CN113024874B - High-sensitivity patterned photonic crystal sensing material and preparation and application thereof - Google Patents
High-sensitivity patterned photonic crystal sensing material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to preparation and application of a high-sensitivity patterned photonic crystal sensing material, and belongs to the field of photonic crystal materials. Comprises a polymer matrix without specific responsiveness, nanoparticles, a first polymer and a second polymer; the nanoparticles self-assemble into periodic structures embedded in a polymer matrix; the first and second polymers are cross-linked to different regions of the polymer matrix, and the first and second polymers are used for swelling or shrinking due to volume when subjected to the same responsive stimulus, so that the distance between the nano-particles embedded in the polymer matrix is changed, and the reflection peak is red-shifted or blue-shifted. By regulating and controlling external conditions, the photonic crystal sensing material can realize high-sensitivity dynamic display of patterns, and can be widely used for measuring response conditions and preparing anti-counterfeiting materials.
Description
Technical Field
The invention belongs to the field of photonic crystal materials, and particularly relates to preparation and application of a high-sensitivity patterned photonic crystal sensing material.
Background
The photonic crystal formed by periodically arranging materials with different dielectric constants in space shows certain structural color due to the special photonic band gap structure, and the photonic band gap of the responsive photonic crystal formed by combining the photonic crystal and the stimulus responsive polymer can be changed along with the change of external conditions. The change is expressed in the form of optical signals, so that the responsive photonic crystal is widely applied to the preparation of materials for sensing, displaying and the like. Compared with a uniform colored coating, the patterned photonic crystal can transmit more abundant information and is widely applied to the aspects of anti-counterfeiting, colorimetric sensing, display and the like. At present, the methods for realizing photonic crystal patterning mainly include template-induced nanoparticle self-assembly, inkjet printing, regional nanoparticle deposition, regional nanoparticle selective modification, and the like, wherein the regional selective modification of the existing photonic crystal structure is widely applied to photonic crystal patterning due to the advantages of strong designability, controllable operation, and the like.
The photonic crystal fingerprint is a patterned responsive photonic crystal material, and is endowed with local responsiveness by carrying out regional selective modification on the photonic crystal material, when the photonic crystal material is stimulated by the outside, the structural parameters or refractive index of the photonic crystal in the modified region are changed, the structural color is locally changed to generate a structural color different from that of a substrate, the pattern is displayed, and the uniform structural color is reappeared after the stimulation disappears, so that the dynamic display of the pattern is realized. However, at present, the stimulus-responsive photonic crystal material is used for pattern display, the response area and range are limited, only the modified part changes with the change of external conditions, the color change range is narrow, the sensitivity is not high, and the requirement of high-sensitivity detection is difficult to meet.
Disclosure of Invention
The invention solves the problems that the photonic crystal sensing material in the prior art has narrow color change range and low sensitivity and is difficult to meet the requirement of high-sensitivity detection. The invention aims to provide a preparation method and application of a high-sensitivity patterned photonic crystal sensing material, which are characterized in that regularly arranged nano particles are embedded into a polymer matrix material without specific response, then two polymers with opposite responsiveness to certain stimulus are introduced into different areas of the matrix material to obtain the high-sensitivity patterned photonic crystal sensing material, the material can show uniform structural color when not stimulated, when corresponding stimulus is applied, the responsive polymers in different areas of the material are changed differently to induce the change of an internal photonic crystal periodic structure to the opposite direction, and a macroscopic material shows the change of a material reflection peak wavelength to the opposite direction, so that the purposes of enhancing the contrast and developing sensitivity of the material color are achieved. Compared with the existing photonic crystal fingerprint material with local response and unidirectional color change, the material has higher identification performance on a target object and more obvious self-expression effect.
According to one aspect of the present invention, there is provided a patterned photonic crystal sensing material comprising a specifically non-responsive polymer matrix, nanoparticles, a first polymer, and a second polymer; the nanoparticles self-assemble into periodic structures embedded in a polymer matrix; the first and second polymers are crosslinked to different regions of the polymer matrix, and the first and second polymers are adapted to swell and shrink in volume, respectively, when subjected to the same responsive stimulus, resulting in a change in the spacing between the nanoparticles embedded in the polymer matrix, thereby causing a simultaneous red-shift and blue-shift of the nanoparticle reflection peak.
Preferably, the polymer matrix without specific responsiveness is a poly (hydroxyalkyl methacrylate) matrix or a polyacrylate matrix;
preferably, the hydroxyalkyl polymethacrylate matrix is hydroxyethyl polymethacrylate or hydroxypropyl polymethacrylate; the polyacrylate matrix is polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, polymethyl acrylate, polyethyl acrylate, 2-acrylic acid-2-methoxyethyl ester polymer, 1, 6-hexanediol diacrylate polymer or polyethylene glycol methacrylate.
