Glucose-responsive one-dimensional photonic crystal film and preparation method and application thereof

Abstract

The present application relates to the technical field of photonic crystal materials and sensing display devices, and particularly relates to a glucose-responsive one-dimensional photonic crystal film and a preparation method and application thereof. The glucose-responsive one-dimensional photonic crystal film comprises a glucose-responsive gel matrix and hydrophilic magnetic photonic nanochains vertically embedded in the glucose-responsive gel matrix; the hydrophilic magnetic photonic nanochains are composed of monodisperse superparamagnetic colloidal nanoparticles arranged in a single-chain one-dimensional nanostructure with an equal particle spacing in a hydrophilic gel shell layer; and the glucose-responsive gel matrix is a product of copolymerization of a hydrophilic monomer and a phenylboronic acid monomer. In the crystal film, the hydrophilic magnetic photonic nanochains serve as a mass transfer channel to promote efficient loading of external glucose in the gel matrix and sufficient reaction with the recognition unit phenylboronic acid, so that glucose response in the human blood glucose threshold range under a physiological environment is realized, and obvious color gamut change is conducive to naked-eye judgment of blood glucose concentration.

Description

Technical Field

[0001] This invention relates to the technical field of photonic crystal materials and sensing and display devices, specifically to glucose-responsive one-dimensional photonic crystal films, their preparation methods, and applications. Background Technology

[0002] Abnormal fluctuations in blood glucose levels can exacerbate vascular endothelial damage, inducing acute glucose metabolism emergencies and chronic complications affecting multiple organs such as the heart, kidneys, eyes, and nervous system. Therefore, real-time blood glucose monitoring is crucial for disease diagnosis and prevention. Currently, various glucose detection methods have been developed, including biochemical analysis, electrochemical sensing, and optical sensing. Among these, optical sensors, represented by phenylboronic acid glucose-responsive photonic crystal sensors, rely on glucose-regulated hydrogel swelling to produce structural color changes. They require no dyes, are visible to the naked eye, and exhibit excellent specificity and reversible stability, making them highly promising for blood glucose monitoring.

[0003] Because phenylboronic acid has a pKa between 8.2 and 8.6, it is mostly hydrophobic and neutral under physiological conditions. The boronic ester formed when it combines with glucose has poor stability, resulting in small gel swelling, a narrow color change window, and insufficient sensing performance. Improving the effective binding efficiency of glucose and phenylboronic acid is the core of optimizing this type of sensor. Under physiological conditions, the hydrophobicity of the boronic acid groups increases the difficulty of glucose molecules diffusing into the gel and undergoing a recognition reaction. Therefore, improving glucose diffusion within the gel matrix has become a new strategy to enhance the response performance of this type of sensor. Chinese patent CN120064256A reports a highly sensitive glucose detector that provides numerous mass transfer channels for glucose through the water absorption and swelling effect of a strongly hydrophilic nanogel, significantly improving the glucose diffusion rate and enhancing the sensitivity of glucose colorimetric detection. In the face of physiological conditions, reported responsive photonic crystal sensors exhibit insensitive responses to changes in glucose concentration within the human blood glucose threshold range, showing insignificant color gamut changes and weak naked-eye recognition. Summary of the Invention

[0004] In view of this, one of the objectives of the present invention is to provide a glucose-responsive one-dimensional photonic crystal film in which hydrophilic magnetic photonic nanochains are vertically oriented and embedded in a glucose-responsive gel film as mass transfer channels, which promotes efficient mass transfer of external glucose in the gel matrix and the function of the colorimetric unit, thereby achieving sensitive response to glucose in a physiological pH=7.4 environment and more convenient naked-eye visibility.

[0005] The second objective of this invention is to provide a method for preparing a glucose-responsive one-dimensional photonic crystal film, which is simple in process and easy to control.

[0006] The third objective of this invention is to provide an application of a glucose-responsive one-dimensional photonic crystal film.

[0007] One of the technical solutions adopted to achieve the objective of this invention is as follows: a glucose-responsive one-dimensional photonic crystal film, comprising a glucose-responsive gel matrix and hydrophilic magnetic photonic nanochains vertically oriented and embedded in the glucose-responsive gel matrix; the hydrophilic magnetic photonic nanochains are composed of monodisperse superparamagnetic colloidal nanoparticles arranged at equal particle spacing in a hydrophilic gel shell to form a single-chain one-dimensional nanostructure; the glucose-responsive gel matrix is ​​a product of copolymerization of a hydrophilic monomer and a phenylboronic acid monomer; and the hydrophilic gel shell is at least one of poly(2-hydroxyethyl)acrylamide, polyacrylamide, poly(N-hydroxymethylacrylamide), and poly(N-acryloylmorpholine).

[0008] In this invention, hydrophilic magnetic photonic nanochains are inserted into a glucose-responsive gel matrix to introduce more and faster glucose molecules into contact with phenylboronic acid, thereby enhancing the sensor's responsiveness. Besides serving as a display unit, the hydrophilic magnetic photonic nanochains also improve the overall hydrophilicity of the crystal film and act as nanogel channels for glucose molecules, rapidly introducing them and simultaneously transporting them to the surrounding glucose-responsive gel network. This increases the amount of glucose introduced, promoting the formation of phenylboronic esters, increasing the negative charge density within the gel matrix. Influenced by Donan equilibrium and charge repulsion, the gel swells; furthermore, the enhanced hydrophilicity of the charged complex further promotes water absorption and swelling of the gel matrix.

[0009] The expansion of the gel matrix causes the stretching of hydrophilic magnetic photonic nanochains, resulting in a color change that enables visual detection even at low glucose concentrations. The hydrophilic magnetic photonic nanochains, acting as mass transfer channels, promote efficient loading of external glucose into the gel matrix and a full reaction with the recognition unit phenylboronic acid, achieving a sensitive response to glucose and naked-eye visibility at a physiological pH of 7.4.

