CN114591511A - Copper-based coordination polymer for simulating natural superoxide dismutase and preparation method and application thereof - Google Patents
Copper-based coordination polymer for simulating natural superoxide dismutase and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper-based coordination polymer for simulating natural superoxide dismutase and a preparation method and application thereof, wherein the copper-based coordination polymer for simulating natural superoxide dismutase with antioxidant activity is prepared from a nitrogen-oxidized bidentate ligand isonicotinic acid and copper sulfate: [ Cu ]4(ino)4(OH)2SO4(H2O)4]nWherein ino is a bidentate ligand isonicotinic acid after nitrogen oxidation; the product has wide application in the field of antioxidation. The preparation method is simple, the cost is low, the yield is high, the product polymer has better superoxide dismutase activity, the foundation is laid for the subsequent synthesis of enzyme-like mimics with better performance, and the foundation is laid for the research of the complex in the field of clinical application of biological medicines.
Description
Technical Field
The invention relates to the research of composite functional materials in the field of biomedicine, in particular to a copper-based coordination polymer simulating natural superoxide dismutase and a preparation method and application thereof.
Background
Coordination Polymers (CPs) are one-dimensional, two-dimensional and three-dimensional infinite chain-like or net-like structures formed by connecting metal ions or metal clusters and bridged organic ligands. The unique properties of metal ions and the potential to design the desired topology have also attracted a wide range of interest to researchers for these CPs. Recently, the research interest of CPs in the field of composite functional materials is increasing, and CPs can be regarded as "enzyme mimics" composite materials, so that great opportunities are provided for us. CPs can not only mimic biological nanomaterials, but also develop some artificially useful materials in the near future.
The redox state in the cell is a determinant of cell fate and should be tightly regulated. Oxidative stress is an important process that is implicated in the etiology of many diseases, including cardiovascular disease, inflammation, and cancer. Oxidative stress refers to a pathological process in which tissue damage is caused by excessive production or decreased scavenging ability of Reactive Oxygen Species (ROS) during a metabolic process, and is an imbalance between antioxidants and pro-oxidants. The antioxidant has neuroprotective effect by scavenging free radicals and inhibiting lipid peroxidation, and can relieve oxidative damage to a certain extent by antioxidant treatment.
Wherein the superoxide anion radical (O)2 ·-) Is the most predominant ROS species in biological systems, and is also hydrogen peroxide (H)2O2) And hydroxyl radicals (. OH), among other ROS species. Therefore, how to eliminate excessive reactive oxygen species in organisms has become a hot spot of contemporary chemical research. ROS scavengers can generally be classified as natural ROS scavengers and non-natural ROS scavengers. Among them, one of the most widely distributed natural ROS scavengers in the organism is the superoxide dismutase (SOD), which is medically known as "scavenger of the human body". The superoxide dismutase has the outstanding characteristics of anti-aging, anti-inflammation and the like. It can catalyze O2 ·-Thereby reducing the amount of ROS species in the body and limiting O2 ·-Is an important member of the natural antioxidant defense system.
Natural superoxide dismutase (Cu, Zn-SOD) is considered to play an indispensable role in the first line of antioxidant defense, being an essential enzyme in natural antioxidant biological systems. There are two active centers in the structure of native Cu, Zn-SOD: cu2+、Zn2+. Research shows that the existence of copper ions is necessary for the activity of Cu, Zn-SOD, which directly acts with superoxide anion free radical, and zinc ions play a role in stabilizing the surrounding environment of the active center in the structure. Enzymatic and non-enzymatic antioxidants play a vital role in protecting the body against peroxidative damage. However, natural enzymes in nature are very sensitive to environment, have poor stability, large molecular weight and low permeability, and are not suitable for being used as active substances in pharmacology, so that the research on the structure and the functional model of the low molecular weight complex as a metal-containing enzyme active center is needed.