Preferably, the first polymer and the second polymer are simultaneously a pH responsive polymer, a temperature responsive polymer, a light responsive polymer, a solvent responsive polymer or an ionic strength responsive polymer.
Preferably, the pH-responsive polymer is a polymer formed from anionic monomers and a polymer formed from cationic monomers; the temperature response polymer is a polymer formed by temperature sensitive monomers with different critical solution temperatures; the photoresponse polymer is a polymer with a main chain or a side chain containing a photoresponse group.
Preferably, the anionic monomer is acrylic acid, crotonic acid, sodium styrene sulfonate, methacrylic acid, ethacrylic acid, crotonic acid or sodium styrene sulfonate; the cationic monomer is aminoethyl acrylate, dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate;
the temperature-sensitive monomer is N-alkyl substituted acrylamide, vinyl methyl ether, ethylene glycol, propylene glycol, vinyl alcohol, vinyl methyl oxazole or vinyl pyrrolidone;
the photoresponse group is of an azobenzene structure, an indene diketone structure or a thiazine structure;
preferably, the N-alkyl substituted acrylamide is N, N-dimethylacrylamide, N-diethylacrylamide, N-dibutylacrylamide, N-dihexylacrylamide, N-isopropylacrylamide, N-isobutylacrylamide, N-tert-butylacrylamide, N-pentylacrylamide, or N-cyclohexylacrylamide.
Preferably, the nanoparticles are inorganic nanoparticles, polymeric nanoparticles or hybrid nanoparticles;
preferably, the inorganic nanoparticles are Fe3O4Or SiO2Nanoparticles; the polymer nano particles are polystyrene and polymethyl methacrylate nano particles; the hybrid nano particles are nano particles formed by polystyrene and polymethyl methacrylate, Fe3O4With SiO2Formed nanoparticles, polyStyrene and SiO2Formed nano particles or polymethyl methacrylate and SiO2The nanoparticles formed.
According to another aspect of the present invention, there is provided a method for preparing any one of the patterned photonic crystal sensing materials, comprising the steps of:
(1) preparing a photonic crystal gel substrate: self-assembling nano particles into a photonic crystal with a periodic structure by an electrorheological method, a magnetorheological method, a gravity deposition method, a capillary force assembly method or a template orientation method, and embedding the photonic crystal with the periodic structure into a polymer matrix without specific responsiveness to obtain a photonic crystal gel substrate;
(2) preparing a patterned photonic crystal sensing material: soaking the photonic crystal gel substrate obtained in the step (1) in a first monomer, adding a photoinitiator, covering a partial region of the photonic crystal gel substrate by using a first mask, carrying out ultraviolet light curing, crosslinking a polymer formed by a non-specific responsive polymer and the first monomer in a region uncovered by the mask to form a gel film, and soaking the gel film in a second monomer, wherein the polymer formed by the first monomer, namely the first polymer and the polymer formed by the second monomer, namely the second polymer are used for swelling and shrinking in volume respectively when being subjected to the same responsive stimulus, so that the space among the nano particles embedded in a polymer matrix is changed, and the reflection peak of the nano particles is subjected to red shift and blue shift simultaneously; adding a photoinitiator, covering the gel film by using a second mask, wherein the areas which can be covered by the first mask and the second mask are different, and carrying out ultraviolet curing again to obtain the patterned photonic crystal sensing material; the patterned photonic crystal sensing material comprises two areas, wherein one area is formed by cross-linking a polymer formed by a polymer without specific responsiveness and a first monomer, and the other area is formed by cross-linking a polymer without specific responsiveness and a second monomer.
Preferably, the nanoparticles are monodisperse spherical nanoparticles with the diameter of 100-300 nm.
Preferably, the polymer matrix without specific responsiveness is a poly (hydroxyalkyl methacrylate) matrix or a polyacrylate matrix;
the first polymer and the second polymer are simultaneously a pH responsive polymer, a temperature responsive polymer, a light responsive polymer, a solvent responsive polymer or an ionic strength responsive polymer.
According to another aspect of the present invention, there is provided the use of any one of the patterned photonic crystal sensing materials for the determination of a response condition or as an anti-counterfeiting material.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) according to the preparation method of the high-sensitivity patterned photonic crystal sensing material, the photonic crystal sensing material can be any one of hydrogel, organic gel and elastomer, the specific response can be any one of pH response, temperature response, solvent response and photoresponse, the photonic crystal sensing material with different responses can be prepared according to different requirements, and the applicability is good; according to the invention, different monomers are selectively polymerized in the substrate material area, so that opposite responses of different areas of the material to the same kind of stimulus can be realized, the structure of the nano particles periodically arranged in the material is changed, the color of the different areas of the material is changed, the color development of the material is more obvious when the material is subjected to the external stimulus by the bidirectional change mechanism, the sensitivity and the self-expression effect of the material in the application of a reagent are improved, the response range of the photonic crystal sensing material to the stimulus is widened, and the naked eye detection limit is improved.
