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CN-122005787-A - Preparation method of MOF composite fiber film for optically controlling release of NO

CN122005787ACN 122005787 ACN122005787 ACN 122005787ACN-122005787-A

Abstract

The invention relates to biomedical materials and discloses a preparation method of a MOF composite fiber membrane for releasing NO by light control, which comprises the steps of 1) dispersing meso-tetra (4-carboxyphenyl) porphine, a regulator and metal salt in an organic solvent by ultrasonic, heating and reacting to obtain porphyrin-based MOF, 2) dispersing the porphyrin-based MOF and NO donor L-arginine in an ethanol aqueous solution, reacting to obtain Arg-MOF, 3) dispersing the Arg-MOF in a dimethyl sulfoxide/dichloromethane mixed solvent by ultrasonic, adding polylactic acid, stirring uniformly to obtain spinning solution, and carrying out electrostatic spinning and drying to obtain the MOF composite fiber membrane for releasing NO by light control. The composite fiber membrane can synchronously generate ROS and NO through near infrared light irradiation, and further generate peroxynitrite with strong oxidability, so that the efficient synergistic killing of bacteria is realized. In addition, the composite fiber membrane has uniform and stable structure, good particle dispersibility, difficult falling off and good synergy between the porphyrin-based MOF and L-arginine.

Inventors

  • GAO YUJIE
  • WANG LIMO
  • WU JINDAN
  • ZHANG ENMING
  • CHEN QIN

Assignees

  • 浙江理工大学

Dates

Publication Date
20260512
Application Date
20260119

Claims (10)

  1. 1. The preparation method of the MOF composite fiber film for optically controlling and releasing NO is characterized by comprising the following steps: 1) Dispersing meso-tetra (4-carboxyphenyl) porphine, a regulator and metal salt in an organic solvent by ultrasonic, heating for reaction, centrifuging, washing and drying to obtain porphyrin-based MOF; The combination of the regulator and the metal salt is one of benzoic acid/ferric chloride hexahydrate, polyvinylpyrrolidone/copper nitrate and benzoic acid/zirconium oxychloride octahydrate; 2) Dispersing porphyrin-based MOF and NO donor L-arginine in ethanol water solution according to the mass ratio of 1 (0.5-1.0), stirring for reaction in a dark place, centrifugally collecting precipitate, and drying to obtain Arg-MOF; 3) Dispersing Arg-MOF in a dimethyl sulfoxide/dichloromethane mixed solvent with the volume ratio of 1 (3-6), adding polylactic acid, uniformly stirring to obtain spinning solution, carrying out electrostatic spinning, and drying to obtain the MOF composite fiber membrane capable of releasing NO by light control; The Arg-MOF accounts for 6-10wt% of the polylactic acid.
  2. 2. The method of claim 1, wherein in step 1) the combination of the modifier and the metal salt is polyvinylpyrrolidone/copper nitrate.
  3. 3. The method according to claim 1 or 2, wherein in step 1), the mass ratio of meso-tetra (4-carboxyphenyl) porphine, the regulator and the metal salt regulator is 1 (25-30): 1-4.
  4. 4. The process according to claim 1 or 2, wherein in step 1), The organic solvent is N, N-dimethylformamide; The ultrasonic dispersion condition is that the power is 180-220W and the time is 5-10 min; the heating reaction condition is that the temperature is 90+/-2 ℃ and the time is 4-5 h ℃; The centrifugation conditions are that the rotation speed is 10000-12000 rpm and the time is 15-20 min; the washing is sequentially carried out by using N, N-dimethylformamide and ethanol; The drying is freeze drying.
  5. 5. The process according to claim 1, wherein in step 2), The concentration of the ethanol water solution is 45-55 vol%; the temperature of the light-shielding stirring reaction is 35-45 ℃ and the time is 20-28 h.
  6. 6. The method of claim 1, wherein in step 3), the mass-volume ratio of the Arg-MOF and the dimethyl sulfoxide/dichloromethane mixed solvent is 3-30 mg/mL.
  7. 7. The method according to claim 1 or 6, wherein in the step 3), the stirring is carried out at room temperature for a period of 6 to 12 h.
  8. 8. The method according to claim 1, wherein in the step 3), the conditions of the electrospinning are that the voltage is 11-13 kV, the advancing speed is 0.002-0.006 mm/s, the needle is 20-22G, the receiving distance is 13-15 cm, the temperature is 28-32 ℃, and the relative humidity is 45-65%.
  9. 9. A MOF composite fiber film releasing NO by light control produced by the production method according to any one of claims 1 to 8.
  10. 10. Use of a MOF composite fiber film releasing NO by light control produced by the production method according to any one of claims 1 to 8 as an antibacterial material.

