Structural color tubular driver and preparation method and application thereof

Abstract

The invention discloses a structural color tubular driver and a preparation method and application thereof.The preparation method includes preparation of a template, preparation of composite hydrogel and acquisition of the structural color tubular driver, and the main method includes the steps that hydrogel pre-polymerization liquid is utilized, the tubular driver is provided with a responsive structural color outer layer and a porous inner layer through a template etching method, and the structural color outer layer and the porous inner layer are combined to form the structural color tubular driver. And an inner layer structure with a hydrophilic property is obtained through internal secondary glue pouring. The prepared structural color tubular driver has photo-thermal responsiveness, the surface is in a visible bright structural color, and the structural color tubular driver is easy to detect; and the inner layer is hydrophilic and has a lubricating function in a liquid drop transfer process, so that the transportation efficiency is effectively improved. The structural color tubular driver has the advantages of being simple in preparation process, convenient to operate and the like, and is suitable for the technical fields of liquid transportation, sensing detection and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of biomaterials, and in particular relates to a structural color tubular actuator and a preparation method and application thereof. Background Art

[0002] Liquid transport is common in chemistry, biology or medicine, and is of high value in scientific research and implementation related to analysis, reaction or diagnosis. Synthetic interfaces with specific wettability, especially porous surfaces with additional lubricating layers, can significantly reduce flow resistance and liquid residue, and have become a research hotspot in the field of liquid transport. These lubricant-infused surfaces can obtain adjustable or even programmable wettability by introducing external field-responsive units, thereby expanding their value for complex liquid operations. Therefore, such smart surfaces have been widely used in water collection, microfluidic operations, chemical reactions and other fields. However, current liquid transport systems are mainly suitable for ideal low-viscosity liquids, while the efficient transport of high-viscosity liquids remains a challenge. In addition, most systems cannot achieve real-time monitoring of the liquid transport process, which limits the timely and effective evaluation of the system's transport function.

[0003] The inner surface of the gastrointestinal system contains lubricating mucus, which can significantly reduce the movement resistance of viscous fluids and easily and efficiently transport chyme with a viscosity of up to 2000 mPa·s under the forward driving force generated by the continuous contraction of adjacent smooth muscles. Inspired by the peristaltic motion of the gastrointestinal system, responsive deformable systems with smooth inner surfaces have been designed for various applications, including viscous fluid microfluidics, solid transfer, soft robotics, and chemical reactions. On the other hand, chameleons can cleverly adjust their skin color to blend into the surrounding environment through the interaction of photons with the guanine nanocrystal lattice. This dynamic and vivid process has led to the emergence of many programmable smart hydrogels with colloidal crystals or inverse opal structures, which are widely used in biosensing and self-reporting systems. Summary of the invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to provide a structural color tubular actuator with a superhydrophilic inner layer and a responsive sensing outer layer, which can be used for efficient transportation and real-time monitoring of high-viscosity liquids, in view of the shortcomings of the existing tubular actuator transportation system, such as low efficiency and inability to report in real time.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A method for preparing a structural color tubular actuator comprises the following steps: (1) Template preparation: The nanospheres are assembled in an orderly manner on the inner and outer walls of the glass tube, and templates with different colors and sizes are obtained by adjusting the particle size of the nanospheres; (2) Preparation of composite hydrogel tubes: Prepare response layer prepolymer solutions of different concentrations, fix the thin glass tube with nano-microspheres on the outer wall in step (1) at the inner axis position of the glass tube with nano-microspheres on the inner wall, inject the response layer prepolymer solution between the two glass tubes, remove the template after solidification, inject the hydrophilic layer prepolymer solution into the holes in the inner layer of the hydrogel, and wait for the hydrophilic layer prepolymer solution to solidify to obtain a composite hydrogel tube; (3) Obtaining a structural color tubular actuator: The composite hydrogel tube in step (2) is immersed in a reducing agent for reduction, and then immersed in deionized water to remove unreacted components, thereby obtaining a structural color tubular actuator.

