CN113201526A - Bifunctional photo-enzyme synergistic catalyst and preparation method and application thereof - Google Patents
Bifunctional photo-enzyme synergistic catalyst and preparation method and application thereofDownload PDFInfo
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Abstract
Translated fromChinese
Description
Technical Field
The invention relates to a bifunctional enzyme-catalyzed synergetic catalyst, and a preparation method and application thereof, and belongs to the technical field of photocatalysis and biocatalysis.
Background
Currently, in the face of increasingly serious problems of energy shortage and environmental pollution, new technologies and efficient processes are considered as effective means for solving environmental problems. As a key factor of green chemistry, the improvement of catalytic efficiency is receiving wide attention. The cooperative catalysis is an efficient, environment-friendly and sustainable chemical synthesis strategy, and reaction substrates can be activated by different active sites at the same time, so that the reaction energy barrier is obviously reduced, and the reaction efficiency and selectivity are improved. The synergistic catalyst has two or more different active sites, and is widely applied to photocatalysis, organic catalysis, electrocatalysis, enzyme catalysis and the like. In a photo-enzyme synergistic catalytic system, the photoreaction activity and the enantiomer selective site of the enzyme exist simultaneously, and the asymmetric organic synthesis can be realized by combining the photocatalysis with the enzyme catalysis.
The enzyme is a biomacromolecule catalyst consisting of a linear sequence of amino acids, has excellent catalytic efficiency, chemical enantiomers and regioselectivity, and thus can be used as a biodegradable green biocatalyst in organic synthesis. Currently, enzymes play an important role in the food, medicine and fine chemical industries, and optimization of industrial processes allows enzymes to catalyze and promote biorenewable energy, polymers, and various types of chemistry. In modern biotechnology, which is rapidly developing, multifunctional lipolytic enzymes play an important role, not only being able to be used under mild reaction conditions, but also being able to utilize a variety of substrates.
However, the wide industrial application of enzymes has been limited due to poor stability of enzymes in organic media, lack of long-term stability, and difficulty in recycling. In addition, the development of a concerted catalytic reaction of lipase and visible light photocatalyst is still in the initial stage. Most reactions are usually carried out in organic solvents, which may lead to a loss of activity to varying degrees, and this loss is irreversible. In addition, the photo-enzymatic concerted catalysis reaction is usually carried out in a homogeneous phase, the catalyst has little recyclability, and when the reaction needs to be carried out at high temperature, the enzyme is at risk of inactivation or even denaturation.
As a solution for promoting industrial application of enzymes, immobilization of enzymes on solid supports has received much attention. The solid support is designed to improve the stability and recoverability of the enzyme, thereby reducing the production cost and improving the industrial value. To date, researchers have developed various strategies to improve enzyme stability and have been, in part, successfully applied in the commercial field. Currently, studies on the immobilization of enzymes have been conducted using Metal Organic Framework (MOF) materials as solid supports.
At this stage, various enzyme immobilization strategies on MOFs have been developed, such as surface adsorption and covalent anchoring have been shown to improve the stability of enzymes under harsh chemical conditions, yet are substantially unprotected by MOFs since the enzymes are immobilized on the surface of MOFs. Other strategies such as co-precipitation and biomineralization combine enzyme molecules and MOF precursors in a solvothermal step, with simultaneous crystal growth and enzyme encapsulation processes, but the heterogeneous distribution of enzyme molecules in the composite crystal makes it difficult to explore the direct environment around each enzyme molecule. Thus, by the immobilization strategy of post-synthesis diffusion of enzymes in MOFs, the most obvious benefit is the physical inhibition of enzyme inactivation and denaturation, i.e. prevention of enzyme denaturation upon heating, dehydration or changes in solution ionic strength. Encapsulation also prevents leaching of the enzyme if the size of the enzyme is matched to the MOF pores. In addition, MOFs can be used to construct both organic and photocatalytic active centers. The common visible light photocatalyst is mainly formed by complexing Ru (II) and Ir (III) transition metals with small molecules such as bipyridyl (bpy) and the like, and the Ru (II) -based molecular catalyst can also be introduced into an MOF structure and shows catalytic activity. The MOF can also introduce an active object into structures such as holes or cages, and simultaneously allows a substrate to enter an internal active site, so that not only can actual catalytic application be met, but also higher performance can be endowed to the MOF.
In prior art homogeneous technology systems, organic and biological systems typically use both acid and base catalysts to catalyze the reaction. The development of a single homogeneous system containing both acidic and basic catalytic centers introduces a problem that the acidic and basic components in the homogeneous system neutralize each other, thereby inhibiting the activity of the catalyst. In heterogeneous systems, however, by immobilizing different catalytically active sites on one substrate, not only is independent function maintained, but it also allows for the co-operation or independent catalysis of one or more steps in a reaction sequence. The fixation of an acidic and a basic catalytic phase prevents the two catalysts from physically interacting and neutralizing each other to finally maintain the activity of the multifunctional catalyst. The unique spatial structure and regular arrangement of MOF materials provides an opportunity to build heterogeneous multifunctional catalysts through MOFs.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a bifunctional photocatalyst synergistic catalyst, the second purpose of the invention is to provide a preparation method of the bifunctional photocatalyst synergistic catalyst, and the third purpose of the invention is to provide the application of the bifunctional photocatalyst synergistic catalyst in asymmetric photocatalyst synergistic reaction.
