CN116854999A - Fast-response photonic crystal heterogeneous gel material, preparation method and application thereof - Google Patents
Fast-response photonic crystal heterogeneous gel material, preparation method and application thereof Download PDFInfo
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- CN116854999A CN116854999A CN202311120815.9A CN202311120815A CN116854999A CN 116854999 A CN116854999 A CN 116854999A CN 202311120815 A CN202311120815 A CN 202311120815A CN 116854999 A CN116854999 A CN 116854999A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
The application relates to the field of preparation of magnetic nano photoelectric materials, in particular to a fast-response photonic crystal heterogeneous gel material, a preparation method and application thereof, which are formed by fixing a responsive photonic crystal nano chain in a non-responsive continuous phase matrix material as a disperse phase after orientation under a magnetic field, wherein the responsive photonic crystal nano chain is a one-dimensional nano structure formed by arranging monodisperse magnetic nano particles at a medium particle spacing in a responsive gel shell layer, and the shell material of the responsive photonic crystal nano chain contracts or expands to cause the particle spacing in the photonic crystal nano chain to change, so that the color of the photonic nano chain is changed, and meanwhile, the volume of the non-responsive continuous phase matrix material is not changed. The stability of the chain is obviously improved, the structural color can be displayed without a magnetic field, the response is quick, the preparation method is simple and convenient, the environment is friendly, and the method has great application prospect in the fields of electrochromic, thermochromic, display devices, sensing and the like.
Description
Technical Field
The application relates to the field of preparation of magnetic nano photoelectric materials, in particular to a photonic crystal heterogeneous gel material with quick response, a preparation method and application thereof.
Background
The responsive photonic crystal Nano-chain is taken as a minimum color development unit (Nano light, 2020, volume 20, 803), the unique structural advantage of the responsive gel with Nano-scale is taken as a shell layer to wrap equidistant monodisperse magnetic particles into a 'pod' structure, which stands out in the traditional responsive photonic crystal sensor, and the Nano-scale responsive polymer shell layer can enable ions or other substances to diffuse rapidly and reach swelling shrinkage balance more rapidly, so that rapid response is realized (the flexible photonic Nano-chain with adjustable photonic band gap, a preparation method thereof and application of CN 104629232A). According to the principle, functional photonic crystal materials such as a temperature-sensitive response type photonic crystal nano chain (a method for regulating and controlling the particle spacing of Fe3O4@PVP@PNIPAM magnetic photonic crystal nano chain CN 110423305A) and a glucose response type photonic crystal nano chain (a glucose response type photonic crystal sensor, a preparation method and a use method thereof CN 110987820A) are prepared.
However, the currently developed responsive photonic crystal nano-chains can only be suspended and dispersed in a liquid, and a magnetic field needs to be continuously applied to enable the photonic nano-chains to maintain orientation so as to display color. In addition, when repeated use is required, the process of washing and redispersion is liable to cause loss, entanglement or breakage of the photonic nanochains, resulting in deterioration of optical properties. Finally, the chain-shaped structure is suspended in the liquid and drifts along with the solution, so that the pollution of the sample is easily caused. The above-mentioned disadvantages limit their application in electrochromic, thermochromic, display device and sensing fields.
Disclosure of Invention
The application aims to provide a photonic crystal heterogeneous gel material with quick response, which aims at the defects that the existing responsive photonic nano-chains are easy to wear, tangle, break and pollute a sample in use and can only be used under the condition of continuously applying a magnetic field, and the responsive photonic nano-chains are fixed in a non-responsive continuous phase matrix material after being oriented as a disperse phase. The responsive photonic crystal nano chain can display structural color without a magnetic field after being fixed, and has good repeated stability and high response speed.
The second purpose of the application is to provide a preparation method of the photonic crystal heterogeneous gel material with quick response, which is simple and convenient, easy to control, and the generated product is nontoxic and harmless and is environment-friendly.
The application further aims to provide an application of the photonic crystal heterogeneous gel material with quick response.