[0006] Specifically, in step (1), the length of the glass tube is 1 cm-20 cm, the inner diameter of the glass tube is 0.1 mm-5 mm, the outer diameter of the glass tube is 0.2 mm-10 mm, and the wall thickness of the glass tube is 0.1 mm-5 mm.

[0007] Specifically, in step (1), the nanospheres are selected from any one of polystyrene microspheres, polyethylene microspheres, and silica microspheres, and the particle size of the microspheres used for assembly on the inner wall of the glass tube is 200nm-400nm, and the particle size of the microspheres used for assembly on the outer wall of the glass tube is 100nm-300nm.

[0008] Specifically, in step (2), the response layer prepolymer solution is a mixed aqueous solution of N-isopropylacrylamide, sodium alginate and graphene oxide, wherein the mass concentration of N-isopropylacrylamide is 5%-20%, the mass concentration of sodium alginate is 0.1%-5%, and the concentration of graphene oxide is 0.5mg / ml-10mg / ml.

[0009] Specifically, in step (2), the response layer prepolymer liquid is cured by ultraviolet irradiation or chemical crosslinking, and the crosslinking agent used is N, N'-methylenebisacrylamide, and its mass concentration in the response layer prepolymer liquid is 0.01%-1%.

[0010] Specifically, in step (2), the method for removing the template is to remove the nano-microspheres by chemical etching and peel the hydrogel from the glass tube.

[0011] Specifically, in step (2), the hydrophilic layer prepolymer liquid is a sodium alginate aqueous solution, wherein the concentration of sodium alginate is 0.1%-5%; the hydrophilic layer prepolymer liquid is cured by chemical crosslinking, and the crosslinking agent used is calcium chloride, and its mass concentration in the hydrophilic layer prepolymer liquid is 1%-10%.

[0012] Specifically, in step (3), the reducing agent is an aqueous solution of hydroiodic acid with a mass concentration of 1%-10%.

[0013] Furthermore, the structural color tubular actuator prepared by the above preparation method is also within the protection scope of the present invention.

[0014] Furthermore, the present invention also claims to protect the application of the above-mentioned structural color tubular actuator in liquid transportation or sensing analysis. Beneficial Effects

[0015] (1) The present invention increases the swelling property of the actuator by adding calcium alginate and increases the super-hydrophilic inner layer by glue-filling technology. Under near-infrared stimulation, the super-hydrophilic layer absorbs the water released from the outer layer and forms a water film on the surface of the inner layer, thereby reducing the liquid transport resistance and droplet residue, and facilitating the efficient transport of high-viscosity droplets.

[0016] (2) The structural color tubular actuator designed in the present invention has an internal hydrophilic layer, which has a lubricating function during liquid transportation, reduces liquid residue, and effectively improves transportation speed and efficiency.

[0017] (3) The structural color tubular actuator prepared by the present invention shrinks the pipeline under near-infrared irradiation, and exhibits bright surface color changes while achieving liquid transportation, thereby realizing real-time reporting of liquid transportation status and real-time self-inspection of pipeline functions. The detection method is simple and rapid, and does not require complex detection equipment. It has high research value in the field of liquid transportation. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0019] Figure 1 It is a preparation flow chart of the structural color tubular actuator of the present invention.

[0020] Figure 2 This is the characterization of the structural color tubular actuator of the present invention. (a) is the overall picture of the structural color tubular actuator, (b) is the periodic nanopore structure on the surface of the structural color tubular actuator, and (c) is the structure of the inner surface of the structural color tubular actuator; (df) are schematic diagrams, EDS characterization and statistical analysis of the Ca element distribution inside the structural color tubular actuator.

[0021] Figure 3 This is the liquid transport application of the tubular actuator of Example 1 of the present invention. (a) is a schematic diagram of the liquid transport process of the tubular actuator, (b) is an optical microscope and schematic diagram of the tubular actuator performing viscous droplet transport, and (c) is the residue conditions at different positions in the tubular actuator observed by fluorescence microscopy. The scales in (b, c) are 0.5 mm, respectively.