Coordination Polymers (CPs) are of great interest due to their attractive structure and potential applications in the fields of crystallography engineering and material science. Among them, organic ligands play a crucial role in the self-assembly process of CPS, and organic ligands containing abundant coordination sites are usually preferred. Therefore, the synthesized stable, nontoxic and high-activity functional coordination polymer material has higher research value as superoxide dismutase mimics (SOD-mimics) and has great potential in the application aspect of clinical medicine.
Disclosure of Invention
The invention provides a copper-based coordination polymer for simulating natural superoxide dismutase and a preparation method thereof, which can overcome the limitation of the natural superoxide dismutase on clinical application.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a copper-based coordination polymer for simulating natural superoxide dismutase, wherein the chemical formula of the copper-based coordination polymer is [ Cu ]4(ino)4(OH)2SO4(H2O)4]nWherein ino is a bidentate ligand isonicotinic acid after nitrogen oxidation; the copper baseThe coordination polymer belongs to a monoclinic system, the space group is C2/C space group, and the molecular formula is C24H26Cu4N4O22S, molecular weight is 1008.72, unit cell parameters are: a = 19.809(8) a, b = 6.844(3) a, c = 19.533(12) a, α = 90 °, β = 140.9 °, γ = 90 °, V = 1670.12 a3。
A preparation method of a copper-based coordination polymer simulating natural superoxide dismutase comprises the following steps:
1) dissolving 0.2 mmoL of isonicotinic acid in 3 mL of deionized water, adding 1 moL/L of sodium hydroxide, adjusting the pH of the solution to 6-10, and then dripping the solution into the bottom of a container;
2) dissolving 0.1 mmoL copper sulfate pentahydrate in 3 mL of N, N-Dimethylformamide (DMF), and dropwise and slowly and uniformly adding along the wall of a container to form a boundary diffusion layer with the solution obtained in the step 1);
3) sealing with sealing film, standing for two days, and separating out blue blocky crystal, i.e. copper-based coordination polymer simulating natural superoxide dismutase.
The copper-based coordination polymer simulating the natural superoxide dismutase is applied as an antioxidant material.
Compared with the prior art, the invention has the beneficial effects that:
1) the preparation method is simple, low in cost and high in yield, and XRD powder diffraction analysis data show that the obtained product is high in purity;
2) copper is an essential element of most aerobic organisms, a structural and catalytic cofactor, and therefore, it plays a major role in many redox metalloenzymes and can serve as a promising mimetic of the enzyme active site. The excellent biological activity of the copper complex stimulates the scientific community to develop novel, high-selectivity and copper-based drugs.
The invention synthesizes a series of copper-based coordination polymers based on the structural characteristics of natural enzymes in organisms. The polymer has better superoxide dismutase activity. Lays a foundation for the subsequent synthesis of enzyme-like mimics with better performance and lays a foundation for the research of the complex in the field of clinical application of biological medicines.
Drawings
FIG. 1 is the structure of isonicotinic oxynitride;
FIG. 2 is a diagram of coordination environment of copper-based coordination polymer simulating natural superoxide dismutase;
FIG. 3 is a diagram of the molecular packing of copper-based coordination polymers mimicking native superoxide dismutase;
FIG. 4 is an X-ray single crystal diffractogram of a copper-based coordination polymer mimicking native superoxide dismutase;
FIG. 5 is a thermogravimetric analysis of a copper-based coordination polymer mimicking native superoxide dismutase;
FIG. 6 is an infrared spectrum of a copper-based coordination polymer mimicking native superoxide dismutase;
FIG. 7 is a graph showing the change of absorbance with time of light irradiation of copper-based coordination polymer solutions of different concentrations simulating natural superoxide dismutase by the NBT photoreduction method;
FIG. 8 is a fitted curve of copper-based coordination polymers mimicking native superoxide dismutase inhibiting the formation of superoxide anion radicals as a function of complex solution concentration.
Detailed Description
The invention will be explained in detail below with reference to the figures and specific examples.
