CN109810258B - MOFs mimic enzyme material using rigid aromatic polycarboxylic acid as ligand and synthetic method - Google Patents
MOFs mimic enzyme material using rigid aromatic polycarboxylic acid as ligand and synthetic method Download PDFInfo
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Abstract
The invention provides a MOFs mimic enzyme material taking rigid aromatic polycarboxylic acid as a ligand and a synthesis method thereof. The method comprises the step of reacting to prepare the MOFs mimic enzyme material by taking a ligand, a metal salt or a hydrate thereof as a reactant in the presence of a solvent, wherein the ligand comprises 3,3',5,5' -biphenyltetracarboxylic acid and 2,2' -bipyridine. The invention purposefully selects the organic ligand and the metal ion for synthesizing the MOFs material, and obtains the MOFs material with good simulated enzyme property and fluorescence property.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a MOFs mimic enzyme material taking rigid aromatic polycarboxylic acid as a ligand and a synthesis method thereof.
Background
MOFs are an abbreviation of Metal-Organic Frameworks, i.e., Metal-Organic framework compounds, are one of Metal-Organic coordination polymers, which are a new class of materials, include Organic ligands and Metal ions in MOFs materials and have typical porous structures, so that they can have a wide range of luminescence phenomena, and provide a unique platform for the development of solid-state luminescent materials because they have certain structural predictability, and in addition, they provide a good environment for fluorophores in crystal form.
The rigid aromatic polycarboxylic acid has a structure of polycarboxylic acid group, so that the coordination mode is very rich, and the rigid aromatic polycarboxylic acid and metal ions can be combined in a chelated and bridged form to form a coordination polymer with a novel space structure from zero dimension to three dimension. The coordination polymer material of the metal-aromatic polycarboxylic acid has good properties of adsorption, catalysis, magnetism, optics and the like, so the coordination polymer material is widely applied to the fields of gas storage and separation, medicine, sensing and the like.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a MOFs mimic enzyme material using rigid aromatic polycarboxylic acid as ligand and a synthesis method thereof.
In order to achieve the above objects and other related objects, the present invention provides a method for synthesizing MOFs mimic enzyme materials using rigid aromatic polycarboxylic acids as ligands, comprising reacting ligands, metal salts or hydrates thereof as reactants in the presence of a solvent to obtain the MOFs mimic enzyme materials, wherein the ligands comprise 3,3',5,5' -biphenyltetracarboxylic acid (i.e. H)4BPTC), 2' -bipyridine.
That is, the reactant may be a ligand and a metal salt, or a hydrate of a ligand and a metal salt.
Alternatively, m is by massTotal ligands：mMetal salt or hydrate thereof(1-2): 1, can also be (1-1.8): 1, can also be (1.2-1.8): 1, can also be (1.2-1.7): 1.
optionally, the solvent includes an organic solvent and an inorganic solvent.
Optionally, the organic solvent is selected from at least one of N, N-dimethylformamide (DMF for short) and ethanol (EtOH for short).
Optionally, the inorganic solvent is selected from water.
Optionally, the volume ratio of the organic solvent to the inorganic solvent is (1-2): (1-2).
Optionally, the metal salt or hydrate thereof is selected from NiSO4、NiSO4·6H2O、CoCl2、CoCl2·6H2At least one of O.
Alternatively, the reaction temperature is 150-.
The invention also provides the MOFs mimic enzyme material prepared by the synthesis method.
As mentioned above, the MOFs mimic enzyme material using rigid aromatic polycarboxylic acid as ligand and the synthesis method thereof have the following beneficial effects: the invention purposefully selects the organic ligand and the metal ion for synthesizing the MOFs material, and obtains the MOFs material with good simulated enzyme property and fluorescence property.
Drawings
FIG. 1.1(a) shows the asymmetric unit diagram for Compound 1.
FIG. 1.1(b) is a diagram showing the coordination environment of Ni ions of Compound 1 of example 1 of the present invention.
Fig. 1.2(a) shows a spatial arrangement diagram of a one-dimensional chain structure of compound 1.
