CN114053964A - ZrO (ZrO)2Microfluidic preparation method of/PS hybrid microspheres, and product and application thereof - Google Patents
ZrO (ZrO)2Microfluidic preparation method of/PS hybrid microspheres, and product and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920002223 polystyrene Polymers 0.000 claims abstract description 54
- 239000002105 nanoparticle Substances 0.000 claims abstract description 53
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 238000003384 imaging method Methods 0.000 claims abstract description 22
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NIJDLRJGRCHJDB-UHFFFAOYSA-N propan-2-ol;propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)O.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] NIJDLRJGRCHJDB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 8
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- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- XXJVPYZAWNJXKT-UHFFFAOYSA-N propan-2-ol;zirconium(4+) Chemical compound [Zr+4].CC(C)O XXJVPYZAWNJXKT-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a ZrO2A microfluidic preparation method of/PS hybrid microspheres and products and application thereof belong to the technical field of hybrid microsphere preparation. The invention relates to ZrO modified by silane coupling agent (methacryloxypropyltrimethoxysilane (MPS)) dissolved2The ZrO is prepared by taking dichloromethane solution of nano particles and Polystyrene (PS) as a disperse phase and polyvinyl alcohol (PVA) aqueous solution as a continuous phase through a focusing micro-fluidic channel2The hybrid microsphere/PS. Due to the modified ZrO2The nano particles and the polymer matrix (PS) have good compatibility, can be uniformly distributed in the microspheres, and the prepared ZrO2the/PS microspheres have good optical transparency, and the refractive index of the hybrid microspheres is changed along with doping ZrO2Increase of nanoparticle contentThe microsphere has more excellent processing performance and controllable refractive index than a single-component microsphere, and has wider application prospect in the field of super-resolution imaging.
Description
Technical Field
The invention belongs to the technical field of hybrid microsphere preparation, and relates to ZrO2A microfluidic preparation method of/PS hybrid microspheres, and a product and application thereof.
Background
Optical microscopes can be used to observe topographical features of an object surface, however, conventional optical microscopes cannot resolve fine features of an object smaller than λ/2(λ -wavelength of light) due to the abbe diffraction limit, resulting in a resolution limit of about 200nm for white light (the limiting resolution is mainly caused by exponential attenuation of high frequency evanescent waves carried by fine features of an object with increasing distance from the object surface).
To break through the diffraction limit, scientists developed different super-resolution imaging techniques over a century, including super-resolution fluorescence imaging, near-field scanning optical microscopy (NSOM) techniques, metamaterial lenses, polar lenses, plasma gratings, etc. However, the above-mentioned super-resolution imaging technology still has some obvious defects, which prevent the wide application of the super-resolution imaging technology in the field of super-resolution imaging, for example: the super-resolution fluorescence imaging technology can only observe the fluorescence labeled sample; the slow scanning speed of the NSOM technology is not suitable for real-time imaging; metamaterial lenses, polar lenses, plasma gratings and the like have the defects of complex preparation process, need of specific excitation light sources and the like. Therefore, there is an urgent need to further develop a super-resolution imaging technique that is simple and practical and can solve the above-mentioned drawbacks.
In recent years, some researchers have employed microspheres of optically clear media (e.g., SiO)2Polystyrene (PS), BaTiO3Etc.) is placed on the surface of the observed sample, and real-time super-resolution imaging of the unmarked sample is realized under the white light illumination condition of the optical microscope. However, these single-component inorganic microspheres or polymer microspheres still have problems of poor processability or low refractive index, and the application thereof in real-time super-resolution imaging causes a problem of low imaging contrast, thereby being limited in practical application.
In recent years, microfluidic technology has been used to prepare a variety of different organic or inorganic microspheres, and by using a flow rate control technique in a microchannel, monodisperse microspheres can be obtained. Therefore, the performance of the prepared monodisperse microsphere is improved, and the application of the monodisperse microsphere in real-time super-resolution imaging can be expanded.
Disclosure of Invention
It is an object of the present invention to provide ZrO2A microfluidic preparation method of the/PS hybrid microspheres; it is another object of the present invention to provide ZrO2a/PS hybrid microsphere; it is another object of the present invention to provide ZrO2The application of the/PS hybrid microspheres in real-time super-resolution imaging.
