CN114908127A - Use of enzyme-TiO 2 Method for catalytic synthesis of nanotube-quantum dot co-assembly - Google Patents
Use of enzyme-TiO 2 Method for catalytic synthesis of nanotube-quantum dot co-assembly Download PDFInfo
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- CN114908127A CN114908127A CN202210670679.XA CN202210670679A CN114908127A CN 114908127 A CN114908127 A CN 114908127A CN 202210670679 A CN202210670679 A CN 202210670679A CN 114908127 A CN114908127 A CN 114908127A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for preparing a polypeptide by using enzyme-TiO 2 The nanotube-quantum dot co-assembly catalytic synthesis method comprises the following specific steps: taking aldehyde ketone reductase as a model, forming an aldehyde ketone reductase protein assembly by using cell disruption supernatant under the assistance of microwaves, and taking TiO 2 the/r-GQDs nanotube is used as a photocatalyst, a rhodium ligand is used as an electron transfer agent, and water is used as a hydrogen donor to regenerate a cofactor NADPH; then, the photocatalysis is further combined with enzyme catalysis to realize the catalytic synthesis of the medical key intermediate under infrared light. The method takes water as a hydrogen donor to realize the regeneration of the coenzyme factor, which is a carbon-negative scheme and is green and sustainable; by the enzyme of the present inventionTiO 2 The nanotube-quantum dot co-assembly mode realizes chemical reaction driven by infrared light, improves the light utilization rate, and is expected to make a contribution to the development of green sustainable catalytic synthesis of fine chemicals and medical intermediates.
Description
Technical Field
The invention relates to an infrared light-driven photo-enzyme concerted catalysis synthesis method, in particular to a method for utilizing enzyme-TiO 2 A method for nanotube-quantum dot co-assembly catalytic synthesis.
Background
Catalysis is a hotspot of research in the chemical field, and common catalysts include metals and complexes thereof, small organic molecules, enzymes (biocatalysts), photocatalysts and the like. At present, all types of catalysts can realize the combination of two or more, thereby realizing the series reaction process. Biological systems can simultaneously catalyze and synthesize complex natural products and metabolites by relying on a plurality of enzymes with good compatibility and selectivity. Oxidoreductases (oxidoreductases) account for about 25% of all enzymes, and can catalyze the hydrogenation reduction of carbon-based small molecules to synthesize target products under mild conditions and high selectivity (100%). However, the process of oxidation-reduction enzyme catalysis of carbon-based small molecule hydrogenation usually requires expensive coenzyme as a second substrate (reducing agent) to participate in the reaction. Therefore, the search for a green, feasible and effective method to achieve efficient regeneration of coenzyme is a hot spot and a difficult point of general attention of researchers. The regeneration process of the photocatalytic coenzyme is most similar to the photosynthesis process in the nature, but because most of the related reaction substances (such as sacrificial agents, electronic conductors, photocatalysts and the like) are in molecular scale, and the energy consumption in the subsequent separation process is large and difficult, the regeneration of the photocatalytic coenzyme is inevitably developed into the construction of a highly integrated photocatalytic coenzyme regeneration system, the process of the system is closer to the photoreaction in the nature, and then the catalytic process of the coupled enzyme is coupled, so that a light-enzyme coupled catalytic system with higher integration level is constructed. The chiral compound obtained by the photocatalytic and enzymatic reduction synergistic reaction system can be further converted into various bioactive molecules and valuable synthetic intermediates, which means that the method has wide application prospects in a plurality of fields including pharmacy. The reason why the photocatalytic and enzymatic synergistic reaction system is successfully constructed is as follows: (1) photochemical reactions typically occur at or near room temperature, consistent with the conditions of enzymatic reactions; (2) photocatalytic reactions typically involve electron and energy transfer, and the resulting intermediates are water stable and compatible with enzymatic reactions. And the combination of the photocatalysis and the enzyme catalysis reaction can be completely used for asymmetric synthesis.