Fig. 1.2(b) and 1.2(c) show spatial arrangement diagrams of a one-dimensional chain structure of compound 1.
FIG. 2.1(a) shows the asymmetric unit diagram for Compound 2.
FIG. 2.1(b) shows the coordination environment of Co ion of compound 2.
Figure 2.2 shows the three-dimensional space structure of compound 2.
FIG. 2.3(a) shows the asymmetric building block diagram for Compound 3.
Figure 2.3(b) shows the 3D structural diagram of compound 3.
Figure 3 shows the differential thermal-thermogravimetric plot of compound 1.
Figure 4 shows the differential heat-thermogravimetric plot of compound 2.
Figure 5 shows the differential heat-thermogravimetric plot of compound 3.
FIG. 6(a) shows ligand H4Solid state emission spectrum of BPTC.
FIG. 6(b) is a graph showing the solid state emission spectrum of Compound 1.
FIG. 6(c) is a graph showing the solid state emission spectrum of Compound 2.
FIG. 6(d) is a graph showing the solid state emission spectrum of Compound 3.
FIG. 7(a) is a graph showing the mimetic enzyme activity of Compound 1.
FIG. 7(b) is a graph showing the mimetic enzyme activity of Compound 2.
FIG. 7(c) is a graph showing the simulated enzyme activity of Compound 3.
FIG. 8 is a graph showing the relationship between the simulated enzyme properties of Compound 1 and the hydrogen peroxide concentration.
FIG. 9 is a graph showing the relationship between the simulated enzyme properties of Compound 1 and the concentration of TMB.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The research significance of the invention is that: organic ligands and metal ions for synthesizing the MOFs material are purposefully selected, so that the MOFs material with good simulated enzyme properties and fluorescence properties is obtained.
Mainly by using H4BPTC and 2,2' -bipyridine (bipy) are taken as ligands, and the metal-organic coordination polymer is synthesized by adopting a solvothermal method under the conditions of different metal salts, different proportions, different solvents and different temperatures. Finally, two metal organic coordination polymers are synthesized, the structures of the two metal organic coordination polymers are analyzed, and infrared spectroscopy, thermogravimetric analysis and fluorescence are carried outAnalysis, and the like. The three compounds synthesized in the following examples all have fluorescent properties and also all have peroxidase mimetic enzyme activity. In the method, the relation between the activity of the peroxidase mimic enzyme of the compound 1 and the concentration of hydrogen peroxide and the concentration of a substrate TMB is researched, and meanwhile, the compound 1 can also generate a very obvious color reaction, so that the method has great potential in practical application.
Example 1
Compound Ni (H)2BPTC)(bipy)(H2O)2]·H2Synthesis of O (1)
The reactants were weighed separately: 0.017g of 3,3',5,5' -biphenyltetracarboxylic acid, 0.015g of 2,2' -bipyridine, 0.026g of NiSO4·6H2O, into the inner liner of a stainless steel reaction vessel, followed by 2mL of DMF and 2mL of H2And O, stirring for 15 minutes, placing the mixture in an oven at 160 ℃ for reaction for 8 days, taking out, and naturally cooling to room temperature to obtain rod-shaped light blue transparent crystals. Then adding DMF: h2The product was washed with a 1: 1O volume mixture and dried to give a product yield of about 69% (based on H)4BPTC)。
This example produces compound 1 for short.
Example 2
Compound Co2(BPTC)(bipy)(H2O)]·H2Synthesis of O (2)
The reactants were weighed separately: 0.050g H4BPTC 0.031g 2,2' -bipyridine, 0.048g CoCl2·6H2O, is added into the inner liner of a stainless steel reaction vessel, and then 3mL of ethanol and 3mL of H are taken2And O, sequentially adding the materials into a reaction container, stirring for 10 minutes, placing the mixture into an oven at 160 ℃ for reaction for 7 days, taking out the mixture, placing the mixture under natural conditions, cooling to room temperature to obtain crystals, wherein the crystals are slender needle-shaped dark purple transparent crystals, and adding EtOH: h2The product was washed with a 1: 1O volume mixture and dried to give a yield of about 87% (based on H)4BPTC)。
This example produces compound 2 for short.