[0022] Figure 4This is the application of the tubular actuator of Example 1 of the present invention in liquid transport under complex paths. (a, b) are the transportation process of viscous liquid along a horizontal serpentine path, and (c) is the residual situation in the tubular actuator observed by fluorescence microscopy. The scale is 5 mm in (a, b) and 0.5 mm in (c).

[0023] Figure 5 It is the self-reporting function of the structural color tubular actuator of Example 2 of the present invention, (a) is a schematic diagram of the structural color change on the surface of the structural color tubular actuator, (b, c) are optical images and spectra of the irradiated part of the structural color tubular actuator, (d) is the spectrum of the structural color tubular actuator in six cycles of contraction under near-infrared light or recovery in ice water, (eh) are schematic diagrams, optical microscope images and spectra of the intact and damaged parts of the structural color tubular actuator, (i, j) are records of leakage of the damaged structural color actuator during liquid transportation, and the scale is 2 mm in (b, f, j), 0.5 mm in (g), and 5 mm in (i). DETAILED DESCRIPTION

[0024] The present invention can be better understood with reference to the following examples. Example 1

[0025] In order to conveniently verify the liquid transport effect of the tubular actuator of the present invention, a tubular actuator having a hydrophilic layer on the inner layer is prepared in this embodiment.

[0026] (1) Template preparation Prepare an alcohol dispersion of silica nanoparticles with a particle size of 100 nm; insert clean glass tubes with an outer diameter of 1 mm into the silica alcohol dispersion respectively, and as the alcohol evaporates, the silica particles are deposited on the surface of the glass tube in an orderly manner.

[0027] (2) Preparation of composite hydrogel A prepolymer solution was prepared, containing 20% ​​N-isopropylacrylamide, 0.5% sodium alginate, 1 mg / ml graphene oxide, 0.1% N, N'-methylenebisacrylamide, 0.075% ammonium persulfate, and 0.5% N, N, N', N'-tetramethylethylenediamine; a thin glass tube with silica particles deposited on the outer wall was fixed at the inner axis position of a clean glass tube and fixed with a transparent epoxy resin; the prepolymer solution was injected between the two glass tubes and penetrated into the gaps between the silica particles. After the hydrogel was solidified, 4% hydrofluoric acid was used to corrode the silica particles and the glass tube, and then 0.5% sodium alginate was injected into the pores of the inner layer of the hydrogel, and immersed in a calcium chloride solution to form a hydrophilic layer.

[0028] (3) Obtaining structural color tubular actuators The composite hydrogel was immersed in a 4% hydroiodic acid aqueous solution for reduction at room temperature overnight, and the hydrogel was immersed in deionized water, and the deionized water was changed three times to remove the unreacted components, and finally a tubular actuator was obtained. Example 2

[0029] Combination Figure 1 The structural color tubular actuator of the present invention is prepared according to the preparation process shown.

[0030] (1) Template preparation Prepare alcohol dispersions of silica nanoparticles with particle sizes of 300 nm and 100 nm; insert a clean glass tube with an inner diameter of 4 mm and a clean glass tube with an outer diameter of 1 mm into the silica alcohol dispersions respectively. As the alcohol evaporates, the silica particles are deposited on the surface of the glass tube in an orderly manner.

[0031] (2) Preparation of composite hydrogel A prepolymer solution was prepared, containing 20% ​​N-isopropylacrylamide, 0.5% sodium alginate, 1 mg / ml graphene oxide, 0.1% N, N'-methylenebisacrylamide, 0.075% ammonium persulfate, and 0.5% N, N, N', N'-tetramethylethylenediamine; a thin glass tube with silica particles deposited on the outer wall was fixed at the inner axis position of a glass tube with silica particles on the inner wall, and fixed with a transparent epoxy resin; the prepolymer solution was injected between the two glass tubes and penetrated into the gaps between the silica particles. After the hydrogel was solidified, 4% hydrofluoric acid was used to corrode the silica particles and the glass tube, and then 0.5% sodium alginate was injected into the pores of the inner layer of the hydrogel, and immersed in a calcium chloride solution to form a hydrophilic layer.