In order to achieve the purpose, the invention provides the following technical scheme:
1. ZrO (ZrO)2The microfluidic preparation method of the/PS hybrid microspheres comprises the following steps:
(1) preparation of dispersed phase solution: dissolving oil soluble ZrO in water2Dissolving nanoparticles and Polystyrene (PS) in dichloromethane (CH)2Cl2) Stirring to mix them uniformly to form uniform solution, namely dispersed phase solution;
(2) preparation of ZrO2The hybrid microsphere/PS: injecting the dispersed phase solution and a polyvinyl alcohol (PVA) continuous phase solution into a focusing micro-fluidic channel at the same time at the flow rate of 2-8 mu L/min and the flow rate of 30-50 mu L/min, and preparing the ZrO through shearing and extruding actions of the continuous phase and the dispersed phase in the micro-channel2The hybrid microsphere/PS.
Preferably, the oil-soluble ZrO2Nanoparticles, Polystyrene (PS) and dichloromethane (CH)2Cl2) The mass ratio of (A) to (B) is 0.023-0.088: 0.2: 5.3.
Further preferably, the oil-soluble ZrO2The nanoparticles were prepared as follows:
(1) reacting zirconium (IV) -isopropanol complex of isopropanol with anhydrous benzyl alcohol under sealed condition to obtain ZrO2The benzyl alcohol solution is centrifuged to obtain solid ZrO2The nano particles are repeatedly washed and centrifuged by absolute ethyl alcohol for purification,
(2) the purified ZrO2Dispersing the nano particles in Tetrahydrofuran (THF) solution containing Methacryloxypropyltrimethoxysilane (MPS), and uniformly mixing to obtain ZrO2MPS/THF dispersion;
(3) ultrasonic post-heating reaction at room temperature, centrifuging to obtain supernatant, concentrating to remove solution to obtain MPS modified ZrO2Nanoparticles (MPS/ZrO)2) Namely oil soluble ZrO2Nanoparticles.
Further preferably, the mass-to-volume ratio of the zirconium (IV) isopropoxide complex to the anhydrous benzyl alcohol in step (1) is 5.6:55, g: mL;
the reaction was carried out at 240 ℃ for 4 days.
Further preferably, the ZrO in the step (2)2The molar ratio of nanoparticles to Methacryloxypropyltrimethoxysilane (MPS) was 1: 0.16.
Preferably, the post-ultrasonic heating reaction in the step (3) is specifically: performing ultrasonic treatment for 30min, and heating at 60 deg.C for reaction for 20 h;
the centrifugation is carried out for 8min at the rotating speed of 1000 rpm.
Preferably, the concentration of polyvinyl alcohol (PVA) in the continuous phase solution of polyvinyl alcohol (PVA) in step (2) is 1 wt%.
Preferably, the polyvinyl alcohol (PVA) continuous phase solution is prepared as follows: dissolving polyvinyl alcohol (PVA) in deionized water, and filtering with microporous membrane with pore diameter not more than 10 μm.