Example 3
The reactants were weighed separately: 0.033g H4BPTC 0.031g 2,2' -bipyridine, 0.053g NiSO4·6H2O, into the inner liner of a stainless steel reaction vessel, and then 4mL of DMF, 4mL of H2And O, sequentially adding the materials into a reaction container, stirring for 20 minutes, placing the mixture into a 160 ℃ oven for reaction for 6 days, taking out the mixture, and naturally cooling to room temperature to obtain rod-shaped emerald green transparent crystals. Then adding DMF: h2The product was washed with a 1: 1O volume mixture and dried to give a product yield of about 56% (baseon H)4BPTC)。
This example produces compound referred to as compound 3.
The crystallographic data of the compounds obtained in examples 1, 2 and 3 are as follows:
TABLE 1 crystallography parameters of the compounds obtained in examples 1, 2 and 3
Crystallographic structure analysis of Compound 1
The crystals of Compound 1 belong to space group P21And c, the ratio of the total weight to the total weight of the product. Fig. 1.1(a) shows an asymmetric unit diagram of compound 1, fig. 1.1(b) shows a Ni ion coordination environment diagram of compound 1, fig. 1.2(a) shows a one-dimensional chain structure diagram of compound 1, and fig. 1.2(b) and fig. 1.2(c) show a one-dimensional structure space arrangement diagram of compound 1. For compound 1, the asymmetric structural unit contains a Ni2+Ion, a H2BPTC2-One bipy molecule, two coordinated water molecules, one free water molecule. Hexa-coordinated Ni2+Respectively with two H2BPTC2-(O1, O5A), one bipy (N1, N2) and two water molecules (O9, O10) form an octahedral coordination configuration.Adjacent Ni2+Between ions through an H2BPTC2-Connected to form a one-dimensional sawtooth structure. The 1D chain and the chain form a 3D supermolecular structure through hydrogen bond action.
Analysis of Crystal Structure of Compound 2 and Compound 3
Fig. 2.3(a) shows an asymmetric structural unit diagram of compound 3, and fig. 2.3(a) shows a 3D structural diagram of compound 3.
Thermal stability analysis of Compound 1, Compound 2, and Compound 3
In the experiment, a HENVEN-HJ HCT-3 thermogravimetric analyzer is used for representing the thermal stability of the compound 1, the compound 2 and the compound 3. The test conditions were as follows: in the air atmosphere, the temperature rise range is set to be 25-820 ℃, the temperature rise speed is set to be 10 ℃/min, and the mass change of the sample is measured.
Fig. 3 shows a differential thermal-thermogravimetric plot of compound 1, fig. 4 shows a differential thermal-thermogravimetric plot of compound 2, and fig. 5 shows a differential thermal-thermogravimetric plot of compound 3.
The metal-organic complex polymers, compound 1, compound 2 and compound 3, are relatively stable at room temperature and in the air. The thermogravimetric division was changed in 3 steps during the stepwise temperature increase.
The differential thermogravimetry results are specifically analyzed as follows:
for compound 1, the first stage change was 3.21% mass loss, which was presumably due to loss of free water molecules in the structure, before the temperature at which mass loss occurred was 95 ℃; the second stage was changed to 6.15% mass loss at 95-290 ℃ presumably due to loss of coordinated water in the structure; the change in the third stage was 69.87% mass loss, with a mass loss temperature of 290-440 ℃, presumably because the ligand had begun to decompose gradually, with a steep increase in the weight loss rate at 410 ℃ and a large energy change, presumably at which time the crystalline framework had collapsed rapidly and the metal oxide had formed. From this it can be seen that the compound is thermally stable well before 400 ℃.
For compound 2, the first stage change was 6.04% mass loss, which was presumably due to the loss of free water molecules before the temperature at which mass loss occurred was 70 ℃; the second stage was varied to 5.95% mass loss at 70-100 ℃ presumably due to loss of coordinated water in the structure; the change in the third stage was 49.71% mass loss and the temperature at which mass loss occurred was 100-450 ℃ presumably because the ligand had begun to decompose gradually, with a steep increase in the rate of weight loss at 400 ℃ and a large energy change, at which point the crystalline framework formed had rapidly collapsed and eventually formed the metal oxide.
