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CN-122012078-A - Preparation method of mesoporous silica nano probe composite electrostatic spinning film material

CN122012078ACN 122012078 ACN122012078 ACN 122012078ACN-122012078-A

Abstract

The invention discloses a preparation method of a mesoporous silica nano probe composite electrostatic spinning film material, and belongs to the technical field of fluorescent sensing materials. According to the invention, organic fluorescent molecules are modified on the surface of mesoporous silica in a stepwise synthesis mode, so that the silica nanoparticle capable of sensing H 2 S is prepared, and then the silica nanoparticle is wrapped by PAN (polyacrylonitrile) and PVP (polyvinylpyrrolidone) matrixes in an electrostatic spinning mode. The sensor not only maintains the characteristic of specific fluorescence identification of fluorescent molecules on H 2 S, but also combines the protection effect of mesoporous silica skeleton and PAN (poly-N-pyrrolidone) PVP (polyvinyl pyrrolidone) matrix, and obtains the fluorescent sensing film with excellent performance.

Inventors

  • GAO MENG
  • BAI YIMEI
  • LI DONGWEI
  • ZHAO XINRU
  • ZHANG XUETAO
  • XIA XIANJIN
  • HU YU

Assignees

  • 山东省科学院新材料研究所

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. The preparation method of the mesoporous silica nano probe composite electrostatic spinning film material is characterized by comprising the following steps of: The mesoporous silica nano probe composite electrostatic spinning film material is prepared by taking mesoporous silica as a raw material, sequentially carrying out amination, modification on carboxybenzaldehyde and modification on 4-azidoaniline to obtain functionalized silica, mixing the functionalized silica with polyacrylonitrile and polyvinylpyrrolidone to prepare electrostatic spinning solution, and carrying out electrostatic spinning.
  2. 2. The method of manufacturing according to claim 1, comprising the steps of: S1, amination, namely mixing and reacting mesoporous silicon dioxide, 3-aminopropyl triethoxysilane and toluene to obtain amino silicon dioxide; S2, modifying the p-carboxybenzaldehyde, namely mixing the amino silicon dioxide and the p-carboxybenzaldehyde for reaction to obtain BH-SiO 2 ; S3, modifying 4-azidoaniline, namely mixing and reacting BH-SiO 2 , 4-azidoaniline hydrochloride and ethanol to obtain functionalized silica; S4, electrostatic spinning, namely dispersing the functionalized silica in a solvent, adding polyacrylonitrile and polyvinylpyrrolidone, mixing, and carrying out electrostatic spinning to obtain the mesoporous silica nano probe composite electrostatic spinning film material.
  3. 3. The preparation method of the mesoporous silica, 3-aminopropyl triethoxysilane and toluene according to claim 2, wherein the dosage ratio of the mesoporous silica to the 3-aminopropyl triethoxysilane to the toluene is 1 g:5-6 mL:50-60 mL, the reaction temperature in the step S1 is 75-80 ℃ and the reaction time is 12-24 h.
  4. 4. The process according to claim 2, wherein the p-carboxybenzaldehyde is activated in a solvent with an activating agent comprising N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride before being mixed with the amino silica.
  5. 5. The preparation method of the BH-SiO 2 is characterized in that the specific step of the step S2 is that p-carboxybenzaldehyde, N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are dissolved in ethanol and activated for 4-12 hours to obtain a solution a, and the amino silicon dioxide is added into the solution a to react for 4-12 hours to obtain the BH-SiO 2 .
  6. 6. The preparation method according to claim 5, wherein the mass ratio of the p-carboxybenzaldehyde, the N-hydroxysuccinimide, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the amino silica is 1-1.2:1-1.2:5-5.5.
  7. 7. The preparation method of claim 2, wherein the mass ratio of BH-SiO 2 to 4-azidoaniline hydrochloride is 5.5-6:1-1.3, and the reaction temperature in step S3 is 75-80 ℃ and the reaction time is 12-24 h.
  8. 8. The preparation method of the multifunctional silica, polyacrylonitrile and polyvinylpyrrolidone according to the mass ratio of 1-1.2:1.2-1.6:1-1.2, wherein the solvent comprises N, N-dimethylformamide, and the parameters of electrostatic spinning are as follows, the spinning speed is 0.2mL/h, the spinning humidity is 50%, the spinning temperature is 27 ℃, and the spinning distance is 20cm.
  9. 9. The mesoporous silica nano probe composite electrostatic spinning film material prepared by the preparation method of any one of claims 1-8.
  10. 10. The use of the mesoporous silica nano probe composite electrostatic spinning film material of claim 9 in H 2 S detection.