The copper-based coordination polymer for simulating natural superoxide dismutase is specifically formed by leading four quinquedentate copper atoms to pass through four carboxyl groups and two mu of oxynitrided isonicotinic acid3OH and a bridged bidentate sulfate group are linked together and Cu can be seen in the center of the building block2O4S is a cage structure. All copper atoms have a square pyramidal coordination around them. Isonicotinic acid oxynitride serves as a bridging ligand, and two copper atoms are bridged respectively through carboxyl oxygen atom double-tooth coordination. The O atom in the N-O group does not participate in the coordination of the Cu (II) atom, but forms a hydrogen bond with the water molecule that participates in the coordination. The S atom in the sulfate group is located at a special position of the spatial structure and acts as a bidentate bridge between the copper atoms Cul and CulB.
Example 1
The preparation method of the novel antioxidant comprises the following steps:
1) weighing isonicotinic acid (0.2 mmoL, 278 mg) and dissolving in 3 mL of deionized water, adding 1 moL/L of sodium hydroxide prepared to adjust the pH of the solution to 6, and adding the solution to the bottom of a test tube by using a dropper;
2) weighing copper sulfate pentahydrate (0.1 mmoL, 250 mg) to dissolve in 3 mL of N, N-Dimethylformamide (DMF), and dropwise and slowly adding into the test tube along the wall of the test tube to form a boundary diffusion layer together with the solution dissolved in the lower layer of ligand;
3) sealing the test tube mouth with a sealing film, and standing. After two days, a small amount of blue blocky crystals precipitated. Wherein, the blue bulk crystal is a target product.
Example 2
The preparation method of the novel antioxidant comprises the following steps:
1) weighing isonicotinic acid (0.2 mmoL, 278 mg) and dissolving in 3 mL of deionized water, adding 1 moL/L of sodium hydroxide prepared to adjust the pH of the solution to 7, and adding the solution to the bottom of a test tube by using a dropper;
2) weighing copper sulfate pentahydrate (0.1 mmoL, 250 mg) to dissolve in 3 mL of N, N-Dimethylformamide (DMF), and dropwise and slowly adding into the test tube along the wall of the test tube to form a boundary diffusion layer together with the solution dissolved in the lower layer of ligand;
3) sealing the test tube mouth with a sealing film, and standing. After five days, blue massive crystals precipitated. Wherein, the blue bulk crystal is a target product.
Example 3
The preparation method of the novel antioxidant comprises the following steps:
1) weighing isonicotinic acid (0.2 mmoL, 278 mg) and dissolving in 3 mL of deionized water, adding 1 moL/L of sodium hydroxide prepared to adjust the pH of the solution to 9, and adding the solution to the bottom of a test tube by using a dropper;
2) weighing copper sulfate pentahydrate (0.1 mmoL, 250 mg) to dissolve in 3 mL of N, N-Dimethylformamide (DMF), and dropwise and slowly adding into the test tube along the wall of the test tube to form a boundary diffusion layer together with the solution dissolved in the lower layer of ligand;
3) sealing the test tube mouth with a sealing film, and standing. After two days, a large amount of blue blocky crystals are separated out, namely the target product.
Example 4
The preparation method of the novel antioxidant comprises the following steps:
1) weighing isonicotinic acid (0.2 mmoL, 278 mg) and dissolving in 3 mL of deionized water, adding 1 moL/L of prepared sodium hydroxide, adjusting the pH of the solution to 10, and adding the solution to the bottom of a test tube by using a dropper;
2) weighing copper sulfate pentahydrate (0.1 mmoL, 250 mg) to dissolve in 3 mL of N, N-Dimethylformamide (DMF), and dropwise and slowly adding into the test tube along the wall of the test tube to form a boundary diffusion layer together with the solution dissolved in the lower layer of ligand;
3) sealing the test tube mouth with a sealing film, and standing. After two days, blue blocky crystals and black flocculent impurities are separated out. Wherein, the blue bulk crystal is a target product.
