CN115282298A - Preparation method and application of monodisperse yttrium-90 polymer microspheres - Google Patents
Preparation method and application of monodisperse yttrium-90 polymer microspheres Download PDFInfo
- Publication number
- CN115282298A CN115282298A CN202210862271.2A CN202210862271A CN115282298A CN 115282298 A CN115282298 A CN 115282298A CN 202210862271 A CN202210862271 A CN 202210862271A CN 115282298 A CN115282298 A CN 115282298A
- Authority
- CN
- China
- Prior art keywords
- microspheres
- yttrium
- monodisperse
- polymer
- polymer microspheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/02—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by the carrier, i.e. characterised by the agent or material covalently linked or complexing the radioactive nucleus
- A61K51/04—Organic compounds
- A61K51/06—Macromolecular compounds, carriers being organic macromolecular compounds, i.e. organic oligomeric, polymeric, dendrimeric molecules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/12—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by a special physical form, e.g. emulsion, microcapsules, liposomes, characterized by a special physical form, e.g. emulsions, dispersions, microcapsules
- A61K51/1241—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by a special physical form, e.g. emulsion, microcapsules, liposomes, characterized by a special physical form, e.g. emulsions, dispersions, microcapsules particles, powders, lyophilizates, adsorbates, e.g. polymers or resins for adsorption or ion-exchange resins
- A61K51/1255—Granulates, agglomerates, microspheres
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method and application of monodisperse yttrium-90 polymer microspheres, wherein the preparation method of the monodisperse yttrium-90 polymer microspheres comprises the following steps: s1) preparing surface chelated carboxyl functional group microspheres by using polymer microspheres; s2) mixing yttrium chloride [90Y ] solution with the microspheres with surface chelated carboxyl functional groups, stirring uniformly, reacting for 0.5-2h at 40-50 ℃, and cleaning with normal saline after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres. The high molecular polymer microsphere has high-capacity surface functional groups, and can fully react with more yttrium chloride (90Y), so that the chelation efficiency of the monodisperse yttrium-90 high molecular microsphere is improved.
Description
Technical Field
The invention relates to the field of tumor radiotherapy drug microspheres, in particular to a preparation method and application of monodisperse yttrium-90 polymer microspheres.
Background
Interventional radiotherapy is one method developed recently for treating tumor effectively, and radioactive microsphere has wide application owing to its double interventional treatment of tumor, including internal radiation, blood vessel embolism, etc.
Yttrium [90Y ] has the following advantages as selective internal radiation therapy: pure beta rays are emitted, the energy is high, the half-life period is short, the penetration distance in vivo is short, and the protection is easy; good stability, harmless decay product, and 95% energy release within two weeks. At present, microspheres for radioactive tumor therapy mainly comprise yttrium [90Y ] glass microspheres and yttrium [90Y ] resin microspheres, but the glass microspheres have too high specific gravity and risk of depositing on the vessel wall and failing to select tumor parts more accurately; the resin microspheres are light in specific gravity, easy to disperse and better in operability, can reach every corner of a tumor along with arterial capillaries of liver cancer, and have good application, but the resin microspheres usually adsorb yttrium [90Y ] through sulfonic acid groups, are too low in adsorption efficiency, are unstable in adsorption, and enable a solution to fall off.
Disclosure of Invention
The invention aims to provide a preparation method and application of monodisperse yttrium-90 polymer microspheres, so as to solve the technical problems.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of monodisperse yttrium-90 polymer microspheres comprises the following steps,
s1) preparing surface chelated carboxyl functional group microspheres by using polymer microspheres;
s2) mixing yttrium chloride [90Y ] solution with the microspheres with surface chelated carboxyl functional groups, stirring uniformly, reacting for 0.5-2h at 40-50 ℃, and cleaning with normal saline after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres.
