CN1141146C - Pure beta ray corrying safe microball and its preparation - Google Patents
Pure beta ray corrying safe microball and its preparation Download PDFInfo
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- CN1141146C CN1141146C CNB001257412A CN00125741A CN1141146C CN 1141146 C CN1141146 C CN 1141146C CN B001257412 A CNB001257412 A CN B001257412A CN 00125741 A CN00125741 A CN 00125741A CN 1141146 C CN1141146 C CN 1141146C
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- safe
- microsphere
- microball
- glass microsphere
- pure beta
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Abstract
The present invention discloses a safe microsphere carried with pure beta rays and a preparation process thereof, which relates to a safe microsphere carried with pure beta rays capable of curing cancer after being activated and a preparation process thereof. The safe microball is made by compounding a glass microsphere carried with pure beta rays and an anticorrosive coating layer applied to the external surface of the glass microsphere by a sol-gel method. The present invention has the largest advantage that radioisotope in not easy to penetrate and move into blood, in-vitro physiological simulation liquid immersion tests show that the dissolution rate of the corresponding nuclide of the safe microsphere is reduced by 1 to 2 orders of magnitude as compared with the dissolution rate of the nuclide of a microsphere without the anticorrosive coating layer. The safe microsphere has no radioactive pollution, high chemical stability, simple preparation process, and safe and reliable operation. The safe microsphere carried with pure beta rays is extensively used for internal radiotherapy to cure cancer.
Description
Technical field
The present invention relates to high being loaded with of a kind of chemical stability and after neutron activation, can produce glass microsphere and the technology thereof of controlling the pure beta ray that cancer uses.
Background technology
Operate on, chemotherapy and radiation is traditional cancer method of controlling.As everyone knows, radiotherapy is bigger than chemotherapy because of its specific aim and motility, and the cancer patient more is ready directly to treat with radiotherapy, tumor is dwindled obtain to operate on chance, or it is downright bad to the greatest extent that tumor cell is killed fully.Although cancerous cell is than the easier absorption ray of normal cell,, normal cell still is subjected to the injury of ray after all.So the roentgendosis of external radiotherapy is generally all little, is not enough to kill and wound all cancerous cell, therefore also influenced curative effect.Early eighties has begun X-ray therapy in the intervention abroad, can emit the isotope of ray and macromolecule resin complexation together, then it is got involved in the in-vivo tumour position.But find that radionuclide combines not firmly with macromolecule, easily come off into ionic condition, flows to each position of whole body, has caused bigger harm during actual the use.
Japanese patent laid-open 5-208918 discloses a kind of method with ion sputtering radiosiotope phosphorus has been infiltrated SiO
2The glass microsphere outer surface layer has been formed the glass microsphere of the phosphatizing that the radiation treatment cancer uses.The phosphorus of the surface layer of the glass microsphere of this invention is dissolved in the blood easily, flows to each position of whole body, works the mischief.For this reason, on January 5th, 1994, Chinese patent of invention CN 1080266 A disclosed a kind of phosphorus 32 P series glass microballoons.It is to form with salt meltings such as phosphate, magnesium silicate, aluminium silicate.The yttrium aluminosilicate glass microsphere that high melt becomes was disclosed U.S. Pat 5011677 in 1991.
Compare with macromolecule resin microsphereThough combining with vitreous body, the radiosiotope of above-mentioned two patents must compare the jail, but, common shortcoming is: still exist the phenomenon that the part radionuclide separates out from the glass microsphere drop, be dissolved in the blood, brought harm, and the glass microsphere of previous patent also contains the impurity ray of suitable intensity except being loaded with the β ray to patient health.
Summary of the invention
The objective of the invention is to design a kind of simple in structure, safe in utilization, the glass microsphere that after neutron activation, becomes a pure beta ray corrying of radionuclide difficult drop-off.Another object of the present invention provides a kind of method of making this safe microball.
To achieve these goals, the present invention is performed such, and safe microball is the glass microsphere by pure beta ray corrying after neutron activation, and the anti-corrosion coating that is coated on its outer surface is composited.Anti-corrosion coating is SiO
2, or/and Al
2O
3, or/and TiO
2, or/and ZrO
2The glass microsphere of pure beta ray corrying is to contain Y
2O
3, SiO
2, Al
2O
3The Y-89 glass microsphere, or contain P
2O
5, Al
2O
3, MgO the P-31 glass microsphere.
