CN114699999B - Preparation method of core-shell silica microspheres based on microfluidic liquid drops - Google Patents
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Abstract
The invention provides a preparation method of core-shell silica microspheres based on microfluidic liquid drops, which comprises the steps of preparing a gradient emulsifying device, modifying a channel, generating liquid drops in the channel, preparing microspheres and the like, wherein monodisperse liquid drops are formed through a gradient emulsifying method in a liquid drop microfluidic technology, a silica precursor solution and caprylic acid glyceride are mutually dissolved in the presence of ethyl acetate to serve as a disperse phase, fluorocarbon oil serves as a continuous phase to form liquid drops with uniform size, volatilization of the ethyl acetate after standing causes the silica precursor solution and the caprylic acid glyceride to be mutually insoluble, and meanwhile, a surfactant in the fluorocarbon oil reacts with the silica precursor solution to solidify the liquid drops, so that the silica microspheres with core-shell structures are formed. On the basis, the content of the silicon dioxide precursor solution and the caprylic/capric glyceride in the disperse phase is changed, and the silicon dioxide microspheres with different core-shell thicknesses are obtained.
Description
Technical Field
The invention relates to a preparation method of core-shell silica microspheres based on microfluidic liquid drops, and belongs to the technical field of microfluidic microfluidics.
Background
With the development of micro-nano technology, the core-shell silica microsphere is widely applied to the fields of drug delivery, biosensing and the like, and has wide development prospect in the field of materials. The preparation method of the core-shell silica microspheres is various. The traditional preparation method of the silica microsphere combines an emulsification method and a sol-gel method, but the method requires huge instruments and equipment, the prepared microsphere has poor monodispersity, and the experimental requirement is difficult to meet when the method is applied to the research of the microsphere with strict size requirement. The Chinese patent with publication number of CN108341415A discloses a preparation method of macroporous silica core-shell microspheres, wherein the macroporous silica core-shell microspheres prepared by the method have a macroporous structure and are obtained by modifying nonporous silica gel microspheres through reaction of nonporous microspheres, organic monomers, cross-linking agents and pore-forming agents, and the prepared microspheres have a size of 1-3 mu m and are used for rapid separation analysis of biological macromolecules. CN110433882a discloses a microfluidic device for preparing capillary liquid drop and a method for preparing single-particle plungers, wherein the device is a microfluidic device made of capillary, and the capillary plungers are prepared by taking tetramethoxysiloxane, polyethylene glycol, acetic acid and ammonia water mixed solution as a disperse phase.
The droplets formed by the droplet microfluidic technology have high monodispersity and gradually develop into a new method for preparing microspheres. The droplet microfluidic technology can be divided into the following according to the geometry of the chip device: co-flow, cross-flow, flow focusing (flow focusing), and gradient emulsification device (step emulsification). Among them, the gradient emulsification method mainly relies on channel geometry and surface tension to form monodisperse droplets, which is a spontaneous process. When the disperse phase enters the end of the parallelization auxiliary channel, the disperse phase is restrained by the surrounding channel walls, and when the disperse phase approaches to a liquid storage tank (the position where the continuous phase is positioned) connected with the auxiliary channel, the fluid becomes tongue-shaped under the action of surface tension. The tongue-shaped fluid is continuously filled into a bulb shape after entering the liquid storage tank, the pressure difference between the bulb-shaped fluid and the dispersed phase still in the auxiliary channel is continuously increased, and finally the neck of the bulb-shaped fluid breaks to form liquid drops. At present, a gradient emulsification method based on microfluidic droplets is not found for preparing core-shell silica microspheres.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a core-shell silica microsphere preparation method based on microfluidic liquid drops.