One of the achievement purposes of the application adopts the technical proposal that: a fast-response photonic crystal heterogeneous gel material is formed by fixing a responsive photonic crystal nano-chain serving as a disperse phase in a non-responsive continuous phase matrix material after orientation under a magnetic field, wherein the responsive photonic crystal nano-chain is a one-dimensional nano-structure formed by arranging monodisperse magnetic nano-particles at equal particle intervals in a responsive gel shell layer, and the shell layer material of the responsive photonic crystal nano-chain contracts or expands to change the particle intervals in the photonic crystal nano-chain and change the color of the photonic nano-chain. But the volume of the matrix material as the nonresponsive continuous phase does not change at this time.
Preferably, the magnetic nanoparticle contains at least one element of iron, cobalt and nickel.
Preferably, the responsive photonic crystal nanochains comprise photonic crystal nanochains that are responsive to at least one of ions, molecules, temperature, electric field.
Preferably, the responsive gel shell layer comprises a pH responsive polymer, a solvent responsive polymer, a temperature responsive polymer, a saccharide responsive polymer, an electric field responsive polymer, and the like.
Preferably, the responsive gel shell layer comprises at least one of the following groups: carboxylic acid, amino, sulfonic acid, hydroxyl, pyridyl, phosphoric acid, amide, phenylboronic acid groups. The pH-responsive polymer includes, but is not limited to, at least one of polyacrylic acid (PAA), polymethacrylic acid (PMAA), polymethyl methacrylate, poly N-acrylamidoacrylic acid, and the like; the ion-responsive polymer includes, but is not limited to, at least one of PAA, PMAA, polystyrene benzenesulfonic acid, polymethacrylic acid sulfonic acid, polyacrylic acid sulfuric acid, etc.; the temperature-sensitive responsive polymer comprises but not limited to poly N-hydroxyethyl acrylamide and poly%NIsopropyl acrylamide (PNIPAM) and poly-N-isopropyl methacrylamide), poly (meth)N,N-at least one of diethyl acrylamide and the like; the solvent-responsive polymer includes, but is not limited to, at least one of polyhydroxyethyl methacrylate (PHEMA), polymethyl methacrylate, and the like; the saccharide-responsive polymer includes, but is not limited to, at least one of poly 3-acrylamidophenylboronic acid (PAAPBA), poly 3-methacrylamidophenylboronic acid, poly 4-vinylphenylboronic acid, etc.; the electric field responsive polymer includes, but is not limited to, at least one of PAA, PMAA, PHEMA, polymethyl methacrylate, poly N-acrylamidoacrylic acid, and the like.
Preferably, the non-responsive continuous phase matrix material is a material that is non-responsive to the detection environment. The non-responsive continuous phase matrix material is a porous material which does not respond when the photonic crystal nano-chain embedded therein responds, and is not the same as the responsive photonic crystal nano-chain shell material embedded therein.
The responsive photonic crystal nano-chain has the characteristics of ion, molecule, temperature and electric field responsiveness, and the thickness of the responsive gel wrapped by the outer layer is tens of nanometers, so that the quick response of the responsive photonic crystal nano-chain is ensured; the response principle is that when the responsive gel shell layer is contacted with a specific substance or influenced by external environment, the shell layer can change the volume to change the inter-particle distance, so that color light with different wavelengths is diffracted.
Preferably, the ion response includes at least one of a pH response, an ionic strength response, an ion selection response, an ion exchange response, and the like; the molecular response includes at least one of a solvent response, a carbohydrate response, a biomolecular response, and the like.
The electric field response comprises at least one of pH electric field response, ion electric field response, electric field force response and the like;
the pH electric field response is that hydrogen ions and hydroxyl ions are generated at the anode and the cathode in a water electrolysis mode so that the pH responsive photonic crystal nano chain is changed; the ion electric field response is to control the directional migration of ions in a system to generate concentration gradient between positive and negative electrodes in an electric field mode so as to form electrostatic shielding influence of different degrees on chains in different areas and further realize the change of diffraction wavelength; the electric field force response is that a charged group is fixed on the main chain of a responsive gel shell layer of the responsive photonic crystal so as to be influenced by an electric field effect, and then the diffraction wavelength is changed.
The non-responsive material matrix as the continuous phase acts as a scaffold to support the responsive photonic crystal nanochains and is not affected by changes in the responsive material or environment; the nonresponsive material is in a liquid state prior to curing and may be cured by chemical or physical means, or the like.