[0032] (3) Obtaining structural color tubular actuators The composite hydrogel was immersed in a 4% hydroiodic acid aqueous solution for reduction at room temperature overnight, and the hydrogel was immersed in deionized water, and the deionized water was changed three times to remove the unreacted components, and finally a structural color tubular actuator was obtained. Figure 2 As shown, (a) is the overall picture of the structural color tubular actuator, (b) is the periodic nanopore structure on the surface of the structural color tubular actuator, and (c) is the structure of the inner surface of the structural color tubular actuator; (df) schematic diagram, EDS characterization and statistical analysis of the Ca element distribution inside the structural color tubular actuator. It can be seen that the surface of the structural color tubular actuator has a periodic nanopore structure, and this unique structure provides it with self-reporting potential; the hydrophilic layer and the response layer are assembled by secondary glue injection, and the structure is stable; the gradient distribution of the calcium alginate hydrophilic layer is presented by the distribution of the Ca element, and the highly hydrophilic inner surface is more likely to form a water film, laying the foundation for the efficient transportation of droplets. Example 3

[0033] The tubular actuator prepared by the present invention has a hydrophilic layer in the inner layer and is applied in liquid transportation.

[0034] A viscous droplet doped with Nile red was injected from the right side into the simple tubular actuator prepared in Example 1. Under near-infrared light irradiation, the tubular actuator showed continuous contraction. As the near-infrared light gradually moved to the left, red viscous liquid flowed out from the left outlet. In order to check the residue of the viscous droplets, cuts were made at different positions of the actuator, and the residual Nile red was evaluated by fluorescence microscopy. The study found that the amount of droplet residue in the tubular actuator was negligible, and the water film formed in the tubular actuator significantly reduced the adhesion of the droplets on the inner surface, effectively improving the transmission efficiency. Figure 3 As shown, (a) is a schematic diagram of the liquid transport process of the tubular actuator, (b) is an optical microscope and schematic diagram of the tubular actuator performing viscous droplet transport, and (c) is the residue conditions at different positions in the tubular actuator observed by fluorescence microscopy. The scales in (b, c) are 0.5 mm, respectively. Example 4

[0035] The inner layer prepared by the invention has the liquid transport function of the hydrophilic layer tubular actuator under complex paths.

[0036] A tubular actuator with a length of 12 cm was prepared according to the method in Example 1, and a viscous droplet doped with Nile red was injected into the tubular actuator from the right side. In addition, a complex channel with a horizontal serpentine path was prepared by a 3D printing method, and the tubular actuator was placed in the channel. Under near-infrared light irradiation, the tubular actuator showed continuous contraction, and as the near-infrared light moved, red viscous liquid flowed out from the left outlet. In order to check the residue of viscous droplets, the actuator was cut and the residual Nile red was evaluated by fluorescence microscopy. The study found that the amount of droplet residue in the tubular actuator was negligible. Therefore, even if the tubular actuator is used in complex channels, it still exhibits a high-efficiency transport capability for viscous droplets, such as Figure 4 As shown, (a, b) are the transport process of viscous liquid along the horizontal serpentine path, and (c) is the residual situation inside the tubular actuator observed by fluorescence microscopy. The scale bar is 5 mm in (a, b) and 0.5 mm in (c). Example 5

[0037] Verification of the self-reporting function of the structural color tubular actuator prepared by the present invention.

[0038] The structural color tubular actuator prepared in Example 2 was irradiated with near-infrared light, and the optical image and spectrum of the irradiated part of the structural color tubular actuator were recorded using an optical microscope and a fiber spectrometer. As the irradiation time increased, the structural color tubular actuator began to shrink, the structural color blue-shifted, and the reflection peak gradually decreased. The structural color tubular actuator was placed in ice water and began to relax, restoring its original diameter and color. When the structural color tubular actuator was damaged or cracked, it was clearly visible through an optical microscope and a fiber spectrometer that gaps appeared in the structural color and the reflection peak weakened. Liquid leakage occurred during the liquid transport experiment, so its optical properties can be used to achieve a self-test function. Figure 5 As shown, (a) is a schematic diagram of the structural color change on the surface of the structural color tubular actuator, (b, c) are optical images and spectra of the irradiated part of the structural color tubular actuator, (d) is the spectrum of the structural color tubular actuator in six cycles of contraction under near-infrared light or ice water recovery, (eh) are schematic diagrams, optical microscope images and spectra of the intact and damaged parts of the structural color tubular actuator, (i, j) are records of leakage of the damaged structural color actuator during liquid transport, and the scale bars are 2 mm in (b, f, j), 0.5 mm in (g), and 5 mm in (i).