The step for preparing microsphere of the present invention is; At first add surfactant and stir in glass microsphere, surfactant can adopt Polyethylene Glycol or silane coupler, and the amount of adding is to add 0.3～0.5 gram surfactant in per 100 gram glass microspheres.Then above-mentioned glass microsphere is immersed in and forms stirring of anti-corrosion coating by containing in the sol solution that ethyl orthosilicate 50-100%, aluminum nitrate 0-30%, butyl titanate 0-20%, zirconium nitrate 0-30% form, make glass microsphere surface layer gelation through above-mentioned processing, then solid-liquid separation is after cyclone drying is removed organic solvent, at room temperature ageing 20-30 days again, 300-600 ℃ of following heating evaporation heat treatment in muffle furnace at last, make its vitrification, promptly make the safe microball of surface-coated anti-corrosion coating of the present invention.Safe microball of the present invention can be loaded with the nucleic Y-90 or the P-32 of emission pure beta ray after neutron activation, have all cancerous cell of human body are all produced the very strong kill capability of killing.
The invention characteristics are with advanced
The biggest advantage of safe microball of the present invention is safe and reliable, owing to applied one deck anti-corrosion coating thin film securely containing radiosiotope glass microsphere appearance, make it have extremely stable chemical property, so being difficult for analysing process by drop, radiosiotope vacillates in the blood, to around the also radioactive pollution of free from admixture ray, have safety very reliably.
Safe microball of the present invention also has an advantage to be: under neutron exposure, the nucleic Y-90 or the P-32 that can be activated and become to contain single pure beta ray, they can successfully get involved in appointed part in the body, use through zoopery and hospital clinical, confirmed that this type of microsphere all has the very strong kill capability of killing to all cancerous cell of human body, particularly especially effective to hepatocarcinoma, colon cancer, cancer of pancreas etc.
It is that preparation method is simple and easy to control that the present invention also has an advantage, and the anti-corrosion coating of the safe microball that makes with method of the present invention can adhere to the surface of glass microsphere securely, and coating can not come off.The composition of anti-corrosion coating can not radiate other any long-life objectionable impurities rays under the activation of neutron ray.Chemical reaction can not take place and change separately characteristic in glass microsphere and anti-corrosion coating.The dissolution rate of radionuclide has reduced by 1～2 order of magnitude than the dissolution rate of the bare glass microsphere that does not apply anti-corrosion coating.
Working of an invention
Concrete structure of the present invention and manufacture method are provided by following embodiment and accompanying drawing thereof.
Fig. 1 is a structural representation of the present invention.
Fig. 2 is a process chart of the present invention.The invention will be further described below in conjunction with accompanying drawing;
At first see also accompanying drawing 1, safe microball of the present invention is by be loaded with pure β after neutron activation The glass microsphere 1 of ray and anti-corrosion coating 2 form. After neutron activation, be loaded with pure beta ray Glass microsphere 1 is to contain Y2O
3、SiO
2、Al
2O
3The Y-89 glass microsphere, or contain P2O
5、Al
2O
3, MgO the P-31 glass microsphere.
Then see also accompanying drawing 2, the method for preparing safe microball of the present invention is as follows: at first will Glass microsphere 1 is put into container, is sprayed into 0.3～0.5 gram surfactant polyethylene or silicon The alkane coupling agent stirs, and makes it the moistening preliminary treatment 3 of finishing. Then above-mentioned glass microsphere 1 is soaked Bubble is by ethyl orthosilicate 50-100%, aluminum nitrate 0-30%, butyl titanate 0-20%, nitric acid In the container of the sol solution that zirconium 0-30% forms, place on the magnetic stirring apparatus and stir, carry out glass The coated gel in glass microballoon surface processes 4. Carry out again Separation of Solid and Liquid 5. Then with glass microsphere 1 Carry out drying 6 with the 40-60 ℃ of equidirectional cyclone dryer that enters of hot blast, it is organic molten to remove part Make wet gel become xerogel after the agent. Under the room temperature ageing 20-30 days, make gel stability 7. Afterwards 300-600 ℃ of lower heating evaporation heat treatment 8 in muffle furnace makes its vitrifying, forms SiO2, or/and Al2O
3, or/and TiO2, or/and ZrO2The present invention of anti-corrosion coating 2 Safe microball.