While many materials are in the photocatalytic contextAll being light-selective, e.g. TiO 2 Like materials generally absorb more strongly in the ultraviolet range, while in recent years TiO has been used 2 Materials have also been studied for their ability to absorb visible light. The structure of the photocatalyst is adjusted on the molecular level, so that the photocatalytic efficiency can be improved, and guidance is provided for the synthesis of the high-quality photocatalyst. Titanium dioxide (TiO) 2 ) Is an important technical material and has a plurality of promising applications in the fields of photocatalysis, solar cells, sensors and the like. TiO 2 2 The movement of electrons and holes in semiconductor nanomaterials is mainly restricted by one-dimensional quantum confinement. The main drawbacks of titanium dioxide are the rapid recombination of the photogenerated electron-hole pairs and the narrow photoresponse, which greatly limits practical applications. Therefore, attempts have been made to improve the photocatalytic activity of titanium dioxide by suppressing the recombination of photo-generated electron-hole pairs and extending the light absorption into the visible light region. Anti-stokes luminescent molecules and materials have received much attention as a new generation luminescent material in the fields of energy, biology and medicine. Their emission wavelength is shorter than the excitation light in which the relevant photophysical processes include up-conversion processes, second harmonic generation and two-photon absorption. Among these, the up-conversion process is most efficient because it involves stable intermediate states.
One of the most promising methods in the future is to generate electricity at low cost by using renewable energy, and solar energy is an endless energy source and has a very important position in the renewable energy. The proportion of infrared light in sunlight is as high as 50%, and how to fully utilize light energy is a research subject for future development.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for utilizing enzyme-TiO 2 A method for nanotube-quantum dot co-assembly catalytic synthesis. The invention utilizes the reduced graphene quantum dots and TiO 2 The nanotubes are combined to form a novel nano composite material, so that the regeneration of NADPH under infrared light is realized, and the catalytic synthesis is further carried out by means of photocatalysis and enzyme catalytic coupling; in the NADPH regeneration system, water is used as a hydrogen donor to replace triethanolamine and ethanol in the traditional regeneration methodDiamine tetraacetic acid or glucose and other substances, so that the problems of impurity introduction and difficult separation in the catalytic process are solved; alternatively, by enzyme-TiO 2 The nanotube-quantum dot co-assembly completes the photo-enzymatic synthesis of the aprepitant key intermediate, improves the light utilization rate, and has certain promotion effect on the development of green and sustainable catalytic synthesis of fine chemicals and medical intermediates.
In order to achieve the purpose, the invention adopts the technical scheme that:
use of enzyme-TiO 2 The nanotube-quantum dot co-assembly catalytic synthesis method comprises the following steps:
(1) taking aldehyde ketone reductase as a model, carrying out covalent crosslinking on the aldehyde ketone reductase by using a diacetylene crosslinking agent under the assistance of microwaves by using cell disruption supernatant to form an enzyme protein assembly;
(2) by using reduced graphene quantum dots and TiO 2 Nanotube bonding to form TiO 2 a/r-GQDs composite material;
(3) with TiO 2 the/r-GQDs is used as a photocatalyst, a rhodium ligand is used as an electron transfer agent, water is used as a hydrogen donor, the cofactor NADPH is regenerated under infrared light, a photo-enzyme catalytic system is established, and the enzyme-TiO is obtained 2 The nanotube-quantum dot co-assembly composite catalytic material;
(4) passing enzyme-TiO under infrared light 2 The nanotube-quantum dot co-assembly is used for catalytically synthesizing a medical key intermediate.
Preferably, the cell disruption supernatant is prepared by: making escherichia coli become a host for inducing aldehyde ketone reductase gene expression, centrifuging to obtain cell sediment, wherein the centrifugation revolution is 7000-9000 rpm, the centrifugation time is 4-8 min, and washing the sediment by using PBS (phosphate buffer solution); resuspending the precipitate in PBS and cracking the cells by ultrasonic treatment, wherein the addition amount of the PBS is 1/6-1/4 of the volume of the original bacterial liquid, the concentration of the PBS is 0.02M, the pH is 7.0, the ultrasonic crushing adopts an ice bath, the power is 300-500W, the crushing time is 8-13 min, and the crushing time is 3s and 7s are stopped every 10 s; and (3) centrifugally separating the soluble and insoluble parts after cell disruption, wherein the rotational speed of centrifugation is 9000-12000 rpm, and the time is 10-20 min, so as to separate and obtain cell disruption supernatant.
