CN102008925B - Method for preparing inorganic/organic composite microspheres - Google Patents
Method for preparing inorganic/organic composite microspheres Download PDFInfo
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- CN102008925B CN102008925B CN2010105938833A CN201010593883A CN102008925B CN 102008925 B CN102008925 B CN 102008925B CN 2010105938833 A CN2010105938833 A CN 2010105938833A CN 201010593883 A CN201010593883 A CN 201010593883A CN 102008925 B CN102008925 B CN 102008925B
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Abstract
The invention relates to a method for preparing inorganic/organic composite microspheres. The method comprises the following steps of: dispersing inorganic nanoparticles and polymer microspheres in a sweller and a dispersing agent; swelling at the temperature of between 40 and 60 DEG C for 30 to 120 minutes; heating a reaction system to the temperature of between 140 and 240 DEG C, and keeping the temperature until the sweller does not reflux; and after the sweller is volatilized completely, cooling the reaction system quickly, centrifuging, washing and drying to obtain the inorganic/organic composite microspheres. By the method, the problem that the nanoparticles leak from the microspheres is solved to a great extent, so that the composite microspheres have high stability. Simultaneously, the effective utilization rate of the nanoparticles is improved; the capacity of the nanoparticles in the microspheres is increased; the preparation process is simple; and the repeatability is high. The nanoparticles are distributed uniformly; moreover, the signal strength of coding can be better controlled by controlling the quantity of the nanoparticles entering the microspheres.
Description
Technical field
The present invention relates to a kind of composite that can be applicable to biomedical sector, especially relate to a kind of method of passing through inorganic/organic complex microsphere of high temperature swelling method preparation.
Background technology
In recent years, biomedical research has obtained the achievement that attracts people's attention at aspects such as functional gene analysis, drug screening and clinical diagnosises.Meanwhile, along with the develop rapidly of combinatorial chemistry, natural product chemistry and genomics, wait that in a large number the compound that screens analysis continues to bring out.How from candidate's system of extensive, complicated bio-related substance, efficiently filtering out target substance apace, to promote the development of biomedical research, is the huge challenge that present bioassay technique faces.
Development on the basis of OBOC (One-Bead-One-Compound) triage techniques that equals at Lam to propose in 1991 and the suspension array technology (Suspension array technology) of coming; Utilization has the microballoon of unique coding characteristic as reaction member, detects, screens and separates all and on same microballoon, accomplish fast; In addition, according to reality screening requirement, can also the kind and the particle diameter of microballoon be optimized.These characteristics have shortened array preparation (Array preparation) time greatly, have improved array density (Array density).The more important thing is; Along with low cytometric analysis; Especially the development of high flux flow cytometer (High-through-put flow cytometry) technology; The detection speed of suspension array technology makes ultrahigh speed multicomponent analysis (Multiplexed analysis) become possibility up to 10000/s.Based on above advantage, coding microball has obtained researcher's extensive concern, and begun should be on large-scale screening compound detects.
At present; The preparation method of coding microball mainly comprises: (1) is self-assembly method layer by layer; Nano particle after the surface modification is fully contacted with microsphere surface; Form through electrostatic adsorption or chemical bond makes nano particle be adsorbed on the carrier microballoons surface, and this method principle is easy, but nano particle comes off easily in the chemical environment of complicacy; (2) copolymerization method; Make nano particle have polymerisable unsaturated bond and monomer carries out copolymerization through surface-functionalized, make nano particle be aggregated to microballoon inside, the coding microball of this kind method preparation; Form with chemical bond between nano particle and the microballoon combines; Can effectively avoid in related application owing to nano particle leaks the problems such as jitter that cause, but system is unstable in polymerization process, the nanoparticle word is prone to inactivation; And the adding of nano particle may produce and must influence the pattern of microballoon and particle diameter, also limited its range of application.(3) normal temperature swelling method with microballoon swelling in being dissolved with the organic solvent of nano particle, makes nano particle be diffused into microballoon inside at normal temperatures.This method can be encoded fast, and the nano particle distribution uniform, but exists nano particle to be prone to the problem of revealing equally.
Summary of the invention
The object of the invention aims to provide a kind of method for preparing inorganic/organic complex microsphere accurately and efficiently; Emphasis solves this bottleneck problem of nano particle leakage in the complex microsphere, further expands coding microball carries out multiple bioanalysis, screening at biomedical sector application.