[0010] Preferably, the superparamagnetic colloidal nanoparticles are Fe3O4@PVP nanoparticles with a particle size of 80~200nm.

[0011] Preferably, the thickness of the hydrophilic gel shell is 10~20 nm.

[0012] Preferably, the molar ratio of the hydrophilic monomer to the phenylboronic acid monomer is 9:1 to 5:5; The hydrophilic monomer includes one or more of N-(2-hydroxyethyl)acrylamide, acrylamide, N-hydroxymethylacrylamide, and N-acryloylmorpholine; The phenylboronic acid monomers include one or more of 3-acrylamidophenylboronic acid and 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid.

[0013] The second objective of this invention is achieved through the following technical solution: a method for preparing the glucose-responsive one-dimensional photonic crystal film, comprising the following steps: Step 1: The hydrophilic magnetic photonic nanochains are mixed uniformly with hydrophilic monomers, phenylboronic acid monomers, a first initiator, and a first crosslinking agent in a first solvent to obtain a prepolymer solution; Step 2: Coat the prepolymer obtained in Step 1 onto the substrate surface, and initiate the polymerization of the prepolymer under the assistance of a magnetic field until it solidifies into a film to obtain the glucose-responsive one-dimensional photonic crystal film.

[0014] Preferably, in step 1, the preparation method of the hydrophilic magnetic photonic nanochain is as follows: superparamagnetic colloidal nanoparticles are mixed evenly with a hydrophilic polymeric monomer, a second initiator and a second crosslinking agent in a second solvent to obtain a mixture, and polymerization is initiated under the induction of a magnetic field to obtain the hydrophilic magnetic photonic nanochain. The concentration of the superparamagnetic colloidal nanoparticles in the mixture is 0.15~0.75 mg / mL; The hydrophilic polymeric monomer is one or more of poly(2-hydroxyethyl)acrylamide, polyacrylamide, poly(N-hydroxymethylacrylamide), and poly(N-acryloylmorpholine), and its concentration in the mixture is 0.05~0.25 mmol / mL; The second initiator is at least one of 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, ammonium persulfate, and potassium persulfate, and its concentration in the mixture is 0.4 mmol / mL to 0.9 mmol / mL; The second crosslinking agent is at least one of N,N-methylenebisacrylamide, hydroxypropyl methacrylate, and ethylene glycol dimethacrylate, and its concentration in the mixture is 0.1 mmol / mL to 0.5 mmol / mL; The second solvent is at least one of dimethyl sulfoxide, a mixture of dimethyl sulfoxide and water, and dimethylformamide; The magnetic field strength is 200~500 Gs, and the polymerization time is 2~10 min.

[0015] Preferably, in step 1, the concentration of the hydrophilic magnetic photonic nanochains in the prepolymer solution is 1.5–4.5 mg / mL; The first initiator is at least one selected from 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, ammonium persulfate, and potassium persulfate, and the amount of initiator used is 0.2% to 5% of the total molar concentration of the hydrophilic monomer and the phenylboronic acid monomer. The first crosslinking agent is at least one of N,N-methylenebisacrylamide, hydroxypropyl methacrylate, and ethylene glycol dimethacrylate, and the amount of the crosslinking agent is 1% to 10% of the total molar concentration of the hydrophilic monomer and the phenylboronic acid monomer; The first solvent is at least one of dimethyl sulfoxide, a mixture of dimethyl sulfoxide and water, and dimethylformamide.

[0016] Preferably, in step 1, the total concentration of hydrophilic monomers and phenylboronic acid monomers in the prepolymer solution is 2-5 mmol / mL, wherein the molar ratio of hydrophilic monomers to phenylboronic acid monomers is 9:1-5:5. The hydrophilic monomers include one or more of N-(2-hydroxyethyl)acrylamide, acrylamide, N-hydroxymethylacrylamide, and N-acryloylmorpholine; Benzylboronic acid monomers include one or more of 3-acrylamidophenylboronic acid and 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid.

[0017] Preferably, in step 2, the magnetic field strength is 500~1000 Gs and the polymerization time is 2~10 min.

[0018] Preferably, step 2 further includes: washing the cured membrane to remove unreacted monomers to obtain the glucose-responsive one-dimensional photonic crystal membrane. Specifically, washing is performed using PBS buffer solution with a pH range of 7.0 to 8.2.

[0019] Preferably, in step 2, the substrate is first subjected to hydrophilic treatment, which involves introducing hydrophilic groups or carbon-carbon double bond groups. The modified substrate forms hydrogen bonds with the gel matrix through carboxyl groups or double bond groups, thereby binding the gel matrix to the substrate surface.

[0020] The third objective of this invention is achieved through the following technical solution: an application of the glucose-responsive one-dimensional photonic crystal film, wherein the glucose-responsive one-dimensional photonic crystal film is applied to a photonic crystal colorimetric sensor to detect blood glucose concentrations in the range of 0-11 mM / L under an environment of pH=7.0~8.2.

[0021] Preferably, the photonic crystal colorimetric sensor includes a substrate and a glucose-responsive one-dimensional photonic crystal film bound to the substrate.

[0022] The beneficial effects of this invention are as follows: The glucose-responsive one-dimensional photonic crystal film of the present invention uses hydrophilic magnetic photonic nanochains as mass transfer channels to promote the efficient loading of external glucose in the gel matrix and the full reaction with the recognition unit phenylboronic acid. It achieves glucose response within the human blood glucose threshold range under physiological pH=7.4 environment and has obvious color gamut changes, which is beneficial for naked-eye visualization to judge blood glucose concentration.

[0023] The glucose-responsive one-dimensional photonic crystal film of the present invention disperses and fixes hydrophilic magnetic photonic nanochains in a glucose-responsive gel matrix and binds them to the substrate. The hydrophilic magnetic photonic nanochains maintain better order and high saturation during deformation. Furthermore, the glucose-responsive photonic crystal film bound to the substrate expands only one-dimensionally along the thickness direction of the gel film during deformation, and the hydrophilic magnetic photonic nanochains are also arranged along the thickness direction of the gel film. The direction of lattice spacing adjustment is consistent with the deformation direction of the gel film, ensuring uniformity during color change.

