Search

CN-121975144-A - Antibacterial material with calcium ion-mediated and photothermal effects, and preparation method and application thereof

CN121975144ACN 121975144 ACN121975144 ACN 121975144ACN-121975144-A

Abstract

The invention discloses an antibacterial material with calcium ion mediation and photothermal effects, and a preparation method and application thereof, and belongs to the technical field of biological medicines. The antibacterial material is a calcium ion loaded porous covalent organic framework polymer BQ-Ca-COF. Carrying out solvothermal reaction on 2,3,5, 6-tetraaminocyclohexa-2, 5-diene-1, 4-dione and cyclohexanecarboxylic acid octahydrate to obtain a porous covalent organic framework polymer, and carrying out metallization reaction on the porous covalent organic framework polymer and calcium chloride under a protective atmosphere to obtain BQ-Ca-COF. The BQ-Ca-COF prepared by the invention has the synergistic effect of controllable release of Ca 2+ and photo-thermal irradiation, has good photo-thermal conversion under 638-nm wavelength laser irradiation, can release calcium ions under infrared (NIR) laser irradiation, increases the permeability of a bacterial film, and synergistically enhances the efficacy of the subsequent photo-thermal action, thereby effectively killing gram-positive and gram-negative bacteria.

Inventors

  • LI WENJING
  • LI JUNLONG
  • JIANG YAN
  • XIAO YUBO
  • XU RAN
  • WANG YIRAN
  • WANG MENGXIAO
  • YANG HUABAO
  • Si Shaohan

Assignees

  • 山东第二医科大学

Dates

Publication Date
20260505
Application Date
20260408

Claims (10)

  1. 1. The antibacterial material with the calcium ion-mediated and photothermal effects is characterized by being a calcium ion-loaded porous covalent organic framework polymer, wherein the porous covalent organic framework polymer is obtained by copolymerizing cyclohexanones and aromatic tetramines serving as monomers.
  2. 2. The antimicrobial material of claim 1, wherein the aromatic tetraamine is 2,3,5, 6-tetraminocyclohexane-2, 5-diene-1, 4-dione.
  3. 3. The antimicrobial material of claim 1, wherein the antimicrobial material has a structural formula: 。
  4. 4. a method for preparing an antibacterial material according to any one of claims 1 to 3, comprising the steps of: (1) Adding 2,3,5, 6-tetraminocyclohexane-2, 5-diene-1, 4-dione and cyclohexanecarboxylic acid octahydrate into an organic solvent for solvothermal reaction, and separating, washing and drying sequentially after the reaction is finished to obtain a porous covalent organic framework polymer; (2) Dispersing the porous covalent organic framework polymer in distilled water under a protective atmosphere, adding excessive calcium salt to obtain a dispersion liquid, stirring to perform metallization reaction, and sequentially centrifuging, washing and drying after the reaction is finished to obtain the antibacterial material with calcium ion mediation and photothermal effects.
  5. 5. The method according to claim 4, wherein in the step (1), the molar ratio of the 2,3,5, 6-tetraminocyclohexane-2, 5-diene-1, 4-dione to cyclohexanecarboxylic acid octahydrate is 1.5:1, the organic solvent is a mixture of ethylene glycol and an acetic acid solution, and the concentration of the acetic acid solution is 6M.
  6. 6. The method according to claim 4, wherein in the step (1), the solvothermal reaction is carried out at 120 ℃ for 72 hours, and the separation is carried out by ultrasonic extraction with distilled water for 24 hours and then Soxhlet extraction with acetone for 24 hours.
  7. 7. The method according to claim 4, wherein in the step (2), the calcium salt is calcium chloride, the concentration of the porous covalent organic framework polymer in the dispersion is 1mg/mL, and the concentration of the calcium salt is 100mM.
  8. 8. The process of claim 4, wherein in step (2), the temperature of the metallization reaction is 25 ℃ for a period of 5 d.
  9. 9. The use of an antibacterial material according to any one of claims 1 to 3 for the preparation of antibacterial drugs.
  10. 10. The use according to claim 9, wherein the antimicrobial material is antimicrobial by releasing Ca 2+ under infrared laser irradiation and producing photothermal effects, both acting together.