The present invention is a kind of new method for preparing inorganic/organic complex microsphere; Compare with traditional normal temperature swelling method; The high temperature swelling method is under higher temperature, to make polymer microballoon generation swelling, has a process that heats up gradually afterwards, and the good solvent of inorganic nano-particle volatilizees gradually; Impel nano particle to get in the inner smaller aperture of microballoon; Final cooling can be embedded into nano particle in the inner loose structure of microballoon effectively, successful restriction nano particle from microballoon, leak, and improved the stability of complex microsphere.The complex microsphere grain nano particle of preparation is evenly distributed, and uniform particle diameter, size are 1~100 μ m.
Of the present invention inorganic/preparation method of organic complex microsphere may further comprise the steps:
1) inorganic nano-particle and polymer microballoon are dispersed in sweller and the dispersant, at 40~60 ℃ of following swellings, swelling time 30~120min;
2) reaction system with step 1 is warming up to 140~240 ℃, and insulation does not reflux to there being sweller;
3) treat that sweller all volatilizees, the reaction system fast cooling is centrifugal, and the oven dry of washing back obtains inorganic/organic composite polymeric thing microballoon.
Described inorganic nano-particle is meant one or more the combination in metal nanoparticle, semiconductor nano particle or the magnetic nano-particle of average grain diameter between 1~100nm.
The preferred Au of described inorganic nano-particle, Ag, CdS, CdSe, CdTe, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdTe/CdS, CdTe/ZnSe, CdSeTe or Fe3O4 one or more combination wherein.
1. described polymer microballoon is to have cross-linked structure, the degree of cross linking 5%~100%, and polymer microsphere with porous or non-porous, and particle diameter is 5~100 μ m, preferable particle size is 5~20 μ m.
Described polymer microballoon comprises, the combination of one or more in polymethyl methacrylate, polyethyl methacrylate, polyacrylate, polystyrene or the polyvinyl chloride.
Said dispersant is one or both in hexadecane, the vaccenic acid.Sweller is one or both in chloroform or the cyclohexane.Sweller is 1: 6~1: 1 with the ratio of the volume of dispersant;
Preparation process of the present invention is preferably under argon shield, to carry out.
The present invention compared with prior art is characterised in that; Swelling largely takes place in microballoon under the condition that higher temperature and structure are not destroyed; Through intensification sweller is constantly volatilized subsequently; And then nano particle meeting generation concentration difference inside and outside microballoon, it can get in the inner smaller aperture of microballoon nano particle as motive force; In last fast cooling process, the constraint effect of strand and microballoon dissipate-swelling can effectively be embedded in the inner loose structure of microballoon nano particle to realize coding.
Advantage of the present invention mainly is, has solved the leakage problem of nano particle from microballoon to a great extent, and has made complex microsphere have good stable property; Improve the effective rate of utilization of nano particle simultaneously, increased the capacity of nano particle in the microballoon; The preparation process is simple, good reproducibility.The nano particle distribution uniform, and can control encoded signals intensity through the amount of the inner nano particle of control entering microballoon better.
Description of drawings
The average grain diameter of using among Fig. 1: the embodiment 1 is that the 15 μ m degrees of cross linking are the stereoscan photograph of 100% mesoporous polystyrene microsphere;
The fluorescence spectrum of the fluorescent microsphere that the high temperature swelling of employing described in Fig. 2: the embodiment 1 method makes;
The fluorescence spectrum of the fluorescent microsphere that the traditional normal temperature swelling method of employing described in Fig. 3: the embodiment 1 makes;
The fluorescence spectrum of the quantum dot fluorescence microballoon that makes among Fig. 4: the embodiment 2;
The fluorescence spectrum of the quantum dot fluorescence microballoon that makes among Fig. 5: the embodiment 3;
The magnetic responsiveness curve of the magnetic microsphere that makes among Fig. 6: the embodiment 5;
The fluorescence spectrum of the composite fluorescence microballoon that makes among Fig. 7: the embodiment 6;
The specific embodiment
Below in conjunction with accompanying drawing embodiments of the invention are made detailed description: present embodiment is being to implement under the prerequisite with technical scheme of the present invention, and given detailed embodiment and process are to further specify of the present invention, rather than limit scope of the present invention.
Embodiment 1
Step 1, weighing 30mg average grain diameter are that the 15 μ m degrees of cross linking are 100% mesoporous polystyrene microsphere, and be as shown in Figure 1; Measuring 100 μ L emission wavelengths is the CdSeTe quantum dot of 588nm; The microballoon that weighs up is joined in the 6mL hexadecane, and ultrasonic being uniformly dispersed joins the quantum dot that weighs up in the 3mL chloroform ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 90min under 50 ℃ with heating pot;
Step 2 is warming up to 180 ℃ with reaction system;
Step 3 is observed no chloroform and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains fluorescent microsphere.
