Two-dimensional metal organic layer based on multi-nitrogen ligand as well as preparation method and application of two-dimensional metal organic layer

Abstract

The invention discloses a two-dimensional metal organic layer based on a multi-nitrogen ligand and a preparation method and application thereof, the structural general formula of the two-dimensional metal organic layer is as shown in the following formula (I), in the formula, N is a nitrogen element, and M is selected from CH or N; y is selected from one or more of CO2 (Zr (mu3-O) 4 (mu3-OH) 4) 1 / 6, CO2 (Hf (mu3-O) 4 (mu3-OH) 4) 1 / 6, Ph-CO2 (Zr (mu3-O) 4 (mu3-OH) 4) 1 / 6 and Ph-CO2 (Hf (mu3-O) 4 (mu3-OH) 4) 1 / 6, and Ph is a benzene ring; the two-dimensional metal organic layer based on the multi-nitrogen ligand disclosed by the invention is novel in structure, and can realize efficient loading of biomacromolecules without remarkably reducing the original biological activity of the biomacromolecules; and the catalyst can also be applied to photocatalysis olefin isomerization and supported enzyme catalysis asymmetric hydrogenation reaction, and has excellent catalytic activity. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of material chemistry, and in particular to a two-dimensional metal organic layer based on polynitrogen ligands, and a preparation method and application thereof. Background Art

[0002] Although biological macromolecules are powerful, they usually have problems such as poor stability, susceptibility to environmental conditions, and low bioavailability. By loading these macromolecules onto specific carrier materials, their stability can be significantly improved, their in vitro and in vivo action time can be prolonged, and their biocompatibility and targeting can be enhanced, thereby expanding their application range and improving their activity. Metal organic frameworks (MOFs) have the characteristics of highly customizable pore structure, large specific surface area, and adjustable chemical and physical properties, making them excellent biomacromolecule loading materials. However, due to the stability of their structure and the rigidity of their ligands, the pores of framework materials are generally only a few angstroms or tens of angstroms. The size of biological macromolecules can often reach more than ten nanometers, which is much larger than the inner diameter of these pores. Even in biomineralization schemes, overly large proteins often significantly affect the occurrence of the mineralization process. Therefore, current research is often limited to smaller proteins such as lipases and proteases.

[0003] The two-dimensional metal-organic layer is a two-dimensional analogue of the metal-organic framework, with a high aspect ratio and a thickness as low as a monolayer. Its surface adsorption has no clear restrictions on the size of the adsorbed substance, and can also greatly reduce the mass transfer resistance generated during the embedding process. Therefore, for large-sized biomacromolecules, the use of two-dimensional metal-organic layer surface adsorption of proteins is a more feasible loading scheme. However, in actual operation, it is found that the loading of two-dimensional metal-organic layers often leads to reduced protein activity. One of the important reasons is that the ligands are often very hydrophobic, and contact with the protein surface causes changes in the protein configuration and thus reduces its catalytic activity. Summary of the invention

[0004] In response to the above-mentioned problems existing in the prior art, the present invention discloses a two-dimensional metal organic layer based on polynitrogen ligands, which has a novel structure and can achieve efficient loading of biological macromolecules without significantly reducing their original biological activity; it can also be used in photocatalytic olefin isomerization and loaded enzyme-catalyzed asymmetric hydrogenation reactions, and has excellent catalytic activity.

[0005] The specific technical solutions are as follows:

[0006] A two-dimensional metal organic layer based on polynitrogen ligands, the general structure of which is shown in the following formula (I):

[0007]

[0008] Wherein, N is nitrogen, and M is selected from CH or N;

[0009] Y is selected from CO2(Zr(μ3-O)4(μ3-OH)4) 1 / 6 、CO2(Hf(μ3-O)4(μ3-OH)4) 1 / 6 ,Ph-CO2(Zr(μ3-O)4(μ3-OH)4) 1 / 6 ,Ph-CO2(Hf(μ3-O)4(μ3-OH)4) 1 / 6 One or more of, Ph is a benzene ring.

