Zinc coordination polymer with bacteriostatic activity, preparation method and application

Abstract

The invention discloses a zinc coordination polymer with bacteriostatic activity as well as a preparation method and application thereof, and belongs to the technical field of metal organic complexes. The chemical formula of the compound is [Zn2 (cfca) (bimb) 2Cl2] n, cfca2 is completely deprotonated 5-(3-carboxyl phenyl) furan-2-formic acid, and bimb is 1, 4-bis (imidazole-L-methyl) toluene. The material has a long-range ordered ring and chain-shaped one-dimensional structure in the b-axis direction, and hydrogen bonds are inserted and connected to form a three-dimensional supramolecular framework. The zinc coordination polymer disclosed by the invention has excellent antibacterial activity, the preparation method is simple, a solvent used in synthesis is green and environment-friendly, and the zinc coordination polymer has a relatively good application prospect in the field of biomedical treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal organic complexes, and in particular relates to a zinc coordination polymer with antibacterial activity, a preparation method and an application thereof. Background Art

[0002] Bacteria are widely distributed in various natural environments, including both beneficial and harmful species. Bacterial infections pose a significant threat to human health. Disinfectants, fungicides, and antibiotics are frequently used to combat bacteria. However, their inappropriate use has led to the emergence of drug-resistant bacteria, making bacterial infections even more difficult to treat. Therefore, developing novel antibacterial agents that do not induce drug resistance is crucial.

[0003] Coordination polymers are a class of materials characterized by periodic network structures formed by the autonomous assembly of metal ions (or metal ion clusters) and organic ligands through coordination. They combine the advantages of both inorganic and organic materials, boasting large surface area, high porosity, diverse framework structures, and a rich variety of sites. Coordination polymers can interact with biomolecules through physical contact, metal ion release, release of organic small molecules, oxidative stress, and photocatalysis, demonstrating broad potential for bioinhibition. In particular, when coordination polymers physically contact bacteria through van der Waals forces and electrostatic interactions, they effectively disrupt their cell membranes, inactivating key cellular components and ultimately leading to bacterial death. Consequently, they are unaffected by bacterial resistance.

[0004] Currently, solvothermal methods are commonly used to prepare coordination polymers with complex structures or high crystallinity. However, many of these methods suffer from complex synthesis conditions, long preparation times (typically 2 to 5 days), and environmentally unfriendly solvents (organic solvents such as acetonitrile and dimethylformamide are commonly used). To address these issues, the present invention aims to provide a zinc coordination polymer with excellent antibacterial activity and a simple, environmentally friendly preparation method. Summary of the Invention

[0005] The first object of the present invention is to provide a zinc coordination polymer with antibacterial activity, the second object of the present invention is to provide a method for preparing the zinc coordination polymer, and the third object of the present invention is to provide applications of the zinc coordination polymer.

[0006] The first object of the present invention is achieved by providing a zinc coordination polymer having antibacterial activity, the chemical formula of which is [Zn2(cfca)(bimb)2Cl2] n , of which cfca 2− is 5-(3-carboxyphenyl)furan-2-carboxylic acid (H2cfca) which has lost two protons, bimb is 1,4-bis(imidazole-L-methyl)toluene, n represents the degree of polymerization, which is a positive integer; the coordination polymer belongs to the triclinic system,P -1 space group, unit cell parameters are a=9.0996(11) Å, b=10.3997(12) Å, c=10.7338(14)Å, α=99.337(4)°, β=99.716(4)°, γ=91.199(4)°, unit cell volume V=986.7(2)Å 3 Each metal zinc ion at the center of the deformed tetrahedral geometry adopts a four-coordinate mode with two bimbs and one cfca 2− and a Cl − They are connected to form long-range ordered ring and chain one-dimensional structures in the b-axis direction, and adjacent chains are interwoven with each other through abundant hydrogen bonds (C−H···O) and connected to form a three-dimensional supramolecular framework.