(2) The high-sensitivity patterned photonic crystal sensing material disclosed by the invention is composed of a polymer matrix material without specific responsiveness, nanoparticles and a responsive polymer. The nano particles are self-assembled into a periodic structure in a polymer base material without specific responsiveness, a substrate material with bright structural color can be obtained, a mask is utilized to carry out area selective modification on the substrate, two polymers with opposite responsiveness to a specific stimulus are respectively polymerized, and the high-sensitivity patterned photonic crystal sensing material is obtained.
(3) The high-sensitivity patterned photonic crystal sensing material shows uniform color when not stimulated by the outside; when the material is stimulated by the outside, the periodic structures of the nano particles in different areas of the material change to different degrees, and the macroscopic material shows that the wavelength of the reflection peak of the material changes to the opposite direction, so that the purposes of enhancing the contrast and the color development sensitivity of the material color are achieved, and the material can be used for measuring response conditions or being used as an anti-counterfeiting material.
(4) Compared with the traditional photonic crystal fingerprint only modifying one responsive monomer, the high-sensitivity patterned photonic crystal sensing material has wide color change range and high sensitivity. The existing photonic crystal fingerprint only modifies a specific area of a photonic crystal template, only the modified area responds when being stimulated, the structural parameters of the internal photonic crystal change, and structural color different from the original background is generated, so that the developing range is narrow, and the detection sensitivity is low.
Drawings
FIGS. 1 and 2 are Fe prepared in example 1, respectively3O4The transmission electron microscope picture of the @ C nano particle and the reflection spectrum and the optical photo of the photonic crystal hydrogel substrate.
FIGS. 3 and 4 are Fe prepared in example 2, respectively3O4The transmission electron microscope picture of the @ C nano particle and the reflection spectrum and the optical photo of the photonic crystal hydrogel substrate.
FIGS. 5 and 6 are Fe prepared in example 3, respectively3O4The transmission electron microscope picture of the @ C nano particle and the reflection spectrum and the optical photo of the photonic crystal hydrogel substrate.
FIG. 7 shows Fe in example 13O4Scanning electron microscopy images of @ C nanoparticles immobilized in a Polyhydroxyethylmethacrylate (PHEMA) matrix.
FIG. 8 is a schematic diagram of the preparation method and the change under the external stimulus of the present invention.
FIG. 9 is a reflection spectrum of the photonic crystal sensor material obtained in example 1 after being placed in a solution having a pH of 3.82 for 1 min.
FIG. 10 is a reflection spectrum of the photonic crystal sensor material obtained in example 1 after being placed in a solution having a pH of 10.23 for 1 min.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: dissolving 0.65g of ferrocene in 65mL of acetone to form a solution, then adding 2.2mL of hydrogen peroxide solution with the mass fraction of 30% into the solution, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal reaction, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 hours; after the reaction is finished, separating, washing and drying the nano particles to obtain the Fe with the size of 120nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4Uniformly dispersing the @ C nano particles, hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEG-DA, the molecular weight is 700g/mol, and the PEG-DA is used as a cross-linking agent) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; fe in each ml of suspension3O4@ C nanoparticles 4mg, HEMA 0.3g, PEG-DA 0.05g and photoinitiator 5 μ L; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with the poly hydroxyethyl methacrylate (PHEMA) as the substrate. FIGS. 1 and 2 are Fe prepared in example 1, respectively3O4Transmission electron microscope picture and photonic crystal of @ C nano-particleReflectance spectra and optical photographs of bulk hydrogel substrates. FIG. 7 shows Fe in this example3O4Scanning electron microscopy images of @ C nanoparticles immobilized in a Polyhydroxyethylmethacrylate (PHEMA) matrix. As can be seen from the figure, Fe3O4The @ C nano particles are regularly arranged under a magnetic field to form an ordered structure and are fixed in a polymer network.
(3) Preparing a patterned photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual HEMA monomer and ethylene glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which is partially provided with polyhydroxyethyl methacrylate/polyacrylic acid (PHEMA/PAA) and partially provided with polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PHEMA/PDMAEMA), namely the photonic crystal sensing material.
Example 2
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: dissolving 0.6g of ferrocene in 60mL of acetone to form a solution, then adding 4mL of hydrogen peroxide solution with the mass fraction of 30% into the solution, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal treatmentReacting, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 h; after the reaction is finished, separating, washing and drying the nano particles to obtain Fe with the size of 150nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4Uniformly dispersing the @ C nano particles, hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEG-DA, molecular weight of 700g/mol) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; fe in each ml of suspension3O4@ C nanoparticles 4mg, HEMA 0.3g, PEG-DA 0.05g and photoinitiator 5 μ L; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with the poly hydroxyethyl methacrylate (PHEMA) as the substrate. FIGS. 3 and 4 are Fe obtained in the present example, respectively3O4The transmission electron microscope picture of the @ C nano particle and the reflection spectrum and the optical photo of the photonic crystal hydrogel substrate.
