CN1394599A - Preparation method of medicinal antimony sulfide nano colloidal particles - Google Patents
Preparation method of medicinal antimony sulfide nano colloidal particles Download PDFInfo
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- CN1394599A CN1394599A CN 01113300 CN01113300A CN1394599A CN 1394599 A CN1394599 A CN 1394599A CN 01113300 CN01113300 CN 01113300 CN 01113300 A CN01113300 A CN 01113300A CN 1394599 A CN1394599 A CN 1394599A
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Abstract
The preparation method of medicinal antimony sulfide nano colloid particles includes the following steps: firstly, preparing antimony sulfide nano crystal seeds with a certain distribution of particle size, then utilziing CH3CSNH2 and heating to make hydrolysis is acid medium to produce S(2-) as S(2-) source necessary for growth of antimony sulfide crystal seeds, controlling a certain condition to make the crystal seeds grow the required particle size. The distribution of particle size of the obtianed product is 30-100 nm, so that it can meet the requirements for clinical application. Said invention is sipmle in preparation process, low in cost and is easy to implement industrial production.
Description
Technical Field
The invention relates to a preparation method of antimony sulfide nano colloidal particles.
Background
The antimony sulfide nano colloidal particles can be used as carriers of radioactive nuclides and have important application value in nuclear medicine.
The literature: eur J nuclear med.1982, 7: 66-70 in 1982 a method for preparing antimony sulfide colloidal particles was reported: the method boils 100 mL of distilled water to remove CO2Gas, let in H2S gas until saturated, 20mL of 1% antimony potassium tartrate was added to the solution followed by 10mL of 3.5% polyvinylpyrrolidone (PVP) and then N2Removing excess H by qi2The S gas was checked with a lead acetate strip and finally filtered through a 0.2 μm microporous membrane. Said antimony sulfideThe nano colloidal particles are dispersed in the obtained filtrate.
The size distribution of the antimony sulfide nano colloidal particles prepared by the method is 2.5-20nm, and the radionuclide is used in the application99mTc marked can only be used as a lymph or bone marrow imaging agent, when the sentinel lymph node is imaged and detected, because the colloid particle size is small, the retention time in the sentinel lymph node is short, and the colloid particle is easy to leak through blood vessels, the imaging and the detection of the sentinel lymph node are difficult, and the application of antimony sulfide nano colloidal particles in the field is limited.
With the development of medical technology, antimony sulfide nano colloidal particles with more excellent performance are expected to meet the development requirement of nuclear medicine.
Disclosure of Invention
The invention aims to provide a preparation method of medicinal antimony sulfide nano colloidal particles, which enables the particle size distribution of the antimony sulfide nano colloidal particles to be between 30 and 100nm, so that the antimony sulfide nano colloidal particles can be used for nuclear medicine after being marked by radioactive nuclides to carry out development and detection on sentinel lymph nodes, and the defects of the prior art can be overcome.
The technical idea of the invention is as follows:
firstly, antimony sulfide nano seed crystal with certain particle size distribution is prepared, and then CH is utilized3CSNH2Heating hydrolysis in acidic medium to produce S2-S required for the growth of antimony sulfide seed crystal2-The source of the seed crystal is controlled to a certain condition, so that the seed crystal grows to the required granularity.
The method of the invention comprises the following steps:
(1) preparing antimony sulfide nano seed crystal:
reacting H at-1-4 deg.C2Introducing S gas into water until saturation, adding a dispersing agent, stirring uniformly, dropwise adding antimony tartrate, and introducing inert gas to drive off residual H in the solution2And S gas is filtered by a microporous membrane of 0.22-2 mu m, the obtained antimony sulfide nano seed crystal is dispersed in the filtrate, the particle size distribution of the antimony sulfide nano seed crystal is 8-12nm, and the antimony sulfide nano seed crystal is stored at room temperature for later use. The above-mentioned inverseThe equation should be as follows:
wherein: x is potassium or sodium;
the addition amount of the dispersant is 1 to 15 percent of the total volume of the solution;
antimony tartrate salt with H2The mol ratio of S is 1: 1-20: 1
The antimony tartrate salt is potassium antimony tartrate or sodium antimony tartrate and a mixture thereof;
the dispersing agent is one or more of polyvinylpyrrolidone (PVP), polyvinyl alcohol or gelatin;
the inert gas is one or more of nitrogen, helium, neon, argon, krypton or xenon;
in the preferred scheme of the invention, the dispersant can be prepared into a solution with the mass concentration of 1-8%, and the antimony tartrate is prepared into a solution with the mass concentration of 0.4-4%;
(2) preparing antimony sulfide nano colloidal particles:
mixing thioacetamide and antimony tartrate uniformly, adding a dispersing agent, adjusting the pH value of the solution to 4.5-6.5 by using acid, then adding the seed crystal in the step (1), and heating in a water bath at 60-100 ℃ for 3-8 h. Cooling to room temperature, filtering with a 0.22-2 μm microporous membrane, dispersing the prepared antimony sulfide nano colloidal particles in the filtrate, wherein the particle size distribution is 30-100nm, and storing at room temperature for later use.