[0007] The second object of the present invention is achieved by providing a method for preparing a zinc coordination polymer, comprising adding 5-(3-carboxyphenyl)furan-2-carboxylic acid, 1,4-bis(imidazole-L-methyl)toluene, and zinc chloride to a mixed solvent of ethanol and water, ultrasonically treating for 10-20 minutes, mixing uniformly, sealing, placing in an oven, reacting at 80-120°C for 4-12 hours, and then slowly cooling to room temperature to obtain colorless block crystals, filtering, washing with ethanol, and drying for 1-2 days to obtain the target zinc coordination polymer; Wherein, the structural formulas of the 5-(3-carboxyphenyl)furan-2-carboxylic acid and 1,4-bis(imidazole-L-methyl)toluene are shown in Formula (I) and Formula (II), respectively: .

[0008] The third object of the present invention is achieved in that the zinc coordination polymer having antibacterial activity is used in the preparation of antibacterial materials.

[0009] The beneficial effects of the present invention are: 1) The zinc coordination polymer material provided by the present invention has excellent antibacterial properties and high inhibitory activity against Staphylococcus aureus and Escherichia coli, providing an ideal material for a new antibacterial agent.

[0010] 2) The preparation method of the zinc coordination polymer provided by the present invention is simple, environmentally friendly, has a high yield, and is suitable for scale-up production. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 is a diagram of the coordination environment of the metal and the ligand in the zinc coordination polymer of the present invention; Figure 2 is a one-dimensional diagram of the ring and chain of the zinc coordination polymer of the present invention; Figure 3 This is a one-dimensional interpenetrating structure diagram formed by the zinc coordination polymer of the present invention through hydrogen bonding; Figure 4 The three-dimensional supramolecular structure diagram of the zinc coordination polymer of the present invention. DETAILED DESCRIPTION

[0012] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the present invention is not limited in any way. Any changes or improvements made based on the teachings of the present invention fall within the scope of protection of the present invention.

[0013] The present invention provides a zinc coordination polymer with antibacterial activity, the chemical formula of the zinc coordination polymer is [Zn2(cfca)(bimb)2Cl2] n , of which cfca 2− is 5-(3-carboxyphenyl)furan-2-carboxylic acid (H2cfca) which has lost two protons, bimb is 1,4-bis(imidazole-L-methyl)toluene, n represents the degree of polymerization, which is a positive integer; the coordination polymer belongs to the triclinic system, P -1 space group, unit cell parameters are a=9.0996(11) Å, b=10.3997(12) Å, c=10.7338(14) Å, α=99.337(4)°, β=99.716(4)°, γ=91.199(4)°, unit cell volume V=986.7(2) Å 3 Each metal zinc ion at the center of the deformed tetrahedral geometry adopts a four-coordinate mode with two bimbs and one cfca 2− and a Cl − They are connected to form long-range ordered ring and chain one-dimensional structures in the b-axis direction, and adjacent chains are interwoven with each other through abundant hydrogen bonds (C−H···O) and connected to form a three-dimensional supramolecular framework.

[0014] The present invention also provides a method for preparing the zinc coordination polymer with antibacterial activity. The preparation method comprises adding 5-(3-carboxyphenyl)furan-2-carboxylic acid, 1,4-bis(imidazole-L-methyl)toluene and zinc chloride to a mixed solvent of ethanol and water, ultrasonicating for 10-20 minutes, mixing uniformly, sealing and placing in an oven, reacting at 80-120° C. for 4-12 hours, and then slowly cooling to room temperature to obtain colorless block crystals, filtering, washing with ethanol, and naturally drying for 1-2 days to obtain the target zinc coordination polymer; Wherein, the structural formulas of the 5-(3-carboxyphenyl)furan-2-carboxylic acid and 1,4-bis(imidazole-L-methyl)toluene are shown in Formula (I) and Formula (II), respectively: .

[0015] The molar ratio of the 5-(3-carboxyphenyl)furan-2-carboxylic acid, 1,4-bis(imidazole-L-methyl)toluene and zinc chloride is 1:1:1-2.

[0016] The volume ratio of the ethanol to water is 1-2:1.