[0010] Specifically, it has the following structural formulas (I-1) to (I-6):

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017] The present invention also discloses a method for preparing the two-dimensional metal organic layer based on polynitrogen ligands, comprising:

[0018] (1) preparing a polynitrogen ligand as shown in the following formulas (II-1) to (II-3);

[0019]

[0020]

[0021] (2) The polynitrogen ligand, a soluble salt of a coordinated metal, a structure regulator and a solvent are mixed to obtain a mixed solution, and the two-dimensional metal organic layer based on the polynitrogen ligand is prepared after a solvent thermal reaction.

[0022] In step (1), the preparation process of the polynitrogen ligand described in formula (II-1) is as follows:

[0023] Using 2-nitrile-5-methyl-pyridine as the raw material, an intermediate product is obtained by heating and melting condensation, and then oxidized by potassium permanganate to obtain a polynitrogen ligand as described in formula (II-1).

[0024] The temperature of the heating melt condensation is 100-140°C, preferably 120°C.

[0025] In the potassium permanganate oxidation, pyridine is used as a solvent, and potassium permanganate is added in the form of a potassium permanganate aqueous solution; the temperature of the oxidation reaction is the reflux temperature.

[0026] In step (1), the preparation process of the polynitrogen ligand described in formula (II-2) is as follows:

[0027] Using 2-nitrile-5-bromo-pyridine as the raw material, the intermediate product I is obtained by heating and melting condensation, and then it is coupled with 4-methylcarbonylphenylboronic acid under the catalysis of tetrakistriphenylphosphine palladium to prepare the intermediate product II, and finally it is hydrolyzed under alkaline conditions to obtain the polynitrogen ligand as described in formula (II-2).

[0028] The temperature of the heating melt condensation is 120-180°C, preferably 150°C.

[0029] The coupling reaction is carried out in a THF / water mixed solvent at a coupling reaction temperature of 60-80°C.

[0030] The hydrolysis reaction is carried out in a KOH aqueous solution at a reaction temperature of 60-80°C.

[0031] In step (1), the preparation process of the polynitrogen ligand described in formula (II-3) is as follows:

[0032] Using 2-nitrile-5-bromo-pyrimidine as the raw material, a condensation reaction is performed to obtain the intermediate product 1, which is then coupled with 4-methylcarbonylphenylboronic acid under the catalysis of tetrakistriphenylphosphine palladium to obtain the intermediate product 2. Finally, a hydrolysis reaction is performed under alkaline conditions to obtain a polynitrogen ligand as described in formula (II-3).

[0033] The condensation reaction is carried out in n-pentanol at a temperature of 120-150°C, preferably 135°C.

[0034] The coupling reaction is carried out in a THF / water mixed solvent at a coupling reaction temperature of 60-80°C.

[0035] The hydrolysis reaction is carried out in the presence of cesium carbonate at a reaction temperature of 60-80°C.

[0036] In step (2):

[0037] The soluble salt of the coordination metal is selected from a soluble zirconium salt and / or a soluble hafnium salt;

[0038] The structure regulator is selected from one or more of benzoic acid, formic acid, and trifluoroacetic acid;

[0039] The solvent is selected from one or more of N,N-dimethylformamide and N,N-dimethylacetamide.

[0040] Preferably, in step (2):

[0041] Based on the addition amount of the polynitrogen ligand as 1 equivalent, the addition amount of the soluble salt of the coordination metal is 3.5 to 28 equivalents, and the addition amount of the structure regulator is 50 to 200 equivalents;

[0042] In the mixed solution, the concentration of the polynitrogen ligand is 2.5 to 7.5 mmol / L;

[0043] The temperature of the solvent thermal reaction is 80-120° C. and the time is 16-48 hours.

[0044] The present invention also discloses the application of the two-dimensional metal organic layer based on polynitrogen ligands in the field of biomacromolecule loading, wherein the biomacromolecule is selected from nucleic acid drugs and / or proteins.

[0045] It has been found through testing that the two-dimensional metal organic layer prepared by the present invention can be used to load biological macromolecules, has a high loading capacity, and has no restrictions on the size of the molecules. More importantly, the loading of the two-dimensional metal organic layer will not significantly reduce the original biological activity of the biological macromolecules.

[0046] Preferably, the two-dimensional metal-organic layer is selected from a two-dimensional metal-organic layer having a structure of formula (I-3), which not only has a high loading capacity for biological macromolecules but also substantially does not affect their original biological activity.