The invention provides a preparation method of core-shell silica microspheres based on microfluidic liquid drops, which comprises the following steps:
step 1, preparing a microfluidic chip (namely a gradient emulsifying device), namely pouring Polydimethylsiloxane (PDMS) on a gradient emulsifying device template and a non-pattern blank template, taking down the blank polydimethylsiloxane after heating and shaping, sealing an upper gradient emulsifying channel and a lower gradient emulsifying channel, punching, cleaning by plasma, and finally sealing the blank polydimethylsiloxane on a glass sheet;
step 2, channel modification, namely injecting a modification liquid into a channel of the gradient emulsifying device, and removing the modification liquid after a certain period of modification;
step 3, generating liquid drops in a channel, namely dissolving a silicon dioxide precursor solution and caprylic capric glyceride in ethyl acetate (ethyl acetate is taken as a solvent, the adding amount of the ethyl acetate is that the silicon dioxide precursor solution and the caprylic capric glyceride are mutually dissolved) according to the volume ratio of 10-50:1, uniformly mixing to form a disperse phase, injecting the disperse phase into a gradient emulsifying device at a certain flow rate, breaking the disperse phase into liquid drops in the channel of the gradient emulsifying device, flowing the liquid drops into a liquid storage tank filled with a continuous phase, standing for a period of time, and solidifying into microspheres;
and 4, collecting the microspheres, and calcining the microspheres in a muffle furnace at 800 ℃ for 2 hours to obtain the core-shell silica microspheres based on microfluidic liquid drops.
According to the invention, micro-droplets are formed by a microfluidic technology, the droplets have high monodispersity, and when the microspheres are formed by subsequent solidification, the microsphere particle size distribution is small, and the microsphere with a core-shell structure is obtained by utilizing the intersolubility of a silicon dioxide precursor solution and caprylic/capric glyceride in the presence of ethyl acetate or not, so that the silicon dioxide microsphere with different core-shell thickness is prepared. The prepared core-shell silica microsphere has no observed pore structure, has the size of about 200 mu m, has an adsorption function, and can adsorb iodine ions in an iodine water solution.
Compared with the traditional preparation method of the core-shell silica microspheres through interface reaction, the prepared core-shell silica microspheres are thin in wall and easy to break, the preparation of the core-shell structure is realized through phase separation between two reagents, and the core-shell thickness can be adjusted by changing the content between the two reagents.
The technical scheme adopted as the further optimization of the invention is as follows:
in the step 1, the gradient emulsifying device consists of a disperse phase main channel, seven parallel auxiliary channels and a liquid storage tank for loading a continuous phase, wherein the main channel is connected with an injection needle of an injection pump in a pluggable manner, the main channel is connected with an inlet of the auxiliary channel, and an outlet of the auxiliary channel is connected with the liquid storage tank; the gradient emulsifying device is made of Polydimethylsiloxane (PDMS).
The microfluidic chip is a gradient emulsifying device, and seven parallel auxiliary channels are integrated, so that the flux of the device is improved.
Further, a continuous phase is arranged in the liquid storage tank, and the continuous phase is fluorocarbon oil.
Further, the modification solution is a mixed solution composed of fluorine-containing trichlorosilane and an electronic fluorination solution (FC 40), and the mixed solution contains 3 volume percent of fluorine-containing trichlorosilane and 97 volume percent of electronic fluorination solution. The modification liquid composed of fluorine-containing trichlorosilane and electronic fluorinated liquid can change the hydrophobicity of the surface of the PDMS channel and prevent liquid drops from adhering to the channel.
In the step 3, because the laplace pressure difference of the end of the auxiliary channel connected with the tip of the disperse phase in the liquid storage tank area is continuously increased, the disperse phase is broken into liquid drops in the area of the end of the auxiliary channel connected with the liquid storage tank, and flows into the liquid storage tank full of the continuous phase, fluorocarbon oil is used as the continuous phase, and after the liquid drops stand for 30-40 min, the silica precursor solution is volatilized and solidified along with ethyl acetate to obtain the silica microspheres.
The silica microsphere has a core-shell structure, a silica precursor solution, the caprylic capric acid glyceride and the ethyl acetate are taken as a disperse phase to form liquid drops, and the silica precursor solution and the caprylic capric acid glyceride are not mutually dissolved by volatilization of the ethyl acetate to obtain the core-shell structure, wherein the silica microsphere is taken as a shell, and the caprylic capric acid glyceride is taken as a core.
Further, the droplets have monodispersity, and the cured silica microspheres also have monodispersity.