Description

Antibacterial material with calcium ion-mediated and photothermal effects, and preparation method and application thereof Technical Field The invention relates to the technical field of biological medicines, in particular to an antibacterial material with calcium ion mediation and photothermal effects, and a preparation method and application thereof. Background Drug-resistant infections directly lead to over million deaths each year, the continued spread of drug-resistant genes is continuously weakening the efficacy of traditional antibiotics, and the characteristic of bacteria forming biofilms is more critical to frosting on snow. Biofilms confer extraordinary antibiotic resistance and immunity against the host to the bacteria, resulting in extremely difficult eradication of the associated infection, often causing chronic lesions, prolonged hospitalization and increased mortality. The dual threat of free form "superbacteria" and recalcitrant biofilms highlights the urgency of developing non-antibiotic therapeutic strategies. To address this challenge, researchers have explored a number of alternative antimicrobial approaches, however, each approach faces significant bottlenecks. Although powerful, metal ions raise concerns about long-term biosafety and environmental accumulation. Organic antimicrobial agents are often limited by volatility, photolytic and short-term issues. Gas therapy faces the challenges of accurate delivery and dose control. The key is that most of these strategies lack specificity for bacterial cells and may inadvertently damage host tissue, thereby delaying wound healing and initiating secondary injury. Furthermore, these methods generally have limitations that have insufficient efficacy on biofilms. Phototherapy (PTT) presents great potential as a non-invasive alternative to traditional antibiotics. PTT physically disrupts bacterial membrane integrity by converting light energy into localized heat energy, triggering rapid cell death, whose unique mechanism of action is not readily induced by resistance, however, its efficacy has several inherent limitations. To overcome these challenges, pre-sensitization of bacterial membranes has become a viable strategy. Increasing bacterial membrane permeability can reduce the temperature threshold required for effective sterilization, thereby reducing the risk of damage to surrounding healthy tissue. There are various methods for improving the permeability of bacterial membranes, such as disruption of bacterial membranes by cationic polymer or cationic molecule interaction with bacterial membranes by cationic groups, or disruption of chemical stability of membrane structure by lysozyme (degradation of peptidoglycan) or enzymes directed against the outer membrane of gram-negative bacteria, or disruption of cell membranes by biologically relevant ion mediation such as calcium ion (Ca 2+), etc. Ca 2+ can interact with phospholipids in bacterial membranes, destroying their structural integrity and enhancing permeability. However, the key to this strategy is the material design, which requires the ability to precisely regulate the release and action of Ca 2+. This ensures that Ca 2+ acts on the bacterial membrane at the proper dosage at the proper time, thereby enhancing the membrane disruption effect while avoiding unnecessary biological interference. If the antibacterial agent is synergistic with the photo-thermal effect, a stronger and more accurate antibacterial system can be constructed. Therefore, controllable loading and release of Ca 2+ ions are needed, and a composite material with strong endogenous photo-thermal characteristics and controllable calcium ion membrane destruction effect is constructed by embedding Ca 2+ into a customized COF framework. While designing a controllable delivery system that meets the above requirements remains a significant challenge for current research. Disclosure of Invention Aiming at the prior art, the invention aims to provide an antibacterial material with calcium ion mediation and photothermal effects, and a preparation method and application thereof. The invention uses cyclohexanecarbon as basic unit, builds basic covalent organic framework with aromatic tetramine, and then carries out calcium metallization to obtain the metal covalent organic framework material BQ-Ca-COF with controlled release of Ca 2+ and synergistic effect of photo-thermal irradiation. BQ-Ca-COF has good photo-thermal conversion under 638 nm wavelength laser irradiation, and can release calcium ions under infrared (NIR) laser irradiation, increase the permeability of a bacterial film, and synergistically enhance the efficacy of the subsequent photo-thermal action, thereby effectively killing gram-positive and gram-negative bacteria. In order to achieve the above purpose, the invention adopts the following technical scheme: The invention provides an antibacterial material with calcium ion-mediated and photothermal effects, which is a