[0047] The invention also discloses the application of the two-dimensional metal organic layer loaded with olefin reductase based on polynitrogen ligands in photocatalytic asymmetric olefin hydrogenation reaction.

[0048] It has been found through testing that the two-dimensional metal organic layer prepared by the present invention can catalyze the cis-trans isomerization of olefins under light conditions, and can achieve asymmetric hydrogenation of olefins after loading olefin reductase on it, and has very high chiral selectivity.

[0049] Compared with the prior art, the present invention has the following advantages:

[0050] The present invention prepares a series of novel two-dimensional metal-organic layers based on a variety of novel polynitrogen ligands. The novel structure achieves efficient loading of biological macromolecules while substantially not affecting their original biological activity. In addition, the novel polynitrogen ligands also give the two-dimensional metal-organic layer more unique optical properties, enabling it to achieve photocatalytic olefin isomerization of olefins and to achieve asymmetric hydrogenation of olefins in series with the loaded olefin reductase. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The H NMR spectrum of the polynitrogen ligand synthesis intermediate TPYP-Me3 prepared in Example 1;

[0052] Figure 2This is the H NMR spectrum of the polynitrogen ligand TPYP-H3 prepared in Example 1;

[0053] Figure 3 This is a scanning electron microscope image of the two-dimensional metal organic layer prepared in Example 1;

[0054] Figure 4 This is a transmission electron microscopy image of the two-dimensional metal organic layer prepared in Example 1;

[0055] Figure 5 The powder X-ray diffraction spectrum and fitting spectrum of the two-dimensional metal organic layer prepared in Example 1;

[0056] Figure 6 This is the H NMR spectrum of the polynitrogen ligand synthesis intermediate TPYT-Br3 prepared in Example 2;

[0057] Figure 7 This is the H NMR spectrum of the polynitrogen ligand synthesis intermediate TPYT-BM3 prepared in Example 2;

[0058] Figure 8 This is the H NMR spectrum of the polynitrogen ligand TPYT-BH3 prepared in Example 2;

[0059] Fig. 9 This is a scanning electron microscope image of the two-dimensional metal organic layer prepared in Example 2;

[0060] Fig.10 This is a transmission electron microscopy image of the two-dimensional metal organic layer prepared in Example 2;

[0061] Fig.11 The powder X-ray diffraction spectrum and fitting spectrum of the two-dimensional metal organic layer prepared in Example 2;

[0062] Fig.12 This is the H NMR spectrum of the polynitrogen ligand synthesis intermediate TPMT-Br3 prepared in Example 3;

[0063] Fig.13 This is the H NMR spectrum of the polynitrogen ligand synthesis intermediate TPMT-BM3 prepared in Example 3;

[0064] Fig.14 This is the H NMR spectrum of the polynitrogen ligand TPMT-BH3 prepared in Example 3;

[0065] Fig.15 This is a scanning electron microscope image of the two-dimensional metal organic layer prepared in Example 3;

[0066] Fig.16 This is a transmission electron microscopy image of the two-dimensional metal organic layer prepared in Example 3;

[0067] Fig.17The powder X-ray diffraction spectrum and fitting spectrum of the two-dimensional metal organic layer prepared in Example 3;

[0068] Fig.18 This is a scanning electron microscope image of a two-dimensional metal organic layer prepared in a comparative example;

[0069] Fig.19 A transmission electron microscope image of a two-dimensional metal organic layer prepared in a comparative example;

[0070] Fig. 20 is the activity diagram of free β-galactosidase and immobilized β-galactosidase;

[0071] Fig.21 Schematic diagram of the photocatalytic asymmetric hydrogenation reaction of Z-configuration olefins (a) and comparison of olefin isomerization and reduction with and without metal organic layer loading (b). DETAILED DESCRIPTION

[0072] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0073] Example 1

[0074] (1) Synthesis of polynitrogen ligand TPYP-H3

[0075]

[0076] 5 g of 2-nitrile-5-methyl-pyridine was placed in a pressure tube and heated at 120°C until it melted. Then 169 mg (0.1 equivalent) of sodium hydroxide was added to the tube. After reacting at 120°C for 36 hours, a black solid was obtained. Column chromatography was used for purification, with dichloromethane and methanol as eluents. Finally, 1.8 g of TPYP-Me3 was obtained, with a yield of about 36%.