(3) Preparing a patterned photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual HEMA monomer and ethylene glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which is partially provided with polyhydroxyethyl methacrylate/polyacrylic acid (PHEMA/PAA) and partially provided with polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PHEMA/PDMAEMA), namely the photonic crystal sensing material.
Example 3
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: dissolving 0.6g of ferrocene in 60mL of acetone to form a solution, then adding 6mL of hydrogen peroxide solution with the mass fraction of 30% into the solution, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal reaction, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 hours; after the reaction is finished, separating, washing and drying the nano particles to obtain the Fe with the size of 190nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4Uniformly dispersing the @ C nano particles, hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEG-DA, molecular weight of 700g/mol) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; fe in each ml of suspension3O4@ C nanoparticles 4mg, HEMA 0.3g, PEG-DA 0.05g and photoinitiator 5 μ L; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with the poly hydroxyethyl methacrylate (PHEMA) as the substrate. FIGS. 5 and 6 are Fe prepared in example 3, respectively3O4The transmission electron microscope picture of the @ C nano particle and the reflection spectrum and the optical photo of the photonic crystal hydrogel substrate.
(3) Preparing a patterned photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual HEMA monomer and ethylene glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which is partially provided with polyhydroxyethyl methacrylate/polyacrylic acid (PHEMA/PAA) and partially provided with polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PHEMA/PDMAEMA), namely the photonic crystal sensing material.
Example 4
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)SiO2preparing nano particles: putting 3mL of ethyl orthosilicate and 100mL of ethanol into a 250mL round-bottom flask, magnetically stirring and uniformly mixing, slowly adding 10mL of ammonia water and 5mL of deionized water, reacting for 5-6 hours at 25 ℃, and stopping reaction to obtain milky suspension. Centrifuging, washing and drying to obtain SiO with the size of 180nm2Nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: SiO prepared in the step (1)2Dispersing the nano particles into absolute ethyl alcohol to prepare a colloidal solution with the concentration of 1 wt%, vertically putting a cleaned glass sheet into the solution, putting the solution into an oven at the temperature of 30 ℃, and obtaining a photonic crystal structure template with three-dimensional periodic arrangement after the ethyl alcohol is completely volatilized; mixing polyethylene glycol methacrylate (PEGMA, M)n475), polyethylene glycol diacrylate (PEG-DA, molecular weight 700g/mol) and photoinitiator (2, 2-diethoxyacetophenone) are homogeneously dispersed inObtaining a prepolymer suspension of the photonic crystal hydrogel substrate in ethylene glycol; dripping the obtained suspension between the glass sheet and a clean glass sheet, and then carrying out ultraviolet curing to obtain a single-network photonic crystal hydrogel film with polyethylene glycol methacrylate (PEGMA) as a substrate;
(3) preparing a photonic crystal sensing material: and (3) soaking the PEGMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet light curing to obtain a photonic crystal hydrogel film with a partial double-network of poly (hydroxyethyl methacrylate)/polyacrylic acid (PEGMA/PAA); and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PEGMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain a double-network photonic crystal hydrogel film with one part of polyhydroxyethyl methacrylate/polyacrylic acid (PEGMA/PAA) and the other part of polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PEGMA/PDMAEMA), namely the photonic crystal sensing material.
Example 5
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)SiO2preparing nano particles: putting 3mL of ethyl orthosilicate and 100mL of ethanol into a 250mL round-bottom flask, magnetically stirring and uniformly mixing, slowly adding 15mL of ammonia water and 8mL of deionized water, reacting for 5-6 hours at 25 ℃, and stopping reaction to obtain milky suspension. Centrifuging, washing and drying to obtain SiO with the size of 220nm2Nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: SiO prepared in the step (1)2Dispersing the nano particles into absolute ethyl alcohol to prepare a colloidal solution with the concentration of 1 wt%, vertically putting a cleaned glass sheet into the solution, putting the solution into an oven at the temperature of 30 ℃, and obtaining a photonic crystal structure template with three-dimensional periodic arrangement after the ethyl alcohol is completely volatilized; mixing polyethylene glycol methacrylate (PEGMA, M)n475), polyethylene glycol diacrylate (PEG-DA, molecular weight 700g/mol) and a photoinitiator (2, 2-diethoxyacetophenone) are uniformly dispersed in ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; dripping the obtained suspension between the glass sheet and a clean glass sheet, and then carrying out ultraviolet curing to obtain a single-network photonic crystal hydrogel film with polyethylene glycol methacrylate (PEGMA) as a substrate;
(3) preparing a photonic crystal sensing material: and (3) soaking the PEGMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet light curing to obtain a photonic crystal hydrogel film with a partial double-network of poly (hydroxyethyl methacrylate)/polyacrylic acid (PEGMA/PAA); and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PEGMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain a double-network photonic crystal hydrogel film with one part of polyhydroxyethyl methacrylate/polyacrylic acid (PEGMA/PAA) and the other part of polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PEGMA/PDMAEMA), namely the photonic crystal sensing material.