Preferably, the non-responsive continuous phase matrix material employed comprises at least one of polyacrylamide, agarose, gelatin, cellulose acetate, nitrocellulose, polyvinyl alcohol, and the like.
The second technical scheme adopted for realizing the purpose of the application is as follows: the preparation method of the photonic crystal heterogeneous gel material with the rapid response comprises the following steps:
dispersing responsive photonic crystal nano chains in a solution containing a non-responsive continuous phase matrix material precursor to obtain a dispersion liquid containing chains;
and step two, placing the dispersion liquid obtained in the step one in a magnetic field, and solidifying the dispersion liquid into a solid material after chain orientation to obtain the photonic crystal heterogeneous gel material with quick response.
Preferably, in the first step, the concentration of the responsive photonic crystal nano-chains in the dispersion is 1-100 mg/ml.
Preferably, in the first step, the concentration of the non-responsive continuous phase matrix material in the precursor solution is 0.001-0.5 g/ml.
Preferably, in the second step, the magnetic field is 50-3000 gauss.
Preferably, the magnetic field size can be selected according to the requirement, the larger the magnetic field strength is, the better the orientation is, and the application is limited by common magnetic field generating equipment, and the magnetic field size is 50-1000 gauss.
The preparation method of the responsive photonic crystal nano chain comprises the following steps:
(1) Uniformly mixing the monodisperse magnetic nanoparticles with a polymerization monomer, an initiator, a cross-linking agent and a solvent to obtain a prepolymer;
(2) Placing the prepolymer liquid obtained in the step (1) under an external magnetic field to initiate polymerization, so as to obtain a responsive photonic crystal nano-chain;
wherein in the step (1), the polymerized monomer is a pH responsive functional monomer or a mixture of pH responsive functional monomers and non-pH responsive monomers; the pH responsive functional monomer is at least one of polymer monomers containing an ionizable group, and the non-pH responsive monomer is at least one of acrylamide, hydroxypropyl acrylamide, methylolacrylamide, methyl methacrylate and hydroxyethyl methacrylate; the particle size of the magnetic nano particles is 50-300nm;
or, in the step (1), the polymerized monomer is a glucose-responsive functional monomer or a mixture of glucose-responsive functional monomers and non-responsive materials; the glucose responsive functional monomer is at least one of 3-acrylamidophenylboric acid, 3-methacrylamidophenylboric acid, 4-vinylphenylboric acid, 2-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylboric acid, 2-amino-5-fluorobenzeneboric acid and 2-amino-4, 5-difluorophenylboric acid, and the non-glucose responsive monomer is acrylamide,N- (2-hydroxypropyl) methacrylamide,N- (2-hydroxypropyl) acrylamide,N-methylolacrylamide,N-at least one of the trimethylol methacrylamides; the particle size of the magnetic nano particles is 50-300nm;
or in the step (1), the polymerization monomer is a temperature-sensitive response functional monomer or a mixture of the temperature-sensitive response functional monomer and a non-response material; the temperature-sensitive responsive functional monomer is at least one of N-isopropyl acrylamide or N-isopropyl methacrylamide, and the non-temperature-sensitive responsive monomer is at least one of acrylamide, hydroxyethyl methacrylate and N-methylolacrylamide; the particle size of the magnetic nano particles is 50-300nm.
The third technical scheme adopted for achieving the purpose of the application is as follows: the fast-response photonic crystal heterogeneous gel material is applied to the fields of electrochromic, thermochromic, display devices, sensing and the like.
The fast-response photonic crystal heterogeneous gel material can realize the function of responding to external physical and chemical stimulus by replacing the fixed responsive photonic crystal nano chain in the non-responsive continuous phase matrix material, and can be applied to the fields of electrochromic, thermochromic, display devices, photoelectric switch converters, sensing and the like.