Description

Preparation method of MOF composite fiber film for optically controlling release of NO Technical Field The invention relates to the field of biomedical materials, in particular to a preparation method of a MOF composite fiber membrane for releasing NO by light control. Background Bacterial infections continue to threaten human health as an important disease type caused by pathogenic microorganisms, and have become a global major public health problem. At present, clinical antimicrobial treatment mainly depends on antibiotics, but long-term abuse thereof leads to continuous appearance of drug-resistant strains, so that the effectiveness of traditional therapies is gradually reduced. Photodynamic therapy (PDT) is considered a very promising antimicrobial strategy due to its advantages of non-invasive, broad-spectrum antimicrobial and low drug resistance. However, conventional photosensitizers face key problems of poor water solubility, poor photostability, low Reactive Oxygen Species (ROS) production efficiency, etc., severely limiting their practical applications. To this end, photosensitive Metal Organic Framework (MOF) materials can be prepared by precisely coordinating photosensitive molecules with metal clusters. The material can effectively improve the photochemical stability and the dispersivity of the traditional photosensitizer, thereby ensuring that the material can efficiently and continuously generate ROS under the illumination of specific wavelength. In addition, the unique porous crystal structure and designability of MOFs enables them to be designed and functionalized at the atomic level to further enhance ROS production capacity and thus improve antimicrobial efficiency. However, the effective diffusion distance of singlet oxygen (1O2) produced by photosensitive MOFs in the aqueous phase is only 100-220 nm, the half-life is only 2-3.5 μs, it is difficult to penetrate the Extracellular Polymeric Substance (EPS) barrier of bacterial biofilm, and the effect on pathogens in the deep layers of the biofilm is limited. The gas therapy just can make up for the defect, and can break through EPS and go deep into the biomembrane by utilizing the high penetrating power of small molecular gas (such as Nitric Oxide (NO)) so as to realize the removal of deep thalli. Common NO donors such as S-nitrosothiols (RSNO), nitrosoglutathione (GSNO) and erythrosin black salts (RBS) can produce NO under exogenous stimuli such as near infrared or ultrasound. However, these donors often produce toxic byproducts, which present potential biosafety issues. L-arginine (L-Arg) is used as a natural NO donor, can be converted into NO and citrulline through the catalysis of ROS, participates in normal physiological metabolism, has high biocompatibility and has NO obvious toxic or side effect. However, endogenous ROS are insufficient to catalyze the sustained production of NO by L-arginine, thereby diminishing its therapeutic effect. Although the photosensitive MOF can provide sufficient exogenous ROS for L-arginine under illumination to realize preliminary synergy of photodynamic therapy and NO gas therapy, the photosensitive MOF still has the problems of uneven structure, easy aggregation of particles, easy falling off from an action position and the like. Therefore, how to construct an adaptive system for a photosensitive MOF and L-Arg synergistic antibacterial system, realizes system stability, strengthening action sustainability and active substance (ROS/NO) release regulation and control, achieves efficient synergistic antibacterial, and becomes a key technology break of the strategy. Disclosure of Invention In order to solve the technical problems, the invention provides a preparation method of an MOF composite fiber membrane for releasing NO by light control. The composite fiber membrane can synchronously generate ROS and NO through near infrared light irradiation, and further generate peroxynitrite (ONOO -) with strong oxidability, so that the high-efficiency synergistic killing of gram-negative bacteria and gram-positive bacteria is realized. In addition, the composite fiber membrane has uniform and stable structure, good particle dispersibility, difficult falling off and good synergy between the porphyrin-based MOF and the L-arginine. The specific technical scheme of the invention is as follows: firstly, the application provides a preparation method of a MOF composite fiber film for optically controlling and releasing NO, which comprises the following steps: 1) And ultrasonically dispersing meso-tetra (4-carboxyphenyl) porphine (TCPP), a regulator and metal salt in an organic solvent, heating for reaction, centrifuging, washing and drying to obtain the porphyrin-based MOF. 2) Dispersing porphyrin-based MOF and NO donor L-arginine (L-Arg) in ethanol water solution, stirring and reacting in dark, centrifugally collecting precipitate, and drying to obtain Arg-MOF. 3) Dispersing Arg-MOF in dimethyl sulfoxide/dichloromethan