[0024] Hydrophilic magnetic photonic nanochains are inserted into a glucose-responsive gel matrix to rapidly introduce more glucose molecules into contact with phenylboronic acid, enhancing the sensor's responsiveness. Besides serving as a display unit, the hydrophilic magnetic photonic nanochains also improve the overall hydrophilicity of the crystal film and act as nanogel channels for glucose molecules. The hydrophilic gel layer rapidly introduces glucose molecules and simultaneously transports them to the surrounding glucose-responsive gel network. This increases the amount of glucose entering, promoting the formation of phenylboronic esters, increasing the negative charge density within the gel. Influenced by Donan equilibrium and charge repulsion, the gel swells; furthermore, the enhanced hydrophilicity of the charged complex further promotes water absorption and swelling. The expansion of the gel matrix causes the magnetic chains to stretch, resulting in a color change and enabling the visual detection of glucose at lower concentrations. Attached Figure Description

[0025] Figure 1 An optical microscope image of the glucose colorimetric sensor obtained in Example 1; Figure 2 The FT-IR spectra of the hydrophilic magnetic photonic nanochains obtained in Example 1 and the glucose colorimetric sensor based on the hydrophilic magnetic photonic nanochain mass transfer channels are shown. Figure 3 This is a comparison diagram of the hydrated particle size of the hydrophilic magnetic photonic nanochains and magnetic nanoparticles obtained in Example 1. Figure 4 The contact angle test diagram of the glucose colorimetric sensor obtained in Example 1 is shown. Figure 5 The image shows the spectrum and digital photograph (inner image) of the hydrophilic magnetic photonic nanochains obtained in Example 1 under glucose concentration of 0 / 50 mmol / L (PBS 7.4). Figure 6 The results of the glucose colorimetric sensor obtained in Example 1 being immersed under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a curve of Bragg diffraction wavelength, and Figure B is a digital photograph. Figure 7 The results of soaking the glucose colorimetric sensor obtained in Example 2 at pH=8.0 and with a glucose concentration of 0~11 mmol / L are shown in Figure A, which is a peak position change diagram of Bragg diffraction wavelength, and Figure B is a digital photograph. Figure 8 The results of soaking the glucose colorimetric sensor obtained in Example 3 at pH=7.0 and with a glucose concentration of 0~11 mmol / L are shown in Figure A, which is a peak position change diagram of Bragg diffraction wavelength, and Figure B is a digital photograph. Figure 9 A digital photograph of the glucose colorimetric sensor obtained in Example 4; Figure 10 The hydration particle size of the hydrophilic magnetic photonic nanochains copolymerized with different concentrations of polymeric monomers in Example 5 in water; Figure 11 A digital photograph of the viscous gel-like substance prepared in Example 5 at a monomer concentration of 0.3 mmol / mL; Figure 12 The diagram shows the peak position changes of the Bragg diffraction wavelength of the colorimetric sensor prepared with N-hydroxymethylacrylamide using hydrophilic magnetic photonic nanochains as mass transfer channels under physiological conditions and with a glucose concentration of 0-11 mmol / L. Figure 13 The image shows the peak position variation of the Bragg diffraction wavelength of the glucose colorimetric sensor obtained in Example 7 and the corresponding digital photograph (color image in the upper right corner). Figure 14 The results of the glucose colorimetric sensor obtained in Example 8 being immersed under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a peak position change graph, and Figure B is a digital photograph. Figure 15 The results of the glucose colorimetric sensor obtained in Example 9 under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a peak position change graph, and Figure B is a digital photograph. Figure 16 This is a graph showing the peak position changes of the glucose colorimetric sensor obtained in Example 11 when it is immersed in physiological conditions with a glucose concentration of 0-11 mmol / L. Figure 17 The peak position changes of the glucose colorimetric sensor obtained in Example 12 when immersed under physiological conditions with a glucose concentration of 0-11 mmol / L. Figure 18The peak position changes of the glucose colorimetric sensor obtained in Example 13 when immersed under physiological conditions with a glucose concentration of 0-11 mmol / L. Figure 19 The peak position changes of the glucose colorimetric sensor obtained in Example 14 under physiological conditions with glucose concentrations ranging from 0 to 11 mmol / L are shown in the diagram. Figure 20 The contact angle test diagram of the glucose colorimetric sensor obtained in Comparative Example 1 is shown. Figure 21 The graph shows the peak position changes of the glucose colorimetric sensor obtained in Comparative Example 1 when it is immersed in physiological conditions with a glucose concentration of 0-11 mmol / L. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0027] Example 1 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and HEAA was 4.42 mmol / mL, the amount of HMPP was 1% of the total amount of AAPBA and HEAA, the mass of BIS was 2.5% of the total amount of AAPBA and HEAA, and the molar ratio of HEAA to AAPBA was 7.5:2.5.

[0028] (2) Take 50 µL of the above prepolymer solution and coat it onto the surface of the double bond modified glass substrate (2 cm × 2 cm × 100 µm). Finally, place the substrate coated with the prepolymer solution under a magnetic field (500 Gs) perpendicular to the gel membrane for 3 minutes and then turn on the ultraviolet lamp for curing (5 minutes). Soak the prepared gel membrane in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and obtain a glucose-responsive one-dimensional photonic crystal membrane (collectively referred to as a glucose colorimetric sensor) bound on the substrate surface.

[0029] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (150 nm in diameter) are mixed uniformly with hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and crosslinking agent N,N-methylenebisacrylamide (BIS) in a 1:1 mixture of dimethyl sulfoxide and water to obtain a mixed solution. Polymerization is initiated under a magnetic field (300 Gs) for 5 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixed solution is 0.45 mg / mL, the concentration of HEAA is 0.25 mmol / mL, the concentration of HMPP is 0.6 mmol / mL, and the concentration of BIS is 0.3 mmol / mL.