As a further optimization, S1 comprises the following steps of S11) preparing polymer microspheres with chloroacetyl chloride functional groups on the surfaces by using the polymer microspheres; s12) preparing hydroxyl polymer microspheres from the chloroacetyl chloride functional group polymer microspheres; s13) preparing surface grafting GMA polymer microspheres by using hydroxyl polymer microspheres; s14) preparing surface grafting GMA polymer microspheres by using hydroxyl polymer microspheres to prepare surface chelating carboxyl functional group microspheres.
As further optimization, adding chloroacetyl chloride and anhydrous aluminum trichloride into the macromolecular microspheres in S11, reacting, cleaning and drying to obtain polymer microspheres with surfaces containing chloroacetyl chloride functional groups; wherein the reaction temperature is 30-40 ℃, the reaction time is 12-24h, and the drying temperature is 80-100 ℃.
And as a further optimization, S12, adding the chloracetyl chloride functional group polymer microspheres into a sodium hydroxide solution, refluxing, cleaning and drying to obtain the hydroxyl polymer microspheres.
As a further optimization, in S13, the hydroxyl polymer microspheres are added into a ceric ammonium nitrate solution, then glycidyl methacrylate is added for reaction for 5-10h, and the surface grafted GMA polymer microspheres are prepared by cleaning after the reaction.
As a further optimization, sodium iminodiacetate is prepared in S14, then GMA polymer microspheres grafted on the surface are added, and the microspheres with surface chelating carboxyl functional groups are prepared by cleaning after reaction, wherein the reaction temperature is 50-60 ℃, and the reaction time is 12-24h.
As a further optimization, the polymer microspheres in S1 are one or more of polystyrene/divinylbenzene copolymer microspheres, polystyrene/triallyl isocyanurate microspheres, polymethyl methacrylate/divinylbenzene copolymer microspheres, or polymethyl methacrylate/triallyl isocyanurate microspheres.
As a further optimization, the polymer microsphere in S1 has the particle size of 100nm-100 μm and the pore diameter of 50-2000 angstroms.
An application of monodisperse yttrium-90 polymer microspheres, wherein the monodisperse yttrium-90 polymer microspheres are used for in vivo tumor radiotherapy.
As a further optimization, the chelating efficiency of the monodisperse yttrium-90 polymer microsphere is more than 99.5%, and the release rate of the monodisperse yttrium-90 polymer microsphere to yttrium-90 is less than 0.001%.
Compared with the prior art, the invention has the beneficial effects that:
1. the high molecular polymer microsphere prepared by the invention has surface functional groups with higher capacity, can improve the adsorption capacity of yttrium-90, can fully react with more yttrium chloride (90Y) to prepare monodisperse yttrium-90 high molecular microspheres, and improves the chelation efficiency of the monodisperse yttrium-90 high molecular microspheres.
2. The preparation process is simple and easy to industrialize.
Drawings
FIG. 1 is an SEM image of monodisperse yttrium-90 polymer microspheres prepared in example 1 of the present invention.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
A monodisperse yttrium-90 polymer microsphere and a preparation method thereof comprise the following steps:
s1) weighing 10g of polystyrene/divinylbenzene microspheres (30 mu m) and 120g of dichloroethane, adding 4.4g of chloroacetyl chloride and 2g of anhydrous aluminum trichloride, reacting for 24h at 30 ℃, sequentially washing with ethanol and deionized water, and drying at 90 ℃ to obtain polymer microspheres with chloroacetyl chloride functional groups on the surfaces;
s2) weighing 5g of chloracetyl chloride functional group microspheres in the S1, adding 10% sodium hydroxide solution, refluxing for 12h, washing for 3 times by using water, and drying at 90 ℃ for later use;
s3) weighing 5g of microspheres in S2, adding 100ml of deionized water, mixing and stirring at 60 ℃, introducing nitrogen to remove oxygen for 1h, and adding 10ml of 0.1M ammonium cerium nitrate solution (dissolved in 1M HNO) 3 And (3) adding 10ml of Glycidyl Methacrylate (GMA) after 30min, reacting for 6h, and repeatedly washing the product with deionized water after the reaction is finished to obtain the polymer microsphere with the GMA grafted on the surface, wherein the polymer microsphere is expressed by Poly-g-GMA.
