step 1（S1）, by 0.5g Na2CO3Be dissolved in 25mL deionized waters, later into above-mentioned solution be added magnesium sulfate and partially
The stabilizer of sodium metasilicate composition（0.02g）, by the HMS of preparation（1.0g）It is distributed in above-mentioned solution, magnetic agitation 6h is obtained molten
Liquid A.0.0016g aminotrimethylenes are added in the aqueous hydrogen peroxide solution for being 50% to 0.8g mass fractions and pitch phosphonic acids stirring
It is even, which is slowly added in solution A, 2h is stirred.After stopping stirring, above-mentioned solution left standstill 50 minutes centrifuges, water later
It washes, vacuum freeze drying, you can obtain load Na2CO3•H2O2HMS, be denoted as H@HMS.
Step 2（S2）, the H HMS powders 20mg that step 1 obtains is distributed in 20mL hexane solutions, later to above-mentioned
2mL ferric oxide nano particles hexane solutions are added in solution（Fe3O4A concentration of 5mg/mL of NPs）, by mixed liquor magnetic agitation
12h, product are washed through centrifugation, n-hexane, you can are obtained target product, that is, loaded the oxidation of SODIUM PERCARBONATE and ferric oxide nano particles
Silicon composite is denoted as H-HMS-Fe.
H-HMS-Fe composite materials prepared by embodiment 1 carry out release in vitro oxygen experiment, experimental method：Experimental group and
Control group is scattered in the PBS of pH 7.4 respectively（Phosphate buffer saline, phosphate buffered saline solution）, later with molten
Solution oxygen analyzer measures the oxygen content in solution respectively.Experimental result is made as shown in Fig. 2, under conditions of being all pH=7.4
PBS solution for the H-HMS-Fe of experimental group is greatly improved compared to the PBS solution dissolved oxygen amount of H-HMS as a control group, explanation
In neutral conditions, the unit interval will produce more oxygen to H-HMS-Fe compared with control group H-HMS.
The radio therapy sensitization of nanocomposite is studied
Respectively with blank control group（X-ray bombardment directly is carried out to clone cell）, to experimental comparison group（Add into clone cell
Enter H-HMS and carries out x-ray bombardment again）And the embodiment of the present invention experimental group（Into clone cell be added H-HMS-Fe again into
Row x-ray bombardment）Clone cell survival rate experiment is carried out, the results are shown in Figure 3, and embodiment experimental group increases with roentgen dose X
Add, clone cell survival rate is significantly reduced compared to control group, it is seen then that H-HMS-Fe of the invention can be used for radio therapy sensitization.
It is demonstrated experimentally that the neutral environment that H-HMS-Fe composite materials provided by the invention are about 7.4 in pH（It is followed including blood
Loop system, extracellular matrix and cytoplasm etc.）Under, oxygen is slowly released, so as to improve the anoxic micro-loop of malignant entity tumor
Border.The faintly acid microenvironment for being about 5 in pH（Intracellular lysosome organelle）Under, release hydroxyl radical free radical（A kind of activity
Oxygen radical）, realize the oxidative damage to tumour cell, and then induce Apoptosis and necrosis, can be used for targeted therapy, carry
High entity tumor curative effect.
In conclusion H-HMS-Fe composite materials provided by the invention, with composite mesopore silicon oxide nanoparticle（HMS）For
Carrier, the nano material have with different levels meso-hole structure, and the aperture of internal layer meso-hole structure is about 2-4nm, outer layer meso-hole structure
Aperture be about 4-10 nm, by the mesoporous interior load SODIUM PERCARBONATE of internal layer（Na2CO3•H2O2）, and in the mesoporous interior load of outer layer
The magnetic ferric oxide nano particles that size is about 4nm（Fe3O4NPs）, the Na of structure biotic environment response2CO3•H2O2@HMS-
Fe3O4, it is abbreviated as H-HMS-Fe.The passive target to tumor tissues is realized using the EPR effects of the nano material itself, later
Improve tumor tissues oxygenation status by generating oxygen around solid tumor tissue to reach, to reach radio therapy sensitization mesh
, there is preferable application prospect.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. a kind of purposes of radio therapy sensitization nano material, which is characterized in that the radio therapy sensitization nano material is load SODIUM PERCARBONATE
With the silica composite material of ferric oxide nano particles, it is denoted as H-HMS-Fe, which can be used for radiotherapy hypersitization medicine
It prepares.