Description

Preparation method of mesoporous silica nano probe composite electrostatic spinning film material Technical Field The invention belongs to the technical field of fluorescent sensing materials, and particularly relates to a preparation method of a mesoporous silica nano probe composite electrostatic spinning film material. Background Hydrogen sulfide (H 2 S) is a colorless, toxic gas with a pungent odor. Can be produced in the processes of nature, industrial production, chemical reaction, protein decomposition and the like. Wherein the human body also has dual roles, and under physiological conditions, the human body can be used as an important cardiovascular protective agent and a nerve regulator for regulating blood pressure and affecting transmission of nerve centers by relaxing vascular smooth muscle, but in specific pathological environments, such as bacterial infection, colon cancer, diabetes mellitus and the like, the concentration of H 2 S generated by the human body can be abnormally increased, so the human body can also be used as a signal molecule for detecting health. Therefore, the development of the H 2 S detection means with rapid response, high sensitivity and strong selectivity has important research significance and practical application value. Currently, common methods for detecting hydrogen sulfide include electrochemical methods, fluorescence sensing methods, chromatography, and the like. The fluorescence sensing method is suitable for on-site detection of H 2 S due to the advantages of high sensitivity, visualization, quick response and the like. Among the sensing methods, the flexible fluorescent sensing film is widely applied to the fields of environment detection, biosensing, intelligent protection and the like due to the characteristics of portability, flexibility, easy operation and the like. The electrostatic spinning technology can prepare the micro/nano fiber film with high specific surface area, and the micro/nano fiber film has the characteristics of easy modification and design, so that an excellent platform is provided for the preparation of the multifunctional composite sensing material, and the development of various high-performance flexible fluorescence sensors is promoted. However, the existing flexible fluorescent sensing film has the defects of low fluorescent efficiency, slow response and the like, and the application of the flexible fluorescent sensing film in H 2 S detection is greatly limited. Based on this, the present invention has been proposed. Disclosure of Invention The invention aims to provide a preparation method of a mesoporous silica nano probe composite electrostatic spinning film material. The present invention utilizes azido schiff base derivative molecules (Az, as shown in fig. 1) with a fluorescent "on" response to hydrogen sulfide to surface modify silica. The silica fluorescent probe with the hydrogen sulfide sensing function is prepared, and the probe is further utilized to prepare the fluorescent sensing film which can be used for detecting H 2 S through an electrostatic spinning method. In order to achieve the above object, the present invention provides the following solutions: The invention provides a preparation method of a mesoporous silica nano probe composite electrostatic spinning film material, which comprises the following steps: s1, amination, namely mixing mesoporous silicon dioxide prepared by a sol-gel method, 3-aminopropyl triethoxysilane and toluene and reacting to obtain amino silicon dioxide (NH 2-SiO2); S2, modifying the p-carboxybenzaldehyde, namely mixing the amino silicon dioxide and the p-carboxybenzaldehyde for reaction to obtain BH-SiO 2; S3, modifying 4-azidoaniline, namely mixing and reacting BH-SiO 2, 4-azidoaniline hydrochloride and ethanol to obtain functionalized silica (Az-SiO 2); s4, electrostatic spinning, namely dispersing the functionalized silica in a solvent, adding Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) to mix, and carrying out electrostatic spinning to obtain the mesoporous silica nano probe composite electrostatic spinning film material. Further, the specific steps of preparing mesoporous silica by utilizing a sol-gel method are that cetyl trimethyl ammonium bromide is dissolved in water, ammonia water is added, stirring is carried out at room temperature uniformly, tetraethyl orthosilicate and n-hexane are added dropwise, heating and stirring are carried out, then ethanol washing is carried out, and vacuum drying is carried out, thus obtaining the mesoporous silica. Further, the volume ratio of the tetraethyl orthosilicate to the n-hexane is 1-2:2-3, the temperature of heating and stirring is 35 ℃, and the time is 6-12 hours. Preferably, the dosage ratio of the mesoporous silica to the 3-aminopropyl triethoxysilane to the toluene is 1 g:5-6 mL:50-60 mL. Preferably, the reaction temperature in the step S1 is 75-80 ℃ and the reaction time is 12-24 hours. Preferably, the p-carboxybenzaldehy