The above reaction equation is as follows:
wherein: x is potassium or sodium.
The molar ratio of thioacetamide to antimony tartrate is 1: 1-20: 1;
the addition amount of the dispersant is 1 to 15 percent of the total volume of the solution;
the adding amount of the seed crystal is 5 to 30 percent of the total volume of the solution
The antimony tartrate salt is potassium antimony tartrate or sodium antimony tartrate and a mixture thereof;
the dispersing agent is one or more of polyvinylpyrrolidone (PVP), polyvinyl alcohol or gelatin;
the acid is one or more ofhydrochloric acid, phosphoric acid or acetic acid;
according to the invention, the dispersant can be prepared into a solution with a mass concentration of 1-8%, the tartaric acid antimony salt can be prepared into a solution with a mass concentration of 0.4-4%, and the thioacetamide can be prepared into a solution with a concentration of 0.01-1 mol.L-1The solution of (1).
As can be seen from the technical scheme disclosed above, in the invention, in the step (1), the particle size distribution of the obtained antimony sulfide nano seed crystal is narrower and is reduced from the original 2.5-20nm to 8-12nm, and in the step (2), CH is utilized to prepare the antimony sulfide nano seed crystal3CSNH2Hydrolysis of (2) to produce S2-S required for the growth of antimony sulfide seed crystal2-Thereby by controlling the CH3CSNH2The hydrolysis speed of the antimony sulfide nano colloidal particle is controlled to generate the particle size of the antimony sulfide nano colloidal particle, so that the obtained product can meet the clinical application requirement. The preparation method has the advantages of simple preparation process, low cost and easy industrial implementation.
Drawings
The antimony sulfide nano seed crystal and the antimony sulfide nano colloidal particle are characterized by a HITACHI-600 transmission electron microscope, and the results are shown in figures 1 and 2. The larger particles in the photograph, which are slightly lighter in color, are the dispersant PVP (particle size distribution 50-300 nm).
FIG. 1 is a TEM photograph of antimony sulfide nano-crystal seeds with a particle size distribution of 8-12 nm.
FIG. 2 is a TEM photograph of antimony sulfide nano colloidal particles with a particle size distribution of 30-100 nm.
Detailed Description
Specific embodiments of the present invention will be further described below by way of examples, which do not limit the scope of the present invention.
Example 1
Firstly, after the deionized water is boiledCooling with ice water, collecting 60mL, introducing H2S gas until saturated. 10mL of 1% dispersant gelatin was added, and after stirring well, 25mL of 0.4% antimony potassium tartrate was added dropwise. Then N is turned on2And (3) filtering for 30min by using a 0.22-micron microporous membrane to obtain antimony sulfide nano seed crystals, wherein the obtained antimony sulfide nano seed crystals are dispersed in the filtrate, and the particle size distribution is 8-12 nm.
Then, 0.01 mol. L-1Mixing thioacetamide and 0.4% antimony potassium tartrate uniformly according to the mol ratio of 20: 1, adding 10mL of 1% dispersant gelatin, adjusting the pH of the solution to 4.5 by using phosphoric acid, adding 5mL of antimony sulfide nano seed crystal, and heating in a water bath at 60 ℃ for 8 hours. Cooling to room temperature, and filtering with 2 μm microporous membrane to obtain desired antimony sulfide nano colloidal particles dispersed in the filtrate, wherein the particle size distribution is as follows: 30-100 nm.
Example 2
Firstly, boiling deionized water, cooling with ice water, collecting 60mL, introducing H2S gas until saturated. 5mL of a mixed solution of 3.5% of dispersant polyvinylpyrrolidone and polyvinyl alcohol is added, and after uniform stirring, 10mL of 1% antimony potassium tartrate is addeddropwise. Then N is turned on2And (3) filtering for 30min by using a 0.22-micron microporous membrane to obtain antimony sulfide nano seed crystals, wherein the obtained antimony sulfide nano seed crystals are dispersed in the filtrate, and the particle size distribution is 8-12 nm.