[0077] Figure 1 H NMR spectrum of the polynitrogen ligand synthetic intermediate (TPYP-Me3) prepared in this example.

[0078]

[0079] Dissolve 0.40g TPYP-Me3 in 25mL pyridine, and then add 90mL KMnO4 aqueous solution (containing 8g KMnO4). After reflux at 100℃ for 96 hours, add 40mL 1mol / L hydrochloric acid to precipitate the product. Centrifuge to obtain the precipitate, and then wash it with methanol to obtain 0.62g TPYP-H3, with a yield of about 98%.

[0080] Figure 2 This is the H-NMR spectrum of the polynitrogen ligand (TPYP-H3) prepared in this example.

[0081] (2) Synthesis of two-dimensional metal-organic layers

[0082] Weigh 40 mg (1 equivalent) of the polynitrogen ligand TPYP-H3 prepared in step (1) and dissolve it in 4 mL of N,N-dimethylformamide, and add 610 μL (92 equivalents) of trifluoroacetic acid to the above solution. Weigh 800 mg (28 equivalents) of zirconium oxychloride octahydrate and dissolve it in 4 mL of N,N-dimethylformamide, and add it to the above ligand solution, and finally add an additional 4 mL of N,N-dimethylformamide. The reaction conditions are 120°C oven for 24 hours.

[0083] Figure 3 , 4 The two-dimensional metal organic layer prepared in this embodiment is shown in the scanning electron microscope image and the transmission electron microscope image, respectively. It can be found from the observation that the two-dimensional metal organic layer prepared in this embodiment has a film-like structure.

[0084] Figure 5 The powder X-ray diffraction spectrum and structural simulation signal of the two-dimensional metal organic layer prepared in this embodiment indicate that its structural formula is as shown in formula (I-1).

[0085] Example 2

[0086] (1) Synthesis of polynitrogen ligand TPYT-BH3

[0087]

[0088] 5g of 2-nitrile-5-bromo-pyridine was placed in a pressure tube and heated at 150°C until it melted. Then 218mg (0.2 equivalent) of sodium hydroxide was added to the tube. After reacting at 150°C for 24 hours, a black solid was obtained. After dissolving it in N-methylpyrrolidone, it was recrystallized and purified with methanol. Finally, 2.3g of TPYT-Br3 was obtained, with a yield of about 46%.

[0089] Figure 6 H NMR spectrum of the polynitrogen ligand synthesis intermediate (TPYT-Br3) prepared in this example.

[0090]

[0091] 1.16 mg TPYT-Br3, 1.71 g 4-methylcarbonylphenylboronic acid (4.5 equivalents) and 5.78 g cesium fluoride (18 equivalents) were added to a THF and water mixed solvent (140 mL THF and 40 mL H2O) after Ar bubbling for 30 min. Ar bubbling was continued for 30 min into the suspension, and then 367 mg tetrakistriphenylphosphine palladium (0.15 equivalents) was added. After heating at 70°C for 72 hours, the precipitate was filtered and washed with methanol to obtain 1.44 g TPYT-BM3, with a yield of about 95%.

[0092] Figure 7 H NMR spectrum of the polynitrogen ligand synthetic intermediate (TPYT-BM3) prepared in this example.

[0093]

[0094] Suspend 0.67g TPYT-BM3 in 25mL methanol, and then add 25mL 1mol / L KOH aqueous solution. After heating at 70℃ for 24 hours, add 50mL water to fully dissolve the product and filter. Take the filtrate, acidify it and precipitate will appear. Filter the precipitate again, wash it with methanol and dry it in a vacuum drying oven to obtain 0.62g TPYT-BH3, with a yield of about 98%.

[0095] Figure 8 This is the H NMR spectrum of the polynitrogen ligand (TPYT-BH3) prepared in this example.

[0096] (2) Synthesis of two-dimensional metal-organic layers

[0097] Weigh 60 mg (1 equivalent) of the polynitrogen ligand TPYT-BH3 prepared in step (1) and dissolve it in 4 mL of N,N-dimethylformamide, and add 610 μL (92 equivalents) of trifluoroacetic acid to the above solution. Weigh 800 mg (28 equivalents) of zirconium oxychloride octahydrate and dissolve it in 1 mL of N,N-dimethylformamide, and add it to the above ligand solution, and finally add an additional 4 mL of N,N-dimethylformamide. The reaction conditions are to stand in an oven at 120°C for 24 hours.