In the fast-response photonic crystal heterogeneous gel material, the response speed of seconds can be realized by the responsive photonic crystal nano-chain, the environmental stimulus signal is quickly converted into an optical signal, the porous nonresponsive material is similar to a bracket, the responsive photonic crystal nano-chain is fixed to maintain orientation and repeated stability, and meanwhile, the porous structure also ensures that the diffusion speed of ions, molecules or other substances in the nonresponsive material is close to or equal to the diffusion speed in a pure liquid environment. Meanwhile, the non-responsive continuous phase matrix material does not have great application prospect in the fields of electrochromic, thermochromic, display devices, sensing and the like.
The application has the following advantages:
(1) According to the fast-response photonic crystal heterogeneous gel material, the non-responsive continuous phase matrix material is used for fixing the responsive photonic crystal nano chains, so that the stability of the chains is remarkably improved, the nano chains are easy to wear, tangle, break, pollute samples and the like when being dispersed in liquid, the optical performance is poor as the quantity of the chains is smaller and smaller along with the increase of the test times, and the fixed heterogeneous material can effectively solve the problems of the chains in the use process.
(2) According to the fast-response photonic crystal heterogeneous gel material, when the responsive photonic crystal nano chains are oriented under a magnetic field before being fixed, the structural color can be displayed without the magnetic field after being fixed. The chains are in a non-oriented state when dispersed in the solution to be detected, stable structural color cannot be displayed without applying a magnetic field, and the chains are very easy to sink under the action of magnetic attraction force in some systems with poor dispersion, so that the convenience of use of the chains is remarkably improved by fixing the chains after orientation.
(3) According to the fast-response photonic crystal heterogeneous gel material, the polymer layer on the surface of the non-responsive material fixed responsive photonic crystal nano chain is only tens of nanometers, the response speed is in the second level, and the non-responsive material with controllable pore size can enable a tested substance to be rapidly diffused and transmitted in the material, so that the response speed of the finally prepared photonic crystal heterogeneous gel material can be completed within 1 minute.
(4) The fast-response photonic crystal heterogeneous gel material can form different shapes when being solidified, can be prepared into films or various shapes adapting to the measured environment in the sensing field, can be prepared into spheres in the switching converter field to enable the spheres to have faster switching speed, and can be prepared into hemispheres in the display device field to realize low angle dependence.
(5) The preparation method is simple and convenient, is easy to control, and the generated product is nontoxic and harmless and is environment-friendly.
(6) The fast-response photonic crystal heterogeneous gel material has great application prospect in the fields of electrochromic, thermochromic, display devices, sensing and the like.
Drawings
FIG. 1 is a physical diagram of a fast response photonic crystal heterogeneous gel material in example 1 of the present application;
FIG. 2 is a field emission scanning electron microscope (FES) of the responsive photonic crystal nanochains and an optical micrograph of the photonic crystal nanochains oriented under a magnetic field in a prepolymerization solution in example 1 of the present application, wherein (a) is the FES and (b) is the optical micrograph;
fig. 3 is a scanning electron microscope image of a cross section of the fast-response photonic crystal hetero gel material parallel to the orientation direction, an optical microscope image of a cross section parallel to the orientation direction, and an optical microscope image of a cross section perpendicular to the orientation direction in example 1 of the present application, wherein (a) is a scanning electron microscope image of a cross section parallel to the orientation direction, (b) is an optical microscope image of a cross section parallel to the orientation direction, and (c) is an optical microscope image of a cross section perpendicular to the orientation direction;
FIG. 4 is a schematic diagram of the preparation and response principle of the fast response photonic crystal heterogeneous gel material of the application;
FIG. 5 is a plot of the shift points of the diffraction peaks of the fast response photonic crystal heterogeneous gel film prepared in this example under different pH conditions;
FIG. 6 is a graph showing the relationship between the rapid response diffraction peak position and the time change of the rapid response photonic crystal heterogeneous gel material in example 1 according to the present application under the condition of switching different pH values;
FIG. 7 is a graph of the results of the cycling stability of the fast response photonic crystal heterogeneous gel material of example 1 of the present application under conditions of switching different pH and the cycling stability after 3 months of sample placement, wherein (a) is a graph of the cycling stability under different pH conditions and (b) is a graph of the results of the cycling stability after 3 months of sample placement;
