Zinc coordination polymer, preparation method and application in virus resistance

Abstract

The invention discloses a preparation method of a zinc coordination polymer and application of the zinc coordination polymer in virus resistance, and belongs to the technical field of metal organic complexes. The chemical formula of the zinc coordination polymer is {[Zn (ndba) (dib)]. H2O} n, ndba2 is obtained by losing two protons from 3, 3-(naphthalene-2, 7-diyl) dibenzoic acid (H2ndba), and dib is diimidazolyl benzene; the zinc coordination polymer material belongs to an orthorhombic system and a Pbca space group, and the cell parameters are as follows: a is equal to 12.9799 (5), b is equal to 15.8775 (6), c is equal to 28.7281 (10), alpha is equal to beta, gamma is equal to 90 degrees, and the cell volume V is equal to 5920.5 (4) 3; each tetracoordinated metal zinc ion is located in the center of the deformed tetrahedron geometrical configuration and connected with two ndba2 and two dib, a long-range ordered one-dimensional tubular structure is formed in the a-axis direction, and the long-range ordered one-dimensional tubular structure and the long-range ordered one-dimensional tubular structure are interspersed and expanded into a three-dimensional supramolecular network. The zinc coordination polymer provided by the invention can effectively inhibit the replication of hepatitis E virus, is obtained by one-step synthesis through a solvothermal method, is simple and feasible in preparation process, short in preparation period, green and environment-friendly in reaction condition and high in yield, and provides an ideal material for a novel virus inhibitor.

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, a preparation method and an application in antiviral treatment. Background Art

[0002] Zinc, as an essential nutrient for the human body, plays an indispensable role in antiviral and immune system maintenance. Adequate zinc content is crucial for skin maintenance and repair of the upper respiratory tract mucosa, and can effectively reduce the risk of viral invasion of the human body. Among them, organic zinc has attracted much attention due to its properties that are more easily absorbed and utilized by organisms. Zinc coordination polymers, formed by zinc cations and organic ligands connected by coordination bonds, have shown unique advantages in the field of biomedicine due to their special physicochemical properties and biocompatibility. Their rich structure, large surface area and flexible functional sites make them very suitable for adsorbing and removing viruses through coordination interactions, electrostatic attraction and π-π interactions. Currently, there are few research reports on zinc coordination polymers in antiviral applications, and some zinc coordination polymer materials have problems such as complex and environmentally unfriendly synthesis conditions, long synthesis cycles and low yields. The present invention aims to provide a zinc coordination polymer with antiviral effects. Summary of the Invention

[0003] The first object of the present invention is to provide a zinc coordination polymer, 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.

[0004] The first object of the present invention is achieved by providing a zinc coordination polymer having the chemical formula: {[Zn(ndba)(dib)]·H2O} n , among which ndba 2− It is obtained by losing two protons from 3,3-(naphthalene-2,7-diyl)dibenzoic acid (H2ndba), dib is diimidazolylbenzene, n represents the degree of polymerization, and is a positive integer; the zinc coordination polymer material belongs to the orthorhombic system, Pbca Space group, unit cell parameters are: a=12.9799(5) Å, b=15.8775(6) Å, c=28.7281(10) Å, α=β=γ=90°, unit cell volume V=5920.5(4) Å 3 Each four-coordinated zinc ion is in a deformed tetrahedral geometry with two ndba 2− It is connected with two dibs to form a long-range ordered one-dimensional tubular structure in the a-axis direction, and interweaves and expands into a three-dimensional supramolecular network.

[0005] The second object of the present invention is achieved by providing a method for preparing a zinc coordination polymer, comprising adding 3,3-(naphthalene-2,7-diyl)dibenzoic acid, diimidazolylbenzene, and zinc perchlorate hexahydrate to a mixed solvent of ethanol and water, ultrasonically treating for 10-20 minutes, mixing uniformly, sealing, placing in an oven, reacting at 70-100° C. for 4-12 hours, and then slowly cooling to room temperature to obtain colorless block crystals, filtering, washing with an ethanol solvent, and drying for 1-2 days to obtain the target zinc coordination polymer material; Wherein, the structural formulas of the 3,3-(naphthalene-2,7-diyl)dibenzoic acid and diimidazolylbenzene are shown in Formula (I) and Formula (II), respectively: .

[0006] The third object of the present invention is achieved in that the zinc coordination polymer is used in antiviral applications, where it exerts an antiviral effect by inhibiting viral replication.