Embodiment 1:
100 grams are contained Y
2O
3, SiO
2, Al
2O
3Y-89 glass microsphere 1 place in the container, the silane coupler surfactant that adds 0.4 gram, pretreatment 3 is finished in stirring, be immersed in then and contain in the 100% teos solution colloidal sol, be placed on the magnetic agitation platform, the coated processing 4 of gelation is carried out in stirring, solid-liquid separation 5 then, and coated glass microsphere is taken out, and carry out cyclone drying 6 in the cyclone dryer import with the equidirectional exsiccant hot blast that enters, after removing the part organic solvent, the 25 day time of ageing makes its polymerization-stable 7 under the room temperature, at last 500-600 ℃ of following heating evaporation heat treatment 8 in muffle furnace, make its vitrification, promptly making surface of the present invention has SiO
2Coating contain the yttrium safe microball.This safety glass diameter of micro ball is in 20～60 mu m ranges.Scribble SiO
2This glass microsphere of coating 30 days yttric dissolution rates in the physiology simulated solution are 9 * 10
-7G/g, and the dissolution rate of bare glass microsphere is 3.6 * 10
-5G/g has reduced by 2 orders of magnitude.Safe microball of the present invention is after neutron activation, and nucleic Y-90 that can pure beta ray corrying has all cancerous cell of human body are all produced the very strong kill capability of killing.
Embodiment 2:
100 grams are contained P
2O
5, Al
2O
3, MgO P-31 glass microsphere 1 at 0.5 gram Polyethylene Glycol, stir, make it moistening, finish pretreatment 3.Then above-mentioned glass microsphere 1 is immersed in can form anti-corrosion coating 2 by containing ethyl orthosilicate 80-90%, stir in the sol solution that aluminum nitrate 10-20% forms, carry out the coated processing 4 of gelation, glass microsphere gelatinous mass through above-mentioned processing, carry out solid-liquid separation 5, the glass microsphere 1 of coating colloidal sol is taken out, carry out cyclone drying 6 in the cyclone dryer import with the equidirectional exsiccant 40-60 ℃ of hot blast that enters, the 30 day time of ageing under the room temperature behind the removal part organic solvent, make its polymerization-stable 7,400-500 ℃ of following heating evaporation heat treatment 8 in muffle furnace at last, make its vitrification, obtaining the surface has SiO
2And Al
2O
3The phosphorous safe microball of coating.The diameter of this safe microball is in 15～55 mu m ranges.Scribble SiO
2And Al
2O
3The dissolution rate of this glass microsphere 30 days phosphorus in the physiology simulated solution of coating is 2.2 * 10
-5G/g, the dissolution rate of bare glass microsphere are 7.9 * 10
-3G/g has reduced by 1～2 order of magnitude.Embodiment 3:
100 grams are contained P
2O
5, Al
2O
3, MgO P-31 glass microsphere 1 at 0.5 gram Polyethylene Glycol, stir, make it moistening, finish pretreatment 3.Then above-mentioned glass microsphere 1 is immersed in can form anti-corrosion coating 2 by containing ethyl orthosilicate 80-95%, stir in the sol solution that butyl titanate 5-20% forms, carry out the coated processing 4 of gelation, glass microsphere gelatinous mass through above-mentioned processing, carry out solid-liquid separation 5, the glass microsphere 1 of coating colloidal sol is taken out, carry out cyclone drying 6 in the cyclone dryer import with the equidirectional exsiccant 40-60 ℃ of hot blast that enters, the 30 day time of ageing under the room temperature behind the removal part organic solvent, make its polymerization-stable 7,400-500 ℃ of following heating evaporation heat treatment 8 in muffle furnace at last, make its vitrification, obtaining the surface has SiO
2And TiO
2The phosphorous safe microball of coating.The diameter of this safe microball is in 15～55 mu m ranges.Scribble SiO
2And TiO
2The dissolution rate of this glass microsphere 30 days phosphorus in the physiology simulated solution of coating is 5.3 * 10
-5G/g, the dissolution rate of bare glass microsphere are 7.9 * 10
-3G/g has reduced by 1～2 order of magnitude.