[0030] Figure 1 The image shown is an optical microscope image of the glucose colorimetric sensor obtained in this embodiment. It can be seen that all the hydrophilic magnetic photonic nanochains are vertically aligned in the gel matrix, and the alignment direction is consistent with the volume change direction of the gel matrix. This is beneficial for introducing glucose smoothly as a nanoscale mass transfer channel, and also for maximizing the effect of the volume change of the matrix caused by glucose on the change of the lattice spacing of the photonic crystal chain.

[0031] Figure 2 The figures show the FT-IR spectra of the hydrophilic magnetic photonic nanochains obtained in this embodiment and the glucose colorimetric sensor based on the hydrophilic magnetic photonic nanochain mass transfer channels. The 1541 cm⁻¹ value appears in the figure. -1 This is due to the vibration of the C=C skeleton in the aromatic ring, indicating the presence of a benzene ring structure, and 1056 cm⁻¹ -1 The characteristic peaks that appear are attributed to the stretching vibrations of aryl BC (Ar), at 1340 cm⁻¹. -1The characteristic peaks observed were due to BO asymmetric stretching vibrations. These peaks only appeared in the FT-IR spectrum of the glucose-responsive one-dimensional photonic crystal film based on the hydrophilic magnetic photonic nanochain mass transfer channel, but were not detected in the FT-IR spectrum of the hydrophilic magnetic photonic nanochain itself. This indicates that the hydrophilic magnetic photonic nanochain does not contain phenylboronic acid. The presence of BO characteristic peaks in the glucose colorimetric sensor suggests that the fabricated glucose colorimetric sensor is a heterostructure. The phenylboronic acid monomers of the response unit exist only in the gel membrane, while the internal hydrophilic magnetic photonic nanochain does not contain these monomers and does not interact with glucose. The color change in this sensor is due to the introduction of external glucose molecules by the highly hydrophilic magnetic photonic nanochain. The glucose molecules then combine with the surrounding gel membrane network containing the response monomers to form phenylboronic acid esters, increasing the negative charge density inside the gel. Influenced by Donnan equilibrium and charge repulsion, the gel swells. Furthermore, the increased hydrophilicity of the charged complex further promotes water absorption and swelling of the gel. The expansion of the gel membrane matrix causes the magnetic chains to stretch, resulting in the color change.

[0032] Figure 3 The image shows a comparison of the hydrated particle size of the hydrophilic magnetic photonic nanochains and magnetic nanoparticles obtained in this embodiment. The diameter of the magnetic chain swollen in water is approximately 293.99 nm, which is 118.12 nm larger than the diameter of the magnetic nanoparticles in water (175.87 nm). This indicates that the hydrophilic mass transfer channel formed by the prepared hydrophilic magnetic photonic nanochains in water is approximately 118.12 nm.

[0033] Figure 4 The contact angle test diagram of the glucose colorimetric sensor obtained in this embodiment shows that the water contact angle of the sensor is 44.7°. Figure 5 The images show the spectra and digital photographs (inner images) of the hydrophilic magnetic photonic nanochains obtained in this embodiment under glucose concentrations of 0 / 50 mmol / L (PBS 7.4). It can be seen that the hydrophilic magnetic photonic nanochains themselves do not have glucose responsiveness, indicating that the hydrophilic magnetic photonic nanochains only serve as nanochannels for introducing glucose and as colorimetric units.

[0034] Figure 6 The results of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a curve of Bragg diffraction wavelength, and Figure B is a digital photograph. It can be seen that under physiological conditions of pH=7.4, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 135 nm from 489 nm to 624 nm, and the corresponding structural color changes from blue to orange-red. Its detection sensitivity is 12.3 nm / mM.

[0035] Example 2 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and HEAA was 4.42 mmol / mL, the amount of HMPP was 1% of the total amount of AAPBA and HEAA, the mass of BIS was 2.5% of the total amount of AAPBA and HEAA, and the molar ratio of HEAA to AAPBA was 7:3.

[0036] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (500 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS buffer solution at pH=8.0 for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0037] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (200 nm in diameter) are mixed uniformly with hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and crosslinking agent N,N-methylenebisacrylamide (BIS) in a 1:1 mixture of dimethyl sulfoxide and water to obtain a mixed solution. Polymerization is initiated under a magnetic field (500 Gs) for 5 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixed solution is 0.75 mg / mL, the concentration of HEAA is 0.25 mmol / mL, the concentration of HMPP is 0.6 mmol / mL, and the concentration of BIS is 0.3 mmol / mL.

[0038] Figure 7The results of immersing the glucose colorimetric sensor obtained in this embodiment in a buffer solution with pH=8.0 and a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a curve of Bragg diffraction wavelength, and Figure B is a digital photograph. It can be seen that under pH=8.0 conditions, when the glucose concentration varies in the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 134 nm from 499 nm to 633 nm, and the corresponding structural color changes from blue-green to red. Its detection sensitivity is 12.2 nm / mM.

[0039] Example 3 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and HEAA was 4.42 mmol / mL, the amount of HMPP was 1% of the total amount of AAPBA and HEAA, the mass of BIS was 2.5% of the total amount of AAPBA and HEAA, and the molar ratio of HEAA to AAPBA was 8:2.

[0040] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand for 3 minutes under a vertical magnetic field (500 Gs) and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in a phosphate buffer solution at pH 7.0 for 24 hours to remove residual DMSO and unreacted monomers, thus obtaining a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface.