2. ZrO prepared according to the microfluidic preparation method2The hybrid microsphere/PS.
3. ZrO of the above2The application of the/PS hybrid microspheres in real-time super-resolution imaging.
The invention has the beneficial effects that: the invention discloses a ZrO2The microfluidic preparation method of the/PS hybrid microsphere mainly comprises the step of modifying ZrO by using a silane coupling agent (methacryloxypropyltrimethoxysilane (MPS))2Dispersing the nanoparticles in dichloromethane solution of Polystyrene (PS) as dispersed phase solution, and using polyvinyl alcohol (PVA) water solution as continuous phase solutionThe continuous phase solution is used for preparing ZrO under the shearing and extrusion action of the continuous phase solution in the microfluidic channel on the dispersed phase solution2The hybrid microsphere/PS. Due to the modified ZrO2The nano particles and the polymer matrix (PS) have good compatibility, can be uniformly distributed in the microspheres, and the prepared ZrO2the/PS microspheres have good optical transparency, and the refractive index of the hybrid microspheres is changed along with doping ZrO2The content of the nano particles is increased, the nano particles have more excellent processing performance and controllable refractive index than single-component microspheres, the resolution can be improved in the application of super-resolution imaging, and the nano particles have wider application prospect.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is MPS-modified ZrO prepared in example 12Nanoparticles (MPS/ZrO)2) (oil-soluble ZrO)2Nanoparticles);
FIG. 2 is a graph showing ZrO prepared in example 1 at a flow rate of the dispersed phase solution of 2. mu.L/min and a flow rate of the polyvinyl alcohol (PVA) continuous phase solution of 50. mu.L/min2SEM image of/PS hybrid microspheres;
FIG. 3 ZrO prepared when the flow rate of the dispersed phase solution was 5. mu.L/min and the flow rate of the polyvinyl alcohol (PVA) continuous phase solution was 50. mu.L/min in example 22SEM image of/PS hybrid microspheres;
FIG. 4 ZrO prepared when the flow rate of the dispersed phase solution was 8. mu.L/min and the flow rate of the polyvinyl alcohol (PVA) continuous phase solution was 50. mu.L/min in example 22SEM image of/PS hybrid microspheres;
FIG. 5 flow rate of the dispersed phase solution in example 3 was 8. mu.L/min, and the solution was polymerizedZrO prepared at a flow rate of 30. mu.L/min of a vinyl alcohol (PVA) continuous phase solution2SEM image of/PS hybrid microspheres;
in FIG. 6, a is a SEM image of the surface of a chip with fine structures having a pitch of 60nm and 75nm on the surface, and b is the pure PS microspheres (b) in comparative example 1 and ZrO prepared in example 1(c) and example 4(d), respectively2the/PS hybrid microspheres are used for real-time super-resolution imaging.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
ZrO (ZrO)2The microfluidic preparation method of the/PS hybrid microspheres comprises the following steps:
(1) preparation of oil-soluble ZrO2Nanoparticle: adding 5.6g of zirconium (IV) isopropoxide-isopropanol complex and 55ml of anhydrous benzyl alcohol into a 100ml polytetrafluoroethylene high-pressure reaction kettle, sealing the reaction kettle, and placing the reaction kettle in a 240 ℃ oven for reacting for 4 days to obtain ZrO2A benzyl alcohol solution; subjecting the obtained ZrO to2The benzyl alcohol solution is centrifuged to obtain solid precipitate which is ZrO2Washing the nano particles with absolute ethyl alcohol, centrifuging again, and performing the washing-centrifuging process for 3 times to obtain purified ZrO2Nanoparticles; the purified ZrO2The nanoparticles are dispersed in Tetrahydrofuran (THF) solution containing Methacryloxypropyltrimethoxysilane (MPS) dissolved therein2Molar ratio of nanoparticles 0.16:1) to obtain ZrO2MPS/THF dispersions (in whichZrO in the dispersion2About 1.2 wt%); subjecting the obtained ZrO to2Performing ultrasonic treatment on the/MPS/THF dispersion at room temperature for 30min, placing in a 60 deg.C oven, heating for reaction for 20 hr, and centrifuging at 1000rpm for 8min to remove ZrO2A small amount of agglomerated precipitate in the dispersion was obtained, and the resulting supernatant was concentrated by a rotary evaporator to remove the THF solvent, to obtain MPS-modified ZrO2Nanoparticles (MPS/ZrO)2) Namely oil soluble ZrO2A TEM image of the nanoparticles is shown in figure 1.
(2) Preparation of dispersed phase solution: 0.023g of oil-soluble ZrO2Nanoparticles and 0.2g Polystyrene (PS) dissolved in 5.3gCH2Cl2And stirring to mix uniformly to obtain a uniform solution, namely the dispersed phase solution.
(3) Preparation of polyvinyl alcohol (PVA) continuous phase solution: polyvinyl alcohol (PVA) is dissolved in deionized water at 90 ℃, and a 1 wt% PVA solution is obtained as a polyvinyl alcohol (PVA) continuous phase solution after filtration by a microporous membrane with the aperture of 1 mu m.
(4) Preparation of ZrO2The hybrid microsphere/PS: mixing the dispersed phase solution and polyvinyl alcohol (PVA) continuous phase solution at a flow rate of 2 muL/min and 50 muL/min in a focusing type micro-fluidic channel to prepare ZrO2The hybrid microsphere/PS.
The ZrO2ZrO in/PS hybrid microspheres2The content of nanoparticles was 10.5 wt%, ZrO2The SEM image of the/PS hybrid microspheres is shown in FIG. 2, and the average particle size is 25 μm.