Embodiment 4:
100 grams are contained P
2O
5, Al
2O
3, MgO P-31 glass microsphere 1 at 0.5 gram Polyethylene Glycol, stir, make it moistening, finish pretreatment 3.Then above-mentioned glass microsphere 1 is immersed in can form anti-corrosion coating 2 by containing ethyl orthosilicate 80-95%, stir in the sol solution that zirconium nitrate 5-20% forms, carry out the coated processing 4 of gelation, glass microsphere gelatinous mass through above-mentioned processing, carry out solid-liquid separation 5, the glass microsphere 1 of coating colloidal sol is taken out, carry out cyclone drying 6 in the cyclone dryer import with the equidirectional exsiccant 40-60 ℃ of hot blast that enters, the 30 day time of ageing under the room temperature behind the removal part organic solvent, make its polymerization-stable 7,400-500 ℃ of following heating evaporation heat treatment 8 in Muffle furnace at last, make its vitrification, obtaining the surface has SiO
2And ZrO
2The phosphorous safe microball of coating.The diameter of this safe microball is in 15～55 mu m ranges.Scribble SiO
2And ZrO
2The dissolution rate of this glass microsphere 30 days phosphorus in the physiology simulated solution of coating is 6.4 * 10
-6G/g, the dissolution rate of bare glass microsphere are 7.9 * 10
-3G/g has reduced by 3 orders of magnitude.
Claims (4)
1, a kind of after neutron activation the safe microball of pure beta ray corrying, it is characterized in that: be composited by glass microsphere that is loaded with pure beta ray (1) and the anti-corrosion coating (2) that is coated on its outer surface thereof through producing after the neutron activation.
2, safe microball according to claim 1 is characterized in that: described anti-corrosion coating (2) is SiO
2, or/and Al
2O
3, or/and TiO
2, or/and ZrO
2
3, safe microball according to claim 1 is characterized in that: described after neutron activation the glass microsphere (1) of pure beta ray corrying be to contain Y
2O
3, SiO
2, Al
2O
3The Y-89 glass microsphere, or contain P
2O
5, Al
2O
3, MgO the P-31 glass microsphere.
4, a kind of after neutron activation the preparation method of the safe microball of pure beta ray corrying, it is characterized in that: at first glass microsphere (1) adding is filled in the container of surfactant, carry out pretreatment (3), then it is immersed in can form anti-corrosion coating (2) by ethyl orthosilicate 50-100%, aluminum nitrate 0-30%, butyl titanate 0-20%, stir in the sol solution that zirconium nitrate 0-30% forms, after finishing the coated processing of gelation (4), filter (5), subsequent again carrying out after cyclone drying (6) removes organic solvent, under the room temperature ageing 20-30 days (7), 300-600 ℃ of following heating evaporation heat treatment (8) in muffle furnace at last, make its vitrification, promptly make the safe microball of surface-coated anti-corrosion coating of the present invention (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001257412A CN1141146C (en) | 2000-10-20 | 2000-10-20 | Pure beta ray corrying safe microball and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001257412A CN1141146C (en) | 2000-10-20 | 2000-10-20 | Pure beta ray corrying safe microball and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288755A CN1288755A (en) | 2001-03-28 |
| CN1141146C true CN1141146C (en) | 2004-03-10 |
Family
ID=4591525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001257412A Expired - Fee Related CN1141146C (en) | 2000-10-20 | 2000-10-20 | Pure beta ray corrying safe microball and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1141146C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040197264A1 (en) * | 2003-04-04 | 2004-10-07 | Alexander Schwarz | Microspheres comprising therapeutic and diagnostic radioactive isotopes |
| TWI675669B (en) * | 2018-03-05 | 2019-11-01 | 白金科技股份有限公司 | Radiative microsphere and preparation method thereof |
| TWI728280B (en) * | 2018-11-21 | 2021-05-21 | 白金科技股份有限公司 | Radioactive microsphere, preparation method thereof and radioactive filler composition |
-
2000
- 2000-10-20 CN CNB001257412A patent/CN1141146C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288755A (en) | 2001-03-28 |
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