For compound 3, the first stage change was 4.64% mass loss, which was presumably due to the loss of free water molecules before the temperature at which mass loss occurred was 80 ℃; the second stage was changed to a mass loss of 7.81% and a mass loss temperature of 80-150 ℃ presumably due to loss of coordinated water in the structure; the change in the third stage was 47.34% mass loss and the temperature at which mass loss occurred was 150-420 c, presumably because the ligand had begun to decompose gradually, with a steep increase in the rate of weight loss at 390 c and a large energy change, presumably at which time the crystalline framework had collapsed rapidly and metal oxide had finally formed.
Analysis of luminescence Properties of Compound 1, Compound 2, and Compound 3
Using fluorescence analysis of ligand H4BPTC and its formation compound 1, compound 2, compound 3 were characterized at room temperature. FIG. 6(a) shows ligand H4The solid state emission spectrum of BPTC, FIG. 6(b) is the solid state emission spectrum of Compound 1, FIG. 6(c) is the solid state emission spectrum of Compound 2, and FIG. 6(d) is the solid state emission spectrum of Compound 3.
Excited by ultraviolet light with the wavelength of 308nm, H4The emission peak of BPTC appears at 369nm, the source of this luminescent property being due to the presence of pi → pi or n → pi electron transitions within the molecule. Under the excitation of ultraviolet light with the wavelength of 300nm, the compound 1 has an emission peak at 306nm and is matched with a ligand H4The emission peaks of BPTC were compared and blue-shifted by 63 nm. Under the excitation of ultraviolet light with the wavelength of 315nm, an emission peak appears at 322nm of the compound 2, and the compound and a ligand H4The emission peaks of BPTC were compared and blue-shifted by 47 nm. Under the excitation of ultraviolet light with the wavelength of 300nm, the compound 3 has an emission peak at 307nm and is matched with a ligand H4The emission peaks of BPTC are compared and blue-shifted by 62 nm. Their fluorescence emission should be mainly ILCT with a doped L → M (4S) transition.
The above characterization and analysis of the fluorescence properties of compound 1, compound 2, and compound 3 indicate that compound 1, compound 2, and compound 3 are all fluorescent materials.
Analysis of mimic enzyme Properties of Compound 1, Compound 2, and Compound 3
The experiment was carried out using unground MOFs material compound 1, ultrasonic dispersion was carried out to obtain a suspension of 1mg/10ml, and MOFs material compound 2 and compound 3 were sufficiently ground and ultrasonic dispersed to obtain a suspension of 1mg/10ml, respectively, to prepare a TMB solution of 1mg/ml, pH 4 of the buffer solution, and hydrogen peroxide concentration 10 mM.
a) And adding 400 mu L of MOFs material suspension into 200 mu L of buffer solution, fully shaking, uniformly mixing, and carrying out ultrasonic treatment, and measuring the ultraviolet spectrum after 30 minutes.
b) And adding 200 mu L of buffer solution and 200 mu L of TMB into 400 mu L of MOFs material suspension, fully shaking, uniformly mixing and ultrasonically treating the mixture for 30 minutes, and then measuring the ultraviolet spectrum.
c) Taking 400 mu L of MOFs material suspension, adding 200 mu L of buffer solution, and adding 200 mu L H2O2The mixture is fully shaken, mixed and ultrasonically mixed with 200 mu L of TMB, and the ultraviolet spectrum is measured after 30 minutes.
Comparing the change of the UV absorption spectrum with the color of the solution in three cases, FIG. 7(a) is a graph of the mimic enzyme activity of Compound 1, FIG. 7(b) is a graph of the mimic enzyme activity of Compound 2, and FIG. 7(c) is a graph of the mimic enzyme activity of Compound 3.