[0041] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (80 nm in diameter) are mixed uniformly with hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and crosslinking agent N,N-methylenebisacrylamide (BIS) in a 1:1 mixture of dimethyl sulfoxide (DMSO) and water to obtain a mixed solution. Polymerization is initiated under a magnetic field (200 Gs) for 5 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixed solution is 0.45 mg / mL, the concentration of HEAA in the mixed solution is 0.15 mmol / mL, the concentration of HMPP in the mixed solution is 0.6 mmol / mL, and the concentration of BIS in the mixed solution is 0.3 mmol / mL. Figure 8 The results of immersing the glucose colorimetric sensor obtained in this embodiment in a buffer solution with pH=7.0 and a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a curve of Bragg diffraction wavelength, and Figure B is a digital photograph. It can be seen that under pH=7.0 conditions, when the glucose concentration varies in the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a redshift of approximately 124 nm from 471 nm to 595 nm, and the corresponding structural color changes from blue-violet to orange-yellow. Its detection sensitivity is 11.3 nm / mM.

[0042] Example 4 The method is the same as in Example 1, but the molar ratios of HEAA and AAPBA in step (1) are 9:1, 8:2, 7.5:2.5, 7:3, 6:4, and 5:5, respectively.

[0043] Figure 9 Digital photographs of glucose colorimetric sensors obtained with different molar ratios of HEAA and AAPBA. Under the same degree of crosslinking, as the molar ratio of HEAA and AAPBA gradually decreases, the initial structural color of the sensor gradually shifts to blue until it becomes colorless. This is because as the content of phenylboronic acid increases, the hydrophobicity of the sensor gradually increases, making it difficult for water molecules to enter the interior of the gel system. This causes the gel network to shrink, compressing the hydrophilic magnetic photonic nanochains within the network and shortening them, ultimately leading to the blue shift.

[0044] Example 5 The method is the same as in Example 1, but the concentrations of the hydrophilic monomer N-(2-hydroxyethyl)acrylamide in the prepolymer solution of the prepared hydrophilic magnetic photonic nanochains are 0 mmol / mL, 0.05 mmol / mL, 0.1 mmol / mL, 0.15 mmol / mL, 0.2 mmol / mL, 0.25 mmol / mL, and 0.3 mmol / mL, respectively.

[0045] Chains copolymerized with monomers of varying concentrations were used as nano-mass transfer channels, where the thickness of the outer gel layer of the hydrophilic magnetic photonic nanochains was related to the monomer concentration. For example... Figure 10 The figure shows the hydrated particle size of hydrophilic magnetic photonic nanochains copolymerized with different concentrations of monomers in water. It can be seen that as the concentration of monomers increases, the hydrated particle size gradually increases, and the hydrated particle size of the hydrophilic magnetic photonic nanochains in water is the width of the nanochannel. Figure 11 The image shown is a physical picture of a viscous gel-like substance prepared at a monomer concentration of 0.3 mmol / mL. Hydrophilic magnetic photonic nanochains could not be prepared at this monomer concentration.

[0046] Example 6 The method is the same as in Example 1, but the polymer monomer used to prepare the hydrophilic magnetic photonic nanochains is N-hydroxymethylacrylamide.

[0047] Chains copolymerized from other hydrophilic monomers can still serve as nano-mass transfer channels to promote the addition of glucose molecules. For example... Figure 12 The image shows the peak position changes of the Bragg diffraction wavelength of a colorimetric sensor using hydrophilic magnetic photonic nanochains prepared with N-hydroxymethylacrylamide as the mass transfer channel under physiological conditions and with glucose concentrations ranging from 0 to 11 mmol / L. It can be seen that under pH=7.4 conditions, when the glucose concentration varies within the range of 0 to 11 mmol / L, the diffraction spectrum of the sensor undergoes a redshift of approximately 117 nm from 486 nm to 603 nm, and the corresponding structural color changes from blue-violet to orange-yellow. Its detection sensitivity is 10.6 nm / mM.

[0048] Example 7 The method is the same as in Example 1. In step (1), the amounts of N,N'-methylenebisacrylamide used are 1%, 2.5%, 5%, 7.5%, and 10% of the total molar concentration of the hydrophilic monomer and the phenylboronic acid monomer, respectively.

[0049] Figure 13 The Bragg diffraction peak position changes of the glucose colorimetric sensor obtained with different amounts of N,N'-methylenebisacrylamide and the corresponding digital photographs (color image in the upper right corner) show that when the amount of N,N'-methylenebisacrylamide increases from 1% to 10%, the initial peak position of the sensor shifts from 668 nm to 452 nm, and the structural color changes from red to purple. This is because the increased cross-linking degree makes the hydrogel network denser, making it difficult for external aqueous solutions to penetrate the hydrogel interior. Ultimately, this leads to network compression, shortening of the internal magnetic chains, and smaller interparticle spacing within the magnetic chains, resulting in a blue shift in the structural color.

[0050] Example 8 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid (AFPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AFPBA and HEAA was 4.42 mmol / mL, the amount of HMPP was 1% of the total amount of AFPBA and HEAA, the mass of BIS was 2.5% of the total amount of AFPBA and HEAA, and the molar ratio of HEAA to AFPBA was 7.5:2.5.

[0051] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (500 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0052] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (particle size 120 nm) are mixed uniformly with the hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), the initiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and the crosslinking agent hydroxypropyl methacrylate in dimethyl sulfoxide (DMSO) to obtain a mixture. Polymerization is initiated for 10 min under the induction of a magnetic field (300 Gs) to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixture is 0.45 mg / mL, the concentration of HEAA in the mixture is 0.25 mmol / mL, the concentration of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone in the mixture is 0.4 mmol / mL, and the concentration of hydroxypropyl methacrylate in the mixture is 0.1 mmol / mL. Figure 14The results of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a peak position change diagram, and Figure B is a digital photograph. It can be seen that under physiological pH=7.4 conditions, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 145 nm from 520 nm to 665 nm, and the corresponding structural color changes from green to red. Its detection sensitivity is 13.2 nm / mM.