Example 2
The flow rates of the dispersed phase solutions in the focusing micro-fluidic channel in the embodiment 1 are respectively changed into 5 mu L/min and 8 mu L/min, other preparation methods are the same as the embodiment 1, and ZrO with different particle sizes is prepared2The hybrid microsphere/PS. When the flow rate of the dispersed phase solution was 5. mu.L/min, the SEM photograph thereof is shown in FIG. 3, and the average particle diameter was 27 μm; when the flow rate of the dispersed phase solution was 8. mu.L/min, the SEM photograph thereof is shown in FIG. 4, and the average particle diameter was 26 μm.
Example 3
Flow of dispersed phase solution in focusing microfluidic channel of example 1The flow rate was changed to 8. mu.L/min and the flow rate of a polyvinyl alcohol (PVA) continuous phase solution was changed to 30. mu.L/min, and ZrO having an average particle size of 31 μm was prepared in the same manner as in example 12The SEM image of the/PS hybrid microspheres is shown in FIG. 5.
Example 4
Oil-soluble ZrO from example 12The added mass of the nanoparticles was changed from 0.023g to 0.088g, the flow rates of the dispersed phase solution and the polyvinyl alcohol (PVA) continuous phase solution were respectively changed to 5. mu.L/min and 50. mu.L/min, respectively, and ZrO was prepared in the same manner as in example 12ZrO with a nano particle content of 30.5 wt%2The hybrid microsphere/PS.
Comparative example 1
According to the preparation method in example 1, ZrO will be prepared2Oil-soluble ZrO added in process of/PS hybrid microspheres2The mass of the nanoparticles was changed to 0g, and ZrO-free was prepared in the same manner as in example 12Pure PS microspheres of nanoparticles.
The ZrO calculated in example 1 and example 4 was calculated according to the formula (1)2ZrO with different nanoparticle contents2The theoretical refractive index of the/PS hybrid microspheres is shown in Table 1.
np＝norg*Vorg+nZrO2*VZrO2 (1)
In the formula (1), norg、nZrO2Respectively represent pure poly-PS and ZrO2The refractive indices of the nanoparticles were 1.59 and 2.2, respectively. Vorg、VZrO2Respectively represents PS and ZrO in the microsphere2Volume fraction occupied by nanoparticles.
TABLE 1 ZrO2ZrO with different nano particle content2Theoretical refractive index of/PS hybrid microsphere
| Microspheres | ZrO2Content of nanoparticles | Refractive index of microsphere |
| Comparative example 1 | 0 | 1.590 |
| Example 1 | 10.5wt％ | 1.600 |
| Example 4 | 30.5wt％ | 1.634 |
ZrO from Table 12ZrO with different nano particle content2The theoretical refractive index test result of the/PS hybrid microspheres shows that ZrO is added into the PS microspheres2Nano particles capable of improving ZrO2Refractive index of hybrid microsphere/PS, and refractive index of hybrid microsphere is dependent on ZrO2ZrO in/PS hybrid microspheres2The increase in the nanoparticle content increases.
ZrO prepared from dispersed phase solution and polyvinyl alcohol (PVA) continuous phase solution in FIGS. 2-5 in focusing type microfluidic channel at different flow rates2It can be seen from the fact that the flow rates of the dispersed phase solution and the polyvinyl alcohol (PVA) continuous phase solution can influence the ZrO prepared by using the/PS hybrid microspheres2Average particle size of/PS hybrid microspheres.
Comparative example 1 was each ZrO-free2PS microspheres of nanoparticles and ZrO prepared in examples 1 and 42The corresponding effect of the/PS hybrid microspheres in the real-time super-resolution imaging process is shown in FIG. 6, wherein a in FIG. 6 is a chip surface SEM image with a fine structure with a surface having a pitch of 60nm and 75nm, and b in FIG. 6 is a chip surface SEM imageThe super-resolution imaging pictures of the chip surface structures observed under an optical microscope by using the microspheres of comparative example 1, example 1 in fig. 6 c and example 4 in fig. 6d respectively. As can be seen from FIG. 6, the microspheres with different refractive indexes are placed on the surface of the chip for real-time super-resolution imaging, which can achieve the amplification effect and improve the imaging resolution, the higher the resolution of the microspheres with larger refractive indexes is, the conventional optical microscope cannot distinguish the fine structure of the surface of the chip with the size less than 200nm, and when a pure PS material is placed on the surface of the chip, the gap characteristic structure with the size of 75nm on the surface of the chip (FIG. 6b) cannot be distinguished, but the ZrO prepared by the method of the present invention is added2After hybridization of the/PS microspheres, the 75nm gap was resolved (FIG. 6 d). It can be seen that the ZrO prepared by the present invention2the/PS hybrid microspheres can greatly improve the resolution when used in the real-time super-resolution imaging process.