[0007] The beneficial effects of the present invention are: 1) The zinc coordination polymer provided by the present invention can effectively inhibit the replication of hepatitis E virus and has the potential for high-efficiency antiviral applications; 2) The preparation process of the zinc coordination polymer provided by the present invention is simple and easy, with a short preparation cycle, and the reaction conditions do not use toxic solvents, which is green and environmentally friendly, and has a high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 is a diagram of the coordination environment of the metal and ligand in the zinc coordination polymer of the present invention; Figure 2 is a one-dimensional tubular structure diagram of the zinc coordination polymer of the present invention; Figure 3 The three-dimensional supramolecular structure diagram of the zinc coordination polymer of the present invention. DETAILED DESCRIPTION

[0009] 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.

[0010] The present invention provides a zinc coordination polymer, the chemical formula of which is: {[Zn(ndba)(dib)]·H2O} n , among which ndba 2− It is obtained by losing two protons from 3,3-(naphthalene-2,7-diyl)dibenzoic acid (H2ndba), dib is diimidazolylbenzene, n represents the degree of polymerization, and is a positive integer; the zinc coordination polymer material belongs to the orthorhombic system, PbcaSpace group, unit cell parameters are: a=12.9799(5) Å, b=15.8775(6) Å, c=28.7281(10) Å, α=β=γ=90°, unit cell volume V=5920.5(4) Å 3 Each four-coordinated zinc ion is in a deformed tetrahedral geometry with two ndba 2− It is connected with two dibs to form a long-range ordered one-dimensional tubular structure in the a-axis direction, and interweaves and expands into a three-dimensional supramolecular network.

[0011] The present invention also provides a preparation method of the zinc coordination polymer. The preparation method comprises the following steps: adding 3,3-(naphthalene-2,7-diyl)dibenzoic acid, diimidazolylbenzene and zinc perchlorate hexahydrate to a mixed solvent of ethanol and water, ultrasonicating for 10-20 minutes, uniformly mixing, sealing, placing in an oven, reacting at 70-100° C. for 4-12 hours, and then slowly cooling to room temperature to obtain colorless block crystals. The crystals are filtered, washed with an ethanol solvent, and dried for 1-2 days to obtain the target zinc coordination polymer material. Wherein, the structural formulas of the 3,3-(naphthalene-2,7-diyl)dibenzoic acid and diimidazolylbenzene are shown in Formula (I) and Formula (II), respectively: .

[0012] The molar ratio of the 3,3-(naphthalene-2,7-diyl)dibenzoic acid, diimidazolylbenzene and zinc perchlorate hexahydrate is 1:1:1-2.

[0013] The volume ratio of the ethanol to water is 1:1-2.

[0014] The present invention further provides an application of the zinc coordination polymer, specifically an application in antiviral treatment, wherein the virus is hepatitis E virus.

[0015] Example 1 1) Add 0.1 mol of 3,3-(naphthalene-2,7-diyl)dibenzoic acid, 0.1 mol of diimidazolylbenzene, and 0.1 mol of zinc perchlorate hexahydrate to 100 mL of a 1:1 ethanol / water mixture. Ultrasonicate for 10 min to mix thoroughly.

[0016] 2) The mixture was sealed and placed in an oven for reaction at 70°C for 4 hours, and then slowly cooled to room temperature to obtain colorless block crystals.

[0017] 3) Filter, wash with ethanol solvent, and dry for 1 day to obtain the target zinc coordination polymer material with a yield of 83%; Under a microscope, a suitable size of zinc coordination polymer block single crystal of Example 1 was selected and X-ray diffracted using a Bruker APEX-II CCD single crystal diffractometer with Mo-Kα treated with a graphite monochromator as the radiation source. ω / 2 θ Diffraction data were collected using a scattering method. After empirical absorption correction of the diffraction data, data restoration, structure elucidation, and structure refinement were performed using SAINT, SHELXT, and SHELXL. Non-hydrogen atomic coordinates and their thermal parameters were corrected using full-matrix least-squares methods, while hydrogen atomic coordinates were obtained through theoretical calculations. Crystallographic diffraction point data and structure refinement parameters are shown in Table 1.

[0018] Table 1 Crystallographic parameters of zinc coordination polymers prepared in Example The zinc coordination polymer material prepared in this example is represented by the chemical formula: {[Zn(ndba)(dib)]·H2O} n , among which ndba 2− It is obtained by losing two protons from 3,3-(naphthalene-2,7-diyl)dibenzoic acid (H2ndba), dib is diimidazolylbenzene, and n represents the degree of polymerization, which is a positive integer. The zinc coordination polymer belongs to the orthorhombic system. Pbca Space group, unit cell parameters are: a=12.9799(5) Å, b=15.8775(6) Å, c=28.7281(10) Å, α=β=γ=90°, unit cell volume V=5920.5(4) Å 3 In the zinc coordination polymer, each four-coordinated metal zinc ion is in a deformed tetrahedral geometric configuration with two ndba 2− and two dib connections ( Figure 1 ), in the a-axis direction, a Figure 2 The long-range ordered one-dimensional tubular structure shown in FIG, and interpenetrates and expands into Figure 3 The three-dimensional supramolecular network shown.