[0053] Example 9 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), acrylamide (AM), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and AM was 4.42 mmol / mL, the amount of HMPP was 0.2% of the total amount of AAPBA and AM, the mass of BIS was 2.5% of the total amount of AAPBA and AM, and the molar ratio of AM to AAPBA was 8.5:1.5.

[0054] (2) 50 µL of the above precursor solution was injected into a double-bond modified glass substrate (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand for 3 minutes under a vertical magnetic field (1000 Gs) and then cured with an ultraviolet lamp for 10 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, obtaining a glucose-responsive one-dimensional photonic crystal film bound to the substrate surface. In step (1), the preparation method of the hydrophilic magnetic photonic nanochains is the same as in Example 1.

[0055] Figure 15 The results of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L are shown in Figure A, which is a peak position change diagram, and Figure B is a digital photograph. It can be seen that under physiological pH=7.4 conditions, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 110 nm from 525 nm to 635 nm, and the corresponding structural color changes from green to red. Its detection sensitivity is 10.0 nm / mM.

[0056] Example 10 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-hydroxymethylacrylamide (NHMA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and NHMA was 2 mmol / mL, the amount of HMPP was 5% of the total amount of AAPBA and NHMA, the mass of BIS was 2% of the total amount of AAPBA and NHMA, and the molar ratio of NHMA to AAPBA was 8:2.

[0057] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand for 3 minutes under a vertical magnetic field (1000 Gs) and then cured with an ultraviolet lamp for 2 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0058] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (particle size 180 nm) are mixed uniformly with hydrophilic monomer N-hydroxymethylacrylamide, initiator 2-hydroxy-2-methylphenylacetone (HMPP), and crosslinking agent N,N'-methylenebisacrylamide (BIS) in dimethyl sulfoxide (DMSO) to obtain a mixture. Polymerization is initiated under a magnetic field (300 Gs) for 3 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixture is 0.45 mg / mL, the concentration of HEAA in the mixture is 0.25 mmol / mL, the concentration of HMPP in the mixture is 0.7 mmol / mL, and the concentration of BIS in the mixture is 0.3 mmol / mL.

[0059] The glucose colorimetric sensor obtained in this embodiment also exhibits good response performance when immersed in a solution with a glucose concentration of 0-11 mmol / L under physiological conditions, and its color-changing ability can range from green to orange.

[0060] Example 11 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution of 3-acrylamidophenylboronic acid (AAPBA), N-hydroxymethylacrylamide (NHMA), hydroxypropyl methacrylate (a crosslinking agent), and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (an initiator) dissolved in dimethyl sulfoxide (DMSO) and water in a 1:1 ratio. The mixture was then homogeneous to obtain a prepolymer solution. The concentration of the hydrophilic magnetic nanochains was 3.0 mg / mL, the total concentration of AAPBA and NHMA was 2 mmol / mL, the amount of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (an initiator) was 2% of the total amount of AAPBA and NHMA, the mass of BIS was 2% of the total amount of AAPBA and NHMA, and the molar ratio of NHMA to AAPBA was 8:2.

[0061] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (500 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0062] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (150 nm in diameter) are mixed uniformly with hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), initiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and crosslinking agent hydroxypropyl methacrylate in a 1:1 ratio of dimethyl sulfoxide (DMSO) and water to obtain a mixture. Polymerization is initiated under a magnetic field (300 Gs) for 5 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixture is 0.45 mg / mL, the concentration of HEAA in the mixture is 0.25 mmol / mL, the concentration of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone in the mixture is 0.5 mmol / mL, and the concentration of hydroxypropyl methacrylate in the mixture is 0.25 mmol / mL.

[0063] Figure 16 The image shows the peak position changes of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L. It can be seen that under physiological pH=7.4 conditions, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 109 nm from 470 nm to 579 nm, and its detection sensitivity is 9.9 nm / mM.

[0064] Example 12 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) Hydrophilic magnetic photonic nanochains were dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent ethylene glycol dimethacrylate, initiator potassium persulfate, and dimethylformamide (DMF), and mixed evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AAPBA and HEAA was 5 mmol / mL, the amount of HMPP was 3% of the total amount of AAPBA and HEAA, the mass of BIS was 2.5% of the total amount of AAPBA and HEAA, and the molar ratio of HEAA to AAPBA was 7.5:2.5.

[0065] (2) 50 µL of the above precursor solution was injected into a double-bond modified glass substrate (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (800 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0066] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (150 nm in diameter) are mixed uniformly with the hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), the initiator potassium persulfate, and the crosslinking agent ethylene glycol dimethacrylate in dimethylformamide (DMF) to obtain a mixture. Polymerization is initiated under a magnetic field (300 Gs) for 2 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixture is 0.45 mg / mL, the concentration of HEAA in the mixture is 0.25 mmol / mL, the concentration of potassium persulfate in the mixture is 0.9 mmol / mL, and the concentration of ethylene glycol dimethacrylate in the mixture is 0.5 mmol / mL.

[0067] Figure 17 The image shows the peak position changes of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L. It can be seen that under physiological pH=7.4 conditions, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift from 491 nm to 620 nm, approximately 129 nm, and its detection sensitivity is 11.7 nm / mM.

[0068] Example 13 A method for preparing a glucose-responsive one-dimensional photonic crystal film includes the following steps: (1) The hydrophilic magnetic photonic nanochains prepared with N-(2-hydroxyethyl)acrylamide were dispersed in a mixed solution of 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid (AFPBA), acrylamide (AM), hydroxypropyl methacrylate as a crosslinking agent, ammonium persulfate as an initiator, and dimethyl sulfoxide (DMSO) and water in a 3:1 ratio. The mixture was stirred evenly to obtain a prepolymer solution. The concentration of the hydrophilic magnetic photonic nanochains was 3.0 mg / mL, the total concentration of AFPBA and HEAA was 3.6 mmol / mL, the amount of HMPP was 1% of the total amount of AFPBA and HEAA, the mass of BIS was 2.5% of the total amount of AFPBA and HEAA, and the molar ratio of HEAA to AFPBA was 7.5:2.5.