Furthermore, the core-shell silica microspheres can be prepared into silica microspheres with different core-shell thicknesses by adjusting the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the disperse phase, wherein the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the disperse phase is respectively 10:1, 20:1, 30:1, 40:1 and 50:1.
Further, the preparation method of the silica precursor solution is as follows: with tetraethyl orthosilicate as the silicon source, 2.7 g of 0.01M hydrochloric acid solution, 3. 3 g ethanol solution and 5.2. 5.2 g tetraethyl orthosilicate were mixed and stirred for 30 min.
According to the invention, monodisperse liquid drops are formed by a gradient emulsion method in a liquid drop microfluidic technology, a silicon dioxide precursor solution and the caprylic/capric glyceride are mutually dissolved in the presence of ethyl acetate to serve as a disperse phase, fluorocarbon oil is used as a continuous phase to form liquid drops with uniform size, the ethyl acetate volatilizes after standing to cause the silicon dioxide precursor solution and the caprylic/capric glyceride to be mutually insoluble, and meanwhile, a surfactant in the fluorocarbon oil reacts with the silicon dioxide precursor solution to solidify the liquid drops, so that the silicon dioxide microsphere with a core-shell structure is formed. On the basis, the content of the silicon dioxide precursor solution and the caprylic/capric glyceride in the disperse phase is changed, and the silicon dioxide microspheres with different core-shell thicknesses are obtained.
The invention also provides application of the core-shell silica microsphere prepared by the method: the core-shell silica microsphere has an adsorption function and is used for adsorbing iodide ions.
Further, the prepared core-shell silica microspheres are added into an iodine aqueous solution, and after standing for one night, the core-shell silica microspheres are compared with an iodine aqueous solution without microspheres, and the ultraviolet absorbance values of the two solutions are measured to verify the application of the microspheres.
The invention has the advantages that the high-monodispersity liquid drops can be generated by adopting a liquid drop microfluidic technology, the silicon dioxide microsphere with uniform size is obtained after solidification, the silicon dioxide microsphere has a core-shell structure, the silicon dioxide microsphere with different core-shell thicknesses can be obtained by changing the volume ratio of a disperse phase, and the prepared microsphere has an adsorption function.
In a word, the preparation method is unique, and the core-shell silicon dioxide microspheres are prepared by a gradient emulsion method in a microfluidic droplet technology, so that the monodisperse microspheres can be obtained, and the droplet generation rate is improved; the reagent for forming the core-shell structure is unique, and because the silicon dioxide precursor solution and the caprylic-capric glyceride can be mutually dissolved in the presence of ethyl acetate, the volatilization of the ethyl acetate after liquid drops are generated, the silicon dioxide precursor solution and the caprylic-capric glyceride are gradually not mutually dissolved, so that the core-shell mechanism is obtained. The core-shell silica microsphere is prepared by one-step droplet-microsphere, and the preparation is quick and the method is simple.
Drawings
FIG. 1 is a schematic and physical diagram of the method of the present invention.
FIG. 2 is a schematic diagram of a gradient emulsifying device in the present invention.
FIG. 3 is a diagram of the present invention showing the results of the formation and solidification of droplets at different dispersed phase volume ratios.
FIG. 4 is a statistical plot of the size of droplets just formed and solidified at different dispersed phase volume ratios in the present invention.
FIG. 5 is an electron micrograph of silica microspheres at different dispersed phase volume ratios in accordance with the present invention.
FIG. 6 is a schematic representation of an aqueous iodine solution after a one-night rest without and with silica microspheres added in the present invention.
FIG. 7 is a graph showing the ultraviolet absorbance of an aqueous iodine solution after leaving the silica microspheres unaddressed and added for one night in the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings: the present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection rights of the present invention are not limited to the following embodiments.