Example 6
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1) preparing PS nano particles: placing 100mL of deionized water, 30mL of styrene and 1mL of methacrylic acid in a 250mL round-bottom flask, and heating to boil, wherein the mixture turns from clear to turbid; dissolving 0.4g of ammonium persulfate in 10mL of deionized water, adding the mixture into the mixture to initiate polymerization, stopping the reaction after the reaction is carried out for 1 hour, and centrifuging, washing and dialyzing the obtained mixture to obtain the PS nanoparticles with the size of 200 nm.
(2) Preparation of photonic crystal hydrogel substrate: dispersing the PS nano particles prepared in the step (1) into absolute ethyl alcohol to prepare a colloidal solution with the concentration of 5 wt%, and then dropping the colloidal solution between two glass sheets to naturally volatilize the colloidal solution to form a photonic crystal structure template; uniformly dispersing hydroxyethyl methacrylate (HEMA), N-Methylene Bisacrylamide (MBA) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; dripping the obtained suspension between the glass sheet and a clean glass sheet, and then carrying out ultraviolet curing to obtain a single-network photonic crystal hydrogel film with poly hydroxyethyl methacrylate (PHEMA) as a substrate;
(3) preparing a photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which is partially provided with polyhydroxyethyl methacrylate/polyacrylic acid (PHEMA/PAA) and partially provided with polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PHEMA/PDMAEMA), namely the photonic crystal sensing material.
Example 7
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1) preparing PS nano particles: placing 100mL of deionized water, 40mL of styrene and 0.5mL of methacrylic acid in a 250mL round-bottom flask, and heating to boil, wherein the mixture turns from clear to turbid; dissolving 0.4g of ammonium persulfate in 10mL of deionized water, adding the mixture into the mixture to initiate polymerization, stopping the reaction after the reaction is carried out for 1 hour, and centrifuging, washing and dialyzing the obtained mixture to obtain the PS nanoparticles with the size of 180 nm.
(2) Preparation of photonic crystal hydrogel substrate: dispersing the PS nano particles prepared in the step (1) into absolute ethyl alcohol to prepare a colloidal solution with the concentration of 5 wt%, and then dropping the colloidal solution between two glass sheets to naturally volatilize the colloidal solution to form a photonic crystal structure; uniformly dispersing hydroxyethyl methacrylate (HEMA), N-Methylene Bisacrylamide (MBA) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; dripping the obtained suspension between the glass sheet and a clean glass sheet, and then carrying out ultraviolet curing to obtain a single-network photonic crystal hydrogel film with poly hydroxyethyl methacrylate (PHEMA) as a substrate;
(3) preparing a photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask complementary to the pattern in the previous step for ultraviolet curing to obtain a double-network photonic crystal hydrogel film, namely the photonic crystal sensing material, with one part of the double-network photonic crystal hydrogel film being poly (hydroxyethyl methacrylate)/poly (acrylic acid) (PHEMA/PAA) and the other part of the double-network photonic crystal hydrogel film being poly (hydroxyethyl methacrylate)/poly (dimethylaminoethyl methacrylate) (PHEMA/PDMAEMA).
Example 8
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1) preparing PS nano particles: placing 100mL of deionized water, 30mL of styrene and 0.5mL of methacrylic acid in a 250mL round-bottom flask, and heating to boil, wherein the mixture turns from clear to turbid; dissolving 0.4g of ammonium persulfate in 10mL of deionized water, adding the mixture into the mixture to initiate polymerization, stopping the reaction after the reaction is carried out for 1 hour, and centrifuging, washing and dialyzing the obtained mixture to obtain the PS nanoparticles with the size of 110 nm.
(2) Preparation of photonic crystal hydrogel substrate: dispersing the PS nano particles prepared in the step (1) into absolute ethyl alcohol to prepare a colloidal solution with the concentration of 5 wt%, and then dropping the colloidal solution between two glass sheets to naturally volatilize the colloidal solution to form a photonic crystal structure; uniformly dispersing hydroxyethyl methacrylate (HEMA), N-Methylene Bisacrylamide (MBA) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; dripping the obtained suspension between the glass sheet and a clean glass sheet, and then carrying out ultraviolet curing to obtain a single-network photonic crystal hydrogel film with poly hydroxyethyl methacrylate (PHEMA) as a substrate;
(3) preparing a photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylic Acid (AA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethylmethacrylate/polyacrylic acid (PHEMA/PAA) double network; and then soaking the gel in deionized water, removing unreacted AA monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl methacrylate (DMAEMA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PAA double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which is partially provided with polyhydroxyethyl methacrylate/polyacrylic acid (PHEMA/PAA) and partially provided with polyhydroxyethyl methacrylate/dimethylaminoethyl methacrylate (PHEMA/PDMAEMA), namely the photonic crystal sensing material.