In the above embodiment, the third embodiment is the most preferred embodiment because the third embodiment has the highest yield and the product is the purest. In the subsequent synthesis of mass production, the reaction ratio (n) of the isonicotinic acid and the copper sulfate can be fixed by nitrogen oxidationino：nCuSO4= 2: 1) and concentration of upper and lower layer reaction solution (C)ino=0.2 mmoL/3 mL H2O；CCuSO4=0.1 mmoL/3 Ml DMF) to achieve high yield and high purity mass production. The chemical formula of the copper-based coordination polymer is as follows: [ Cu ]4(ino)4(OH)2SO4(H2O)4]nWherein n is a positive integer, and ino is the nitrogen-oxidized bidentate ligand isonicotinic acid. The analysis of X-ray single crystal diffraction shows that the copper-based coordination polymer is monoclinic system, belongs to C2/C space group and has a molecular formula of C24H26Cu4N4O22S, molecular weight is 1008.72, unit cell parameters are: a = 19.809(8) a, b = 6.844(3) a, c = 19.533(12) a, α = 90 °, β = 140.9 °, γ = 90 °, V = 1670.12 a3。
FIG. 1 shows the structure of functional organic ligand oxynitriding isonicotinic acid, which can coordinate through carboxyl and N-O bond after oxynitriding, and is bidentate coordination ligand. Copper base for simulating natural superoxide dismutaseThe coordination environment of the coordination polymer is shown in FIG. 2, Cu4(ino)4(OH)2SO4(H2O)4In the structure, four pentacoordinated copper atoms are linked together via the carboxyl groups of four oxynitrided isonicotinic acids, two μ 3-OH groups and a bridging bidentate sulfuric acid group, and Cu can be seen in the center of the structural unit2O4S is a cage structure. The molecular stacking diagram is shown in FIG. 3. All copper atoms have a square pyramidal coordination around them. Isonicotinic acid oxynitride acts as a bridging ligand, bridging two copper atoms respectively by bidentate coordination of the carboxyl oxygen atom. The S atom in the sulfate group is located at a special position of the spatial structure and acts as a bidentate bridge between the copper atoms Cul and CulB.
The bond length of Cul coordinated with the carboxyl oxygen O2 and O5 of isonicotinic oxynitride and the μ 3-OH oxygen on the substrate plane is in the range of 1.92-1.99A, the axial Cul-O8 bond length is 1.98A, and the bond length of Cul-O1 on the substrate plane is 2.15A. The coordination configuration of Cu2 contains O1, carboxyl oxygen O6 and O3 in mu 3-OH and two water molecules O10 and O11 participating in coordination, and the bond length range is 1.94-1.99A, which corresponds to the bond length of Cul-O on the substrate plane. Two μ 3-OH groups connect together two uncoordinated half-structures in a building block in a special bridging manner. The bond length of Cu-mu 3-OH ranges from 1.94 to 1.99A, the bond angle of Cul-O1-CulB is 92.2 degrees, and the bond angle of Cu2-O1-Cul is 117.1 degrees.
FIG. 4 is a simulated spectrum of X-ray powder diffraction pattern of the obtained copper-based coordination polymer simulating natural superoxide dismutase and X-ray single crystal diffraction structure of the complex, and the peak positions of the two are consistent, which shows that the purity of the sample is high. FIG. 5 shows that the copper-based coordination polymer simulating natural superoxide dismutase has better thermal stability.
The SOD activity test of the copper-based coordination polymer simulating the natural superoxide dismutase is carried out by taking riboflavin/methionine/nitrotetrazolium chloride (NBT) as a substrate and measuring by an NBT photoreduction method. O is2 ·The yellowish NBT is reduced to purple formazan. SODm by catalysis of O2 ·By disproportionation reaction to form O2And H2O2Thereby inhibiting the formation of purple formazan. Thus, the darker the blue color of the reaction solution after the photoreduction reaction, the lower the enzyme activity, and conversely, the higher the enzyme activity. In the NBT photoreduction reaction, NBT and O are involved2 ·-reaction and copper-based coordination polymers with O2 ·The reaction, which is two dynamic competing reactions, proceeds simultaneously. Thus, the simulant scavenges O2 ·The ability is equivalent to the SOD activity of the mimic.