[0098] Fig. 9 , 10 The two-dimensional metal organic layer prepared in this embodiment is shown in the scanning electron microscope image and the transmission electron microscope image, respectively. It can be found from the observation that the two-dimensional metal organic layer prepared in this embodiment has a film-like structure.

[0099] Fig.11 The powder X-ray diffraction spectrum and structural simulation signal of the two-dimensional metal organic layer prepared in this example indicate that its structural formula is as shown in formula (I-2).

[0100] Example 3

[0101] (1) Synthesis of polynitrogen ligand TPMT-BH3

[0102]

[0103] 10 mL of n-pentanol was added to a mixture of 5 g of 2-nitrile-5-bromo-pyrimidine, 237 μL of N,N-diisopropylethylamine (0.05 equivalent) and 133 mg of ammonium bromide (0.05 equivalent). After heating at 135°C for 24 hours, methanol was added to the suspension to precipitate the product. The product was recrystallized and purified with NMP and methanol to obtain about 2.5 g of TPMT-Br3, with a yield of about 50%.

[0104] Fig.12 This is the H-NMR spectrum of the polynitrogen ligand synthesis intermediate (TPMT-Br3) prepared in this example.

[0105]

[0106] 1.5 g TPMT-Br3, 2.2 g (4-(methoxycarbonyl)phenyl)boric acid (4.5 equivalents) and 7.43 g cesium fluoride (18 equivalents) were added to a THF and water mixed solvent (250 mL THF and 80 mL H2O) after Ar bubbling for 30 min. Ar bubbling was continued for 30 min into the suspension, and then 471 mg of tetrakistriphenylphosphine palladium (0.15 equivalents) was added. After heating at 70°C for 72 hours, the precipitate was filtered and washed with methanol to obtain 1.95 g TPMT-BM3, with a yield of about 95%.

[0107] Fig.13 This is the H-NMR spectrum of the polynitrogen ligand synthetic intermediate (TPMT-BM3) prepared in this example.

[0108]

[0109] Suspend 1.5g of TPMT-BM3 in 120mL of N-methylpyrrolidone, and then add 5.4g of cesium carbonate (8 equivalents) and 80mL of water. After heating at 70°C for 24 hours, add 160mL of water to fully dissolve the product and filter. Take the filtrate, acidify it and a precipitate will appear. Filter the precipitate again, wash it with methanol and dry it in a vacuum drying oven to obtain 1.2g of TPMT-BH3, with a yield of about 80%.

[0110] Fig.14 This is the H NMR spectrum of the polynitrogen ligand (TPMT-BH3) prepared in this example.

[0111] (2) Synthesis of two-dimensional metal-organic layers

[0112] Weigh 60 mg (1 equivalent) of the polynitrogen ligand TPMT-BH3 prepared in step (1) and dissolve it in 4 mL of N,N-dimethylformamide, and add 610 μL (92 equivalents) of trifluoroacetic acid to the above solution. Weigh 800 mg (28 equivalents) of zirconium oxychloride octahydrate and dissolve it in 1 mL of N,N-dimethylformamide, and add it to the above ligand solution, and finally add an additional 4 mL of N,N-dimethylformamide. The reaction conditions are to stand in an oven at 120°C for 24 hours.

[0113] Fig.15 , 16 The two-dimensional metal organic layer prepared in this embodiment is shown in the scanning electron microscope image and the transmission electron microscope image, respectively. It can be found from the observation that the two-dimensional metal organic layer prepared in this embodiment has a film-like structure.

[0114] Fig.17 The powder X-ray diffraction spectrum and structural simulation signal of the two-dimensional metal organic layer prepared in this example indicate that its structural formula is as shown in formula (I-3).

[0115] Comparative Example

[0116] Weigh 40 mg (1 equivalent) of organic ligand BTB (commercially available) and dissolve it in 4 mL of N,N-dimethylformamide, and add 610 μL (92 equivalents) of trifluoroacetic acid to the above solution. Weigh 800 mg (28 equivalents) of zirconium oxychloride octahydrate and dissolve it in 1 mL of N,N-dimethylformamide, and add it to the above ligand solution, and finally add an additional 4 mL of N,N-dimethylformamide. The reaction conditions are to stand in an oven at 120°C for 24 hours.