FIG. 8 is an optical micrograph of the color of an electric field responsive agar heterogeneous membrane of example 2 of the present application over time under energized conditions;
FIG. 9 is a graph showing the relationship between the diffraction peak position and the cyclic stability of the fast response photonic crystal heterogeneous gel material according to the embodiment 3 of the present application in the environment of switching different solvents (dimethylsulfoxide-deionized water), wherein (a) is the relationship between the diffraction peak position and the cyclic stability;
FIG. 10 is a graph showing the relationship between the diffraction peak position and the time variation and the cyclic stability graph of the fast response photonic crystal heterogeneous gel material in example 4 according to the present application, wherein (a) is the relationship between the diffraction peak position and the time variation, and (b) is the cyclic stability graph;
FIG. 11 is a graph showing the relationship between the diffraction peak position and the time variation and the cyclic stability of the fast response photonic crystal heterogeneous gel material according to the embodiment 5 of the present application, wherein (a) is the relationship between the diffraction peak position and the time variation, and (b) is the cyclic stability;
FIG. 12 is a schematic diagram showing the internal structure of a hemispherical structure of a fast response photonic crystal hetero-gel material according to example 6 of the present application;
FIG. 13 is a plot of diffraction peak shift movement points for a fast response photonic crystal heterogeneous gel material at different voltages in example 10 of the present application;
description of the reference numerals
10. A responsive polymer; 20. magnetic nanoparticles; 30. responsive magnetic photon nanochains; 40. a non-responsive material.
Detailed Description
The present application will be further described with reference to the following examples and drawings, but the content of the present application is not limited to the following examples.
Responsive magnetic nanochains were prepared using the preparation method described in the prior patent application number CN104629232A, CN110423305A (temperature response), CN110987820a (glucose response).
The responsive polymer materials used in the embodiments of the present application are all materials disclosed in the prior art, and all the responsive polymer materials can achieve the object of the present application, and are not limited to the responsive polymer materials described in the embodiments.
Example 1 (ion response: pH response)
(1) Taking 40 mu L of agarose solution dissolved in dimethyl sulfoxide (DMSO) with the concentration of 0.1g/ml, heating, adding 80 mu L of DMSO and 280 mu L of water, uniformly mixing to obtain a prepolymer solution, and dispersing the pH-responsive photonic crystal nano-chains into the prepolymer solution to obtain a chain dispersion solution.
(2) Heating the dispersion liquid prepared in the step (1) to 80 ℃ in a water bath kettle, shaking uniformly, taking a proper amount of dispersion liquid drops between two glass plates, applying a magnetic field to cool and solidify the dispersion liquid to obtain a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film twice by using deionized water for standby, wherein the magnetic field is 400Gs as shown in figure 1.
From the top view of the digital image of the product of this example in fig. 1, it can be seen from the figure that the material can diffract structural color even when no magnetic field is applied, the fast-response hetero-gel material in this example is a circular thin film with a diameter of 2cm, and its shape and size can be changed as needed in other examples, and the function of the fast-response hetero-gel material of the present application is not limited by shape and size.
Fig. 2 is a scanning electron microscope image of the pH-responsive photon nanochain prepared in step 2 of this example and an optical micrograph of the chain after magnetic field orientation is applied in the prepolymer solution dispersed in step 3, wherein (a) is the scanning electron microscope image and (b) is the micrograph of the chain after magnetic field orientation is applied in the prepolymer solution dispersed in step 3.
Fig. 3 is a scanning electron microscope image of a cross section of the pH-responsive physically fixed hetero gel film prepared in step 4 of this example in parallel to the orientation direction, an optical microscope image of a cross section in parallel to the orientation direction, and an optical microscope image of a cross section perpendicular to the orientation direction, wherein (a) is a scanning electron microscope image of a cross section in parallel to the orientation direction, (b) is an optical microscope image of a cross section in parallel to the orientation direction, and (c) is an optical microscope image of a cross section perpendicular to the orientation direction.
FIG. 4 is a schematic representation of the preparation and response principle of a heterogeneous gel film.
Fig. 5 is a plot of the shift points of the diffraction peaks of the fast response photonic crystal heterogeneous gel film prepared in this example under different pH conditions.
FIG. 6 is a graph showing the rapid response diffraction peak position change with time when the pH of the buffer solution is switched from 4.0 to 8.0, showing that the material reaches a steady state at 30 s.