Preferably, the rhodium ligand of the electron transfer agent is rhodium trichloride-pentamethylcyclopentadiene-dipropargyl bipyridine derivative, and the final concentration of the rhodium ligand is 0.5 mM-3 mM.
Preferably, TiO in the reaction system is catalyzed by a photo-enzyme 2 The final concentration of the/r-GQDs composite material is 0.5 mg/mL -1 ～5mg·mL -1 。
Preferably, the microwave temperature is 5-25 ℃, the power is 5-40W, and the time is 1-5 min.
Preferably, the temperature of the photo-enzyme catalysis is 20-40 ℃, and the time is 10-24 h.
In order to improve the light utilization rate, infrared light is used as a light source, preferably, the light intensity of the infrared light is 20-80 mW cm in the light-enzyme catalysis process -2 Wavelength of infrared lamp>800nm。
Preferably, the diyne crosslinking agent is 5,6,11, 12-tetrahydrodibenzo [ a, e ]]Cyclooctene, and a diyne crosslinking agent were dissolved in isopropanol to give a concentration of 0.5 mg/mL -1 ～1mg·mL -1 。
Preferably, the medical key intermediate is aprepitant intermediate (R) -1- [3, 5-bis (trifluoromethyl) ] phenethyl alcohol, and the (R) -1- [3, 5-bis (trifluoromethyl) ] phenethyl alcohol is synthesized by photo-enzyme coupling catalysis under infrared light, wherein the catalytic yield is 84.18%, and the ee value is more than 99.98%.
Firstly, carrying out covalent crosslinking on aldehyde ketone reductase by using cell disruption supernatant fluid and using a cyclooctyne crosslinking agent under the assistance of microwaves to form an enzyme protein assembly; secondly, synthesis of TiO by hydrothermal method 2 Synthesizing a rhodium ligand by a chemical method, and characterizing materials by SEM, TEM, XRD and the like; finally, under the infrared lamp (>800nm) photocatalytic cycling of the NADPH system is feasible; forming enzyme-titanium dioxide nanotube-quantum dot co-assembly, and catalytically synthesizing (R) -1- [3, 5-bis (trifluoromethyl) under infrared light]And (3) phenethyl alcohol. In the method, water is used as a hydrogen donor, and TiO is used as a hydrogen donor 2 the/r-GQDs composite material is used as a photocatalyst, a rhodium ligand is used as an electron transfer agent, and a substrate 3, 5-bis (trifluoromethyl) acetophenone and isopropanol are used asThe substrate solvent is used for synthesizing the pharmaceutical key intermediate by photo-enzyme concerted catalysis.
The present invention utilizes enzyme-TiO 2 The nanotube-quantum dot co-assembly realizes wide spectrum absorption and biocatalytic synthesis. Photo-enzyme coupling catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) under infrared light]Phenethyl alcohol, with a catalytic yield of 84.18% and an ee value of over 99.98%. In the research, the catalytic synthesis reaction driven by infrared light is realized, the light utilization rate is greatly improved, the absorption band of a spectrum is expanded, the green sustainable development is realized, and the method is expected to make a contribution to the development of the green sustainable catalytic synthesis of fine chemicals and medical intermediates.
The invention has the beneficial effects that:
(1) the method has the advantages that the cofactor NADPH is regenerated by photocatalysis, and the photocatalysis is usually carried out under mild conditions at room temperature, can be combined with enzyme catalytic reaction, and cannot influence the activity of enzyme;
(2) in the photocatalysis process, water is used as a hydrogen donor, so that a byproduct caused by using other organic reagents as the hydrogen donor is avoided, and the sustainable development of environmental protection is realized;
(3) to increase the light utilization, TiO is used 2 The absorption wave band of light is expanded by assembling the nano tube-quantum dot, and the combination of the nano tube-quantum dot and enzyme catalysis proves that the nano tube-quantum dot is an advanced green sustainable catalyst, and the catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) by an enzyme protein assembly under infrared spectroscopy is realized]Phenyl ethyl alcohol;
(4) using enzyme-TiO 2 The nanotube-quantum dot co-assembly realizes wide-spectrum absorption and biocatalytic synthesis, greatly improves the light utilization rate, and has certain promotion effect on the development of green and sustainable catalytic synthesis of fine chemicals and medical intermediates.