2. the purposes of radio therapy sensitization nano material as described in claim 1, which is characterized in that the H-HMS-Fe includes point
The HMS of hierarchical structure, the HMS have internal layer meso-hole structure and outer layer meso-hole structure, wherein there is load in internal layer meso-hole structure
Na2CO3•H2O2, in outer layer meso-hole structure load have ferric oxide nano particles.
3. the purposes of radio therapy sensitization nano material as claimed in claim 2, which is characterized in that the internal layer meso-hole structure
Aperture is 2-4nm.
4. the purposes of radio therapy sensitization nano material as claimed in claim 2, which is characterized in that the outer layer meso-hole structure
Aperture is 4-10nm.
5. the purposes of radio therapy sensitization nano material as described in claim 1, which is characterized in that the preparation method of the H-HMS-Fe
It comprises the steps of：
Step 1, H@HMS are prepared, it includes：
Step 1.1, by Na2CO3It is dissolved in deionized water, stabilizer is added, stirs evenly, adds HMS, stir so that HMS
It is uniformly dispersed；
Step 1.2, aminotrimethylene fork phosphonic acids is added into aqueous hydrogen peroxide solution and stirs evenly, is slow added into step
In the rapid 1.1 obtained finely dispersed solution of HMS, 1.5-3h is stirred；A period of time is stood, is centrifuged, is washed, it is dry, it is born
Carry Na2CO3•H2O2HMS powders, be denoted as H@HMS；
Step 2, H-HMS-Fe is prepared：Above-mentioned H@HMS are distributed in n-hexane, ferric oxide nano particles are added, by mixed liquor
Magnetic agitation 12h-24h, through centrifugation, n-hexane is washed, and the silica for obtaining load SODIUM PERCARBONATE and ferric oxide nano particles is compound
Material is denoted as H-HMS-Fe.
6. the purposes of radio therapy sensitization nano material as claimed in claim 5, which is characterized in that the stabilizer is by magnesium sulfate
It is formed with sodium metasilicate, wherein magnesium sulfate：Sodium metasilicate is 5 by quality ratio:1-10:1.
7. the purposes of radio therapy sensitization nano material as claimed in claim 5, which is characterized in that in step 1.1, sodium carbonate it is dense
The mass ratio of degree ranging from 10mg/mL-50mg/mL, sodium carbonate and HMS are 1% ~ 100%.
8. the purposes of radio therapy sensitization nano material as claimed in claim 5, which is characterized in that in step 1.2, hydrogen peroxide with
The molar ratio of sodium carbonate is 0.5:1~2:1.
9. the purposes of radio therapy sensitization nano material as claimed in claim 5, which is characterized in that in step 2, H@HMS and oxidation
The molar ratio of Fe nanometer particles is 10:1~20:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109481677A (en) * | 2018-11-30 | 2019-03-19 | 上海交通大学医学院附属第九人民医院 | A kind of nanocomposite and its preparation method and application of temperature-responsive sustained release oxygen |
| CN109738627A (en) * | 2018-12-18 | 2019-05-10 | 权冉(银川)科技有限公司 | A kind of immune method for treating material and its digitization detection tumour Dynamic Mechanism of Chinese medicine |
| CN114751461A (en) * | 2022-04-13 | 2022-07-15 | 南京海关工业产品检测中心 | Novel ferrite and synthesis method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109481677A (en) * | 2018-11-30 | 2019-03-19 | 上海交通大学医学院附属第九人民医院 | A kind of nanocomposite and its preparation method and application of temperature-responsive sustained release oxygen |
| CN109481677B (en) * | 2018-11-30 | 2021-06-29 | 上海交通大学医学院附属第九人民医院 | Temperature-responsive oxygen slow-release nanocomposite and preparation method and application thereof |
| CN109738627A (en) * | 2018-12-18 | 2019-05-10 | 权冉(银川)科技有限公司 | A kind of immune method for treating material and its digitization detection tumour Dynamic Mechanism of Chinese medicine |
| CN109738627B (en) * | 2018-12-18 | 2019-09-13 | 权冉(银川)科技有限公司 | A kind of immune method for treating material and its digitization detection tumour Dynamic Mechanism of Chinese medicine |
| CN114751461A (en) * | 2022-04-13 | 2022-07-15 | 南京海关工业产品检测中心 | Novel ferrite and synthesis method and application thereof |
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