Example 1 preparation of core-shell silica microspheres in gradient emulsion apparatus
And processing the photoresist male die with the specific pattern by adopting a standard photoetching process to obtain a gradient emulsifying device template, wherein the template is provided with positive patterns corresponding to a main channel, a secondary channel and a liquid storage tank on the gradient emulsifying device. And pouring the prepolymer of the Polydimethylsiloxane (PDMS) on the positive template respectively until the height of the prepolymer is flush with the positive template, pouring the prepolymer of the Polydimethylsiloxane (PDMS) on the blank template without patterns, and performing vacuum degassing respectively, and then heating, curing and shaping. After cooling, peeling the polydimethylsiloxane block with the channel pattern, punching, cleaning by plasma, sealing the polydimethylsiloxane block with the channel pattern and the blank polydimethylsiloxane block, and sealing the polydimethylsiloxane block with the glass substrate to form the microfluidic gradient emulsion chip, wherein the microfluidic gradient emulsion chip consists of a disperse phase main channel, seven parallel auxiliary channels and a liquid storage tank for loading a continuous phase, one end of the main channel is connected with an injection needle of an injection pump in a pluggable manner, the other end of the main channel is connected with an inlet of the auxiliary channel, and an outlet of the auxiliary channel is connected with the liquid storage tank (see figure 2). The liquid storage tank is internally provided with a continuous phase, and the continuous phase is fluorocarbon oil.
Injecting the modification liquid into the channel of the gradient emulsifying device, modifying for 30min, removing the modification liquid, and repeating the operation twice. The modification solution is a mixed solution composed of fluorine-containing trichlorosilane and electronic fluoridation solution (FC 40), wherein the mixed solution contains 3 volume percent of fluorine-containing trichlorosilane and 97 volume percent of electronic fluoridation solution.
After finishing the modification, injecting the disperse phase into the chip through an injection pump at a certain flow rate, and as the Laplacian pressure difference of the end of the auxiliary channel connected with the tip of the disperse phase in the liquid storage tank area is continuously increased, the disperse phase breaks into liquid drops, the liquid drops enter the liquid storage tank filled with the continuous phase, and after standing for 30-40 min, the silica precursor solution is solidified into microspheres along with volatilization of ethyl acetate (see figures 1, 3 and 4, the volume ratio of the silica precursor solution to the caprylic capric glyceride in figure 3 is A, D:20:1, B, E:30:1, C and F:50:1 respectively). The silica precursor solution and the glyceryl caprylate caprate are respectively dissolved in ethyl acetate according to the volume ratio of 20:1, 30:1 and 50:1 (the amount of the added ethyl acetate is enough to dissolve the two components mutually), and are uniformly mixed to form a disperse phase. The preparation method of the silica precursor solution is as follows: with tetraethyl orthosilicate as the silicon source, 2.7 g of 0.01M hydrochloric acid solution, 3. 3 g ethanol solution and 5.2. 5.2 g tetraethyl orthosilicate were mixed and stirred for 30 min. And placing the microsphere in a muffle furnace, and calcining at 800 ℃ for 2 hours to remove the caprylic/capric glyceride in the microsphere, so as to obtain the microsphere with the core-shell structure.
In addition, silica microspheres with different core-shell thicknesses were prepared by changing the volume ratio of the silica precursor solution to the caprylic capric glyceride in the disperse phase to 10:1, 30:1 and 50:1 (see FIG. 5, the volume ratios of the silica precursor solution to the caprylic capric glyceride are A, B, C10:1;D, E, F:20:1, G, H, I:30:1, J and K, L:50:1 respectively).
Example 2 application verification of core-shell silica microspheres
Adding the prepared core-shell silica microspheres into an iodine aqueous solution, standing for one night, comparing with an iodine aqueous solution without microspheres, and observing the color change of the solution, wherein A represents the iodine aqueous solution without microspheres as shown in fig. 6; b represents an aqueous iodine solution to which the microspheres are added, and ultraviolet absorbance values of the two solutions are measured simultaneously, and the result is shown in FIG. 7.
The foregoing is merely illustrative of the embodiments of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art will appreciate that modifications and substitutions are within the scope of the present invention, and the scope of the present invention is defined by the appended claims.
