CN114699999A - Preparation method of core-shell silica microspheres based on microfluidic droplets - Google Patents
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Abstract
The invention provides a method for preparing core-shell silica microspheres based on microfluidic droplets, which comprises the steps of preparing a gradient emulsification device, modifying a channel, generating droplets in the channel, preparing the microspheres and the like, wherein monodisperse droplets are formed by a gradient emulsification method in a droplet microfluidic technology, a silica precursor solution and 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 droplets with uniform size, the volatilization of the ethyl acetate after standing causes the silica precursor solution and the caprylic capric glyceride to be mutually dissolved, and meanwhile, a surfactant in the fluorocarbon oil reacts with the silica precursor solution to solidify the droplets, so the silica microspheres with the core-shell structure are formed. On the basis, the content of the silicon dioxide precursor solution and the content of the caprylic capric acid glyceride in the dispersed phase are 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 silicon dioxide microspheres based on microfluidic droplets, belonging to the technical field of microfluidic droplets.
Background
With the development of micro-nano technology, the core-shell silica microspheres are widely applied to the fields of drug delivery, biosensing and the like, and have wide development prospects in materials science. The preparation method of the core-shell silicon dioxide microspheres is various. The traditional preparation method of the silicon dioxide microspheres combines an emulsification method and a sol-gel method, but the method requires huge instruments and equipment, has poor monodispersity of the prepared microspheres, and is difficult to meet experimental requirements when applied to research with strict requirements on the sizes of the microspheres. The retrieval shows that Chinese patent with publication number CN108341415A discloses a preparation method of macroporous silica core-shell microspheres, the 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 with organic monomers, a cross-linking agent and a pore-forming agent, and the size of the prepared microspheres is 1-3 μm and is used for rapid separation and analysis of biomacromolecules. CN110433882A discloses a capillary drop microfluidic device and a single-particle plunger preparation method, wherein the device is a microfluidic device made of a capillary, and the capillary plunger is prepared by taking mixed solution of tetramethoxysiloxane, polyethylene glycol, acetic acid and ammonia water as disperse phase.
The liquid drops formed by the liquid drop microfluidic technology have high monodispersity and are gradually developed into a new method for preparing microspheres. Droplet microfluidics can be classified according to the geometry of the chip device as follows: co-flow (co-flow), cross-flow (cross-flow), flow focusing (flow focusing), and gradient emulsification devices (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 dispersed phase enters the tail end of the parallelization secondary channel, the dispersed phase is restrained by the walls of the peripheral channels, and when the dispersed phase approaches a liquid storage pool (where the continuous phase is located) connected with the secondary channel, the liquid is changed into a tongue shape under the action of surface tension. After the tongue-shaped fluid enters the liquid storage tank, the tongue-shaped fluid is continuously filled into a bulb shape, the pressure difference between the bulb-shaped fluid and the dispersed phase still in the secondary channel is continuously increased, and finally the neck of the bulb-shaped fluid is broken to form liquid drops. At present, the preparation of core-shell silica microspheres based on a gradient emulsification method of microfluidic droplets is not found.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing core-shell silica microspheres based on microfluidic droplets, which overcomes the defects of the prior art.
The invention provides a preparation method of core-shell silicon dioxide microspheres based on microfluidic droplets, which comprises the following steps:
step 1, preparing a micro-fluidic chip (namely a gradient emulsifying device), namely pouring Polydimethylsiloxane (PDMS) on a template of the gradient emulsifying device and a non-pattern hollow template, heating and shaping the template and taking the template down, sealing the blank polydimethylsiloxane on an upper gradient emulsifying channel and a lower gradient emulsifying channel, punching, cleaning 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 emulsification device, and removing the modification liquid after modification for a certain time;
step 3, generating liquid drops in the channel and preparing microspheres, namely dissolving a silicon dioxide precursor solution and caprylic/capric glyceride in ethyl acetate according to the volume ratio of 10-50: 1 (the ethyl acetate is used as a solvent, and the adding amount of the ethyl acetate is that the silicon dioxide precursor solution and the caprylic/capric glyceride can be mutually dissolved), uniformly mixing to form a dispersion phase, injecting the dispersion phase into a gradient emulsifying device at a certain flow velocity, breaking the dispersion 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, standing for a period of time, and solidifying into the microspheres;
and 4, collecting the microspheres, and calcining the microspheres in a muffle furnace at 800 ℃ for 2 hours to obtain the core-shell silicon dioxide microspheres based on the microfluidic droplets.