In summary, the invention discloses ZrO2The microfluidic preparation method of the/PS hybrid microsphere mainly comprises the step of modifying ZrO by using a silane coupling agent (methacryloxypropyltrimethoxysilane (MPS))2Nano particles are doped into Polystyrene (PS) and then are sheared and dispersed with polyvinyl alcohol (PVA) continuous phase solution in a focusing type micro-fluidic channel to prepare ZrO2The hybrid microsphere/PS. Due to the modified ZrO2The nano particles and the polymer matrix (PS) have good compatibility, can be uniformly distributed in the microspheres, and the prepared ZrO2the/PS microspheres have good optical transparency, and the refractive index of the hybrid microspheres is changed along with doping ZrO2The content of the nano particles is increased, and the nano particles have more excellent processing performance and controllable refractive index than single-component microspheres, and have wider application prospect in the field of super-resolution imaging.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. ZrO (ZrO)2The microfluidic preparation method of the/PS hybrid microspheres is characterized by comprising the following steps:
(1) preparation of dispersed phase solution: dissolving oil soluble ZrO in water2Dissolving nano particles and polystyrene in dichloromethane, and stirring to uniformly mix the nano particles and the polystyrene to form a uniform solution, namely a dispersed phase solution;
(2) preparation of ZrO2The hybrid microsphere/PS: injecting the dispersed phase solution and the polyvinyl alcohol continuous phase solution into a focusing micro-fluidic channel at the flow rate of 2-8 mu L/min and the flow rate of 30-50 mu L/min simultaneously, and preparing the ZrO through shearing and extruding the continuous phase and the dispersed phase in the micro-channel2The hybrid microsphere/PS.
2. The microfluidic preparation method of claim 1, wherein the oil-soluble ZrO2The mass ratio of the nano particles to the polystyrene to the dichloromethane is 0.023-0.088: 0.2: 5.3.
3. Microfluidic preparation method according to claim 2, characterized in that the oil-soluble ZrO is2The nanoparticles were prepared as follows:
(1) reacting zirconium isopropoxide-isopropanol complex with anhydrous benzyl alcohol under sealed condition to obtain ZrO2The benzyl alcohol solution is centrifuged to obtain solid ZrO2The nano particles are repeatedly washed and centrifuged by absolute ethyl alcohol for purification,
(2) the purified ZrO2Dispersing the nano particles in tetrahydrofuran solution containing methacryloxypropyltrimethoxysilane, and uniformly mixing to obtain ZrO2MPS/THF dispersion;
(3) ultrasonic post-heating reaction at room temperature, centrifuging to obtain supernatant, concentrating to remove solution to obtain MPS modified ZrO2The nano particles are oil-soluble ZrO2Nanoparticles.
4. The microfluidic preparation method according to claim 3, wherein the mass-to-volume ratio of the zirconium isopropoxide-isopropanol complex to the anhydrous benzyl alcohol in step (1) is 5.6:55, g: mL;
the reaction was carried out at 240 ℃ for 4 days.
5. The microfluidic preparation method according to claim 3, wherein the ZrO in step (2)2The molar ratio of the nanoparticles to methacryloxypropyltrimethoxysilane was 1: 0.16.
6. The microfluidic preparation method according to claim 2, wherein the post-ultrasonic heating reaction in step (3) is specifically: performing ultrasonic treatment for 30min, and heating at 60 deg.C for reaction for 20 h;
the centrifugation is carried out for 8min at the rotating speed of 1000 rpm.
7. The microfluidic preparation method according to claim 1, wherein the concentration of polyvinyl alcohol in the continuous phase solution of polyvinyl alcohol in step (2) is 1 wt%.
8. The microfluidic preparation method according to claim 1, wherein the polyvinyl alcohol continuous phase solution is prepared according to the following method:
dissolving polyvinyl alcohol in deionized water, and filtering with microporous membrane with pore diameter not more than 10 μm.
9. ZrO prepared by the microfluidic preparation method according to any one of claims 1 to 82The hybrid microsphere/PS.
10. The ZrO 2 of claim 92The application of the/PS hybrid microspheres in real-time super-resolution imaging.
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