[0019] Example 2 1) Add 0.1 mol of 3,3-(naphthalene-2,7-diyl)dibenzoic acid, 0.1 mol of diimidazolylbenzene, and 0.2 mol of zinc perchlorate hexahydrate to 100 mL of a 1:1 ethanol / water mixture. Ultrasonicate for 10 min to mix thoroughly.

[0020] 2) The mixture was sealed and placed in an oven for reaction at 100°C for 12 hours, and then slowly cooled to room temperature to obtain colorless block crystals.

[0021] 3) After filtering, washing with ethanol solvent and drying for 2 days, the target zinc coordination polymer material was obtained with a yield of 84%.

[0022] Example 3 1) Add 0.1 mol of 3,3-(naphthalene-2,7-diyl)dibenzoic acid, 0.1 mol of diimidazolylbenzene, and 0.1 mol of zinc perchlorate hexahydrate to 100 mL of a 1:1 ethanol / water mixture. Ultrasonicate for 10 min to mix thoroughly.

[0023] 2) The mixture was sealed and placed in an oven for reaction at 70°C for 4 hours, and then slowly cooled to room temperature to obtain colorless block crystals.

[0024] 3) Filter, wash with ethanol solvent, and dry for 1-2 days to obtain the target zinc coordination polymer material with a yield of 83%.

[0025] Test Example 1: Anti-Hepatitis E Virus Activity Test of the Zinc Coordination Polymer of the Present Invention Human hepatoma cell line (Huh7) was seeded into 24-well plates and cultured in 10% FBS DMEM at 37°C in a 5% CO2 incubator until the cell density reached 70%-80%. The culture medium was discarded, and the cells were washed three times with 1× PBS. 100 μL / well of 2% FBS DMEM was added, along with 50 μL / well of genotype 4 hepatitis E virus solution (virus copy number 10) 7 The cells were incubated at 37°C, 5% CO₂ incubator for 2 hours. The viral solution was discarded, and the cells were washed three times with 1× PBS. 1 mL / well of 10% FBS DMEM was added, along with 0.1 mg of the zinc coordination polymer prepared in Examples 1 to 3. An untreated control group (with an equal volume of solvent) was also added. The cells were incubated at 37°C, 5% CO₂ incubator for 48 hours, and the supernatant and cells were collected. RNA was extracted, cDNA was reverse-transcribed, and viral replication was measured by qRT-PCR (Table 2). The inhibitory effect of the zinc coordination polymer on HEV replication was investigated. The results are shown in Table 2.

[0026] Table 2 Inhibition of Hepatitis E Virus Replication by Zinc Coordination Polymers As can be seen from Table 2, the zinc coordination polymer of the present invention can significantly inhibit the replication of hepatitis E virus.

Claims

1. A zinc coordination polymer, characterized in that The chemical formula of the zinc coordination polymer is: {[Zn(ndba)(dib)]·H2O} n , among which ndba 2− It is obtained by losing two protons from 3,3-(naphthalene-2,7-diyl)dibenzoic acid (H2ndba), dib is diimidazolylbenzene, n represents the degree of polymerization, and is a positive integer; the zinc coordination polymer material belongs to the orthorhombic system, Pbca Space group, unit cell parameters are: a=12.9799(5) Å, b=15.8775(6) Å, c=28.7281(10) Å, α=β=γ=90°, unit cell volume V=5920.5(4) Å 3 Each four-coordinated zinc ion is in a deformed tetrahedral geometry with two ndba 2− It connects with two dibs to form a long-range ordered one-dimensional tubular structure in the a-axis direction, and interweaves and expands into a three-dimensional supramolecular network.

2. The method for preparing the zinc coordination polymer according to claim 1, characterized in that: 3,3-(naphthalene-2,7-diyl)dibenzoic acid, diimidazolylbenzene and zinc perchlorate hexahydrate 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 70-100°C for 4-12 hours, and then slowly cooled to room temperature to obtain colorless block crystals, which are filtered, washed with ethanol solvent, and dried for 1-2 days to obtain the target zinc coordination polymer material; Wherein, the structural formulas of the 3,3-(naphthalene-2,7-diyl)dibenzoic acid and diimidazolylbenzene are shown in Formula (I) and Formula (II), respectively: 。 3. The method for preparing the zinc coordination polymer according to claim 2, wherein: The molar ratio of the 3,3-(naphthalene-2,7-diyl)dibenzoic acid, diimidazolylbenzene and zinc perchlorate hexahydrate is 1:1:1-2.

4. The method for preparing the zinc coordination polymer according to claim 2, wherein: The volume ratio of the ethanol to water is 1:1-2.

5. The use of the zinc coordination polymer according to claim 1 in antiviral treatment, characterized in that: The virus is hepatitis E virus.

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