[0117]

[0118] Fig.18 , 19 The two-dimensional metal organic layer prepared in this comparative example is shown in the scanning electron microscope image and the transmission electron microscope image, respectively. It can be found from the observation that the two-dimensional metal organic layer prepared in this comparative example also has a film-like structure.

[0119] Performance Testing:

[0120] 1. Large size protein loading

[0121] 10 μL of β-galactosidase solution (20 mg / mL) was mixed with 100 μL of two-dimensional metal organic layer aqueous suspension (1 mg / mL) prepared in Examples 1, 2, 3 and Comparative Examples, respectively, and shaken in a shaker at 10°C for 20 minutes. The two-dimensional metal organic layer was then separated by centrifugation. 25 μL of supernatant was mixed with 5 μL of 6x protein electrophoresis loading buffer and boiled at 100°C for 10 minutes. After the mixed solution was cooled to room temperature, polyacrylamide gel electrophoresis was performed. The gel was then stained with Coomassie Brilliant Blue. The protein on the gel will be colored blue, while the gel without protein will not be colored. The image was decolorized, and the adsorption amount of the protein was then determined based on the grayscale. It was calculated by the above method that the loading amounts of β-galactosidase for the two-dimensional metal-organic layer I-1 prepared in Example 1, the two-dimensional metal-organic layer I-2 prepared in Example 2, the two-dimensional metal-organic layer I-3 prepared in Example 3 and the two-dimensional metal-organic layer prepared in the comparative example were 1 g / g, 210 mg / g, 740 mg / g and 1 g / g, respectively.

[0122] The activity of free β-galactosidase and immobilized β-galactosidase was then determined based on GB / T 33409-2016. Fig. 20 As shown, the β-galactosidase fixed by the two-dimensional metal-organic layer of Ⅰ-2 and Ⅰ-3 basically completely retained its original activity, while the activity of the β-galactosidase fixed by the two-dimensional metal-organic layer of Ⅰ-1 decreased; and the activity of the β-galactosidase fixed by the two-dimensional metal-organic layer prepared in the comparative example decreased significantly again, and the activity was less than 50%.

[0123] The above tests show that the two-dimensional metal organic layer prepared by the present invention can be used to load biological macromolecules, has a high loading capacity, and has no restrictions on the size of the molecules. The examples show the three metal organic layers for galactosidase The loading of the enzyme is not affected and the catalytic activity of the enzyme is not affected after loading.

[0124] 2. Photocatalytic olefin isomerization and enzyme-catalyzed asymmetric hydrogenation

[0125] 50 μL of old yellow enzyme II (OYE2, 49.2 nmol / L) was mixed with 100 μL of the two-dimensional metal organic layer (Ⅰ-3) (1 mmol / L) prepared in Example 3, and then 100 nmol of nicotinamide adenine dinucleoside phosphate, 12.5 μmol of glucose, 0.55 nmol of glucose dehydrogenase, and 125 μL of HEPES buffer (pH=7.5, 10 mmol / L) and 2.5 μmol of Z-configuration olefin substrate ((Z)-3-cyano-3-phenylacrylate) were added. After reacting at 460 nm under blue light at 15°C for 14 hours, the product distribution was determined by chiral gas chromatography. In the experiment without the metal organic layer as the control group, only 100 μL (Ⅰ-3) was replaced with 100 μL of pure water, keeping the total volume unchanged, and the other steps were exactly the same as the experimental group.

[0126] Fig.21 Figure a is a schematic diagram of the photocatalytic asymmetric hydrogenation reaction of Z-configuration olefins. The reaction is divided into two steps. The first step is the isomerization reaction of the Z configuration into the E configuration, and the second step is the hydrogenation reduction reaction. Fig.21 Figure b shows the comparison of olefin isomerization and reduction with and without metal organic layer loading. The comparison shows that OYE2 selectively catalyzes the hydrogenation of E-configuration olefin substrates, but not Z-configuration substrates. Therefore, the reaction cannot proceed in the sample without metal organic layer. The two-dimensional metal organic layer (I-3) prepared by the present invention can catalyze the cis-trans isomerization of olefins under light conditions, and can realize asymmetric hydrogenation of olefins after loading olefin reductase on it, with very high chiral selectivity.