S4) adding 1.6g of iminodiacetic acid (IDA) and 1g of NaOH to 50ml of water to form the sodium salt of IDA, and adding 1g of Poly-g-GMA microspheres and 2M Na thereto 2 CO 3 Adjusting the pH value of the solution to 10-11, stirring the mixed solution at 60 ℃ for reaction for 12h, repeatedly washing the particles by deionized water after the reaction is finished, and expressing the product by Poly-g-GMA-IDA.
S5) weighing 20g of 1M yttrium chloride [90Y ] solution, fully mixing with the Poly-g-GMA-IDA microspheres, uniformly stirring and mixing for 40-80 minutes at 40-50 ℃, and repeatedly washing for 5 times by using normal saline water after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres.
By detection, the particle size of the microsphere prepared in the embodiment is 30 μm, and CV =3%; the maximum radioactivity activity of the single yttrium-90 polymer microsphere is 2000Bq.
Example 2
A preparation method and application of monodisperse yttrium-90 polymer microspheres comprise the following steps:
s1) weighing 10g of polystyrene/triallyl isocyanurate microspheres (25 mu m) and 120g of dichloroethane, adding 4.4g of chloroacetyl chloride and 2g of anhydrous aluminum trichloride, reacting for 24h at 30 ℃, sequentially washing with ethanol and deionized water, and drying at 90 ℃ to obtain polymer microspheres with surfaces containing chloroacetyl chloride functional groups;
s2) weighing 5g of chloracetyl chloride functional group microspheres in the S1, adding 10% sodium hydroxide solution, refluxing for 12h, washing for 3 times by using water, and drying at 90 ℃ for later use;
s3) weighing 5g of microspheres in S2, adding 100ml of deionized water, mixing and stirring at 60 ℃, introducing nitrogen to remove oxygen for 1h, and adding 10ml of 0.1M ammonium cerium nitrate solution (dissolved in 1M HNO) 3 In the preparation process), adding 10ml of Glycidyl Methacrylate (GMA) after 30min, reacting for 6h, repeatedly washing the product with deionized water after the reaction is finished, and obtaining polymer microspheres with GMA grafted on the surface, wherein the polymer microspheres are expressed by Poly-g-GMA;
s4) first 1.6g of iminodiacetic acid (IDA) and 1g of NaOH were added to 50ml of water to form the sodium salt of IDA, and then 1g of Poly-g-GMA microspheres and 2M Na were added thereto 2 CO 3 Adjusting the pH value of the solution to 10-11, stirring the mixed solution at 60 ℃ for reaction for 12h, repeatedly washing particles with deionized water after the reaction is finished, and expressing a product by Poly-g-GMA-IDA;
s5) weighing 20g of 1M yttrium chloride [90Y ] solution, fully mixing with the Poly-g-GMA-IDA microspheres, uniformly stirring and mixing for 40-80 minutes at 40-50 ℃, and repeatedly washing for 5 times by using normal saline water after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres.
By detection, the particle size of the microsphere prepared in the embodiment is 25 μm, and CV =2.9%; the maximum radioactivity activity of the single yttrium-90 polymer microsphere is 2100Bq.