Drawings
FIG. 1 is a schematic diagram of a photo-enzymatic process;
FIG. 2 is TiO 2 Characterization of the/r-GQDs composite material (A, scanning electron microscope image; B, XRD image);
FIG. 3 is a Fourier transform Infrared Spectroscopy (FT-IR) characterization;
FIG. 4 is the result of ultraviolet detection of NADPH regeneration under infrared light;
FIG. 5 is a Photoluminescence (PL) spectrum;
FIG. 6 shows the HPLC spectrum detection result of 3,5-BTAP reduced by photo-enzyme catalysis.
Detailed Description
The present invention is further described with reference to the following specific examples, which are not intended to be limiting, but are intended to be exemplary in nature and not to be limiting, and all equivalent modifications and equivalents of the known art that are within the spirit and scope of the present invention are intended to be protected by the present invention.
Example 1
Referring to FIG. 1, a method of using enzyme-TiO 2 The nanotube-quantum dot co-assembly catalytic synthesis method comprises the following specific steps:
(1) making escherichia coli become a host for inducing aldehyde ketone reductase gene expression, centrifuging to obtain cell sediment, wherein the centrifugation revolution is 7000-9000 rpm, the centrifugation time is 4-8 min, and washing the sediment by using PBS (phosphate buffer solution); resuspending the precipitate in PBS and cracking the cells by ultrasonic treatment, wherein the addition amount of the PBS is 1/6-1/4 of the volume of the original bacterial liquid, the concentration of the PBS is 0.02M, the pH is 7.0, the ultrasonic crushing adopts an ice bath, the power is 300-500W, the crushing time is 8-13 min, and the crushing time is 3s and 7s are stopped every 10 s; and (3) centrifugally separating the soluble and insoluble parts after cell disruption, wherein the rotational speed of centrifugation is 9000-12000 rpm, and the time is 10-20 min, so as to separate and obtain cell disruption supernatant.
(2) A diyne crosslinking agent (5,6,11, 12-tetrahydrodibenzo [ a, e ]]Cyclooctene was dissolved in isopropanol at a concentration of 0.66 mg/mL -1 ) Suspending the mixture in 1mL of AKR-114-189 cell disruption supernatant, placing the container containing the mixture in a microwave reactor equipped with a cooling module, and irradiating at 10 ℃ and 10W for 3 min; and then separating the enzyme protein assembly by a centrifugal mode to obtain the aldehyde ketone reductase protein assembly.
(3) Synthesis of bipropynyl bipyridine derivative
To the known compounds 2,2 '-bipyridine-4, 4' -dimethanol (500mg, 2.3Mm) and NaH (27)6mg, 11.5mM) in dry DMF (10mL) was added propiolic bromide (595 μ L, 6.9mM) and the mixture was stirred at room temperature for 4h until TLC (n-hexane-EtOAc; 2: 1) indicating complete conversion of the starting material. MeOH was carefully added to neutralize excess NaH and the solvent was evaporated. The residue is dissolved in CH 2 Cl 2 (20mL) followed by H 2 O (20mL) and brine (20 mL). The organic layer was separated and dried (Na) 2 SO 4 ) Filtered and evaporated in vacuo. Purification by flash chromatography using n-hexane/EtOAc (3:1) as eluent gave the pure compound. Subsequently, a small amount of the obtained pure compound was dissolved in deuterated chloroform and acetonitrile, respectively, and the compound was confirmed by nuclear magnetic and mass spectrometry.