Like Fig. 2, the fluorescence spectrum of the quantum dot fluorescence microballoon that the high temperature swelling method that adopts for this patent makes, as scheme visiblely, its fluorescence intensity did not take place still to keep higher intensity than high attenuation in the time of the 30th day; Like Fig. 3, for adopting the fluorescence intensity of the quantum dot fluorescence microballoon that traditional normal temperature swelling method makes, as to scheme visiblely, bigger decay has taken place in its fluorescence intensity in the time of the 30th day.This explanation, the restriction that the fluorescent microsphere of the high temperature swelling method preparation that the present invention uses is successful quantum dot leakage and have good stable property, quantum dot can effectively be embedded in the microballoon, successfully limited the fluorescence decay that the leakage because of quantum dot causes.Under the same conditions, the fluorescence intensity of the fluorescent microsphere of high temperature swelling method preparation obviously is better than the fluorescence intensity of the fluorescent microsphere of normal temperature method preparation, and this explanation high temperature swelling method has increased the capacity of quantum dot in the microballoon, has improved the effective rate of utilization of quantum dot.Observe fluorescence spectrum and can know do not squint in the fluorescent emission peak position, the peak type is sharp-pointed, and half-peak breadth is narrower.
Embodiment 2
Step 1, getting the 5mg average grain diameter and be the 1 μ m degree of cross linking and be 5% poly (methyl methacrylate) micro-sphere and 20 μ L emission wavelengths is the CdSe quantum dot of 541nm, the microballoon that weighs up is joined in the 3mL hexadecane ultrasonic being uniformly dispersed; The quantum dot of measuring is joined in the cyclohexane of 1mL ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 30min under 60 ℃ with heating pot;
Step 2 is warming up to 140 ℃ with reaction system;
Step 3 is observed no cyclohexane and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains fluorescent microsphere.As shown in Figure 4, the fluorescent emission peak position of the quantum dot fluorescence microballoon that makes is at the 541nm place, and peak shape is good and half-peak breadth is narrower.
Embodiment 3
Step 1, getting the 20mg average grain diameter and be the 10 μ m degrees of cross linking and be 20% polyethyl methacrylate microballoon and 60 μ L emission wavelengths is the CdSe/ZnS quantum dot of 650nm, the microballoon that weighs up is joined in the 6mL vaccenic acid ultrasonic being uniformly dispersed; The quantum dot of measuring is joined in the cyclohexane of 4mL ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 60min under 60 ℃ with heating pot;
Step 2 is warming up to 140 ℃ with reaction system;
Step 3 is observed no cyclohexane and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains fluorescent microsphere.As shown in Figure 5, the fluorescent emission peak position of the quantum dot fluorescence microballoon that makes is at the 650nm place, and peak shape is good and half-peak breadth is narrower.
Embodiment 4
Step 1, getting the 30mg average grain diameter and be the 100 μ m degrees of cross linking and be 50% has the complex microsphere and the 3mgAu nano particle of hole polystyrene/EMA, the microballoon that weighs up is joined in the 6mL vaccenic acid ultrasonic being uniformly dispersed; The Au nano particle of measuring is joined in the 6mL chloroform ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 60min under 40 ℃ with heating pot;
Step 2 is warming up to 140 ℃ with reaction system;
Step 3 is observed no chloroform and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains nanometer Au complex microsphere.
Step 1, getting the 30mg average grain diameter is that the 15 μ m degrees of cross linking are 100% mesoporous polystyrene microsphere and 5mgFe3O4 magnetic nano-particle, the microballoon that weighs up is joined in 4mL hexadecane carbon and the 4mL cyclohexane ultrasonic being uniformly dispersed; The Fe3O4 nano particle of measuring is joined in the chloroform of 2mL ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 90min under 50 ℃ with heating pot;
Step 2 is warming up to 240 ℃ with reaction system;
Step 3 is observed no chloroform and cyclohexane and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains magnetic microsphere.As shown in Figure 6, the magnetic saturation intensity of the magnetic microsphere that makes is higher;
Embodiment 6
Step 1, getting the 30mg average grain diameter is that the 15 μ m degrees of cross linking are 80% mesoporous polystyrene microsphere, 30 μ L emission wavelengths are the oil-soluble quantum dot of 564nm and 650nm, the microballoon that weighs up are joined in the 6mL hexadecane ultrasonic being uniformly dispersed; The quantum dot that weighs up is joined in 2mL chloroform and the 1mL cyclohexane ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 120min under 50 ℃ with heating pot;
Step 2 is warming up to 180 ℃ with reaction system;
Step 3 is observed no chloroform and cyclohexane and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains the composite fluorescence microballoon.As shown in Figure 7, the fluorescent emission peak position of the quantum dot composite fluorescent microballoon that makes is at 564nm and 650nm place, bimodal can be fully separated, peak shape is good and half-peak breadth is narrower.