Example 3
A preparation method and application of monodisperse yttrium-90 polymer microspheres comprise the following steps:
s1) weighing 10g of polystyrene/divinylbenzene microspheres (50 mu m) and 120g of dichloroethane, adding 4.4g of chloroacetyl chloride and 2g of anhydrous aluminum trichloride, reacting for 24h at 30 ℃, sequentially washing with ethanol and deionized water, and drying at 90 ℃ to obtain polymer microspheres with chloroacetyl chloride functional groups on the surfaces;
s2) weighing 5g of chloracetyl chloride functional group microspheres in the S1, adding 10% sodium hydroxide solution, refluxing for 12h, washing for 3 times by using water, and drying at 90 ℃ for later use;
s3) weighing 5g of microspheres in S2, adding 100ml of deionized water, mixing and stirring at 60 ℃, introducing nitrogen to remove oxygen for 1h, and adding 10ml of 0.1M ammonium cerium nitrate solution (dissolved in 1M HNO) 3 In the preparation process), adding 10ml of Glycidyl Methacrylate (GMA) after 30min, reacting for 6h, repeatedly washing the product with deionized water after the reaction is finished, and obtaining polymer microspheres with GMA grafted on the surface, wherein the polymer microspheres are expressed by Poly-g-GMA;
s4) first 1.6g of iminodiacetic acid (IDA) and 1g of NaOH are added to 50ml of water to form the sodium salt of IDA, to which 1g of Poly-g-GMA microspheres and 2M Na are then added 2 CO 3 Adjusting the pH value of the solution to 10-11, stirring the mixed solution at 60 ℃ for reaction for 12h, repeatedly washing particles by deionized water after the reaction is finished, and expressing a product by Poly-g-GMA-IDA;
s5) weighing 20g of 1M yttrium chloride [90Y ] solution, fully mixing with the Poly-g-GMA-IDA microspheres, uniformly stirring and mixing for 40-80 minutes at 40-50 ℃, and repeatedly washing for 5 times by using normal saline water after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres.
By detection, the particle size of the microsphere prepared in the embodiment is 50 μm, and CV =2.8%; the maximum radioactivity energy of the single yttrium-90 polymer microsphere is 2000Bq.
Comparative example 1
The resin microspheres and glass microspheres of yttrium 90Y on the market were compared with the polymer microspheres of example 2 of the present invention, and the comparative data are shown in the following table.
The data show that the monodisperse yttrium-90 polymer microsphere prepared by the invention has more excellent comprehensive performance, and has less microsphere amount per GBq and higher single microsphere radioactivity ratio on the premise of having smaller density.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of monodisperse yttrium-90 polymer microspheres is characterized by comprising the following steps,
s1) preparing surface chelated carboxyl functional group microspheres by using polymer microspheres;
s2) mixing yttrium chloride [90Y ] solution with the microspheres with surface chelated carboxyl functional groups, stirring uniformly, reacting for 0.5-2h at 40-50 ℃, and cleaning with normal saline after the reaction is finished to prepare the monodisperse yttrium-90 polymer microspheres.
2. The method for preparing monodisperse yttrium-90 polymeric microspheres according to claim 1, wherein S1 comprises the following steps,
s11) preparing polymer microspheres with chloracetyl chloride functional groups on the surfaces by using the polymer microspheres;
s12) preparing hydroxyl polymer microspheres from the chloroacetyl chloride functional group polymer microspheres;
s13) preparing surface grafting GMA polymer microspheres by using hydroxyl polymer microspheres;
s14) preparing surface grafting GMA polymer microspheres by using hydroxyl polymer microspheres to prepare surface chelating carboxyl functional group microspheres.
3. The method for preparing monodisperse yttrium-90 polymeric microspheres according to claim 2, wherein chloroacetyl chloride and anhydrous aluminum trichloride are added to the polymeric microspheres in S11, and after the reaction, the polymeric microspheres with chloroacetyl chloride functional groups on the surface are prepared by cleaning and drying; wherein the reaction temperature is 30-40 ℃, the reaction time is 12-24h, and the drying temperature is 80-100 ℃.
4. The method for preparing monodisperse yttrium-90 polymeric microspheres according to claim 2, wherein the chloroacetyl chloride functional group polymeric microspheres are added into sodium hydroxide solution at S12, and then the hydroxyl polymeric microspheres are obtained after refluxing, cleaning and drying.
5. The method for preparing monodisperse yttrium-90 polymeric microspheres of claim 2, wherein the hydroxyl polymer microspheres are added into ceric ammonium nitrate solution in S13, then glycidyl methacrylate is added for reaction for 5-10h, and the GMA polymer microspheres grafted on the surface are prepared by cleaning after the reaction.