Then, 0.1 mol. L-1Mixing thioacetamide and 1% antimony potassium tartrate uniformly according to the mol ratio of 10: 1, adding 5mL of a mixed solution of 3.5% of dispersant polyvinylpyrrolidone and polyvinyl alcohol, adjusting the pH of the solution to 5.5 by hydrochloric acid, adding 10mL of antimony sulfide nano seed crystal, and heating in a water bath at 85 ℃ for 6 hours. Cooling to room temperature, and filtering with 2 μm microporous membrane to obtain desired antimony sulfide nano colloidal particles dispersed in the filtrate, wherein the particle size distribution is as follows: 30-100 nm.
Example 3
Firstly, boiling deionized water, cooling with ice water, taking 80mL, introducing H2S gas until saturated. Adding 1mL of 8% dispersant polyvinylpyrrolidone, stirring, and adding 4% wine dropwiseAnd 2.5mL of potassium antimonite. Then N is turned on2Gas is introduced for 30min, and filtered with 0.22 μm microporous membrane to obtain antimony sulfide nanometer seed crystal dispersed in the filtrate with granularity ofThe cloth is 8-12 nm.
Then, 1 mol. L-1Mixing thioacetamide and 4% antimony potassium tartrate uniformly according to the mol ratio of 1: 1, adding 1mL of 8% dispersant polyvinylpyrrolidone, adjusting the pH of the solution to 6.5 by using acetic acid, adding 25mL of antimony sulfide nano seed crystal, and heating in a water bath at 100 ℃ for 3 hours. Cooling to room temperature, and filtering with 2 μm microporous membrane to obtain desired antimony sulfide nano colloidal particles dispersed in the filtrate, wherein the particle size distribution is as follows: 30-100 nm.
Claims (7)
1. A preparation method of medicinal antimony sulfide nano colloidal particles is characterized by comprising the following steps:
(1) preparing antimony sulfide nano seed crystal:
h is to be2Introducing S gas into water until saturation, adding a dispersing agent, stirring uniformly, adding tartaric acid antimony salt, introducing inert gas, and filtering by using a microporous membrane to obtain a filtrate for dispersing antimony sulfide nano seed crystals;
(2) preparing antimony sulfide nano colloidal particles:
mixing thioacetamide and antimony tartrate uniformly, adding a dispersing agent, adjusting the pH value of the solution to be 4.5-6.5 by using acid, then adding the seed crystal in the step (1), heating at 60-100 ℃, cooling, and filtering by using a microporous membrane to obtain a filtrate of the dispersed antimony sulfide nano colloidal particles.
The antimony tartrate salt is potassium antimony tartrate or sodium antimony tartrate and a mixture thereof;
the dispersing agent is one or more of polyvinylpyrrolidone, polyvinyl alcohol or gelatin;
2. the method of claim 1, wherein the dispersant of step (1) and step (2) is added in an amount of 1% to 15% of the total volume of the solution; antimony tartrate salt with H2The mol ratio of S is 1: 1-20: 1, the mol ratio of thioacetamide to antimony tartrate is 1: 1-20: 1, and the addition amount of the seed crystal is 5-30% of the total volume of the solution.
3.Such as rightThe method according to claim 1, wherein the dispersant is prepared as a solution having a mass concentration of 1 to 8%, the antimony tartrate is prepared as a solution having a mass concentration of 0.4 to 4%, and the thioacetamide is prepared as a solution having a concentration of 0.01 to 1 mol.L-1The solution of (1).
4. The method of claim 2, wherein the dispersant is formulated into a solution having a mass concentration of 1-8%, the antimony tartrate is formulated into a solution having a mass concentration of 0.4-4%, and the thioacetamide is formulated into a solution having a concentration of 0.01-1 mol-L-1The solution of (1).
5. A method according to any one of claims 1 to 4, wherein the acid is one or more of hydrochloric acid, phosphoric acid or acetic acid.