The invention forms micro-droplets by a micro-fluidic technology, the droplets have high monodispersity, and when the droplets are solidified into microspheres subsequently, the particle size distribution of the microspheres is small, and meanwhile, the microspheres with a core-shell structure are obtained by utilizing the intersolubility of a silicon dioxide precursor solution and caprylic/capric glyceride in the presence or absence of ethyl acetate, so that the silicon dioxide microspheres with different core-shell thicknesses are prepared. The prepared core-shell silica microspheres have no observed porous structure, have the size of about 200 mu m, have the adsorption function and can adsorb iodide ions in an iodine aqueous solution.
The core-shell structure is prepared by separating two reagents, and the thickness of the core shell can be adjusted by changing the content between the two reagents.
The technical scheme for further optimizing the invention is as follows:
in the step 1, the gradient emulsifying device consists of a dispersed phase main channel, seven parallelization 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 material used by the gradient emulsifying device is Polydimethylsiloxane (PDMS).
The micro-fluidic chip is a gradient emulsifying device, and simultaneously integrates seven parallel auxiliary channels, so that the flux of the device is improved.
Furthermore, a continuous phase is filled in the liquid storage tank, and the continuous phase is fluorocarbon oil.
Further, the modification liquid is a mixed solution composed of fluorine-containing trichlorosilane and an electronic fluorination liquid (FC 40), and the mixed solution contains 3 vol% of fluorine-containing trichlorosilane and 97 vol% of the electronic fluorination liquid. The modification liquid composed of the fluorine-containing trichlorosilane and the electronic fluorinated liquid can change the hydrophobicity of the surface of the PDMS channel and prevent liquid drops from being adhered to the channel.
In the step 3, because the Laplace pressure difference at the tip of the dispersed phase in the region where the tail end of the auxiliary channel is connected with the liquid storage tank is continuously increased, the dispersed phase is broken into liquid drops in the region where the tail end of the auxiliary channel is connected with the liquid storage tank, the liquid drops flow into the liquid storage tank filled with the continuous phase, fluorocarbon oil is used as the continuous phase, and after the liquid drops are kept still for 30-40 min, the silicon dioxide precursor solution is solidified along with the volatilization of ethyl acetate to obtain the silicon dioxide microspheres.
The silicon dioxide microsphere has a core-shell structure, a silicon dioxide precursor solution, caprylic/capric glyceride and ethyl acetate are used as dispersed phases to form liquid drops, and the silicon dioxide precursor solution and the caprylic/capric glyceride are immiscible through volatilization of the ethyl acetate to obtain the core-shell structure, wherein the silicon dioxide microsphere is a shell, and the caprylic/capric glyceride is a core.
Furthermore, the liquid drops have monodispersity, and the cured silica microspheres also have monodispersity.
Further, 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 dispersed phase, wherein the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the dispersed phase is 10:1, 20:1, 30:1, 40:1 and 50:1 respectively.
Further, the preparation method of the silica precursor solution is as follows: tetraethyl orthosilicate was used as a silicon source, and 2.7 g of a 0.01M hydrochloric acid solution, 3 g of an ethanol solution and 5.2 g of tetraethyl orthosilicate were mixed and stirred for 30 min.
The invention forms monodisperse droplets by a gradient emulsification method in a droplet microfluidic technology, takes a silicon dioxide precursor solution and caprylic capric glyceride which are mutually dissolved in the presence of ethyl acetate as a disperse phase, takes fluorocarbon oil as a continuous phase to form droplets with uniform size, the volatilization of the ethyl acetate after standing can lead the silicon dioxide precursor solution and the caprylic capric glyceride to be mutually dissolved, and simultaneously, a surfactant in the fluorocarbon oil reacts with the silicon dioxide precursor solution to solidify the droplets, thus forming the silicon dioxide microspheres with the core-shell structure. On the basis, the content of the silicon dioxide precursor solution and the content of the caprylic capric acid glyceride in the dispersed phase are changed, and the silicon dioxide microspheres with different core-shell thicknesses are obtained.
The invention also provides an application of the core-shell silica microspheres prepared by the method, which comprises the following steps: the core-shell silica microspheres have an adsorption function and are 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 prepared 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 droplet micro-fluidic technology can be adopted to generate droplets with high monodispersity, silicon dioxide microspheres with uniform size are obtained after solidification, the silicon dioxide microspheres have a core-shell structure, the silicon dioxide microspheres with different core-shell thicknesses can be obtained by changing the volume ratio of dispersed phases, and the prepared microspheres have an adsorption function.