[0017] The present invention further provides the use of the zinc coordination polymer with antibacterial activity in the preparation of antibacterial materials. The zinc coordination polymer has a significant inhibitory effect on Staphylococcus aureus and Escherichia coli.

[0018] Example 1 1) Add 0.1 mol of 5-(3-carboxyphenyl)furan-2-carboxylic acid, 0.1 mol of 1,4-bis(imidazole-L-methyl)toluene, and 0.1 mol of zinc chloride to 50 mL of a 1:1 ethanol / water mixture and sonicate for 10 min. 2) The mixture was sealed and placed in an oven for reaction at 80°C for 4 hours, and then slowly cooled to room temperature to obtain colorless block crystals; 3) The colorless block crystals were filtered, washed with ethanol, and dried naturally for 1 day to obtain the zinc coordination polymer. The yield of the zinc coordination polymer crystals was calculated to be 87%.

[0019] Select the zinc coordination polymer single crystal of Example 1 of appropriate size under a microscope, use Mo-Kα treated with graphite monochromator as radiation source on X-ray single crystal diffractometer, and take ω / 2 θ Diffraction points were collected using a scattering method. All diffraction data were absorption corrected using the SADABS program. Data reduction and structure elucidation were performed using the SAINT and SHELXTL programs, respectively. The coordinates and anisotropy of non-hydrogen atoms were refined using the full-matrix least squares method. Hydrogen atoms were determined using the theoretical hydrogenation method. The crystallographic diffraction point data and structure refinement parameters are shown in Table 1 below.

[0020] Table 1 Crystallographic parameters of zinc coordination polymers of Example 1 The chemical formula of the zinc coordination polymer obtained in this example is [Zn2(cfca)(bimb)2Cl2] n , of which cfca 2− is 5-(3-carboxyphenyl)furan-2-carboxylic acid (H2cfca) which has lost two protons, bimb is 1,4-bis(imidazole-L-methyl)toluene, n is the degree of polymerization, which is a positive integer; the coordination polymer material belongs to the triclinic system, P-1 space group, unit cell parameters are a=9.0996(11) Å, b=10.3997(12) Å, c=10.7338(14) Å, α=99.337(4)°, β=99.716(4)°, γ=91.199(4)°, unit cell volume V=986.7(2) Å 3 Each metal zinc ion at the center of the deformed tetrahedral geometry adopts a four-coordinate mode with two bimbs and one cfca 2− and a Cl − connect( Figure 1 ), forming a long-range ordered ring and chain one-dimensional structure in the b-axis direction ( Figure 2 ), adjacent chains are interwoven with each other through abundant hydrogen bonds (C−H···O) and connected to form a three-dimensional supramolecular framework ( Figure 3 and Figure 4 ).

[0021] Example 2 1) Add 0.1 mol of 5-(3-carboxyphenyl)furan-2-carboxylic acid, 0.1 mol of 1,4-bis(imidazole-L-methyl)toluene, and 0.2 mol of zinc chloride to 50 mL of a 1:1 ethanol / water mixture and sonicate for 20 min. 2) The mixture was sealed and placed in an oven for reaction at 120°C for 12 hours, and then slowly cooled to room temperature to obtain colorless block crystals; 3) The colorless block crystals were filtered, washed with ethanol, and dried naturally for 2 days to obtain the zinc coordination polymer. The yield of the zinc coordination polymer crystals was calculated to be 86%.

[0022] Example 3 1) Add 0.1 mol of 5-(3-carboxyphenyl)furan-2-carboxylic acid, 0.1 mol of 1,4-bis(imidazole-L-methyl)toluene, and 0.1 mol of zinc chloride to 50 mL of a 2:1 ethanol / water mixture and sonicate for 10 min. 2) The mixture was sealed and placed in an oven for reaction at 80°C for 12 hours, and then slowly cooled to room temperature to obtain colorless block crystals; 3) The colorless block crystals were filtered, washed with ethanol, and dried naturally for 1 day to obtain the zinc coordination polymer. The yield of the zinc coordination polymer crystals was calculated to be 87%.