6. The method for preparing monodisperse yttrium-90 polymer microspheres according to claim 2, wherein sodium iminodiacetate is prepared in S14, and then surface graft GMA polymer microspheres are added, and after reaction, the microspheres are washed to prepare surface chelate carboxyl functional group microspheres, wherein the reaction temperature is 50-60 ℃ and the reaction time is 12-24h.
7. The method of claim 1, wherein the polymeric microspheres in S1 are one or more of polystyrene/divinylbenzene copolymer microspheres, polystyrene/triallyl isocyanurate microspheres, polymethyl methacrylate/divinylbenzene copolymer microspheres, or polymethyl methacrylate/triallyl isocyanurate microspheres.
8. The method for preparing monodisperse yttrium-90 polymeric microspheres according to claim 1, wherein the polymeric microspheres in S1 have a particle size of 100nm-100 μm and a pore size of 50-2000 angstroms.
9. Use of monodisperse yttrium-90 polymer microspheres according to any one of claims 1 to 8 in vivo tumor radiotherapy.
10. The use of monodisperse yttrium-90 polymer microspheres according to claim 9, wherein the chelating efficiency of the monodisperse yttrium-90 polymer microspheres is greater than 99.5%, and the release rate of yttrium-90 is less than 0.001%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210862271.2A CN115282298B (en) | 2022-07-21 | 2022-07-21 | Preparation method and application of monodisperse yttrium-90 polymer microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210862271.2A CN115282298B (en) | 2022-07-21 | 2022-07-21 | Preparation method and application of monodisperse yttrium-90 polymer microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115282298A true CN115282298A (en) | 2022-11-04 |
| CN115282298B CN115282298B (en) | 2023-10-20 |
Family
ID=83824288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210862271.2A Active CN115282298B (en) | 2022-07-21 | 2022-07-21 | Preparation method and application of monodisperse yttrium-90 polymer microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115282298B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117257996A (en) * | 2023-07-06 | 2023-12-22 | 北京普尔伟业生物科技有限公司 | Suspension containing radioactive microspheres and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078362A2 (en) * | 1999-06-22 | 2000-12-28 | Aventis Research & Technologies Gmbh & Co. Kg | Stable, radioactively marked nanoparticles, method for the production and utilization thereof |
| US20040258614A1 (en) * | 2003-06-20 | 2004-12-23 | University Of Maryland, Baltimore | Microparticles for microarterial imaging and radiotherapy |
| US20060067883A1 (en) * | 2004-09-24 | 2006-03-30 | Biosphere Medical, Inc. | Microspheres capable of binding radioisotopes, optionally comprising metallic microparticles, and methods of use thereof |
| CN106729953A (en) * | 2016-12-29 | 2017-05-31 | 苏州恒瑞迦俐生生物医药科技有限公司 | A kind of functional modification Polyvinyl Alcohol Embolization microballoon and preparation method thereof |
| CN111202871A (en) * | 2018-11-21 | 2020-05-29 | 白金科技股份有限公司 | Radioactive microsphere and radioactive filler composition |
| CN111603575A (en) * | 2020-02-28 | 2020-09-01 | 彭盛 | Radioactive embolism microsphere with core-shell structure and preparation method and application thereof |
| CN114259956A (en) * | 2021-12-14 | 2022-04-01 | 苏州知益微球科技有限公司 | Preparation method of polymer microsphere with comb-shaped surface structure |
-
2022
- 2022-07-21 CN CN202210862271.2A patent/CN115282298B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078362A2 (en) * | 1999-06-22 | 2000-12-28 | Aventis Research & Technologies Gmbh & Co. Kg | Stable, radioactively marked nanoparticles, method for the production and utilization thereof |
| US20040258614A1 (en) * | 2003-06-20 | 2004-12-23 | University Of Maryland, Baltimore | Microparticles for microarterial imaging and radiotherapy |
| US20060067883A1 (en) * | 2004-09-24 | 2006-03-30 | Biosphere Medical, Inc. | Microspheres capable of binding radioisotopes, optionally comprising metallic microparticles, and methods of use thereof |