[0069] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (500 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0070] In step (1), the hydrophilic magnetic photonic nanochains are prepared as follows: Fe3O4@PVP nanoparticles (150 nm in diameter) are mixed uniformly with the hydrophilic monomer N-(2-hydroxyethyl)acrylamide (HEAA), the initiator ammonium persulfate, and the crosslinking agent hydroxypropyl methacrylate in dimethyl sulfoxide (DMSO) to obtain a mixture. Polymerization is initiated under a magnetic field (300 Gs) for 10 min to obtain the hydrophilic magnetic photonic nanochains. The concentration of Fe3O4@PVP nanoparticles in the mixture is 0.45 mg / mL, the concentration of HEAA in the mixture is 0.25 mmol / mL, the concentration of ammonium persulfate in the mixture is 0.4 mmol / mL, and the concentration of hydroxypropyl methacrylate in the mixture is 0.1 mmol / mL.

[0071] Figure 18The image shows the peak position changes of the glucose colorimetric sensor obtained in this embodiment under physiological conditions with a glucose concentration of 0-11 mmol / L. It can be seen that under physiological pH=7.4 conditions, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 150 nm, from 513 nm to 663 nm, and its detection sensitivity is 13.6 nm / mM.

[0072] Example 14 The method is the same as in Example 1, but the concentrations of the hydrophilic magnetic photonic nanochains in step (1) are 1.5 mg / mL, 2.25 mg / mL, and 4.5 mg / mL, respectively.

[0073] Figure 19 This example shows a comparison of peak position changes for glucose colorimetric sensors obtained with different concentrations of hydrophilic magnetic photonic nanochains, immersed under physiological conditions with glucose concentrations ranging from 0 to 11 mmol / L. This is in conjunction with the peak position changes observed in Example 1 when the concentration of hydrophilic magnetic photonic nanochains was 3.0 mg / mL. Figure 6 Comparative analysis of peak position changes shows that the glucose response performance initially increases and then decreases with increasing concentration of hydrophilic magnetic photonic nanochains. When the concentration of hydrophilic magnetic photonic nanochains increases from 1.5 mg / mL to 3.0 mg / mL, the glucose response performance improves. This is because with the increase in the concentration of hydrophilic magnetic photonic nanochains, more hydrophilic channels are embedded in the membrane, allowing more glucose molecules to be introduced into the reaction system to participate in the reaction. However, when the concentration of hydrophilic magnetic photonic nanochains reaches 4.5 mg / mL, the glucose response performance decreases again. This is because at this point, the proportion of non-glucose-responsive monomers in the glucose-responsive one-dimensional photonic crystal membrane is large, while the proportion of glucose-responsive monomers is small, leading to a decrease in glucose response performance.

[0074] Comparative Example 1 A method for preparing a glucose colorimetric sensor embedded with magnetic nanoparticles includes the following steps: (1) A DMSO dispersion of Fe3O4@PVP colloidal nanoparticles (particle size 145 nm) was dispersed in a mixed solution consisting of 3-acrylamidophenylboronic acid (AAPBA), N-(2-hydroxyethyl)acrylamide (HEAA), crosslinking agent N,N'-methylenebisacrylamide (BIS), initiator 2-hydroxy-2-methylphenylacetone (HMPP), and dimethyl sulfoxide (DMSO). The mixture was stirred until homogeneous to obtain a prepolymer solution. The concentration of Fe3O4@PVP colloidal nanoparticles was 3.0 mg / mL, the total concentration of AAPBA and HEAA was 4.42 mmol / mL, the amount of HMPP was 1% of the total amount of AAPBA and HEAA, the mass of BIS was 2.5% of the total amount of AAPBA and HEAA, and the molar ratio of HEAA to AAPBA was 7.5:2.5.

[0075] (2) 50 µL of the above precursor solution was injected into a glass substrate modified with double bonds (2 cm × 2 cm × 100 µm). Finally, the prepolymer solution was allowed to stand under a vertical magnetic field (500 Gs) for 3 minutes and then cured with an ultraviolet lamp for 5 minutes. The prepared gel membrane was immersed in PBS 7.4 buffer solution for 24 hours to remove residual DMSO and unreacted monomers, and a glucose-responsive one-dimensional photonic crystal membrane bound to the substrate surface was obtained.

[0076] Figure 20 The contact angle test diagram of the glucose colorimetric sensor obtained in this comparative example shows that the water contact angle of the sensor is 71.6°. Compared with the water contact angle of the photonic crystal film with embedded hydrophilic magnetic photonic nanochains obtained in Example 1, it is found that the glucose colorimetric sensor obtained in Example 1 is more hydrophilic, and water molecules and glucose molecules can enter the film more easily and in greater quantities.

[0077] Figure 21 The peak position change diagram of the glucose colorimetric sensor obtained in this comparative example under physiological conditions with a glucose concentration of 0-11 mmol / L shows that under physiological pH=7.4, when the glucose concentration changes within the range of 0-11 mmol / L, the diffraction spectrum of the sensor undergoes a red shift of approximately 73 nm, shifting from 460 nm to 533 nm, and its detection sensitivity is 6.6 nm / mM.