The technical scheme is as follows: the bifunctional photocatalyst is a metal organic framework material Ru-HP-UiO-67-GH, wherein lipase is wrapped inside the bifunctional photocatalyst, the metal organic framework material Ru-HP-UiO-67-GH is bis (2, 2' -bipyridine) - (5, 5' -dicarboxyl-2, 2' -bipyridine) ruthenium chloride is bonded on any one or more edges of a octahedron HP-UiO-67-GH, the octahedron HP-UiO-67-GH is a mesoporous UiO-67-GH structure, and the average pore diameter of mesopores is 8-12 nm.
Furthermore, the average particle size of Ru-HP-UiO-67-GH particles of the metal organic framework material is 500-3000 nm, and the particle size of the particles is the distance between the opposite corners of the regular octahedron. HP in the octahedral HP-UiO-67-GH represents mesopores.
Further, the lipase is porcine pancreas lipase, wheat germ lipase or mucor miehei lipase.
Furthermore, the content of Ru element on the Ru-HP-UiO-67-GH framework of the metal organic framework material is 0.5-1.0 mu mol/mg-1The metal organic framework material Ru-HP-UiO-67-GH coating greaseThe content of lipase is 1-2 mg.mg-1。
Further, the pig pancreatic lipase size is 8nm × 8nm × 25 nm.
The preparation method of the bifunctional photo-enzyme synergistic catalyst comprises the following steps:
(1) using ZrCl4And ligand 4, 4' -biphenyldicarboxylic acid and glacial acetic acid to prepare UiO-67;
(2) using UiO-67 and ligand bpdc- [ NO-2]2Preparing UiO-67-GH, activating the UiO-67-GH in vacuum, and performing heat treatment to obtain HP-UiO-67-GH with a mesoporous structure;
(3) preparing a metal organic framework material Ru-HP-UiO-67-GH by using a mesoporous structure HP-UiO-67-GH and a ligand Ru (II) complex, and activating the metal organic framework material Ru-HP-UiO-67-GH in vacuum;
(4) and (3) wrapping lipase in the activated metal organic framework material Ru-HP-UiO-67-GH to obtain the bifunctional photocatalyst.
Further, the step (3) comprises the following steps:
(3.1) dissolving a mesoporous structure HP-UiO-67-GH and a ligand Ru (II) complex in DMF, and carrying out ultrasonic treatment to obtain a mixture;
(3.2) placing the mixture in a high-pressure reaction kettle, reacting in an oven, centrifugally separating a product, and washing with DMF (dimethyl formamide) and acetone respectively to obtain a metal organic framework material Ru-HP-UiO-67-GH;
(3.3) soaking a metal organic framework material Ru-HP-UiO-67-GH in acetone, and performing vacuum activation;
further, in the step (3.1), the mass ratio of the mesoporous structure HP-UiO-67-GH to the ligand Ru (II) complex is 4: 1-12: 1.
Further, the step (4) comprises the following steps:
dissolving lipase in water to obtain a lipase solution, adding a metal organic framework material Ru-HP-UiO-67-GH into the lipase solution, standing at room temperature, centrifugally separating a product, washing with water, and freeze-drying to obtain the bifunctional photocatalyst.
Furthermore, the mass ratio of the lipase to the metal organic framework material Ru-HP-UiO-67-GH is 2.5: 1-5: 1.
The invention relates to application of a bifunctional photo-enzyme synergistic catalyst in 2-aryl indole and derivatives thereof and asymmetric photo-enzyme synergistic reaction of ketone compounds.
Further, the 2-aryl indole and the derivatives thereof are 2-phenyl indole, 5-bromo-2-phenyl-1H-indole, 5-methyl-2-phenyl-1H-indole, 5-methoxy-2-phenyl-1H-indole, 1-methyl-2-phenyl-1H-indole or 1-chloro-2-phenyl-1H-indole, and the ketone compound is acetone or 2-butanone.
Further, the application of the bifunctional photocatalyst in the asymmetric photocatalyst synergistic reaction of 2-aryl indole and derivatives thereof and ketone compounds comprises the following steps:
(1) mixing 2-aryl indole and its derivatives with bifunctional enzyme-optical synergistic catalyst, and adding ketone compound and ethanol;
(2) at room temperature and O2In the atmosphere, a white light lamp is used for irradiating and reacting;
(3) monitoring the reaction by thin layer chromatography, filtering after the reaction is finished, concentrating the filtrate under vacuum condition, and purifying the residue by column chromatography with petroleum ether/ethyl acetate as eluent to obtain the catalytic product.
Further, in the step (1), the mass ratio of the 2-arylindole and the derivative thereof to the bifunctional photocatalyst is 1.16: 1-5.8: 1, the volume ratio of the ketone compound to the ethanol is 1.5: 1-2.5: 1, and in the step (3), the reaction time is 70-90 hours.
The mechanism of the bifunctional photo-enzyme synergistic catalyst in the asymmetric photo-enzyme synergistic reaction is as follows: the Ru (II) complex can be used as a photosensitizer to be excited into Ru (II) free radicals under the irradiation of visible light, and can complete the photo-oxidation-reduction catalytic cycle under the action of oxygen, and in the process, a substrate 2-phenylindole and derivatives thereof are used as a reduction quencher to be converted into 2-phenyl-3H-indole-3-ketone and derivatives thereof. Then 2-phenyl-3H-indole-3-ketone and derivatives thereof are activated by the active center of lipase in the mesoporous structure HP-UiO-67-GH to form a protonized imine intermediate, and the substrate 2-phenyl indole and derivatives thereof and ketone compounds form acetone anions with an enol group under the action of the active center of the lipase. And finally, attacking the protonated imine intermediate by acetone anions with enol groups to obtain an asymmetric optical enzyme synergistic product.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the average pore diameter of the synthesized mesopore UiO-67 is matched with the size of lipase, so that the problem of enzyme leaching in the immobilization and subsequent reaction processes is solved, and the loss of enzyme activity is reduced.
(2) The invention uses Ru (II) complex to modify the mesopore UiO-67, so that the mesopore UiO-67 is combined with a photocatalysis site, has the property of a visible light photocatalyst and solves the problem of activity loss of the photocatalyst in an organic solvent.
(3) The bifunctional photo-enzyme synergistic catalyst prepared by the invention has good catalytic activity in asymmetric photo-enzyme synergistic reaction.
(4) The bifunctional photo-enzyme synergistic catalyst prepared by the invention has non-homogeneous property, solves the problem of low yield of a homogeneous reaction system, and improves the efficiency of asymmetric photo-enzyme synergistic reaction.
Drawings
FIG. 1 is a schematic structural diagram of a bifunctional photo-enzyme co-catalyst;
FIG. 2 is a powder X-ray diffraction pattern of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH;
FIG. 3 is a scanning electron micrograph of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH;
FIG. 4 is a powder X-ray energy spectrum of Ru-HP-UiO-67-GH;
FIG. 5 is a powder X-ray diffraction pattern of PPL @ Ru-HP-UiO-67-GH;
FIG. 6 is the N of Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH2Adsorption-desorption isotherm diagram;
FIG. 7 is a graph of the pore size distribution of Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
1. Preparation ofligand 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylic acid (bpdc- [ NO)2]2)
(1) 5.00g (18.5mmol) of dimethyl (1,1 '-biphenyl) -4, 4' -dicarboxylate was added to 50mL of concentrated sulfuric acid solution and mixed, and the mixture was stirred at room temperature for 5min to obtain a first mixture. 3mL of nitric acid was added to 6mL of concentrated sulfuric acid and mixed, and then a mixed solution of nitric acid and concentrated sulfuric acid was dropwise added to the first mixture, and dropwise added at room temperature for about 15min to obtain a second mixture. The second mixture was stirred at room temperature for 1.5h, then poured into ice with formation of a beige solid.
(2) The beige solid was collected by vacuum filtration and washed with water to give a beige solid product which wasdimethyl 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylate of the formula:
(3) 2.00g (5.6mmol) ofdimethyl 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylate were dissolved in 50mL of tetrahydrofuran and 50mL of 4% KOH and mixed. The mixture was heated to 60 ℃ overnight. After cooling, the liquid is separated, and the water layer is acidified by concentrated hydrochloric acid to obtain a white solid product. The white solid was collected by vacuum filtration and washed with water to give theunstable ligand 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylic acid (bpdc- [ NO)2]2) The structural formula is as follows:
2. preparation of bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride ([ Ru (bpy))2(5,5’-dcbpy)]Cl2)
(1) 160mg (0.33mmol) of the compound cis-bis (2, 2-bipyridine) ruthenium (II) dichloride and101mg (0.42mmol) of 2,2 '-bipyridine-5, 5' -dicarboxylic acid was added to a mixed solution of ethanol and water (V/V ═ 1:1) in an amount of 20mL, and the mixture was mixed with N2Reflux for 12h and concentrate to give a solid. The solid was recrystallized from 20mL of a mixed solution of methanol and diethyl ether (V/V ═ 1:9) to give ru (ii) as a complex bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride ([ ru (bpy))2(5,5’-dcbpy)]Cl2) The structural formula is as follows:
3. synthesis of UiO-67
67mg of ZrCl were weighed490mg of 4, 4' -Biphenyldicarboxylic acid (H)2bpdc) and 3.0mL of glacial acetic acid in DMF (15mL), and after the mixture was sonicated for 30min, the mixture was transferred to a 50mL Teflon autoclave and reacted in an oven at 120 ℃ for 24 h. The product was cooled to room temperature, purified by centrifugation, and washed with DMF and acetone (3X 10mL) respectively to give UiO-67.
4. Synthesis of UiO-67-GH
120mg of UiO-67 and 60mg of ligand bpdc- [ NO ] were weighed2]2Dissolved in DMF (20 mL). After 30min of ultrasonic treatment, the mixture was placed in a 50mL Teflon autoclave and reacted in an oven at 120 ℃ for 24 h. After ligand exchange, the product was centrifuged and washed with DMF and acetone (3X 10mL), respectively. Then drying for 12h under the vacuum condition of 150 ℃ for activation, and removing the solvent to obtain the activated UiO-67-GH.
5. Synthesis of HP-UiO-67-GH
The activated UiO-67-GH (about 120mg) was placed in a tube furnace and heated at 420 ℃ for 30min under argon. After cooling to room temperature, the product HP-UiO-67-GH is obtained, and the product HP-UiO-67-GH is activated again for 12 hours under the vacuum condition of 150 ℃ to obtain the activated HP-UiO-67-GH.
6. Preparation of Ru-HP-UiO-67-GH
Weighing 120mg of activated HP-UiO-67-GH and 30mg of ligand [ Ru (bpy ]2(5,5’-dcbpy)]Cl2Dissolved in DMF (20 mL). Super-superAfter 30min of sonication, the mixture was transferred to a 50mL Teflon autoclave and reacted in an oven at 120 ℃ for 24 h. And (3) after centrifugal separation, washing the product with DMF and acetone (3X 10mL) respectively to obtain Ru-HP-UiO-67-GH, then soaking the product in acetone for 3 days, and activating the product for 24 hours at 120 ℃ under dynamic vacuum to obtain the activated Ru-HP-UiO-67-GH.
7. Preparation of PPL @ Ru-HP-UiO-67-GH
50mg of porcine pancreatic lipase PPL (Allan, cat. 9001-62-1) was weighed and dissolved in 10mL of deionized water to obtain a 5mg/mL lipase solution. Then 20mg of activated Ru-HP-UiO-67-GH was added to the solution. The mixture was allowed to stand at room temperature for 2 h. Then, the product was centrifuged and washed 3 times with distilled water. And finally, drying by adopting a freeze-drying method to obtain a product PPL @ Ru-HP-UiO-67-GH, wherein the structural schematic diagram is shown in figure 1.
EXAMPLE 2 preparation of PPL @ Ru-HP-UiO-67-GH
1.Ligand 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylic acid (bpdc- [ NO)2]2) Bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride ([ Ru (bpy))2(5,5’-dcbpy)]Cl2) The preparation of UiO-67, UiO-67-GH and HP-UiO-67-GH is the same as in example 1.
2. Preparation of Ru-HP-UiO-67-GH
Weighing 120mg of activated HP-UiO-67-GH and 10mg of ligand [ Ru (bpy ]2(5,5’-dcbpy)]Cl2Dissolved in DMF (20 mL). After 30min of sonication, the mixture was transferred to a 50mL Teflon autoclave and reacted in an oven at 120 ℃ for 24 h. And (3) after centrifugal separation, washing the product with DMF and acetone (3X 10mL) respectively to obtain Ru-HP-UiO-67-GH, then soaking the product in acetone for 3 days, and activating the product for 24 hours at 120 ℃ under dynamic vacuum to obtain the activated Ru-HP-UiO-67-GH.
3. Preparation of PPL @ Ru-HP-UiO-67-GH
50mg of porcine pancreatic lipase PPL (from Aladdin, cat. No. 9001-62-1) was weighed and dissolved in 10mL of deionized water to give a 5mg/mL lipase solution. Then 20mg of activated Ru-HP-UiO-67-GH was added to the solution. The mixture was allowed to stand at room temperature for 2 h. Then, the product was centrifuged and washed 3 times with distilled water. And finally, drying by adopting a freeze-drying method to obtain a product PPL @ Ru-HP-UiO-67-GH.
EXAMPLE 3 preparation of PPL @ Ru-HP-UiO-67-GH
1.Ligand 2,2' -dinitro- (1,1 ' -biphenyl) -4,4 ' -dicarboxylic acid (bpdc- [ NO)2]2) Bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride ([ Ru (bpy))2(5,5’-dcbpy)]Cl2) The preparation of UiO-67, UiO-67-GH, HP-UiO-67-GH and Ru-HP-UiO-67-GH is as in example 1.
2. Preparation of PPL @ Ru-HP-UiO-67-GH
100mg of porcine pancreatic lipase PPL (Allan, cat. 9001-62-1) was weighed and dissolved in 10mL of deionized water to obtain a 10mg/mL lipase solution. Then 20mg of activated Ru-HP-UiO-67-GH was added to the solution. The mixture was allowed to stand at room temperature for 2 h. Then, the product was centrifuged and washed 3 times with distilled water. And finally, drying by adopting a freeze-drying method to obtain a product PPL @ Ru-HP-UiO-67-GH.
EXAMPLE 4 determination of the Ru element content on the Ru-HP-UiO-67-GH skeleton of the Metal-organic framework Material
The content of Ru element on the framework of the Ru-HP-UiO-67-GH metal organic framework material obtained in the example 1 is tested by adopting an inductively coupled plasma mass spectrometer (ICP), and the content of Ru element on the framework of the Ru-HP-UiO-67-GH metal organic framework material obtained in the example 1 is 0.5 mu mol/mg-1。
EXAMPLE 5 determination of the content of Ru-HP-UiO-67-GH-Encapsulated Lipase, a Metal organic framework Material
The product PPL @ Ru-HP-UiO-67-GH obtained in example 1 is subjected to lipase content determination by using a microplate reader. At an absorbance value at 595nm, 100. mu.L of the residual enzyme solution and 900. mu.L of deionized water were added to 5mL of Coomassie Brilliant blue solution. Measuring the absorbance value of the supernatant at 595nm after developing for several minutes, comparing with the standard enzyme content, and obtaining the metal organic framework material Ru-HP-UiO-67-GH with the content of 1.45 mg.mg.mg of the encapsulated lipase obtained in example 1-1。
Example 6 powder X-ray diffraction of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH
The powder X-ray diffraction results of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH obtained in example 1 are shown in FIG. 2, and FIG. 2 is a powder X-ray diffraction pattern of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH, wherein the curve shown by Simmulated is the simulation result of powder X-ray diffraction of UiO-67. As can be seen from FIG. 2, in the range of 5-10degrees 2 theta, characteristic peaks of the UiO-67-GH, the HP-UiO-67-GH, the Ru-HP-UiO-67-GH and the PPL @ Ru-UiO-67-GH all appear in the structure of the UiO-67, which shows that the prepared UiO-67-GH has excellent crystallinity, the HP-UiO-67-GH maintains the crystallinity during the heat treatment ligand removal process, the Ru-HP-UiO-67-GH maintains the crystallinity, and the PPL @ Ru-HP-UiO-67-GH maintains the crystallinity during the enzyme immobilization process.
Example 7 Electron microscopy scanning of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH
Scanning with an electron microscope was performed on the UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH obtained in example 1, and the results are shown in FIG. 3. FIG. 3 is a scanning electron microscope image of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH, wherein a is UiO-67-GH, b is HP-UiO-67-GH, c is Ru-HP-UiO-67-GH, and d is PPL @ Ru-HP-UiO-67-GH. As can be seen from FIG. 3, UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH all show octahedral or near-octahedral forms with complete structures, the average particle diameters of the particles of UiO-67-GH, HP-UiO-67-GH, Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH are respectively 1000nm, 1000nm and 2000nm, and the three-dimensional structures are maintained when the particles are not collapsed in the experimental process.
EXAMPLE 8Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH powder X-ray Spectroscopy
The Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH obtained in example 1 were subjected to X-ray energy spectrum analysis, and an X-ray energy spectrum analysis image of the Ru-HP-UiO-67-GH is shown in FIG. 4. FIG. 4 is a powder X-ray energy spectrum of Ru-HP-UiO-67-GH, wherein a is the Ru-HP-UiO-67-GH energy spectrum analysis region, b is Zr element in Ru-HP-UiO-67-GH, c is O element in Ru-HP-UiO-67-GH, and d is Ru element in Ru-HP-UiO-67-GH. As can be seen from FIG. 4, in the region where Ru-HP-UiO-67-GH exists, the zirconium element shown in FIG. 4b and the ruthenium element shown in FIG. 4d are well dispersed on the solid surface, indicating that the modified form has uniform structural and chemical properties, and also indicating that the Ru complex is successfully exchanged as a ligand to the bone structure, rather than simply entering the pores of Ru-HP-UiO-67-GH. The powder X-ray diffraction pattern of PPL @ Ru-HP-UiO-67-GH is shown in FIG. 5. FIG. 5 is a powder X-ray diffraction pattern for PPL @ Ru-HP-UiO-67-GH, wherein a is the energy spectrum analysis region for PPL @ Ru-HP-UiO-67-GH, b is the Zr element in PPL @ Ru-HP-UiO-67-GH, c is the O element in PPL @ Ru-HP-UiO-67-GH, d is the Ru element in PPL @ Ru-HP-UiO-67-GH, and e is the S element in PPL @ Ru-HP-UiO-67-GH. As can be seen from FIG. 5, the existence of a skeleton structure in which Zr and O elements are PPL @ Ru-HP-UiO-67-GH is shown in FIGS. 5b and 5c, and the uniform distribution of Ru element in FIG. 5d demonstrates that the Ru complex successfully exchanges with 4, 4-biphenyldicarboxylic acid as a ligand and that there is no leaching of the Ru complex after lipase immobilization. The homogeneous distribution of the S element in FIG. 5e demonstrates the successful immobilization of the lipase.
Example 9 Nitrogen adsorption-desorption testing of Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH
Nitrogen adsorption-desorption tests of the samples Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH before and after the immobilized enzyme obtained in example 1 showed the results shown in Table 1, FIG. 6 and FIG. 7, respectively.
Table 1 nitrogen adsorption-desorption test results of samples before and after immobilization of enzyme
As can be seen from Table 1, the N of the composite PPL @ Ru-HP-UiO-67-GH after immobilization of the lipase PPL2The absorption capacity is obviously lower than that of a supporting material Ru-HP-UiO-67-GH, Brunauer-Emmet-Teller (BET) specific surface area is reduced from 294.0 to 34.8m2Pore volume decreased from 0.119633 to 0.014540cm3Per g, it was confirmed that the lipase entered the pore structure of Ru-HP-UiO-67-GH.
FIG. 6 is the N of Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH2Adsorption-desorption isotherm diagram, as shown in FIG. 6It is known that both Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH show typical type IV isotherms, which indicates that a mesoporous structure exists in the sample Ru-HP-UiO-67-GH before immobilization, and a mesoporous structure without lipase encapsulation may exist in the sample PPL @ Ru-HP-UiO-67-GH after immobilization, so that the sample shows the type IV isotherm.
FIG. 7 is a graph of the pore size distribution of Ru-HP-UiO-67-GH and PPL @ Ru-HP-UiO-67-GH, from which FIG. 7 it can be seen that there is a distinct peak at 10nm for Ru-HP-UiO-67-GH, while in the pore size distribution of PPL @ Ru-HP-UiO-67-GH, the peak at 10nm disappears and only a small peak appears at 1-2nm, indicating that there is a mesoporous structure within the Ru-HP-UiO-67 material and a pore size of 10nm, whereas the mesopore of PPL @ Ru-HP-UiO-67-GH disappears and only remains, indicating that PPL is located within the structure of Ru-HP-UiO-67-GH.
Example 10 asymmetric Photoenzymic synergy of different 2-Arylindoles and derivatives thereof
1. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
2. 81.0mg of 5-bromo-2-phenyl-1H-indole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. Eluting with petroleum ether/ethyl acetate (20:1-5:1) by column chromatography on silica gelThe residue was purified to give the catalytic product (S) -5-bromo-2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
3. 61.8mg of 5-methyl-2-phenyl-1H-indole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -5-bromo-2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
4. 66.6mg of 5-methoxy-2-phenyl-1H-indole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -5-methoxy-2- (2-oxopropyl) -2-phenylindol-3-one. The e.e. values were determined using high performance liquid chromatography with a Chiralcel OD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e. values of the resulting product are shown in table 2.
5. 61.8mg of 1-methyl-2-phenyl-1H-indole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. Reaction ofAfter completion, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2- (p-tolyl) indol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
6. 67.8mg of 1-chloro-2-phenyl-1H-indole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (4-chlorophenyl) -2- (2-oxopropyl) indol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
7. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed out, 2.4mL of 2-butanone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (3-oxobutanone-2-yl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H chromatography column. Wherein the chiral column and liquid phase conditions used and the e.e.% values of the resulting product are shown in table 2.
Table 2 e.e.% values of the product of the synergistic reaction of asymmetric photo-enzymes and its hplc conditions
As can be seen from table 2, the e.e.% values of the products show different results due to the influence of the location and electronic properties. 5-bromo-2-phenyl-1H-indole, 1-chloro-2-phenyl-1H-indole have electron withdrawing groups, and the catalytic products (S) -5-bromo-2- (2-oxopropyl) -2-phenylindol-3-one, and (S) -2- (4-chlorophenyl) -2- (2-oxopropyl) indol-3-one have higher e.e.% values than the catalytic products obtained with 5-methyl-2-phenyl-1H-indole and 5-methoxy-2-phenyl-1H-indole, 1-methyl-2-phenyl-1H-indole. The (S) -2- (4-chlorophenyl) -2- (2-oxopropyl) indol-3-one obtained by reacting 2-phenylindole with 2-butanone has a lower e.e.% value due to its greater steric hindrance. Therefore, the bifunctional photo-enzyme synergistic catalyst has a certain application range to asymmetric photo-enzyme synergistic reaction.
Example 11 comparative experiment of asymmetric photo-enzyme synergistic reaction under different experimental conditions
1. The test method comprises the following steps: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
2. Unencapsulated lipase assay: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27mmol) and 1mL of ethanol are added to the mixtureRoom temperature and O2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
3. Experiment of non-bonded Ru element: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ HP-UiO-67-GH were taken, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled to room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
4、N2In place of O2Experiment: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under N2Atmosphere (N)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
5. Air instead of O2Experiment: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed and 2m of this was addedL acetone (27mmol) and 1mL ethanol were reacted at room temperature under an air atmosphere with a 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
6. Experiments in the dark: 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon) for 70 h. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% values were determined by high performance liquid chromatography with a ChiralpakAD-H column, the results of which are shown in table 3.
TABLE 3 product of the synergistic reaction of asymmetric photo-enzymes under different conditions
| No. | Change of conditions | Yield/%) | e.e./％ |
| 1 | PPL@Ru-HP-UiO-67-GH | 27 | 93 |
| 2 | Ru-HP-UiO-67-GH instead of PPL @ Ru-HP-UiO-67-GH | N.R. | -- |
| 3 | PPL@HP-UiO-67-GHPPL@Ru-HP-UiO-67-GH | N.R. | -- |
| 4 | N2Substituted for O2 | N.R. | -- |
| 5 | Substitution of air for O2 | trace | -- |
| 6 | Under dark conditions | N.R. | -- |
As can be seen from table 3, the yield of the product was 27% and the e.e.% value was 93% without changing the reaction conditions. No reaction was observed with Ru-HP-UiO-67-GH and PPL @ HP-UiO-67-GH as catalysts, i.e.in the absence of the lipase PPL or Ru complex. Reaction in N2When carried out under an atmosphere, no product was detected, and when the reaction was carried out under an air atmosphere, only slight reaction was obtainedAmount of product, and when the reaction was carried out in the dark, no product was detected as well. As shown above, irradiation with visible light, photocatalyst, Lipase PPL and O2Plays a crucial role in the asymmetric photo-enzyme synergistic reaction.
Example 12 asymmetric Photoenzymic concerted reaction of 2-phenylindole with acetone
1. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 10mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel with petroleum ether/ethyl acetate (20:1-5:1) eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H column, which was 46% for the e.e.% value. The yield was 5%.
2. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 50mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (27mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H column, which has an e.e.% value of 34%. The yield was 14%.
3. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 1.5mL of acetone (20mmol) and 1mL of ethanol were added, and the mixture was cooled to room temperature and O2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was in vacuoConcentrate under air. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H column, which was 78% for the e.e.% value. The yield was 19%.
4. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2.5mL of acetone (34mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure of O2Atmosphere (O)2Balloon), the reaction was irradiated with 36W fluorescent lamp for 70 hours. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H column, which was 38% for the e.e.% value. The yield was 25%.
5. 58.0mg of 2-phenylindole (0.3mmol, 1.0eq) and 20mg of PPL @ Ru-HP-UiO-67-GH were weighed in, 2mL of acetone (34mmol) and 1mL of ethanol were added, and the mixture was cooled at room temperature under reduced pressure2Atmosphere (O)2Balloon) and the reaction was performed for 90 hours by irradiation with a 36W fluorescent lamp. The reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was removed from the reaction mixture by filtration and the organic phase was concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product (S) -2- (2-oxopropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H column, which was 56% for the e.e.% value. The yield was 28%.
Comparative example 1 comparative experiment with prior art asymmetric photo-enzyme synergistic reaction
58.0mg of 2-phenylindole (0.3mmol, 1.0eq), 29mg of PPL, 5mg of Ru (bpy)3Cl2·6H2O, 2mL of acetone (27mmol) and 1mL of ethanol were added thereto at room temperature under the action of O2Atmosphere (O)2Balloon), a 36W fluorescent lamp is used for lightingCarrying out injection reaction for 70 h. The reaction was monitored by thin layer chromatography. After completion of the reaction, 10mL of ethyl acetate was added, and the mixture was washed with water. Organic phase in anhydrous Na2SO4Dried, filtered and concentrated under vacuum. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (20:1-5:1) as eluent to give the catalytic product. The e.e.% value was determined using high performance liquid chromatography with a ChiralpakAD-H chromatography column. The results, which compare the yield and e.e.% value of the product (S) -2- (2-oxopropyl) -2-phenylindol-3-one of example 1, are shown in table 4.
TABLE 4 comparison of the results of the homogeneous and heterogeneous asymmetric photo-enzyme synergistic reaction
| Name (R) | Reaction system | Yield/%) | e.e./％ |
| Example 1 | Heterogeneous phase | 27 | 93 |
| Comparative example 1 | 9 | 97 |
As can be seen from Table 4, the heterogeneous reaction catalyzed by PPL @ Ru-HP-UiO-67-GH gave the product (S) -2- (2-oxopropyl) -2-phenylindoleThe yield of-3-one was 27%, while lipase and Ru (bpy)3Cl2·6H2The yield of the O co-catalyzed homogeneous reaction is only 9%. In addition, the heterogeneous reaction product had an e.e.% value of 93%, similar to the homogeneous reaction. The result shows that the immobilized enzyme PPL @ Ru-HP-UiO-67-GH can simultaneously play the dual functions of a visible light photocatalyst and an enzyme catalyst.
Claims (12)
1. The bifunctional photocatalyst is characterized in that a metal organic framework material Ru-HP-UiO-67-GH is internally wrapped by lipase, the metal organic framework material Ru-HP-UiO-67-GH is bis (2, 2' -bipyridine) - (5, 5' -dicarboxyl-2, 2' -bipyridine) ruthenium chloride is bonded on any one or more edges of a octahedron HP-UiO-67-GH, the octahedron HP-UiO-67-GH is of a mesoporous UiO-67-GH structure, and the average pore diameter of mesopores is 8-12 nm.
2. The bifunctional photo-enzyme synergistic catalyst as claimed in claim 1, wherein the lipase is porcine pancreatic lipase, wheat germ lipase or mucor miehei lipase.
3. The bifunctional photo-enzyme synergistic catalyst as claimed in claim 1, wherein the content of Ru element in the Ru-HP-UiO-67-GH skeleton of the metal-organic skeleton material is 0.5-1.0 μmol-mg-1The content of the metal organic framework material Ru-HP-UiO-67-GH coated lipase is 1-2 mg.mg-1。
4. The method for preparing the bifunctional photo-enzyme co-catalyst as claimed in claim 1, comprising the steps of:
(1) using ZrCl4And ligand 4, 4' -biphenyldicarboxylic acid and glacial acetic acid to prepare UiO-67;
(2) using UiO-67 and ligand bpdc- [ NO-2]2Preparing UiO-67-GH, activating the UiO-67-GH in vacuum, and performing heat treatment to obtain HP-UiO-67-GH with a mesoporous structure;
(3) preparing a metal organic framework material Ru-HP-UiO-67-GH by using a mesoporous structure HP-UiO-67-GH and a ligand Ru (II) complex, and activating the metal organic framework material Ru-HP-UiO-67-GH in vacuum;
(4) and (3) wrapping lipase in the activated metal organic framework material Ru-HP-UiO-67-GH to obtain the bifunctional photocatalyst.
5. The method for preparing the bifunctional photo-enzyme co-catalyst according to claim 4, wherein the step (3) comprises the following steps:
(3.1) dissolving a mesoporous structure HP-UiO-67-GH and a ligand Ru (II) complex in DMF, and carrying out ultrasonic treatment to obtain a mixture;
(3.2) placing the mixture in a high-pressure reaction kettle, reacting in an oven, centrifugally separating a product, and washing with DMF (dimethyl formamide) and acetone respectively to obtain a metal organic framework material Ru-HP-UiO-67-GH;
(3.3) soaking a metal organic framework material Ru-HP-UiO-67-GH in acetone, and activating in vacuum.
6. The preparation method of the bifunctional photo-enzyme co-catalyst according to claim 5, wherein in the step (3.1), the mass ratio of the mesoporous structure HP-UiO-67-GH to the ligand Ru (II) complex is 4: 1-12: 1.
7. The method for preparing the bifunctional photo-enzyme co-catalyst according to claim 4, wherein the step (4) comprises the following steps:
dissolving lipase in water to obtain a lipase solution, adding a metal organic framework material Ru-HP-UiO-67-GH into the lipase solution, standing at room temperature, centrifugally separating a product, washing with water, and freeze-drying to obtain the bifunctional photocatalyst.
8. The preparation method of the bifunctional photo-enzyme synergistic catalyst according to claim 7, wherein the mass ratio of the lipase to the metal-organic framework material Ru-HP-UiO-67-GH is 2.5: 1-5: 1.
9. The use of the bifunctional enzyme photocatalyst of claim 1 in the asymmetric enzyme-catalyzed reaction of 2-arylindoles and derivatives thereof with ketones.
10. The use according to claim 9, wherein the 2-arylindole and its derivatives are 2-phenylindole, 5-bromo-2-phenyl-1H-indole, 5-methyl-2-phenyl-1H-indole, 5-methoxy-2-phenyl-1H-indole, 1-methyl-2-phenyl-1H-indole or 1-chloro-2-phenyl-1H-indole, and the ketone compound is acetone or 2-butanone.
11. The use of claim 9, characterized by the steps of:
(1) mixing 2-aryl indole and its derivatives with bifunctional enzyme-optical synergistic catalyst, and adding ketone compound and ethanol;
(2) at room temperature and O2In the atmosphere, a white light lamp is used for irradiating and reacting;
(3) monitoring the reaction by thin layer chromatography, filtering after the reaction is finished, concentrating the filtrate under vacuum condition, and purifying the residue by column chromatography with petroleum ether/ethyl acetate as eluent to obtain the catalytic product.
12. The use of claim 9, wherein in step (1), the mass ratio of the 2-arylindole and the derivative thereof to the bifunctional photo-enzyme synergistic catalyst is 1.16:1 to 5.8:1, the volume ratio of the ketone compound to the ethanol is 1.5:1 to 2.5:1, and in step (3), the reaction time is 70 to 90 hours.
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| CN114632551A (en)* | 2022-02-22 | 2022-06-17 | 东南大学 | A kind of bifunctional chiral catalyst and its preparation method and application |
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| CN114736895A (en)* | 2022-03-21 | 2022-07-12 | 中南林业科技大学 | Method for preparing immobilized enzyme by using UiO-66 metal organic framework |
| CN114736895B (en)* | 2022-03-21 | 2024-04-02 | 中南林业科技大学 | A method for preparing immobilized enzymes using UiO-66 metal-organic frameworks |
| CN114534791A (en)* | 2022-03-24 | 2022-05-27 | 东南大学 | Multifunctional heterogeneous catalyst and preparation method and application thereof |
| CN114534791B (en)* | 2022-03-24 | 2023-11-03 | 东南大学 | Multifunctional heterogeneous catalyst and preparation method and application thereof |
| CN116083411A (en)* | 2023-03-23 | 2023-05-09 | 北京理工大学 | Heterogeneous photo-enzyme coupling catalyst, preparation method and application thereof |
| CN117399071A (en)* | 2023-09-20 | 2024-01-16 | 东南大学 | Chiral bifunctional catalyst UiO-67-Pro-Ru and preparation method and application thereof |
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