6. The method of any one of claims 1 to 4, wherein the filtration is performed with a 0.22 to 2 μm microporous membrane.
7. The method of claim 5, wherein the filtration is performed with a 0.22 to 2 μm microporous membrane.
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| CN100363266C (en) * | 2006-06-02 | 2008-01-23 | 中国科学院长春应用化学研究所 | Process for preparing sodium antimony sulfide microwires and array thereof |
| US7588828B2 (en) | 2004-04-30 | 2009-09-15 | Nanoco Technologies Limited | Preparation of nanoparticle materials |
| US7674844B2 (en) | 2006-04-05 | 2010-03-09 | Nanoco Technologies Limited | Labelled beads |
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| US7867557B2 (en) | 2005-08-12 | 2011-01-11 | Nanoco Technologies Limited | Nanoparticles |
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| CN101164892B (en) * | 2006-10-16 | 2011-12-28 | 中国科学院福建物质结构研究所 | Super-high density information storage material antimony potassium sulfide and synthesis method thereof |
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| US8563348B2 (en) | 2007-04-18 | 2013-10-22 | Nanoco Technologies Ltd. | Fabrication of electrically active films based on multiple layers |
| US8597730B2 (en) | 2008-08-07 | 2013-12-03 | Nanoco Technologies Ltd. | Surface functionalised nanoparticles |
| US8741177B2 (en) | 2008-07-19 | 2014-06-03 | Nanoco Technologies Ltd. | Method for producing aqueous compatible nanoparticles |
| US8784701B2 (en) | 2007-11-30 | 2014-07-22 | Nanoco Technologies Ltd. | Preparation of nanoparticle material |
| US8847197B2 (en) | 2009-09-23 | 2014-09-30 | Nanoco Technologies Ltd. | Semiconductor nanoparticle-based materials |
| US8859442B2 (en) | 2010-04-01 | 2014-10-14 | Nanoco Technologies Ltd. | Encapsulated nanoparticles |
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| US8957401B2 (en) | 2009-09-23 | 2015-02-17 | Nanoco Technologies, Ltd | Semiconductor nanoparticle-based materials |
| US9598283B1 (en) | 2015-09-25 | 2017-03-21 | Sharp Laboratories Of America, Inc. | Synthesis method for controlling antimony selenide nanostructure shapes |
| CN110590407A (en) * | 2019-09-27 | 2019-12-20 | 合肥汉甲陶瓷科技有限公司 | Firing method for uniformly distributing cracks on surface of crack glaze ceramic |
| CN115417454A (en) * | 2022-08-30 | 2022-12-02 | 武汉大学 | Sb 2 S 3 Preparation method of thin film and solar cell |
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2001
- 2001-07-06 CN CN 01113300 patent/CN1394599A/en active Pending
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| US7803423B2 (en) | 2004-04-30 | 2010-09-28 | Nanoco Technologies Limited | Preparation of nanoparticle materials |
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| US7867557B2 (en) | 2005-08-12 | 2011-01-11 | Nanoco Technologies Limited | Nanoparticles |
| US7867556B2 (en) | 2005-10-28 | 2011-01-11 | Nanoco Technologies Limited | Controlled preparation of nanoparticle materials |
| US7674844B2 (en) | 2006-04-05 | 2010-03-09 | Nanoco Technologies Limited | Labelled beads |
| CN100363266C (en) * | 2006-06-02 | 2008-01-23 | 中国科学院长春应用化学研究所 | Process for preparing sodium antimony sulfide microwires and array thereof |
| CN101164892B (en) * | 2006-10-16 | 2011-12-28 | 中国科学院福建物质结构研究所 | Super-high density information storage material antimony potassium sulfide and synthesis method thereof |
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| US9251922B2 (en) | 2007-11-30 | 2016-02-02 | Nanoco Technologies, Ltd. | Preparation of nanoparticle material |
| US8337720B2 (en) | 2008-02-25 | 2012-12-25 | Nanoco Technologies, Ltd. | Semiconductor nanoparticle capping agents |
| US8741177B2 (en) | 2008-07-19 | 2014-06-03 | Nanoco Technologies Ltd. | Method for producing aqueous compatible nanoparticles |
| US8597730B2 (en) | 2008-08-07 | 2013-12-03 | Nanoco Technologies Ltd. | Surface functionalised nanoparticles |
| US8394976B2 (en) | 2008-11-04 | 2013-03-12 | Nanoco Technologies, Ltd. | Surface functionalised nanoparticles |
| US8921827B2 (en) | 2008-11-19 | 2014-12-30 | Nanoco Technologies, Ltd. | Semiconductor nanoparticle-based light-emitting devices and associated materials and methods |
| US8847197B2 (en) | 2009-09-23 | 2014-09-30 | Nanoco Technologies Ltd. | Semiconductor nanoparticle-based materials |
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| US8859442B2 (en) | 2010-04-01 | 2014-10-14 | Nanoco Technologies Ltd. | Encapsulated nanoparticles |
| US9159590B2 (en) | 2010-04-01 | 2015-10-13 | Nanoco Technologies, Ltd. | Encapsulated nanoparticles |
| US9598283B1 (en) | 2015-09-25 | 2017-03-21 | Sharp Laboratories Of America, Inc. | Synthesis method for controlling antimony selenide nanostructure shapes |
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| CN115417454A (en) * | 2022-08-30 | 2022-12-02 | 武汉大学 | Sb 2 S 3 Preparation method of thin film and solar cell |
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