In a word, the preparation method is unique, and the core-shell silicon dioxide microspheres are prepared by a gradient emulsification 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 leads the silicon dioxide precursor solution and the caprylic/capric glyceride to be gradually immiscible, thereby obtaining the core-shell structure. The core-shell silica microspheres are prepared by one step through liquid drop-microspheres, the preparation is rapid, 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 view of a gradient emulsifying apparatus according to the present invention.
FIG. 3 is a diagram of the composition of the invention immediately after droplet formation and solidification at different dispersed phase volume ratios.
FIG. 4 is a statistical plot of the sizes of droplets just formed and after solidification for different volume ratios of the dispersed phase in the present invention.
FIG. 5 is an electron microscope image of silica microspheres in different volume ratios of dispersed phases in the present invention.
FIG. 6 is a schematic view of an aqueous iodine solution of the present invention after standing overnight without adding silica microspheres.
FIG. 7 is a graph showing the UV absorption photometry of an aqueous iodine solution after standing overnight without adding silica microspheres in the present invention.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the drawings as follows: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection authority of the present invention is not limited to the following embodiments.
Example 1 preparation of core-shell silica microspheres in a gradient emulsification device
And processing the photoresist male die with a specific pattern by adopting a standard photoetching process to obtain a template of the gradient emulsifying device, wherein the template is provided with a positive pattern corresponding to a main channel and an auxiliary channel on the gradient emulsifying device and a liquid storage tank. And respectively pouring prepolymers of Polydimethylsiloxane (PDMS) on the male template until the height of the prepolymers is flush with that of the male template, simultaneously pouring the prepolymers of the PDMS on a non-pattern hollow template, respectively carrying out vacuum degassing, heating for curing and shaping. And after cooling, stripping the polydimethylsiloxane block with the channel pattern, perforating, carrying out plasma cleaning, sealing the polydimethylsiloxane block with the channel pattern with a blank polydimethylsiloxane block, and then sealing the polydimethylsiloxane block with the blank polydimethylsiloxane block with a glass substrate to form the microfluidic gradient emulsification chip, wherein the microfluidic gradient emulsification chip consists of a dispersed phase main channel, seven parallel auxiliary channels and a liquid storage pool 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 pool (see figure 2). The liquid storage tank is filled with a continuous phase which is fluorocarbon oil.
And injecting the modifying liquid into a channel of the gradient emulsifying device, modifying for 30min, removing the modifying liquid, and repeating the operation twice. The modifying solution is a mixed solution composed of fluorine-containing trichlorosilane and electronic fluorination solution (FC 40), wherein the mixed solution contains 3 vol% of fluorine-containing trichlorosilane and 97 vol% of electronic fluorination solution.
After finishing modification, injecting the dispersed phase into the chip at a certain flow rate through a syringe pump, and breaking the dispersed phase into droplets due to the continuously increased laplace pressure difference of the tip of the dispersed phase connected with the liquid storage pool area at the tail end of the auxiliary channel, allowing the droplets to enter the liquid storage pool filled with the continuous phase, standing for 30-40 min, and then solidifying the silica precursor solution into microspheres along with the volatilization of ethyl acetate (see fig. 1, fig. 3 and fig. 4, wherein the volume ratio of the silica precursor solution to caprylic capric glyceride in fig. 3 is A, D: 20:1, B, E: 30:1, C, F: 50:1, respectively). Wherein, the silicon dioxide precursor solution and the caprylic capric glyceride are respectively dissolved in ethyl acetate (the amount of the added ethyl acetate is that the two are mutually dissolved) according to the volume ratio of 20:1, 30:1 and 50:1, and the mixture is uniformly mixed to form a dispersed phase. The preparation method of the silica precursor solution is as follows: tetraethyl orthosilicate was used as a silicon source, and 2.7 g of a 0.01M hydrochloric acid solution, 3 g of an ethanol solution and 5.2 g of tetraethyl orthosilicate were mixed and stirred for 30 min. And (3) placing the microspheres in a muffle furnace, calcining at 800 ℃ for 2 hours, and removing the caprylic/capric glyceride in the microspheres to obtain the microspheres with the core-shell structure.