[0039] The present invention provides a structural color tubular actuator and its preparation method and application ideas and methods. There are many methods and ways to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A method for preparing a structural color tubular actuator, characterized in that: The steps include: (1) Template preparation: The nanospheres are assembled in an orderly manner on the inner and outer walls of the glass tube, and templates with different colors and sizes are obtained by adjusting the particle size of the nanospheres; (2) Preparation of composite hydrogel tubes: Prepare response layer prepolymer solutions of different concentrations, fix the thin glass tube with nano-microspheres on the outer wall in step (1) at the inner axis position of the glass tube with nano-microspheres on the inner wall, inject the response layer prepolymer solution between the two glass tubes, remove the template after solidification, inject the hydrophilic layer prepolymer solution into the holes in the inner layer of the hydrogel, and wait for the hydrophilic layer prepolymer solution to solidify to obtain a composite hydrogel tube; (3) Obtaining a structural color tubular actuator: The composite hydrogel tube in step (2) is immersed in a reducing agent for reduction, and then immersed in deionized water to remove unreacted components, thereby obtaining a structural color tubular actuator.

2. The method for preparing the structural color tubular actuator according to claim 1, characterized in that: In step (1), the length of the glass tube is 1 cm-20 cm, the inner diameter of the glass tube is 0.1 mm-5 mm, the outer diameter of the glass tube is 0.2 mm-10 mm, and the wall thickness of the glass tube is 0.1 mm-5 mm.

3. The method for preparing the structural color tubular actuator according to claim 1, characterized in that: In step (1), the nanospheres are selected from any one of polystyrene microspheres, polyethylene microspheres, and silica microspheres. The particle size of the microspheres assembled on the inner wall of the glass tube is 200nm-400nm, and the particle size of the microspheres assembled on the outer wall of the glass tube is 100nm-300nm.

4. The method for preparing the structural color tubular actuator according to claim 1, characterized in that: In step (2), the response layer prepolymer solution is a mixed aqueous solution of N-isopropylacrylamide, sodium alginate and graphene oxide, wherein the mass concentration of N-isopropylacrylamide is 5%-20%, the mass concentration of sodium alginate is 0.1%-5%, and the concentration of graphene oxide is 0.5mg / ml-10mg / ml.

5. The method for preparing the structural color tubular actuator according to claim 1, characterized in that: In step (2), the response layer prepolymer liquid is cured by ultraviolet irradiation or chemical crosslinking, and the crosslinking agent used is N, N'-methylenebisacrylamide, and its mass concentration in the response layer prepolymer liquid is 0.01%-1%.

6. The method for preparing a structural color tubular actuator according to claim 1, characterized in that: In step (2), the method for removing the template is to remove the nano-microspheres by chemical etching and peel the hydrogel from the glass tube.

7. The method for preparing a structural color tubular actuator according to claim 1, characterized in that: In step (2), the hydrophilic layer prepolymer liquid is a sodium alginate aqueous solution, wherein the concentration of sodium alginate is 0.1%-5%; the hydrophilic layer prepolymer liquid is cured by chemical crosslinking, and the crosslinking agent used is calcium chloride, and its mass concentration in the hydrophilic layer prepolymer liquid is 1%-10%.

8. The method for preparing a structural color tubular actuator according to claim 1, characterized in that: In step (3), the reducing agent is an aqueous solution of hydroiodic acid with a mass concentration of 1%-10%.

9. A structural color tubular actuator prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the structural color tubular actuator according to claim 9 in liquid transportation or sensing analysis.

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