Fig. 7 is a graph showing the cyclic stability of the fast response photonic crystal hetero gel film prepared in this example when the buffer solution was cyclically switched to pH 4.0 to 8.0 and a graph showing the results of testing the cyclic stability of the hetero gel film after 3 months of the hetero gel film were placed, wherein (a) is a graph showing the cyclic stability under different pH conditions and (b) is a graph showing the results of testing the cyclic responsiveness of the hetero gel film after 3 months of the hetero gel film were placed.
Example 2 (ion response: electric field response)
(1) Taking 40 mu L of agarose solution dissolved in DMSO with the concentration of 0.1g/ml, heating, adding 80 mu L of DMSO and 280 mu L of water, uniformly mixing to obtain a prepolymer solution, and dispersing the ion-responsive photonic crystal nano-chains into the prepolymer solution to obtain a chain dispersion solution.
(2) Heating the dispersion liquid prepared in the step (1) to 80 ℃ in a water bath kettle, shaking uniformly, taking a proper amount of dispersion liquid drops between two glass plates, applying a magnetic field to cool and solidify the dispersion liquid drops to obtain a photonic crystal heterogeneous gel film with quick response, washing the obtained photonic crystal heterogeneous gel film twice by using a sodium chloride (NaCl) solution with the ionic strength of 50mM, fully swelling and balancing the photonic crystal heterogeneous gel film, placing the heterogeneous gel film between two pieces of Indium Tin Oxide (ITO) conductive glass, packaging the two pieces of ITO conductive glass, and respectively connecting an anode and a cathode on the two pieces of ITO glass.
Fig. 8 is an optical micrograph of the color of the fast response photonic crystal hetero-gel film prepared in this example in a negative electrode region over time.
Example 3 (molecular response: chemical curing solvent response)
(1) Dispersing the molecular response photonic crystal nano chain into a precursor liquid composed of Acrylamide (AM), BIS, HMPP, EG and water, and shaking uniformly to obtain a prepolymer liquid.
(1) And (3) placing a proper amount of the pre-polymerization liquid prepared in the step (2) between two glass plates, applying a magnetic field for 30 seconds, irradiating with ultraviolet light while keeping the magnetic field unchanged, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for later use.
Fig. 9 is a graph showing the relationship between the diffraction peak position and the cyclic stability of the fast response photonic crystal heterogeneous gel film prepared in this example in the environment of switching different solvents (dimethylsulfoxide-deionized water), wherein (a) is the relationship between the diffraction peak position and the cyclic stability.
Example 4 (molecular response: glucose response)
(1) And dispersing glucose-responsive photonic crystal nano chains into a precursor liquid composed of AM, BIS, HMPP, EG and water, and uniformly shaking to obtain a prepolymer liquid.
(2) And (3) placing a proper amount of the pre-polymerization liquid prepared in the step (1) between two glass plates, applying a magnetic field for 30 seconds, irradiating with ultraviolet light while keeping the magnetic field unchanged, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for later use.
Fig. 10 is a graph showing the diffraction peak position versus time and a graph showing the cycling stability of the fast response photonic crystal hetero-gel film prepared in this example when the concentration of the glucose solution (glucose solution-deionized water) was switched, wherein (a) is a graph showing the diffraction peak position versus time, and (b) is a graph showing the cycling stability.
Example 5 (pH heterogeneous Membrane chemical curing)
(1) And dispersing the pH-responsive photonic crystal nano-chains into a precursor liquid composed of AM, BIS, HMPP, EG and water, and uniformly shaking to obtain a prepolymer liquid.
(2) And (3) placing a proper amount of the pre-polymerization liquid prepared in the step (1) between two glass plates, applying a magnetic field for 30 seconds, irradiating with ultraviolet light while keeping the magnetic field unchanged, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for later use.
Fig. 11 is a graph showing the relationship between the diffraction peak position and the time variation and a graph showing the cyclic stability of the fast response photonic crystal hetero gel film prepared in this example under the condition of switching different pH (pH 4 to 8), wherein (a) is the relationship between the diffraction peak position and the time variation and (b) is the graph showing the cyclic stability.