Example 9
The embodiment is a preparation method of a pH-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: dissolving 0.65g of ferrocene in 65mL of acetone to form a solution, then adding 2.2mL of hydrogen peroxide solution with the mass fraction of 30% into the solution, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal reaction, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 hours; after the reaction is finished, separating, washing and drying the nano particles to obtain the Fe with the size of 120nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4@ C nanoparticles, hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEG-DA, molecular weight 700g/mol, makingCrosslinking agent) and photoinitiator (2, 2-diethoxyacetophenone) are uniformly dispersed in ethylene glycol to obtain prepolymer suspension of the photonic crystal hydrogel substrate; fe in each ml of suspension3O4@ C nanoparticles 4mg, HEMA 0.3g, PEG-DA 0.05g and photoinitiator 5 μ L; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with the poly hydroxyethyl methacrylate (PHEMA) as the substrate.
(3) Preparing a patterned photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual HEMA monomer and ethylene glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in methacrylic acid (MAA) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film with a polymethyl hydroxyethyl methacrylate/polymethyl methacrylate (PHEMA/PMAA) double network on the local part; and then soaking the gel in deionized water, removing unreacted monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a dimethylaminoethyl acrylate (DMAEA) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PMAA double-network part with a mask which is complementary with the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain the double-network photonic crystal hydrogel film which partially comprises polyhydroxyethyl methacrylate/polymethacrylic acid (PHEMA/PMAA) and partially comprises polyhydroxyethyl methacrylate/polydimethylaminoethyl acrylate (PHEMA/PDMAEA), namely the photonic crystal sensing material.
Example 10
The embodiment is a preparation method of a temperature-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: 0.65g of ferrocene was dissolved in 65mL of acetone to form a solution, and then added to the solutionAdding 2.2mL of hydrogen peroxide solution with the mass fraction of 30%, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal reaction, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 hours; after the reaction is finished, separating, washing and drying the nano particles to obtain the Fe with the size of 120nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4Uniformly dispersing the @ C nano particles, hydroxyethyl methacrylate (HEMA), polyethylene glycol diacrylate (PEG-DA, the molecular weight is 700g/mol, and the PEG-DA is used as a cross-linking agent) and a photoinitiator (2, 2-diethoxyacetophenone) into ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with the poly hydroxyethyl methacrylate (PHEMA) as the substrate.
(3) Preparing a patterned photonic crystal sensing material: soaking the PHEMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual HEMA monomer and ethylene glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in N-Vinyl Pyrrolidone (VP) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film locally provided with a polyhydroxyethyl methacrylate/polyvinylpyrrolidone (PHEMA/PVP) double network; and then soaking the gel in deionized water, removing unreacted monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in an N-isopropylacrylamide (NIPAM) aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PHEMA/PVP double-network part with a mask which is complementary with the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain a double-network photonic crystal hydrogel film, namely the photonic crystal sensing material, wherein one part of the double-network photonic crystal hydrogel film is provided with poly (hydroxyethyl methacrylate)/polyvinylpyrrolidone (PHEMA/PVP), and the other part of the double-network photonic crystal hydrogel film is provided with poly (hydroxyethyl methacrylate)/poly (N-isopropyl acrylamide) (PHEMA/PNIPAM).
Example 11
The embodiment is a preparation method of a solvent-responsive high-sensitivity patterned photonic crystal sensing material, and the preparation method comprises the following steps:
(1)Fe3O4preparation of @ C nanoparticles: dissolving 0.65g of ferrocene in 65mL of acetone to form a solution, then adding 2.2mL of hydrogen peroxide solution with the mass fraction of 30% into the solution, and stirring for 30min to obtain a mixed solution of solvothermal reaction; then transferring the mixed solution into a reaction kettle for solvothermal reaction, wherein the reaction temperature is controlled at 210 ℃, and the reaction time is 72 hours; after the reaction is finished, separating, washing and drying the nano particles to obtain the Fe with the size of 120nm3O4@ C nanoparticles.