[0078] The above embodiments merely illustrate implementation methods of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A glucose-responsive one-dimensional photonic crystal film, characterized in that, The invention includes a glucose-responsive gel matrix and hydrophilic magnetic photonic nanochains vertically oriented and embedded in the glucose-responsive gel matrix. The hydrophilic magnetic photonic nanochains are composed of monodisperse superparamagnetic colloidal nanoparticles arranged at equal interparticle spacing in a hydrophilic gel shell to form a single-chain one-dimensional nanostructure. The glucose-responsive gel matrix is ​​a product of copolymerization of hydrophilic monomers and phenylboronic acid monomers. The preparation method of the hydrophilic magnetic photonic nanochain is as follows: superparamagnetic colloidal nanoparticles are mixed with hydrophilic polymeric monomers, a second initiator and a second crosslinking agent in a second solvent to obtain a mixed solution, and polymerization is initiated under the induction of a magnetic field to obtain the hydrophilic magnetic photonic nanochain. The concentration of the superparamagnetic colloidal nanoparticles in the mixture is 0.15~0.75 mg / mL; The hydrophilic polymeric monomer is one or more of N-(2-hydroxyethyl)acrylamide and N-hydroxymethylacrylamide; The second crosslinking agent is at least one of N,N-methylenebisacrylamide, hydroxypropyl methacrylate, and ethylene glycol dimethacrylate.

2. The glucose-responsive one-dimensional photonic crystal film according to claim 1, characterized in that, The superparamagnetic colloidal nanoparticles are Fe3O4@PVP nanoparticles with a particle size of 80~200 nm. The thickness of the hydrophilic gel shell is 10~20 nm.

3. The glucose-responsive one-dimensional photonic crystal film according to claim 1, characterized in that, The molar ratio of the hydrophilic monomer to the phenylboronic acid monomer is 9:1 to 5:5; The hydrophilic monomer includes one or more of N-(2-hydroxyethyl)acrylamide, acrylamide, N-hydroxymethylacrylamide, and N-acryloylmorpholine; The phenylboronic acid monomers include one or more of 3-acrylamidophenylboronic acid and 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid.

4. A method for preparing a glucose-responsive one-dimensional photonic crystal film according to any one of claims 1-3, characterized in that, Includes the following steps: Step 1: The hydrophilic magnetic photonic nanochains are mixed uniformly with hydrophilic monomers, phenylboronic acid monomers, a first initiator, and a first crosslinking agent in a first solvent to obtain a prepolymer solution; Step 2: Coat the prepolymer obtained in Step 1 onto the substrate surface, and initiate the polymerization of the prepolymer under the assistance of a magnetic field until it solidifies into a film to obtain the glucose-responsive one-dimensional photonic crystal film.

5. The method for preparing a glucose-responsive one-dimensional photonic crystal film according to claim 4, characterized in that: In step 1, the preparation method of the hydrophilic magnetic photonic nanochain is as follows: superparamagnetic colloidal nanoparticles are mixed evenly with hydrophilic polymeric monomers, a second initiator and a second crosslinking agent in a second solvent to obtain a mixture, and polymerization is initiated under the induction of a magnetic field to obtain the hydrophilic magnetic photonic nanochain. The concentration of the superparamagnetic colloidal nanoparticles in the mixture is 0.15~0.75 mg / mL; The hydrophilic polymeric monomer is one or more of N-(2-hydroxyethyl)acrylamide and N-hydroxymethylacrylamide, and its concentration in the mixture is 0.05~0.25 mmol / mL; The second initiator is at least one of 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, ammonium persulfate, and potassium persulfate, and its concentration in the mixture is 0.4 mmol / mL to 0.9 mmol / mL; The second crosslinking agent is at least one of N,N-methylenebisacrylamide, hydroxypropyl methacrylate, and ethylene glycol dimethacrylate, and its concentration in the mixture is 0.1 mmol / mL to 0.5 mmol / mL; The second solvent is at least one of dimethyl sulfoxide, a mixture of dimethyl sulfoxide and water, and dimethylformamide; The magnetic field strength is 200~500 Gs, and the polymerization time is 2~10 min.

6. The method for preparing the glucose-responsive one-dimensional photonic crystal film according to claim 4, characterized in that: In step 1, the concentration of the hydrophilic magnetic photonic nanochains in the prepolymer solution is 1.5–4.5 mg / mL; The first initiator is at least one selected from 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, ammonium persulfate, and potassium persulfate, and the amount of initiator used is 0.2% to 5% of the total molar concentration of the hydrophilic monomer and the phenylboronic acid monomer. The first crosslinking agent is at least one of N,N-methylenebisacrylamide, hydroxypropyl methacrylate, and ethylene glycol dimethacrylate, and the amount of the crosslinking agent is 1% to 10% of the total molar concentration of the hydrophilic monomer and the phenylboronic acid monomer; The first solvent is at least one of dimethyl sulfoxide, a mixture of dimethyl sulfoxide and water, and dimethylformamide.

7. The method for preparing the glucose-responsive one-dimensional photonic crystal film according to claim 4, characterized in that: In step 1, the total concentration of hydrophilic monomers and phenylboronic acid monomers in the prepolymer solution is 2-5 mmol / mL, and the molar ratio of hydrophilic monomers to phenylboronic acid monomers is 9:1-5:

5. The hydrophilic monomers include one or more of N-(2-hydroxyethyl)acrylamide, acrylamide, N-hydroxymethylacrylamide, and N-acryloylmorpholine; Benzylboronic acid monomers include one or more of 3-acrylamidophenylboronic acid and 4-(2-acrylamidoethylcarbamoyl)-3-fluorophenylboronic acid.

8. The method for preparing the glucose-responsive one-dimensional photonic crystal film according to claim 4, characterized in that: In step 2, the magnetic field strength is 500~1000 Gs, and the polymerization time is 2~10 min.

9. The application of a glucose-responsive one-dimensional photonic crystal film according to any one of claims 1-3 or a glucose-responsive one-dimensional photonic crystal film prepared by the preparation method according to any one of claims 4-8, characterized in that, The glucose-responsive one-dimensional photonic crystal film was applied to a photonic crystal colorimetric sensor to detect blood glucose concentrations in the range of 0 to 11 mM / L under an environment of pH 7.0 to 8.

2.

10. The application according to claim 9, characterized in that, The photonic crystal colorimetric sensor includes a substrate and a glucose-responsive one-dimensional photonic crystal film bound to the substrate.

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