Claims (9)
1. The preparation method of the core-shell silica microsphere based on the microfluidic liquid drop is characterized by comprising the following steps of:
step 1, preparing a gradient emulsifying device, namely pouring polydimethylsiloxane on a gradient emulsifying device template and a non-pattern blank template, taking down the blank polydimethylsiloxane after heating and shaping, sealing the blank polydimethylsiloxane under an upper gradient emulsifying channel, punching, cleaning by plasma, and finally sealing the blank polydimethylsiloxane on a glass sheet;
step 2, channel modification, namely injecting a modification liquid into a channel of the gradient emulsifying device, and removing the modification liquid after a certain period of modification; the modification solution is a mixed solution composed of fluorine-containing trichlorosilane and electronic fluoridation solution;
step 3, generating liquid drops in a channel, namely dissolving a silicon dioxide precursor solution and caprylic/capric glyceride in ethyl acetate according to the volume ratio of 10-50:1, uniformly mixing to form a disperse phase, injecting the disperse phase into a gradient emulsifying device at a certain flow rate, breaking the disperse phase into liquid drops in the channel of the gradient emulsifying device, allowing the liquid drops to flow into a liquid storage tank filled with a continuous phase, and solidifying the liquid drops into microspheres after standing for a period of time; the continuous phase is fluorocarbon oil;
and 4, collecting the microspheres, and calcining the microspheres in a muffle furnace at 800 ℃ for 2 hours to obtain the core-shell silica microspheres based on microfluidic liquid drops.
2. The method for preparing the core-shell silica microspheres based on microfluidic droplets according to claim 1, wherein in the step 1, the gradient emulsifying device is composed of a dispersed phase main channel, seven parallel auxiliary channels and a liquid storage tank for loading a continuous phase, the main channel is connected with an injection needle of an injection pump in a pluggable manner, the main channel is connected with an inlet of the auxiliary channel, and an outlet of the auxiliary channel is connected with the liquid storage tank; the gradient emulsifying device is made of polydimethylsiloxane.
3. The method for preparing the core-shell silica microspheres based on microfluidic droplets according to claim 1, wherein the mixed solution contains 3% by volume of fluorine-containing trichlorosilane and 97% by volume of electronic fluorinated solution; the modification liquid composed of fluorine-containing trichlorosilane and electronic fluorinated liquid can change the hydrophobicity of the surface of the PDMS channel and prevent liquid drops from adhering to the channel.
4. The method for preparing the core-shell silica microspheres based on microfluidic liquid drops according to claim 1, wherein in the step 3, the pressure difference of the laplace at the end of the secondary channel connected with the tip of the dispersed phase in the liquid storage tank area is continuously increased, the dispersed phase is broken into liquid drops at the end of the secondary channel connected with the liquid storage tank area, the liquid drops flow into the liquid storage tank filled with the continuous phase, fluorocarbon oil is used as the continuous phase, and the silica precursor solution is solidified along with the volatilization of ethyl acetate after the liquid drops stand for 30-40 min, so that the silica microspheres are obtained.
5. The method for preparing core-shell silica microspheres based on microfluidic droplets according to claim 4, wherein the droplets have monodispersity and the cured silica microspheres have monodispersity.
6. The preparation method of the core-shell silica microsphere based on the microfluidic liquid drops, which is characterized in that the core-shell silica microsphere is prepared into silica microspheres with different core-shell thicknesses by adjusting the volume ratio of a silica precursor solution to caprylic/capric glyceride in a disperse phase, wherein the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the disperse phase is respectively 10:1, 20:1, 30:1, 40:1 and 50:1.
7. The method for preparing the core-shell silica microspheres based on microfluidic droplets according to claim 1, wherein the method for preparing the silica precursor solution is as follows: 2.7 g of 0.01M hydrochloric acid solution, 3 g ethanol solution and 5.2 g tetraethyl orthosilicate were mixed and stirred for 30 min.
8. Use of the core-shell silica microspheres prepared according to any one of claims 1 to 7, wherein the core-shell silica microspheres have an adsorption function for adsorbing iodide ions.
9. The use of a core-shell silica microsphere according to claim 8, wherein the prepared core-shell silica microsphere is added to an aqueous iodine solution, and after standing for one night, the core-shell silica microsphere is compared with an aqueous iodine solution without microspheres, and ultraviolet absorbance values of the two solutions are measured to verify the use of the microsphere.
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