As shown in the figure, compound 1, compound 2 and compound 3 alone do not show obvious absorption peaks, while the MOFs-TMB system shows weak absorption peaks at 652nm (compound 1), 650nm (compound 2) and 652nm (compound 3), which are considered to be generated by TMB. However, MOFs-H2O2The TMB reaction system showed strong absorption peaks at 652nm (Compound 1), 650nm (Compound 2), and 652nm (Compound 3). The results indicate that all three MOFs materials have strong catalytic effects on the reaction.
Research on relationship between mimic enzyme property of compound 1 and hydrogen peroxide concentration
An experiment for investigating the ability of test compound 1 to mimic the enzyme was conducted by using unground compound 1 and dispersing it with ultrasound to obtain a suspension of 1mg/10ml, preparing a solution of 1mg/ml of TMB (3,4, 5-trimethoxybenzaldehyde) and adjusting the pH of the buffer to 4 (hydrogen peroxide concentration of 0 to 10 mM).
400 μ L of Compound 1 solution was added to 200 μ L of buffer, and 200 μ L H was added2O2Fully shaking with 200 mu L TMB, uniformly mixing and performing ultrasonic treatment, and measuring the ultraviolet absorption spectrum after 30 minutes. The concentration of hydrogen peroxide is 0-10mM, and ultraviolet absorption spectra of different hydrogen peroxide concentrations are compared, as shown in FIG. 8, which is a relationship between the simulated enzyme property of compound 1 and hydrogen peroxide concentration, and a relationship between hydrogen peroxide concentration and ultraviolet absorption value in the range of 0-5mM. The fitting constant R was 0.97.
Studies of relationships between mimic enzymatic Properties of Compound 1 and TMB concentration
An investigation experiment for exploring the enzyme properties of compound 1 (TMB solution concentration of 0 to 4mg/ml) was conducted by using compound 1 not ground to obtain a suspension of 1mg/10ml by ultrasonic dispersion and formulating a hydrogen peroxide concentration of 0.1mM and a buffer pH of 4.
400 μ L of Compound 1 solution was added to 200 μ L of buffer, and 200 μ L H was added2O2Fully shaking and uniformly mixing with 200 mu L TMB, and carrying out ultrasonic treatment for 30 minutes and then measuring the ultraviolet absorption spectrum. The concentration of TMB solution was 0-4mM, and the UV absorption spectra were compared for different concentrations of hydrogen peroxide, and FIG. 9 is a graph showing the relationship between the simulated enzyme properties of Compound 1 and the concentration of TMB. As shown, the relationship between TMB concentration and UV absorbance in the range of 0-4 mM. The fitting constant R was 0.97.
The above examples utilize 3,3',5,5' -biphenyltetracarboxylic acid (H)4BPTC) as a main ligand and 2,2' -bipyridine as an auxiliary ligand, three metal-organic coordination polymers which are not reported by the prior literature, namely compounds 1, 2 and 3, are synthesized under the condition of solvothermal, and the structures and the performances of the compounds are characterized. Compounds 2 and 3 are both H4BPTC, 2' -bipyridine and metal ions are coordinated together to form a metal-organic coordination polymer with the same crystal structure. The metal ion involved in the formation of compound 2 is Co2+The metal ion involved in the formation of the compound 3 is Ni2+. The organic ligand and the metal ion of the compound 1 and the compound 3 are completely the same, but the structures are completely different. The compound 1 is a one-dimensional chain structure which is arranged in parallel to form a crystal structure of the compound, and the compound 3 is a three-dimensional framework structure. The fluorescence property is analyzed, the compound 1 generates fluorescence at 306nm, and the compound 2 generates fluorescence at 322 nm; compound 3 fluoresces at 307 nm. Differential thermogravimetric analysis showed that both compounds completely lost their framework structure at 400 ℃.
Furthermore, compounds 1, 2 and 3 all demonstrated peroxidase activity by uv absorption spectroscopy. The peroxidase activity of compound 1 was also demonstrated as a function of the concentration of hydrogen peroxide and the concentration of substrate TMB.