The experimental results are shown in fig. 7 and fig. 8, fig. 7 is a graph showing the change of the absorbance of the solution of the copper-based coordination polymer solution with different concentrations under the irradiation of a xenon light source by the NBT photo-reduction method for the copper-based coordination polymer simulating the natural superoxide dismutase along with the illumination time, fig. 8 is a fitting curve showing that the copper-based coordination polymer simulating the natural superoxide dismutase inhibits the generation of superoxide anion radicals along with the change of the concentration of the copper-based coordination polymer solution, and the copper-based coordination polymer simulating the natural superoxide dismutase prepared by the invention is proved to have good SOD activity.
Claims (3)
1. The copper-based coordination polymer simulating natural superoxide dismutase is characterized in that the chemical formula of the copper-based coordination polymer is [ Cu ]4(ino)4(OH)2SO4(H2O)4]nWherein ino is a bidentate ligand isonicotinic acid after nitrogen oxidation; the copper-based coordination polymer belongs to a monoclinic system, a space group is a C2/C space group, and the molecular formula is C24H26Cu4N4O22S, molecular weight is 1008.72, unit cell parameters are: a = 19.809(8) a, b = 6.844(3) a, c = 19.533(12) a, α = 90 °, β = 140.9 °, γ = 90 °, V = 1670.12 a3。
2. A method for preparing the copper-based coordination polymer which mimics natural superoxide dismutase as claimed in claim 1, comprising the steps of:
1) dissolving 0.2 mmoL of isonicotinic acid in 3 mL of deionized water, adding 1 moL/L of sodium hydroxide, adjusting the pH of the solution to 6-10, and then dripping the solution into the bottom of a container;
2) dissolving 0.1 mmoL of copper sulfate pentahydrate in 3 mL of N, N-dimethylformamide, and uniformly adding dropwise and slowly along the wall of the container to form a boundary diffusion layer together with the solution obtained in the step 1);
3) sealing with sealing film, standing for two days, and separating out blue blocky crystal, i.e. copper-based coordination polymer simulating natural superoxide dismutase.
3. Use of the copper-based coordination polymer that mimics natural superoxide dismutase of claim 1 as an antioxidant material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118126339A (en) * | 2024-01-30 | 2024-06-04 | 广东药科大学 | Complex with antioxidant whitening effect and preparation method and application thereof |
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| US20130316978A1 (en) * | 2012-05-23 | 2013-11-28 | Rempex Pharmaceuticals, Inc. | Boronic acid derivatives and therapeutic uses thereof |
| CN103613536A (en) * | 2013-12-13 | 2014-03-05 | 四川生科力科技有限公司 | Industrialized preparation method of 2-copper picolinate |
| CN108822300A (en) * | 2018-05-17 | 2018-11-16 | 陕西科技大学 | The copper coordination polymer and its preparation method and application of nitrogenous oxidative function group |
| CN112174999A (en) * | 2020-11-02 | 2021-01-05 | 兰州理工大学 | Titanium metal complex post-modification product with anticancer activity and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316978A1 (en) * | 2012-05-23 | 2013-11-28 | Rempex Pharmaceuticals, Inc. | Boronic acid derivatives and therapeutic uses thereof |
| CN103613536A (en) * | 2013-12-13 | 2014-03-05 | 四川生科力科技有限公司 | Industrialized preparation method of 2-copper picolinate |
| CN108822300A (en) * | 2018-05-17 | 2018-11-16 | 陕西科技大学 | The copper coordination polymer and its preparation method and application of nitrogenous oxidative function group |
| CN112174999A (en) * | 2020-11-02 | 2021-01-05 | 兰州理工大学 | Titanium metal complex post-modification product with anticancer activity and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118126339A (en) * | 2024-01-30 | 2024-06-04 | 广东药科大学 | Complex with antioxidant whitening effect and preparation method and application thereof |
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