In addition, silica microspheres with different core-shell thicknesses were prepared by changing the volume ratios of the silica precursor solution to the caprylic/capric glyceride to 10:1, 30:1 and 50:1 in the dispersed phase (see fig. 5, the volume ratios of the silica precursor solution to the caprylic/capric glyceride were A, B, C10:1, D, E, F: 20:1, G, H, I: 30:1 and J, 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 were added, and the ultraviolet absorbance values of both solutions were measured at the same time, and the results are shown in FIG. 7.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can understand that the modifications or substitutions within the technical scope of the present invention are included in the scope of the present invention, and therefore, the scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of core-shell silica microspheres based on microfluidic droplets is characterized by comprising the following steps:
step 1, preparing a gradient emulsifying device, namely pouring polydimethylsiloxane on a template of the gradient emulsifying device and a non-pattern hollow template, heating and shaping, taking down the template, sealing the blank polydimethylsiloxane at the upper part and the lower part of a gradient emulsifying channel, punching, cleaning by plasma, and finally sealing the blank polydimethylsiloxane to a glass sheet;
step 2, channel modification, namely injecting a modification liquid into a channel of the gradient emulsification device, and removing the modification liquid after modification for a certain time;
step 3, generating liquid drops in the channel and preparing microspheres, 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 dispersed phase, injecting the dispersed phase into a gradient emulsifying device at a certain flow velocity, breaking the dispersed 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, standing for a period of time, and solidifying into the microspheres;
and 4, collecting the microspheres, and calcining the microspheres in a muffle furnace at 800 ℃ for 2 hours to obtain the core-shell silicon dioxide microspheres based on the microfluidic droplets.
2. The method for preparing core-shell silica microspheres based on microfluidic droplets according to claim 1, wherein in step 1, the gradient emulsification device comprises a dispersed phase main channel, seven parallelized 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 material used by the gradient emulsifying device is polydimethylsiloxane.
3. The preparation method of the core-shell silica microspheres based on the microfluidic droplets as claimed in claim 2, wherein a continuous phase is filled in the liquid storage tank, and the continuous phase is fluorocarbon oil.
4. The method for preparing the core-shell silica microspheres based on the microfluidic droplets according to claim 1, wherein the modifying solution is a mixed solution composed of fluorine-containing trichlorosilane and an electronic fluorination solution, and the mixed solution contains 3 vol% of fluorine-containing trichlorosilane and 97 vol% of the electronic fluorination solution; the modification liquid composed of the fluorine-containing trichlorosilane and the electronic fluorinated liquid can change the hydrophobicity of the surface of the PDMS channel and prevent liquid drops from being adhered to the channel.
5. The method for preparing core-shell silica microspheres based on microfluidic droplets according to claim 1, wherein in step 3, as the laplace pressure difference at the tip of the dispersed phase connected to the reservoir region at the end of the secondary channel is increased continuously, the dispersed phase is broken into droplets in the reservoir region connected to the end of the secondary channel, the droplets flow into the reservoir filled with the continuous phase, fluorocarbon oil is used as the continuous phase, and after the droplets are left to stand for 30-40 min, the silica precursor solution is solidified along with the volatilization of ethyl acetate to obtain the silica microspheres.
6. The method for preparing the core-shell silica microspheres based on the microfluidic droplets as claimed in claim 5, wherein the droplets have monodispersity, and the cured silica microspheres also have monodispersity.
7. The method for preparing the core-shell silica microspheres based on the microfluidic droplets according to claim 6, wherein the core-shell silica microspheres can be prepared to obtain silica microspheres with different core-shell thicknesses by adjusting the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the dispersed phase, and the volume ratio of the silica precursor solution to the caprylic/capric glyceride in the dispersed phase is 10:1, 20:1, 30:1, 40:1, and 50:1, respectively.
8. The preparation method of the core-shell silica microsphere based on the microfluidic droplets as claimed in claim 1, wherein the preparation method of the silica precursor solution is as follows: 2.7 g of a 0.01M hydrochloric acid solution, 3 g of an ethanol solution and 5.2 g of tetraethyl orthosilicate were mixed and stirred for 30 min.
9. Use of core shell silica microspheres prepared according to the method of claims 1 to 8, wherein the core shell silica microspheres have an adsorption function for adsorbing iodide ions.
10. The use of core-shell silica microspheres according to claim 9, wherein the prepared core-shell silica microspheres are added to an aqueous iodine solution, and after standing overnight, the prepared core-shell silica microspheres are compared with an aqueous iodine solution without microspheres, and the uv absorbance values of the two solutions are measured to verify the use of the microspheres.
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