(2) Preparation of photonic crystal hydrogel substrate: fe prepared in the step (1)3O4@ C nanoparticles, polyethylene glycol methacrylate (PEGMA, M)n475), polyethylene glycol diacrylate (PEG-DA, molecular weight 700g/mol, as a cross-linking agent) and a photoinitiator (2, 2-diethoxyacetophenone) are uniformly dispersed in ethylene glycol to obtain a prepolymer suspension of the photonic crystal hydrogel substrate; and (3) carrying out ultraviolet curing on the obtained suspension liquid drop between two glass sheets with the thickness of 300 mu m under the external magnetic field intensity of 800(Gs) to obtain the single-network photonic crystal hydrogel film with polyethylene glycol methacrylate (PEGMA) as the substrate.
(3) Preparing a patterned photonic crystal sensing material: and (3) soaking the PEGMA single-network photonic crystal hydrogel film obtained in the step (2) in deionized water, removing the residual glycol solvent, replacing the deionized water for 2-3 times, soaking the gel in an Acrylamide (AM) aqueous solution with the concentration of 40mg/mL, adding 20mg of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, and placing the gel in a refrigerator in a dark place for 24 hours. Covering a part of the hydrogel film with a mask, and carrying out ultraviolet curing to obtain a photonic crystal hydrogel film with a polyethylene glycol methacrylate/polyacrylamide (PEGMA/PAM) double network locally; and then soaking the gel in deionized water to remove unreacted monomers and an initiator, replacing the deionized water for 2-3 times, soaking the gel in a hydroxyethyl methacrylate aqueous solution with the concentration of 40mg/mL, adding 20mg of the photoinitiator, and placing the gel in a refrigerator in a dark place for 24 hours. Covering the PEGMA/PAM double-network part with a mask which is complementary to the pattern in the previous step, and carrying out ultraviolet curing in the presence of the mask to obtain a double-network photonic crystal hydrogel film, namely the photonic crystal sensing material, wherein one part of the double-network photonic crystal hydrogel film is provided with polyethylene glycol methacrylate/polyacrylamide (PEGMA/PAM), and the other part of the double-network photonic crystal hydrogel film is provided with polyethylene glycol methacrylate/polyhydroxyethyl methacrylate (PEGMA/PHEMA).
Example 12
The patterned photonic crystal sensing material prepared in example 1 is subjected to a test of reflection peak change under a certain pH condition. FIG. 8 is a schematic diagram of the preparation method and the change under the external stimulus of the present invention. FIG. 9 is a reflection spectrum of the photonic crystal sensor material obtained in example 1 after being placed in a solution having a pH of 10.82 for 1 min. As can be seen from FIG. 9, when the sensor hydrogel is not stimulated (when the pH of the solution is 8.32), the sensor hydrogel of the photonic crystal is uniform in color, and the position of a reflection peak is about 487 nm; when external stimulation is applied (the pH value of the solution is changed to 10.23), the positions of reflection peaks in different areas of the photonic crystal hydrogel are changed, the position of a partial reflection peak with acrylic acid is changed from 487nm to about 540nm, and red shift is generated; on the other hand, in the portion where dimethylaminoethyl methacrylate is externally polymerized, the position of the reflection peak is changed from 487nm to about 453nm, and blue shift is generated. FIG. 10 is a reflection spectrum of the photonic crystal sensor material obtained in example 1 after being placed in a solution having a pH of 3.82 for 1 min. As can be seen from FIG. 10, when the sensor hydrogel is not stimulated (when the pH of the solution is 8.32), the sensor hydrogel of the photonic crystal is uniform in color, and the position of a reflection peak is about 487 nm; when external stimulation is applied (the pH value of the solution is changed to 3.82), the positions of reflection peaks in different areas of the photonic crystal hydrogel are changed, the position of a partial reflection peak with acrylic acid is changed from 487nm to about 455nm, and blue shift is generated; on the other hand, in the case of a portion having dimethylaminoethyl methacrylate outside, the position of the reflection peak was changed from 487nm to about 530nm, and a red shift occurred. The photonic crystal sensing material can realize the change of the colors of different areas of the material to opposite directions when being stimulated by the outside, and improves the contrast ratio and the detection sensitivity of the colors.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (13)
1. A patterned photonic crystal sensing material, which is characterized by comprising a polymer matrix without specific responsiveness, nanoparticles, a first polymer and a second polymer; the nanoparticles self-assemble into periodic structures embedded in a polymer matrix; the first and second polymers are crosslinked to different regions of the polymer matrix, and the first and second polymers are adapted to swell and shrink in volume, respectively, when subjected to the same responsive stimulus, resulting in a change in the spacing between the nanoparticles embedded in the polymer matrix, thereby causing a simultaneous red-shift and blue-shift of the nanoparticle reflection peak.
2. The patterned photonic crystal sensing material of claim 1, wherein the polymer matrix without specific responsivity is a polyhydroxyalkyl methacrylate matrix or a polyacrylate matrix.