Example 6 (thermo-sensitive film chemical curing)
(1) Dispersing the temperature-sensitive response photonic crystal nano-chains into a precursor liquid composed of AM, BIS, HMPP, EG and water, and uniformly shaking to obtain a prepolymer liquid.
(2) And (3) placing a proper amount of the pre-polymerization liquid prepared in the step (1) between two glass plates, applying a magnetic field for 30 seconds, irradiating with ultraviolet light while keeping the magnetic field unchanged, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for later use.
The fast response photonic crystal heterogeneous gel film prepared by the embodiment can realize fast response of peak position of 100nm wavelength under different temperature switching environments, the response time is within 20 seconds, and the fast response photonic crystal heterogeneous gel film can be circularly switched for at least 10 times.
Example 7 (pH heterogeneous PVA physically cured film)
(1) And dispersing the pH-responsive photonic crystal nano-chains into a precursor solution consisting of polyvinyl alcohol (PVA), DMSO and water, and uniformly shaking to obtain a prepolymer solution.
(2) And (3) placing a proper amount of the prepolymer liquid prepared in the step (1) between two glass plates, applying a magnetic field to freeze for 6 hours at the temperature of minus 18 ℃, then thawing for 4 hours at the room temperature, recycling for 3 times to prepare the photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for standby.
Example 8 (temperature sensitive heterogeneous gelatin chemical curing film)
(1) Dispersing the temperature-sensitive response photonic crystal nano chain into a precursor liquid composed of methacrylamide gelatin, 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator 2959), polyethylene glycol diacrylate and water, and shaking uniformly to obtain a prepolymer liquid.
(2) And (3) placing a proper amount of the pre-polymerization liquid prepared in the step (1) between two glass plates, applying a magnetic field for 30 seconds, irradiating with ultraviolet light while keeping the magnetic field unchanged, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and flushing the obtained photonic crystal heterogeneous gel film with deionized water for two times for later use.
Example 9 (hemispherical)
(1) Taking 40 mu L of agarose solution dissolved in DMSO with the concentration of 0.1g/ml, heating, adding 80 mu L of DMSO and 280 mu L of water, uniformly mixing to obtain a prepolymer solution, and dispersing the pH-responsive photonic crystal nano-chains into the prepolymer solution to obtain a chain dispersion solution.
(2) Dispersing the photonic crystal nano-chains prepared in the step (1) in agarose solution to obtain a chain dispersion, wherein the concentration of the chains in the dispersion is 100mg/ml, the concentration of the agarose is 0.01g/ml, and the volume ratio of dimethyl sulfoxide to water in a dispersion solvent is 3:7.
(3) Heating the dispersion liquid prepared in the step (2) to 80 ℃ in a water bath kettle, shaking uniformly, taking a proper amount of dispersion liquid drops on a plane with a spherical magnet placed below, cooling and solidifying to obtain hemispherical fast-response photonic crystal heterogeneous gel, flushing the heterogeneous gel twice by using deionized water for standby, and applying a magnetic field in a radial shape as shown in fig. 12.
Fig. 12 is a schematic diagram showing an internal structure of a hemispherical structure formed by the fast-response photonic crystal hetero-gel material in this embodiment.
Example 10 (electric field response: electrostatic screening)
(1) And dispersing the photonic crystal nano-chains corresponding to the electric field (the photonic crystal nano-chains corresponding to the electric field adopted in the embodiment are the same as the photonic crystal nano-chains responding to the pH, and the photonic crystal nano-chains responding to the pH also have the effect of responding to the electric field) into a precursor liquid consisting of the NaCl solution of AM, BIS, HMPP, DMSO, and uniformly shaking to obtain a prepolymer liquid.
(2) And (3) placing the prepolymer liquid prepared in the step (1) between two pieces of ITO conductive glass, packaging, applying a magnetic field for 60 seconds, keeping the magnetic field unchanged, simultaneously irradiating with ultraviolet light, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and respectively connecting positive and negative electrodes on the two pieces of ITO glass.