[0127] The above-mentioned embodiments are preferred embodiments, but the protection scope of the present invention is not limited thereto. A person skilled in the art can easily understand the spirit of the present invention based on the above-mentioned embodiments and make different extensions and changes. However, as long as they do not deviate from the spirit of the present invention, they are all within the protection scope of the present invention.

Claims

1. A two-dimensional metal organic layer based on polynitrogen ligands, characterized in that: The general structural formula is shown in the following formula (I): Wherein, N is nitrogen, and M is selected from CH or N; Y is selected from CO2(Zr(μ3-O)4(μ3-OH)4) 1 / 6 、CO2(Hf(μ3-O)4(μ3-OH)4) 1 / 6 ,Ph-CO2(Zr(μ3-O)4(μ3-OH)4) 1 / 6 ,Ph-CO2(Hf(μ3-O)4(μ3-OH)4) 1 / 6 One or more of, Ph is a benzene ring.

2. The two-dimensional metal organic layer based on polynitrogen ligands according to claim 1, characterized in that: It has the following structural formula (I-1) to (I-6):

3. A method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 1 or 2, characterized in that: include: (1) preparing a polynitrogen ligand as shown in the following formulas (II-1) to (II-3); (2) The polynitrogen ligand, a soluble salt of a coordinated metal, a structure regulator and a solvent are mixed to obtain a mixed solution, and the two-dimensional metal organic layer based on the polynitrogen ligand is prepared after a solvent thermal reaction.

4. The method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 3, characterized in that: In step (1), the preparation process of the polynitrogen ligand described in formula (II-1) is as follows: Using 2-nitrile-5-methyl-pyridine as the raw material, an intermediate product is obtained by heating and melting condensation, and then oxidized by potassium permanganate to obtain a polynitrogen ligand as described in formula (II-1).

5. The method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 3, characterized in that: In step (1), the preparation process of the polynitrogen ligand described in formula (II-2) is as follows: Using 2-nitrile-5-bromo-pyridine as the raw material, the intermediate product I is obtained by heating and melting condensation, and then it is coupled with 4-methylcarbonylphenylboronic acid under the catalysis of tetrakistriphenylphosphine palladium to prepare the intermediate product II, and finally it is hydrolyzed under alkaline conditions to obtain the polynitrogen ligand as described in formula (II-2).

6. The method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 3, characterized in that: In step (1), the preparation process of the polynitrogen ligand described in formula (II-3) is as follows: Using 2-nitrile-5-bromo-pyrimidine as the raw material, a condensation reaction is performed to obtain the intermediate product 1, which is then coupled with 4-methylcarbonylphenylboronic acid under the catalysis of tetrakistriphenylphosphine palladium to obtain the intermediate product 2. Finally, a hydrolysis reaction is performed under alkaline conditions to obtain a polynitrogen ligand as described in formula (II-3).

7. The method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 3, characterized in that: In step (2): The soluble salt of the coordination metal is selected from a soluble zirconium salt and / or a soluble hafnium salt; The structure regulator is selected from one or more of benzoic acid, formic acid, and trifluoroacetic acid; The solvent is selected from one or more of N,N-dimethylformamide and N,N-dimethylacetamide.

8. The method for preparing a two-dimensional metal organic layer based on polynitrogen ligands according to claim 3, characterized in that: In step (2): Based on the addition amount of the polynitrogen ligand as 1 equivalent, the addition amount of the soluble salt of the coordination metal is 3.5 to 28 equivalents, and the addition amount of the structure regulator is 50 to 200 equivalents; In the mixed solution, the concentration of the polynitrogen ligand is 2.5 to 7.5 mmol / L; The temperature of the solvent thermal reaction is 80-120° C. and the time is 16-48 hours.

9. An application of the two-dimensional metal organic layer based on polynitrogen ligands according to claim 1 or 2 in the field of biomacromolecule loading, characterized in that: The biomacromolecules are selected from nucleic acid drugs and / or proteins.

10. Use of the two-dimensional metal organic layer based on polynitrogen ligands supported olefin reductase according to claim 1 or 2 in photocatalytic olefin isomerization and enzyme-catalyzed asymmetric hydrogenation reactions.

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