3. The patterned photonic crystal sensing material of claim 2, wherein the hydroxyalkyl polymethacrylate matrix is hydroxyethyl polymethacrylate or hydroxypropyl polymethacrylate; the polyacrylate matrix is polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, polymethyl acrylate, polyethyl acrylate, 2-acrylic acid-2-methoxyethyl ester polymer, 1, 6-hexanediol diacrylate polymer or polyethylene glycol methacrylate.
4. The patterned photonic crystal sensing material of claim 1, wherein said first polymer and said second polymer are simultaneously a pH responsive polymer, a temperature responsive polymer, a photo responsive polymer, a solvent responsive polymer or an ionic strength responsive polymer.
5. The patterned photonic crystal sensing material of claim 4, wherein said pH-responsive polymer is a polymer formed from anionic monomers and a polymer formed from cationic monomers; the temperature response polymer is a polymer formed by temperature sensitive monomers with different critical solution temperatures; the photoresponse polymer is a polymer with a main chain or a side chain containing a photoresponse group.
6. The patterned photonic crystal sensing material of claim 5, wherein said anionic monomer is acrylic acid, crotonic acid, sodium styrene sulfonate, methacrylic acid, ethacrylic acid, crotonic acid or sodium styrene sulfonate; the cationic monomer is aminoethyl acrylate, dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate;
the temperature-sensitive monomer is N-alkyl substituted acrylamide, vinyl methyl ether, ethylene glycol, propylene glycol, vinyl alcohol, vinyl methyl oxazole or vinyl pyrrolidone;
the photoresponse group is of an azobenzene structure, an indene diketone structure or a thiazine structure.
7. The patterned photonic crystal sensing material of claim 6, wherein said N-alkyl substituted acrylamide is N, N-dimethylacrylamide, N-diethylacrylamide, N-dibutylacrylamide, N-dihexylacrylamide, N-isopropylacrylamide, N-isobutylacrylamide, N-tert-butylacrylamide, N-pentylacrylamide, or N-cyclohexylacrylamide.
8. The patterned photonic crystal sensing material of claim 1, wherein said nanoparticles are inorganic nanoparticles, polymeric nanoparticles or hybrid nanoparticles.
9. The patterned photonic crystal sensing material of claim 8, wherein said inorganic nanoparticles are Fe3O4Or SiO2Nanoparticles; the polymer nano particles are polystyrene and polymethyl methacrylate nano particles; the hybrid nano particles are nano particles formed by polystyrene and polymethyl methacrylate, Fe3O4With SiO2Formed nanoparticles, polystyrene and SiO2Formed nano particles or polymethyl methacrylate and SiO2The nanoparticles formed.
10. The method of making a patterned photonic crystal sensing material of any of claims 1 to 9, comprising the steps of:
(1) preparing a photonic crystal gel substrate: self-assembling nano particles into a photonic crystal with a periodic structure by an electrorheological method, a magnetorheological method, a gravity deposition method, a capillary force assembly method or a template orientation method, and embedding the photonic crystal with the periodic structure into a polymer matrix without specific responsiveness to obtain a photonic crystal gel substrate;
(2) preparing a patterned photonic crystal sensing material: soaking the photonic crystal gel substrate obtained in the step (1) in a first monomer, adding a photoinitiator, covering a partial region of the photonic crystal gel substrate by using a first mask, carrying out ultraviolet light curing, crosslinking a polymer formed by a non-specific responsive polymer and the first monomer in a region uncovered by the mask to form a gel film, and soaking the gel film in a second monomer, wherein the polymer formed by the first monomer, namely the first polymer and the polymer formed by the second monomer, namely the second polymer are used for swelling and shrinking in volume respectively when being subjected to the same responsive stimulus, so that the space among the nano particles embedded in a polymer matrix is changed, and the reflection peak of the nano particles is subjected to red shift and blue shift simultaneously; adding a photoinitiator, covering the gel film by using a second mask, wherein the areas which can be covered by the first mask and the second mask are different, and carrying out ultraviolet curing again to obtain the patterned photonic crystal sensing material; the patterned photonic crystal sensing material comprises two areas, wherein one area is formed by cross-linking a polymer formed by a polymer without specific responsiveness and a first monomer, and the other area is formed by cross-linking a polymer without specific responsiveness and a second monomer.
11. The method for preparing the patterned photonic crystal sensing material according to claim 10, wherein the nanoparticles are monodisperse spherical nanoparticles with a diameter of 100-300 nm.
12. The method for preparing the patterned photonic crystal sensing material according to claim 10, wherein the polymer matrix without specific responsiveness is a poly (hydroxyalkyl methacrylate) matrix or a polyacrylate matrix;
the first polymer and the second polymer are simultaneously a pH responsive polymer, a temperature responsive polymer, a light responsive polymer, a solvent responsive polymer or an ionic strength responsive polymer.
13. Use of a patterned photonic crystal sensing material according to any of claims 1 to 9 for the determination of a response condition or as a security material.
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