In conclusion, the invention purposefully selects the organic ligand and the metal ion for synthesizing the MOFs material, and obtains the MOFs material with good simulated enzyme property and fluorescence property.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (1)
1. An application of MOFs material using rigid aromatic polycarboxylic acid as ligand as mimic enzyme is characterized in that: the MOFs material includes compound 1: [ Ni (H)2BPTC)(bipy)(H2O)2]·H2O, Compound 2: [ Co ] A2(BPTC)(bipy)(H2O)]·H2O and 3, and 1, 2 and 3 have fluorescence property and peroxide mimic enzyme activity;
compound 1: ni (H)2BPTC)(bipy)(H2O)2]·H2The synthesis method of O comprises the following steps:
the reactants were weighed separately: 0.017g of 3,3',5,5' -biphenyltetracarboxylic acid, 0.015g of 2,2' -bipyridine, 0.026g of NiSO4·6H2O, into the inner liner of a stainless steel reaction vessel, followed by 2mL of DMF and 2mL of H2And O, stirring for 15 minutes, placing the mixture in an oven at 160 ℃ for reaction for 8 days, taking out, naturally cooling to room temperature to obtain a rod-shaped light blue transparent crystal, and adding DMF: h2Washing the product with a mixed solution with the volume ratio of O being 1:1, and drying to obtain a product compound 1;
compound 2: co2(BPTC)(bipy)(H2O)]·H2The synthesis method of O comprises the following steps: the reactants were weighed separately: 0.050g H4BPTC 0.031g 2,2' -bipyridine, 0.048g CoCl2·6H2O, is added into the inner liner of a stainless steel reaction vessel, and then 3mL of ethanol and 3mL of H are taken2And O, sequentially adding the materials into a reaction container, stirring for 10 minutes, placing the mixture into an oven at 160 ℃ for reaction for 7 days, taking out the mixture, placing the mixture under natural conditions, cooling to room temperature to obtain crystals, wherein the crystals are slender needle-shaped dark purple transparent crystals, and adding EtOH: h2Washing the product with a mixed solution with the volume ratio of O being 1:1, and drying to obtain a product compound 2;
the synthesis method of the compound 3 comprises the following steps:
the reactants were weighed separately: 0.033g H4BPTC 0.031g 2,2' -bipyridine, 0.053g NiSO4·6H2O, into the inner liner of a stainless steel reaction vessel, and then 4mL of DMF, 4mL of H2And O, sequentially adding the materials into a reaction container, stirring for 20 minutes, placing the mixture into an oven at 160 ℃ for reaction for 6 days, taking out the mixture, naturally cooling to room temperature to obtain rod-shaped emerald green transparent crystals, and adding DMF: h2Washing the product with the mixed solution with the volume ratio of O being 1:1, and drying to obtain the product compound 3.
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| CN105254681A (en) * | 2015-09-19 | 2016-01-20 | 洛阳师范学院 | 3, 3', 4, 5'-Biphenyltetracarboxylic acid and 4, 4'-bipyridine mixed cobalt complex, and preparation method and applications thereof |
| CN106046032A (en) * | 2016-06-06 | 2016-10-26 | 三峡大学 | MOF (metal-organic framework) material constructed on basis of pentabasic aromatic carboxylic acid as well as synthesis method and catalytic application of MOF material |
| CN106349282A (en) * | 2016-08-01 | 2017-01-25 | 洛阳师范学院 | 3,3',4,5'-biphenyl tetracarboxylic acid and 4,4'-bipyridine mixed cadmium-lead complex and preparation method and application thereof |
| CN108368241A (en) * | 2016-01-26 | 2018-08-03 | 夏玲 | MOFs as the catalyst for ring-opening polymerisation |
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| CN108368241A (en) * | 2016-01-26 | 2018-08-03 | 夏玲 | MOFs as the catalyst for ring-opening polymerisation |
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| CN106349282A (en) * | 2016-08-01 | 2017-01-25 | 洛阳师范学院 | 3,3',4,5'-biphenyl tetracarboxylic acid and 4,4'-bipyridine mixed cadmium-lead complex and preparation method and application thereof |
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