Embodiment 7
Step 1; Getting the 30mg particle diameter is that the 20 μ m degrees of cross linking are that 100% mesoporous polystyrene microsphere, 3mgFe3O4 magnetic nanoparticle and 30 μ L emission wavelengths are the oil-soluble quantum dot of 588nm; The microballoon that weighs up is joined in 3mL hexadecane and the 3mL vaccenic acid ultrasonic being uniformly dispersed; In chloroform that the Fe3O4 magnetic nanoparticle of measuring and quantum dot are joined 3mL and the cyclohexane of 3mL, ultrasonic being uniformly dispersed; Join in the there-necked flask after two individual system are mixed; Install air setting device, air-breather and heater; Heat up insulation 120min under 50 ℃ with heating pot;
Step 2 is warming up to 180 ℃ with reaction system;
Step 3 is observed no chloroform and cyclohexane and is refluxed, and insulation 10min removes heater, fast cooling, and centrifuge washing 4 times obtains the magnetic fluorescence complex microsphere.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the preparation method of inorganic/organic complex microsphere is characterized in that may further comprise the steps:
1) inorganic nano-particle and polymer microballoon are dispersed in sweller and the dispersant, at 40~60 ℃ of following swellings, swelling time 30~120min; Described inorganic nano-particle is meant one or more the combination in metal nanoparticle, semiconductor nano particle or the magnetic nano-particle of average grain diameter between 1~100nm; Described polymer microballoon is to have cross-linked structure, and the degree of cross linking 5%~100 ﹪, and the polymer microsphere with porous or non-porous, particle diameter are 5~100 μ m; Dispersant is one or both in hexadecane, the vaccenic acid; Sweller is one or both in chloroform or the cyclohexane;
2) above-mentioned reaction system is warming up to 140~240 ℃, and insulation does not reflux to there being sweller;
3) treat that sweller all volatilizees, the reaction system fast cooling is centrifugal, and the oven dry of washing back obtains inorganic/organic composite polymeric thing microballoon.
2. preparation method according to claim 1 is characterized in that described inorganic nano-particle is selected from Au, Ag, CdS, CdSe, CdTe, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdTe/CdS, CdTe/ZnSe, CdSeTe or Fe
3O
4The combination of wherein one or more.
3. preparation method according to claim 1 is characterized in that described polymer microballoon, comprises one or more the combination in polymethyl methacrylate, polyethyl methacrylate, polyacrylate, polystyrene or the polyvinyl chloride.
4. preparation method according to claim 1 is characterized in that the sweller and the ratio of the volume of dispersant are 1:6~1:1;
5. preparation method according to claim 1 is characterized in that the preparation process is under argon shield, to carry out.
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CN102302918A (en) * | 2011-06-13 | 2012-01-04 | 天津大学 | Magnetic fluorescent composite microsphere and method for preparing same |
CN102430372B (en) * | 2011-08-29 | 2013-08-28 | 浙江理工大学 | Preparation method of strawberry-shaped organic-inorganic nanometer composite microsphere |
CN106479483A (en) * | 2016-09-23 | 2017-03-08 | 北京海岸鸿蒙标准物质技术有限责任公司 | A kind of streaming Fluorescent Microsphere Standards matter and preparation method thereof |
CN109652061B (en) * | 2019-01-28 | 2022-03-08 | 广东普加福光电科技有限公司 | Quantum dot/polymer microsphere composite material, preparation method and application |
CN110187116B (en) * | 2019-05-28 | 2022-05-31 | 苏州百源基因技术有限公司 | Mesoporous microsphere, preparation and application thereof |
CN114192079B (en) * | 2021-12-13 | 2022-09-30 | 广州光驭超材料有限公司 | Magnetic hollow polymer microsphere and preparation method and application thereof |
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CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
CN1775657A (en) * | 2005-10-24 | 2006-05-24 | 南京大学 | Method for preparing submicron metal/dielectric composite medium microball for nano shell structure |
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US5762959A (en) * | 1992-05-29 | 1998-06-09 | Vivorx, Inc. | Microencapsulation of cells |
WO2002047665A3 (en) * | 2000-12-07 | 2003-07-24 | Harvard College | Methods and compositions for encapsulating active agents |
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