[0023] Test Example 1 Antibacterial Activity Test of Zinc Coordination Polymer Materials Inoculate Staphylococcus aureus and Escherichia coli into 5 mL of LB liquid medium and place it in a constant temperature shaker at 37°C and 200 rpm for full shaking activation. Dilute the activated bacterial solution to 105 The cells were divided into an experimental group and a blank control group. The experimental group's bacterial suspension was supplemented with 0.1 mg of the zinc coordination polymer prepared in Example 1 and mixed. The blank control group contained the original bacterial suspension without the zinc coordination polymer. Both groups were incubated at the same temperature and shaking speed under a 30W incandescent lamp for 20 minutes. The treated bacterial suspension was evenly spread on the surface of the solid culture medium and incubated at 37°C and constant temperature and humidity for 12 hours using the spread plate method. The colonies were counted and the inhibition rate was calculated.

[0024] Results: The test results show (Table 2) that the zinc coordination polymer of the present invention has an antibacterial rate of up to 99.9% against Escherichia coli and up to 95.8% against Staphylococcus aureus after 12 hours of incubation.

[0025] Table 2 Antibacterial rate of zinc coordination polymers In summary, the zinc coordination polymer prepared by the present invention has excellent antibacterial properties and has a good inhibitory effect on Staphylococcus aureus and Escherichia coli.

[0026] The above content is merely an illustration of the embodiments of the present invention and does not constitute a limitation on the scope of patent protection of the present invention. Any equivalent structural transformation or equivalent process adjustment implemented based on the contents of the present invention specification, as well as any direct or indirect application to other related technical fields, shall be deemed to be covered by the scope of patent protection of the present invention.

Claims

1. A zinc coordination polymer with antibacterial activity, characterized in that: The chemical formula of the zinc coordination polymer is [Zn2(cfca)(bimb)2Cl2] n , of which cfca 2− is 5-(3-carboxyphenyl)furan-2-carboxylic acid (H2cfca) which has lost two protons, bimb is 1,4-bis(imidazole-L-methyl)toluene, n represents the degree of polymerization, which is a positive integer; the coordination polymer belongs to the triclinic system, P -1 space group, unit cell parameters are a=9.0996(11) Å, b=10.3997(12) Å, c=10.7338(14) Å, α=99.337(4)°, β=99.716(4)°, γ=91.199(4)°, unit cell volume V=986.7(2) Å 3 Each metal zinc ion at the center of the deformed tetrahedral geometry adopts a four-coordinate mode with two bimbs and one cfca 2− and a Cl − They are connected to form long-range ordered ring and chain one-dimensional structures in the b-axis direction, and adjacent chains are interwoven with each other through abundant hydrogen bonds (C−H···O) and connected to form a three-dimensional supramolecular framework.

2. The method for preparing the zinc coordination polymer with antibacterial activity according to claim 1, characterized in that: 5-(3-carboxyphenyl)furan-2-carboxylic acid, 1,4-bis(imidazole-L-methyl)toluene and zinc chloride are added to a mixed solvent of ethanol and water, ultrasonicated for 10-20 minutes, mixed evenly, sealed and placed in an oven, reacted at 80-120°C for 4-12 hours, and then slowly cooled to room temperature to obtain colorless block crystals, which are filtered, washed with ethanol, and dried for 1-2 days to obtain the target zinc coordination polymer; Wherein, the structural formulas of the 5-(3-carboxyphenyl)furan-2-carboxylic acid and 1,4-bis(imidazole-L-methyl)toluene are shown in Formula (I) and Formula (II), respectively: 。 3. The method for preparing the zinc coordination polymer with antibacterial activity according to claim 2, characterized in that: The molar ratio of the 5-(3-carboxyphenyl)furan-2-carboxylic acid, 1,4-bis(imidazole-L-methyl)toluene and zinc chloride is 1:1:1-2.

4. The method for preparing the zinc coordination polymer with antibacterial activity according to claim 2, characterized in that: The volume ratio of the ethanol to water is 1-2:

1.

5. Use of the zinc coordination polymer with antibacterial activity according to claim 1 in the preparation of antibacterial materials.

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