| CN106729953A (en) * | 2016-12-29 | 2017-05-31 | 苏州恒瑞迦俐生生物医药科技有限公司 | A kind of functional modification Polyvinyl Alcohol Embolization microballoon and preparation method thereof |
| CN111202871A (en) * | 2018-11-21 | 2020-05-29 | 白金科技股份有限公司 | Radioactive microsphere and radioactive filler composition |
| CN111603575A (en) * | 2020-02-28 | 2020-09-01 | 彭盛 | Radioactive embolism microsphere with core-shell structure and preparation method and application thereof |
| CN114259956A (en) * | 2021-12-14 | 2022-04-01 | 苏州知益微球科技有限公司 | Preparation method of polymer microsphere with comb-shaped surface structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117257996A (en) * | 2023-07-06 | 2023-12-22 | 北京普尔伟业生物科技有限公司 | Suspension containing radioactive microspheres and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115282298B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115282298B (en) | Preparation method and application of monodisperse yttrium-90 polymer microspheres | |
| JP7207765B2 (en) | A Method for Preparing Amidoxime-Functionalized Hollow Porous Polymeric Microbeads as Emulsion Templates | |
| CA2292621C (en) | Process and apparatus for production of bi-213 cations | |
| CN104120256B (en) | A kind of method of magnetic polymer microsphere rare-earth separating ion | |
| CN113244895B (en) | Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres | |
| CN103007892A (en) | Preparation method for magnetic polymer composite microsphere | |
| CN102580701A (en) | Preparation method of arsenic removal resin | |
| CN101693750B (en) | Preparation method of macroporous absorption resin | |
| WO2020228558A1 (en) | Radioactive particle, preparation method therefor, and use thereof | |
| CN113058661A (en) | Preparation method of macroporous acrylic acid weak acid cation exchange resin | |
| CA2589894A1 (en) | Radionuclide-chitosan complex having an improved stabilized gelatin in administering them to the body and their preparation method | |
| CN111330548A (en) | Preparation method of adsorption resin composite aluminum lithium adsorbent | |
| CN106362703A (en) | Improved carageenan-chitosan polyelectrolyte microspheres as well as preparation method and application thereof | |
| CN106693901A (en) | Stable attapulgite adsorbent and preparation method thereof | |
| CN115607694B (en) | Radioactive carbon microsphere and its preparation method and application | |
| WO2020228559A1 (en) | Radioactive particle, preparation method therefor, and use thereof | |
| JP2014065846A (en) | Ferrocyanide conjugated vinyl polymer, preparation of the same, and cesium ion adsorption material containing the same | |
| CN115944753A (en) | Organic-inorganic composite radiotherapy microspheres and preparation method thereof | |
| CN103933954A (en) | Preparation method of magnetic polypyrrole and method of adsorbing nitrate in water | |
| CN114099765B (en) | Photo-initiated cross-linked polyvinyl alcohol drug-loaded embolism microsphere and preparation method thereof | |
| CN115888852A (en) | Preparation process of acrylate weak acid cation exchange resin | |
| CN115120749A (en) | Preparation method of radiotherapy microspheres and radiotherapy microspheres | |
| CN112808322A (en) | Cleaning and regeneration synergist for water treatment ion exchange resin | |
| CN108636386A (en) | Biomass-based functional material of a kind of multiple intelligent response and its preparation method and application | |
| CN108970593A (en) | A kind of phenolic aldehyde trace resin particle preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Room 403, Building 1, Zone II, Nanocity, No. 333 Xingpu Road, Suzhou Industrial Park, Jiangsu Province, 215000 Applicant after: SUZHOU KNOWLEDGE & BENEFIT SPHERE TECH. Co.,Ltd. Address before: 215000 East Side of Chang'an Road, Wujiang Economic and Technological Development Zone, Suzhou City, Jiangsu Province (Science and Technology Pioneering Park) Applicant before: SUZHOU KNOWLEDGE & BENEFIT SPHERE TECH. Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |