CN113201526B - Difunctional photo-enzyme synergistic catalyst and preparation method and application thereof - Google Patents

Difunctional photo-enzyme synergistic catalyst and preparation method and application thereof Download PDF

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CN113201526B
CN113201526B CN202110404230.4A CN202110404230A CN113201526B CN 113201526 B CN113201526 B CN 113201526B CN 202110404230 A CN202110404230 A CN 202110404230A CN 113201526 B CN113201526 B CN 113201526B
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indole
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CN113201526A (en
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程林
张成龙
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Southeast University
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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    • C12N9/14—Hydrolases (3)
    • C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
    • C12N9/18—Carboxylic ester hydrolases (3.1.1)
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Abstract

The invention discloses a bifunctional photo-enzyme synergistic catalyst and a preparation method and application thereof, wherein the preparation method of the bifunctional photo-enzyme synergistic catalyst comprises the steps of utilizing an unstable ligand to modify a metal-organic framework material through ligand exchange, then removing the unstable ligand through a heat treatment process to obtain a mesoporous metal-organic framework material, and then utilizing the photo-catalyst to modify the mesoporous metal-organic framework material through ligand exchange to obtain the mesoporous metal-organic framework material with photocatalytic performance; and then wrapping the lipase inside the mesoporous metal organic framework material with photocatalytic performance. The bifunctional photo-enzyme synergistic catalyst can be used for catalyzing asymmetric photo-enzyme synergistic reaction of 2-aryl indole and derivatives and ketone compounds. The bifunctional photo-enzyme synergistic catalyst has heterogeneity, namely photo-catalytic property and enzyme catalytic property, and improves the catalytic efficiency of the enzyme.

Description

Difunctional photo-enzyme synergistic catalyst and preparation method and application thereof
Technical Field
The invention relates to a bifunctional photo-enzyme synergistic catalyst, a preparation method and application thereof, and belongs to the technical field of photocatalysis and biocatalysis.
Background
Currently, new technologies and efficient processes are considered as effective means for solving environmental problems, facing increasingly serious problems of energy shortage and environmental pollution. As a key factor of green chemistry, improvement of catalytic efficiency has been receiving a great deal of attention. Synergistic catalysis is a high-efficiency, environment-friendly and sustainable chemical synthesis strategy, and reaction substrates can be simultaneously activated by different active sites, 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 the photo-enzyme synergistic catalytic system, photo-reaction activity and enzyme enantioselective sites exist simultaneously, and asymmetric organic synthesis can be realized by combining photocatalysis and enzyme catalysis.
The enzyme is a biological macromolecular catalyst composed of linear sequences of amino acids, has excellent catalytic efficiency, chemical enantiomer and regioselectivity, and can be used as a biodegradable green biological catalyst in organic synthesis. Currently, enzymes play an important role in the food, pharmaceutical and fine chemicals industries, and the optimization of industrial processes allows enzymes to catalyze the promotion of renewable energy sources, polymers, and various types of chemistry. In the rapidly developing modern biotechnology, multifunctional lipolytic enzymes play an important role, not only in mild reaction conditions, but also with a variety of substrates.
However, the enzyme has a limited wide range of industrial applications due to its poor stability in organic media, lack of long-term stability, and difficulty in recycling. In addition, the development of the synergistic catalytic reaction of lipase and visible light photocatalyst is still in the initiation stage. Most reactions are usually carried out in organic solvents, which may lead to a different degree of loss of activity of both, and this loss is irreversible. In addition, the photo-enzymatic co-catalytic reaction is usually carried out in a homogeneous phase, the catalyst is hardly recyclable, and the enzyme is at risk of deactivation or even denaturation when the reaction needs to be carried out at high temperature.
As a solution to promote industrial application of enzymes, immobilization of enzymes on solid supports has received a great deal of attention. The design of the solid support can improve the stability and the recyclability 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 partially successfully applied in the commercial field. Currently, metal Organic Framework (MOF) materials have been studied for immobilization of enzymes as solid supports.
At this stage, immobilization strategies for various enzymes on MOFs, such as surface adsorption and covalent anchoring, have been developed, which have been demonstrated to improve the stability of the enzyme under harsh chemical conditions, however, since the enzyme is immobilized on the surface of the MOF, it is essentially unprotected by the MOF. Other strategies such as co-precipitation and biomineralization, where enzyme molecules and MOF precursors are combined in a solvothermal step, with simultaneous crystal growth and enzyme encapsulation processes, however, the uneven distribution of enzyme molecules in the composite crystal makes it difficult to explore the immediate environment around each enzyme molecule. Thus, by the immobilization strategy of the post-synthetic diffusion of the enzyme in the MOF, 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 ionic strength of the solution. Encapsulation also prevents leaching of the enzyme if the size of the enzyme matches the MOF pore size. In addition, MOFs can be used to build up organic catalytic and photocatalytic active sites. Common visible light photocatalysts are mainly formed by complexing Ru (II) and Ir (III) transition metals with small molecules such as bipyridine (bpy) and the like, and molecular catalysts based on Ru (II) can also be introduced into MOF structures and show catalytic activity. The MOF can also introduce active objects into structures such as holes or cages, and the like, and simultaneously allows substrates to enter internal active sites, so that the MOF not only can meet the practical catalytic application, but also can endow the MOF with higher performance.
In prior art homogeneous 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 acid and basic catalytic centers introduces the problem that the acid component and the basic component in the homogeneous system are mutually neutralized, thereby inhibiting the activity of the catalyst. However, in heterogeneous systems, by immobilizing different catalytically active sites on a substrate, not only is the independent function maintained, but also the cooperative or independent catalysis of one or more steps in a reaction sequence is allowed. Fixing an acidic and basic catalytic site prevents the two catalysts from physically interacting and neutralizing each other to ultimately maintain the activity of the multifunctional catalyst. The unique spatial structure and regular arrangement of the MOF materials provides opportunities for constructing heterogeneous multifunctional catalysts by MOF.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a bifunctional photo-enzyme synergistic catalyst, the second object of the invention is to provide a preparation method of the bifunctional photo-enzyme synergistic catalyst, and the third object of the invention is to provide the application of the bifunctional photo-enzyme synergistic catalyst in asymmetric photo-enzyme synergistic reaction.
The technical scheme is as follows: the bifunctional photo-enzyme synergistic catalyst is a metal organic framework material Ru-HP-UiO-67-GH internally wrapped with lipase, the metal organic framework material Ru-HP-UiO-67-GH is bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride bonded on any one or more edges of an regular octahedron HP-UiO-67-GH, the regular octahedron HP-UiO-67-GH is a medium-pore UiO-67-GH structure, and the average pore diameter of the medium pores is 8-12 nm.
Further, 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 angles of the regular octahedron. HP in the regular octahedron HP-UiO-67-GH represents mesopores.
Further, the lipase is porcine pancreatic lipase, wheat germ lipase or Mucor miehei lipase.
Further, the Ru element content of the metal organic framework material Ru-HP-UiO-67-GH framework is 0.5-1.0 mu mol.mg -1 The content of the Ru-HP-UiO-67-GH coated lipase of the metal organic framework material is 1-2 mg.mg -1 。
Further, the porcine pancreatic lipase size was 8nm×8nm×25nm.
The preparation method of the bifunctional photo-enzyme synergistic catalyst comprises the following steps:
(1) By ZrCl 4 And ligand 4,4' -biphthalic acid and glacial acetic acid to prepare UiO-67;
(2) Using UiO-67 and ligand bpdc- [ NO 2 ] 2 Preparing UiO-67-GH, vacuum activating the UiO-67-GH, and performing heat treatment to obtain a mesoporous structure HP-UiO-67-GH;
(3) Preparing a metal organic framework material Ru-HP-UiO-67-GH by using a mesoporous structure HP-UiO-67-GH and ligand Ru (II) complex, and vacuum-activating the metal organic framework material Ru-HP-UiO-67-GH;
(4) And wrapping lipase in the activated metal organic framework material Ru-HP-UiO-67-GH to prepare the bifunctional photo-enzyme synergistic catalyst.
Further, the step (3) includes the following steps:
(3.1) dissolving the intermediate pore structure HP-UiO-67-GH and ligand Ru (II) complex in DMF, and carrying out ultrasonic treatment to obtain a mixture;
(3.2) placing the mixture into a high-pressure reaction kettle, reacting in a baking oven, centrifugally separating a product, and washing the product with DMF and acetone respectively to obtain a metal organic framework material Ru-HP-UiO-67-GH;
(3.3) soaking the metal organic framework material Ru-HP-UiO-67-GH in acetone, and vacuum activating;
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) includes 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, centrifuging the product, washing with water, and freeze-drying to obtain the bifunctional photo-enzyme synergistic catalyst.
Further, 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 an application of a bifunctional photo-enzyme synergistic catalyst in asymmetric photo-enzyme synergistic reaction of 2-aryl indole and derivatives thereof and ketone compounds.
Further, the 2-aryl indole and the derivative 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 photo-enzyme synergistic catalyst in the asymmetric photo-enzyme synergistic reaction of 2-aryl indole and derivatives thereof and ketone compounds comprises the following steps:
(1) Mixing 2-aryl indole and its derivative with bifunctional photo-enzyme synergistic catalyst, and adding ketone compound and ethanol;
(2) At room temperature and O 2 Under the atmosphere, using a white light lamp to irradiate and react;
(3) Monitoring the reaction by adopting a thin layer chromatography, filtering after the reaction is finished, concentrating the filtrate under a vacuum condition, and purifying the residue by using a column chromatography by taking petroleum ether/ethyl acetate as an eluent to obtain a catalytic product.
Further, in the step (1), the mass ratio of the 2-aryl indole and the derivative thereof to the bifunctional photo-enzyme synergistic catalyst 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 h.
The mechanism of the bifunctional photo-enzyme synergistic catalyst in the asymmetric photo-enzyme synergistic reaction: ru (II) complexes can be excited as Ru (II) free radicals under irradiation of visible light as photosensitizers, and complete photooxidation-reduction catalytic cycle under the action of oxygen, in the process, substrate 2-phenylindole and derivatives thereof are converted into 2-phenyl-3H-indol-3-one and derivatives thereof as reduction quenchers. Subsequently, the 2-phenyl-3H-indol-3-one and the derivative thereof are activated by the active center of the lipase in the mesoporous structure HP-UiO-67-GH to form a protonic imine intermediate, and the substrate 2-phenylindole and the derivative thereof and the ketone compound form an acetonyl anion with an enol group under the action of the active center of the lipase. Finally, the acetone anion with enol groups attacks the protonated imine intermediate to obtain an asymmetric photo-enzyme synergistic product.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The average pore diameter of the synthesized mesoporous UiO-67 is matched with the size of lipase, so that the problems of immobilization and enzyme leaching in the subsequent reaction process are solved, and the loss of enzyme activity is reduced.
(2) The invention uses Ru (II) complex to modify the mesoporous UiO-67, so that the mesoporous UiO-67 combines 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 prepared bifunctional photo-enzyme synergistic catalyst has good catalytic activity in asymmetric photo-enzyme synergistic reaction.
(4) The prepared bifunctional photo-enzyme synergistic catalyst has heterogeneity, 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 diagram of a bifunctional photo-enzyme co-catalyst structure;
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 microscope image 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 N of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH 2 Adsorption-desorption isotherm plot;
FIG. 7 shows pore size distribution plots of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
1. Preparation of ligand 2,2' -dinitro- (1, 1' -biphenyl) -4,4' -dicarboxylic acid (bpdc- [ NO) 2 ] 2 )
(1) 5.00g (18.5 mmol) 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 the mixed solution of nitric acid and concentrated sulfuric acid was added dropwise to the first mixture at room temperature for about 15min, to obtain a second mixture. The second mixture was stirred at room temperature for 1.5h and then poured into ice with a beige solid.
(2) The off-white solid was collected by vacuum filtration and washed with water to give the off-white solid product as dimethyl 2,2' -dinitro- (1, 1' -biphenyl) -4,4' -dicarboxylate of the formula:
(3) 2.00g (5.6 mmol) of dimethyl 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. Cooling, separating liquid, acidifying the water layer with concentrated hydrochloric acid to obtain white solid product. The white solid was collected by vacuum filtration and washed with water to give the labile 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)]Cl 2 )
(1) 160mg (0.33 mmol) of the compound cis-bis (2, 2-bipyridine) ruthenium (II) dichloride and 101mg (0.42 mmol) of 2,2 '-bipyridine-5, 5' -dicarboxylic acid were added to 20mL of a mixed solution of ethanol and water (V/V=1:1), and the mixture was mixed under N 2 Reflux 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) complex as bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride ([ Ru (bpy) ] 2 (5,5’-dcbpy)]Cl 2 ) The structural formula is as follows:
3. synthesis of UiO-67
67mg of ZrCl was weighed out 4 90mg of 4,4' -biphthalic acid (H) 2 bpdc) and 3.0mL of glacial acetic acid were dissolved in DMF (15 mL), 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 24h. After cooling the product to room temperature, it was purified by centrifugation and washed with DMF and acetone (3X 10 mL), respectively, to give UiO-67.
4. Synthesis of UiO-67-GH
120mg of UiO-67 and 60mg of ligand bpdc- [ NO were weighed out 2 ] 2 Dissolved in DMF (20 mL). After sonication for 30min, the mixture was placed in a 50mL polytetrafluoroethylene autoclave and reacted in an oven at 120℃for 24h. After ligand exchange, the product was centrifuged and washed with DMF and acetone (3X 10 mL), respectively. Drying at 150deg.C under vacuum for 12 hr for activation, and removing solvent to obtain activated UiO-67-GH.
5. Synthesis of HP-UiO-67-GH
The activated UiO-67-GH (about 120 mg) was placed in a tube furnace and heated for 30min at 420℃in an argon atmosphere. After cooling to room temperature, the product HP-UiO-67-GH is obtained, and is subjected to vacuum at 150 ℃ for activating again for 12 hours, so that the activated HP-UiO-67-GH is obtained.
6. Preparation of Ru-HP-UiO-67-GH
120mg of activated HP-UiO-67-GH and 30mg of ligand [ Ru (bpy) were weighed out 2 (5,5’-dcbpy)]Cl 2 Dissolved in DMF (20 mL). After sonication for 30min, the mixture was transferred to a 50mL polytetrafluoroethylene autoclave and reacted in an oven at 120℃for 24h. After centrifugal separation, washing the product with DMF and acetone (3X 10 mL) respectively to obtain Ru-HP-UiO-67-GH, soaking the product in acetone for 3 days, and activating the product under dynamic vacuum at 120 ℃ for 24 hours to obtain activated Ru-HP-UiO-67-GH.
7. Preparation of PPL@Ru-HP-UiO-67-GH
50mg of porcine pancreatic lipase PPL (Aladin, cat# 9001-62-1) was weighed out and dissolved in 10mL of deionized water to obtain a lipase solution of 5 mg/mL. 20mg of activated Ru-HP-UiO-67-GH were then added to the solution. The mixture was allowed to stand at room temperature for 2h. The product was then centrifuged and washed 3 times with distilled water. Finally, the product PPL@Ru-HP-UiO-67-GH is obtained by adopting a freeze drying method for drying, and 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)]Cl 2 ) Preparation of UiO-67, uiO-67-GH and HP-UiO-67-GH was as in example 1.
2. Preparation of Ru-HP-UiO-67-GH
120mg of activated HP-UiO-67-GH and 10mg of ligand [ Ru (bpy) were weighed out 2 (5,5’-dcbpy)]Cl 2 Dissolved in DMF (20 mL). After sonication for 30min, the mixture was transferred to a 50mL polytetrafluoroethylene autoclave and reacted in an oven at 120℃for 24h. After centrifugal separation, washing the product with DMF and acetone (3X 10 mL) respectively to obtain Ru-HP-UiO-67-GH, soaking the product in acetone for 3 days, and activating the product under dynamic vacuum at 120 ℃ for 24 hours to obtain activated Ru-HP-UiO-67-GH.
3. Preparation of PPL@Ru-HP-UiO-67-GH
50mg of porcine pancreatic lipase PPL (from Allatin, cat. No. 9001-62-1) was weighed out into 10mL deionized water to give a 5mg/mL lipase solution. 20mg of activated Ru-HP-UiO-67-GH were then added to the solution. The mixture was allowed to stand at room temperature for 2h. The product was then centrifuged and washed 3 times with distilled water. Finally, the product PPL@Ru-HP-UiO-67-GH is obtained by adopting a freeze drying method for drying.
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)]Cl 2 ) Preparation of UiO-67, uiO-67-GH, HP-UiO-67-GH and Ru-HP-UiO-67-GH was as in example 1.
2. Preparation of PPL@Ru-HP-UiO-67-GH
100mg of porcine pancreatic lipase PPL (Aladin, cat# 9001-62-1) was weighed out and dissolved in 10mL of deionized water to obtain a 10mg/mL lipase solution. 20mg of activated Ru-HP-UiO-67-GH were then added to the solution. The mixture was allowed to stand at room temperature for 2h. The product was then centrifuged and washed 3 times with distilled water. Finally, the product PPL@Ru-HP-UiO-67-GH is obtained by adopting a freeze drying method for drying.
Example 4 determination of the content of Ru element on the Metal organic framework Material Ru-HP-UiO-67-GH framework
The Ru element content on the skeleton of the metal organic skeleton material Ru-HP-UiO-67-GH obtained in the example 1 is tested by adopting an inductively coupled plasma mass spectrometer (ICP), and the Ru element content on the skeleton of the metal organic skeleton material Ru-HP-UiO-67-GH obtained in the example 1 is 0.5 mu mol.mg -1 。
Example 5 determination of the content of the Metal organic framework Material Ru-HP-UiO-67-GH coated Lipase
The product PPL@Ru-HP-UiO-67-GH obtained in example 1 was subjected to lipase content measurement by using a microplate reader. Absorbance at 595nm, 100 μl of residual enzyme solution and 900 μl of deionized water were added to 5mL of coomassie brilliant blue solution. After several minutes of color development, the absorbance value of the supernatant at 595nm is measured, and compared with the standard enzyme content, the content of Ru-HP-UiO-67-GH coated lipase which is the metal organic framework material obtained in example 1 is 1.45mg.mg -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
Powder X-ray diffraction was performed on 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. 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 graph shown by Simulised is a simulation result of powder X-ray diffraction of UiO-67. As can be seen from FIG. 2, in the interval of 5-10 degrees 2 theta, the characteristic peaks of the structures UiO-67-GH, HP-UiO-67-GH, ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH all appear, which indicates that the prepared UiO-67-GH has excellent crystallinity, the crystallinity of the HP-UiO-67-GH is maintained during the ligand removal process, the crystallinity of the Ru-HP-UiO-67-GH is maintained, and the crystallinity of the PPL@Ru-HP-UiO-67-GH is maintained during the enzyme immobilization process.
EXAMPLE 7 scanning electron microscopy of UiO-67-GH, HP-UiO-67-GH, ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH
The results of electron microscopic scanning 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. 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 an octahedral or near-octahedral morphology with complete structure, and 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 1000nm, and 2000nm, respectively, and collapse does not occur during the experimental process, so that the three-dimensional structure is maintained.
EXAMPLE 8 powder X-ray Spectrometry analysis of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH
The Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH obtained in example 1 were subjected to X-ray spectroscopy, and an X-ray spectroscopy image of 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 an analysis area of the Ru-HP-UiO-67-GH energy spectrum, 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 is present, 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 Ru complex has uniform structure and chemical properties, and also indicates successful exchange of the Ru complex as a ligand to the bone structure, rather than simple entry into 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 of PPL@Ru-HP-UiO-67-GH, wherein a is a PPL@Ru-HP-UiO-67-GH energy spectrum analysis region, b is a Zr element in PPL@Ru-HP-UiO-67-GH, c is an O element in PPL@Ru-HP-UiO-67-GH, d is a Ru element in PPL@Ru-HP-UiO-67-GH, and e is an S element in PPL@Ru-HP-UiO-67-GH. As can be seen from FIG. 5, the existence of the skeleton structure of PPL@Ru-HP-UIO-67-GH as Zr and O shown in FIG. 5b and FIG. 5c, and the uniform distribution of Ru in FIG. 5d prove that Ru complex is successfully exchanged with 4, 4-diphthalic acid as ligand, and that Ru complex is not leached after lipase immobilization. The uniform distribution of the S element in FIG. 5e demonstrates successful immobilization of the lipase.
EXAMPLE 9 Nitrogen adsorption-Desorption test of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH
Nitrogen adsorption-desorption tests were performed on the samples Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH before and after the immobilized enzyme obtained in example 1, and the results are shown in Table 1, FIG. 6 and FIG. 7, respectively.
TABLE 1 Nitrogen adsorption-Desorption test results of samples before and after immobilized enzyme
As is clear from Table 1, after immobilization of the lipase PPL, the composite material PPL@Ru-HP-UiO-67-GH was N 2 The absorption capacity is obviously lower than that of the supporting material Ru-HP-UiO-67-GH, and the specific surface area of Brunauer-Emmet-Teller (BET) is reduced from 294.0 to 34.8m 2 Per g, the pore volume was reduced from 0.119633 to 0.014540cm 3 And/g, the lipase is proved to enter into the pore structure of Ru-HP-UiO-67-GH.
FIG. 6 is N of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH 2 Adsorption-desorption isotherms As can be seen from FIG. 6, ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH both exhibit typical type IV isotherms, indicating the presence of a mesoporous structure in the pre-immobilization sample Ru-HP-UiO-67-GH, and the possible presence of a pore structure after immobilization that does not encapsulate lipase, resulting in a type IV isotherms.
FIG. 7 shows pore size distribution plots of Ru-HP-UiO-67-GH and PPL@Ru-HP-UiO-67-GH, and it is apparent from FIG. 7 that there is a distinct peak at 10nm and that the peak at 10nm disappears and only a small peak at 1-2nm appears in the pore size distribution plot of Ru-HP-UiO-67-GH, indicating that there is a mesoporous structure within the Ru-HP-UiO-67 material and that the mesopores of the pore size is 10nm and that only micropores remain to be maintained, indicating that PPL is located within the mesoporous structure of Ru-HP-UiO-67-GH.
Example 10 asymmetric photo-enzymatic synergistic reaction of different 2-arylindoles and their derivatives
1. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a chiralpak ad-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
2. 81.0mg of 5-bromo-2-phenyl-1H-indole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
3. 61.8mg of 5-methyl-2-phenyl-1H-indole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH were weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol were added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction is completed, lead toThe 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
4. 66.6mg of 5-methoxy-2-phenyl-1H-indole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was determined by high performance liquid chromatography with a Chiralcel OD-H column. Wherein the chiral column and liquid phase conditions were used and the e.e. values of the resulting products are shown in table 2.
5. 61.8mg of 1-methyl-2-phenyl-1H-indole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2- (p-tolyl) indol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
6. 67.8mg of 1-chloro-2-phenyl-1H-indole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH were weighed out and 2mL of acetone was added(27 mmol) and 1mL ethanol at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) indol-3-one. The e.e.% value was determined using high performance liquid chromatography with a Chiralcel OD-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
7. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2.4mL of 2-butanone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxetan-2-yl) -2-phenylindol-3-one. The e.e.% value was determined using high performance liquid chromatography with a chiralpak ad-H column. Wherein the chiral column and liquid phase conditions used and the e.e.% value of the resulting product are shown in table 2.
TABLE 2 product e.e.% values of asymmetric photo-enzymatic synergistic reactions and conditions for high performance liquid chromatography
As can be seen from table 2, the e.e.% value of the product shows different results due to the influence of position and electronic properties. The 5-bromo-2-phenyl-1H-indole, 1-chloro-2-phenyl-1H-indole has an electron withdrawing group, which catalyzes the product (S) -5-bromo-2- (2-oxypropyl) -2-phenylindol-3-one, the e.e. value of (S) -2- (4-chlorophenyl) -2- (2-oxypropyl) indol-3-one being higher than the product obtained by catalyzing 5-methyl-2-phenyl-1H-indole and 5-methoxy-2-phenyl-1H-indole, 1-methyl-2-phenyl-1H-indole. And (S) -2- (4-chlorophenyl) -2- (2-oxypropyl) 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 for asymmetric photo-enzyme synergistic reaction.
Example 11 comparative experiments on asymmetric photo-enzymatic synergistic reactions under different experimental conditions
1. The test method comprises the following steps: 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
2. Uncoated lipase assay: 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
3. Non-bonded Ru element experiment: and 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@HP-UiO-67-GH, 2mL of acetone (27 mmol) and 1mL of ethanol were added at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
4、N 2 Instead of O 2 Experiment: 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and N 2 Atmosphere (N) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
5. Air instead of O 2 Experiment: 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added and the reaction is allowed to proceed for 70h at room temperature under an air atmosphere using a 36W fluorescent lamp. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
6. Experiment under dark conditions: weighing and weighing58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH, 2mL of acetone (27 mmol) and 1mL of ethanol were added at room temperature and O 2 Atmosphere (O) 2 Balloon) was reacted for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e. value was measured by high performance liquid chromatography with a chiralpak ad-H column, and the results are shown in table 3.
TABLE 3 conditions of the products of the asymmetric photo-enzymatic synergistic reactions under different conditions
No. Condition change Yield/% e.e./％
1 PPL@Ru-HP-UiO-67-GH 27 93
2 Ru-HP-UiO-67-GH replaces PPL@Ru-HP-UiO-67-GH N.R. --
3 PPL@HP-UiO-67-GHPPL@Ru-HP-UiO-67-GH N.R. --
4 N 2 Substitute O 2 N.R. --
5 Air substitute O 2 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. In the case of Ru-HP-UiO-67-GH and PPL@HP-UiO-67-GH as catalysts, i.e.in the absence of lipase PPL or Ru complexes, no reaction was observed. Reaction at N 2 When the reaction was carried out in an atmosphere, no product was detected, and when the reaction was carried out in an air atmosphere, only a trace amount of product was obtained, and when the reaction was carried out in the dark, no product was detected as well. The above shows that irradiation with visible light, photocatalyst, lipase PPL and O 2 Plays a critical role in the synergistic reaction of asymmetric photo-enzymes.
EXAMPLE 12 asymmetric photo-enzymatic synergistic reaction of 2-phenylindole with acetone
1. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 10mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. Using thin sheetsThe reaction was monitored by layer chromatography. After the reaction was completed, 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) as eluent to give the catalytic product (S) -2- (2-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined by high performance liquid chromatography with a chiralpak ad-H column and was 46%. The yield was 5%.
2. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 50mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (27 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined by high performance liquid chromatography with a chiralpak ad-H column and was 34%. The yield was 14%.
3. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 1.5mL of acetone (20 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined by high performance liquid chromatography with a chiralpak ad-H column and was 78%. The yield was 19%.
4. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2.5mL of acetone (34 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. Thin layer chromatography is adopted for counter reactionMonitoring should be performed. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined by high performance liquid chromatography with a chiralpak ad-H column and was 38%. The yield was 25%.
5. 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq) and 20mg of PPL@Ru-HP-UiO-67-GH are weighed out, 2mL of acetone (34 mmol) and 1mL of ethanol are added, at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 90 hours. The reaction was monitored by thin layer chromatography. After the reaction was completed, 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-oxypropyl) -2-phenylindol-3-one. The e.e.% value was determined by high performance liquid chromatography with a chiralpak ad-H column and was 56%. The yield was 28%.
Comparative example 1 comparative experiment of asymmetric photo-enzyme synergistic reaction with the prior art
According to the prior art, 58.0mg of 2-phenylindole (0.3 mmol,1.0 eq), 29mg of PPL,5mg of Ru (bpy) are weighed out 3 Cl 2 ·6H 2 O, 2mL of acetone (27 mmol) and 1mL of ethanol were added at room temperature and O 2 Atmosphere (O) 2 Balloon), the reaction was irradiated with a 36W fluorescent lamp for 70h. 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. The organic phase is in anhydrous Na 2 SO 4 Drying, filtering, and concentrating 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 chiralpak ad-H column. The results are shown in Table 4, compared with the yield and e.e.% value of the product (S) -2- (2-oxypropyl) -2-phenylindol-3-one of example 1.
TABLE 4 comparison of the cases of homogeneous and heterogeneous asymmetric photo-enzymatic synergistic reaction products
Name of the name Reaction system Yield/% e.e./％
Example 1 Heterogeneous phase 27 93
Comparative example 1 Homogeneous phase 9 97
As can be seen from Table 4, the heterogeneous reaction catalyzed by PPL@Ru-HP-UiO-67-GH gave a yield of 27% of (S) -2- (2-oxypropyl) -2-phenylindol-3-one, while lipase and Ru (bpy) 3 Cl 2 ·6H 2 O co-catalyzes homogeneous reactions with yields of only 9%. Furthermore, the heterogeneous reaction product has an e.e. value of 93%, similar to a homogeneous reaction. The result shows that the immobilized enzyme PPL@Ru-HP-UiO-67-GH can play the dual roles of a visible light photocatalyst and an enzyme catalyst.

Claims (3)

1. A bifunctional photo-enzyme synergistic catalyst is characterized in that the bifunctional photo-enzyme synergistic catalyst is metal internally wrapped with porcine pancreatic lipaseThe organic framework material Ru-HP-UiO-67-GH, wherein the metal organic framework material Ru-HP-UiO-67-GH is formed by bonding bis (2, 2' -bipyridine) - (5, 5' -dicarboxy-2, 2' -bipyridine) ruthenium chloride on any one or more edges of an octahedral HP-UiO-67-GH, the octahedral HP-UiO-67-GH is a mesoporous UiO-67-GH structure, the average pore diameter of the mesopores is 8-12 nm, and the content of Ru element on the metal organic framework material Ru-HP-UiO-67-GH framework is 0.5 mu mol.mg -1 The content of the Ru-HP-UiO-67-GH coated pig pancreas lipase serving as the metal organic framework material is 1.45mg mg −1 。
2. The method for preparing the bifunctional photo-enzyme synergistic catalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) By ZrCl 4 And ligand 4,4' -biphthalic acid and glacial acetic acid to prepare UiO-67;
(2) Using UiO-67 and ligand bpdc- [ NO 2 ] 2 The ligand exchange was performed by reaction in an oven at 120℃for 24h, washing with DMF and acetone (3X 10 mL). Drying at 150deg.C under vacuum for 12 hr for activation, removing solvent to obtain UiO-67-GH, heating at 150deg.C under argon atmosphere for 30min, cooling, and activating at 150deg.C under vacuum for 12 hr to obtain mesoporous structure HP-UiO-67-GH;
(3) Dissolving a mesoporous structure HP-UiO-67-GH and bis (2, 2 '-bipyridine) - (5, 5' -dicarboxy-2, 2 '-bipyridine) ruthenium chloride in DMF, reacting for 24 hours in an oven at 120 ℃, washing with DMF and acetone (3X 10 mL) to obtain Ru-HP-UiO-67-GH, soaking with acetone for 3 days, and activating for 24 hours under 120 ℃ dynamic vacuum to obtain activated Ru-HP-UiO-67-GH, wherein the mass ratio of the mesoporous structure HP-UiO-67-GH to bis (2, 2' -bipyridine) - (5, 5 '-dicarboxy-2, 2' -bipyridine) ruthenium chloride is 4:1;
(4) And wrapping the pig pancreas lipase in the activated metal organic framework material Ru-HP-UiO-67-GH to obtain the bifunctional photo-enzyme synergistic catalyst, wherein the mass ratio of the pig pancreas lipase to the metal organic framework material Ru-HP-UiO-67-GH is 2.5:1.
3. The use of a bifunctional photo-enzyme co-catalyst according to claim 1 in an asymmetric photo-enzyme co-reaction of 2-arylindole and its derivatives with ketones, comprising the steps of:
(1) Mixing 2-aryl indole and derivatives thereof with a bifunctional photo-enzyme synergistic catalyst, and then adding a ketone compound and ethanol, wherein the mass ratio of the 2-aryl indole and derivatives thereof to the bifunctional photo-enzyme synergistic catalyst is 1.16:1-5.8:1, and the volume ratio of the ketone compound to the ethanol is 1.5:1-2.5:1;
(2) At room temperature and O 2 Under the atmosphere, using a 36W fluorescent lamp to irradiate and react for 70 hours;
(3) Monitoring the reaction by adopting a thin layer chromatography, filtering after the reaction is finished, concentrating the filtrate under a vacuum condition, and purifying the residue by using a column chromatography with petroleum ether/ethyl acetate as an eluent to obtain a catalytic product, wherein the reaction time is 70-90 h;
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, the ketone compound is acetone or 2-butanone,
the ketone compound is acetone, and when 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, the obtained catalytic products are (S) -2- (2-oxypropyl) -2-phenyl indol-3-one, (S) -5-bromo-2- (2-oxypropyl) -2-phenyl indol-3-one, (S) -5-methoxy-2- (2-oxypropyl) -2-phenyl indol-3-one, (S) -2- (2-oxypropyl) -2- (p-tolyl) indol-3-one and (S) -2- (4-chlorophenyl) -2- (2-oxypropyl) indol-3-one respectively;
the ketone compound is 2-butanone, and when the 2-aryl indole and the derivative thereof are 2-phenyl indole, the obtained catalytic product is (S) -2- (3-oxetan-2-yl) -2-phenyl indol-3-ketone.
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