Fig. 13 is a graph showing the shift of diffraction peak of the fast response photonic crystal heterogeneous gel film prepared in this example under different voltages, wherein the principle of color development is that sodium ions dispersed in the system are directionally migrated under the action of an electric field, and the main chain groups in the enriched responsive gel in the negative electrode region are influenced by electrostatic shielding effect, so that the responsive gel is contracted to cause the blue shift of diffraction peak.
Example 11 (electric field response: electric field compression)
(1) And dispersing the pH-responsive photonic crystal nano-chains into a precursor liquid composed of AM, BIS, HMPP, DMSO, and uniformly shaking to obtain a prepolymer liquid.
(2) And (3) placing the prepolymer liquid prepared in the step (1) between two pieces of ITO conductive glass, packaging, applying a magnetic field for 60 seconds, keeping the magnetic field unchanged, simultaneously irradiating with ultraviolet light, polymerizing for 6 minutes to prepare a photonic crystal heterogeneous gel film with quick response, and respectively connecting positive and negative electrodes on the two pieces of ITO glass.
The fast response photonic crystal heterogeneous gel film prepared by the embodiment can realize the movement of 118nm wavelength peak position under the condition of applying an 8V electric field.
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A fast-response photonic crystal heterogeneous gel material is characterized in that: the non-responsive continuous phase matrix material is characterized in that the non-responsive continuous phase matrix material is formed by fixing a responsive photonic crystal nano-chain serving as a disperse phase in the non-responsive continuous phase matrix material after the responsive photonic crystal nano-chain is oriented under a magnetic field, wherein the responsive photonic crystal nano-chain is of a one-dimensional nano-structure formed by arranging monodisperse magnetic nano-particles at medium particle intervals in a responsive gel shell layer, and a shell layer substance of the responsive photonic crystal nano-chain contracts or expands to change the particle intervals in the photonic crystal nano-chain, so that the color of the photonic nano-chain is changed, and meanwhile, the volume of the non-responsive continuous phase matrix material is not changed.
2. The fast response photonic crystal heterogeneous gel material of claim 1, wherein: the magnetic nano particles contain at least one element of iron, cobalt and nickel.
3. The fast response photonic crystal heterogeneous gel material of claim 1, wherein: the responsive photonic crystal nanochains include photonic crystal nanochains that are responsive to at least one of ions, molecules, temperature, and electric fields.
4. A fast responding photonic crystal heterostructure gel material according to claim 3, characterized in that: the ion response includes at least one of a pH response, an ionic strength response, an ion selection response, an ion exchange response; the molecular response includes at least one of a solvent response, a carbohydrate response, a biomolecular response, and the electric field response includes at least one of a pH electric field response, an ionic electric field response, and an electric field force response.
5. A fast responding photonic crystal heterostructure gel material according to claim 3, characterized in that: the responsive gel shell layer comprises at least one of carboxylic acid, amino, sulfonic acid, hydroxyl, pyridyl, phosphoric acid, amide, phenylboronic acid groups.
6. A method of preparing a fast responding photonic crystal heteroscedure gel material according to any of claims 1-5, comprising the steps of:
step one, dispersing responsive photonic crystal nano chains in a precursor solution containing a non-responsive continuous phase matrix material to obtain a dispersion liquid containing chains;
and step two, placing the dispersion liquid obtained in the step one in a magnetic field, and solidifying the dispersion liquid into a solid material after chain orientation to obtain the photonic crystal heterogeneous gel material with quick response.
7. The method for preparing the fast-response photonic crystal heterogeneous gel material according to claim 6, wherein the method comprises the following steps: in the first step, the concentration of the responsive photonic crystal nano chains in the dispersion liquid is 1-100 mg/ml.
8. The method for preparing the fast-response photonic crystal heterogeneous gel material according to claim 6, wherein the method comprises the following steps: in the first step, the concentration of the non-responsive continuous phase matrix material in the precursor solution is 0.001-0.5 g/ml.
9. The method for preparing the fast-response photonic crystal heterogeneous gel material according to claim 6, wherein the method comprises the following steps: in the second step, the magnetic field is 50-3000 gauss.
10. Use of a fast responding photonic crystal heteroscedastic gel material according to any one of claims 1-5, characterized in that: the method is applied to the fields of electrochromic, thermochromic, display devices, photoelectric switch converters and sensing.
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