Synthesis of rhodium ligands
[Cp*Rh(bipy)Cl]The synthesis method of Cl comprises two steps: reacting RhCl 3 ·H 2 A methanol mixture of O and one equivalent of 1,2,3,4, 5-pentamethylcyclopentadiene was refluxed at 65 ℃ under nitrogen for 15 h. At room temperature, the solvent was then removed under vacuum and the residue was washed with diethyl ether to remove excess hexamethylbenzene. The remaining oily red crystals were extracted with chloroform and the solution was dried over anhydrous magnesium sulfate. After evaporation under reduced pressure, the residue was recrystallized from chloroform-benzene. The product was dissolved in methanol and two equivalents of 2, 2-bipyridine (bis-propynylpyridine derivative) were added and the suspension was almost immediately purged to give a pale yellow solution. After reacting for 1h, drying in a vacuum drying oven. [ Cp Rh (bipy) Cl]Cl is easily hydrolyzed to [ Cp Rh (bipy)) (H 2 O)] 2+ Solutions (100mM) were prepared in water and stored at room temperature.
(4)TiO 2 Preparation of/r-GQDs nano-tube
TiO 2 the/r-GQDs composite material is obtained by a hydrothermal method: 0.2g of TiO 2 Mixing with 40mL of r-GQDs suspension; the mixture was stirred continuously at room temperature for 4 hours to obtain a homogeneous suspension; collection of TiO by centrifugation 2 (iv)/r-GQDs, washed three times with distilled water and vacuum dried at 60 ℃ overnight; TiO 2 2 The scanning electron microscope image of the/r-GQDs composite material is shown in FIG. 2A; the XRD pattern is shown in fig. 2B.
(5) To be provided withTiO 2 the/r-GQDs is used as a photocatalyst, a rhodium ligand is used as an electron transfer agent, water is used as a hydrogen donor, the cofactor NADPH is regenerated under infrared light, a photo-enzyme catalytic system is established, and the enzyme-TiO is obtained 2 The nanotube-quantum dot co-assembly catalysis composite material.
(6) enzyme-TiO 2 Nanotube-quantum dot co-assembly for catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl)]Detecting the catalytic result of the phenethyl alcohol by using a high performance liquid chromatograph.
Example 2
By using TiO 2 Generating up-conversion regeneration NADPH by/r-GQDs nanotube
Rhodium trichloride-pentamethylcyclopentadiene-bispropynopyridine complex (aqueous solution) and NADP + And TiO 2 the/r-GQDs nano tube and the solvent are pure water, and are prepared into reaction liquid with the total volume of 25 mL-50 mL. The light irradiation is carried out for 2 hours, samples are taken every 15min, the light absorption value is measured at 340nm by an ultraviolet spectrophotometer, the total number is 8, and the data is drawn into a trend line. Under the condition of ensuring that other experimental conditions are not changed, TiO in the experiment is respectively added 2 the/r-GQDs nano-tube and NADP + And doubling the number of samples, and regenerating a search control for the intensity of NADPH in the whole system.
TiO to be successfully synthesized 2 the/r-GQDs nano tube regenerates NADPH under infrared light. As shown in FIG. 3, when a normal amount of TiO is used 2 The absorbance value of ultraviolet light at 340nm is not high when the/r-GQDs nano-tube is used, and the nano-tube shows a trend of declining greatly after 105min, which indicates that the amount of the regenerated NADPH is small under the condition. Followed by the addition of TiO 2 The amount of/r-GQDs nano-tube is Threefold (TiO) 2 r-GQDs), and the results showed that the amount of NADPH increased compared to that before doubling (fig. 4d), increasing with time, reaching a maximum at 105 min. Consider possibly NADP + Too small to limit the entire photocatalytic reaction, and then NADP is added + After increasing the amount of NADPH, there was a clear increase in the amount of NADPH (FIG. 4 a). Also reached a maximum at 105min, reaching 61.44% yield by comparison with the standard curve NADPH. While, when TiO is used 2 Nanotube to NADPIn the regeneration experiment of H, NADPH absorption was still detectable at 340nm in the UV (FIGS. 4 b-c).
Example 3
enzyme-TiO 2 The nano tube-quantum dot is assembled together and catalyzed and synthesized under infrared light to obtain (R) -1- [3, 5-bis (trifluoromethyl)]Phenylethanolic acid
On the basis of the previous experiments, the infrared lamp is specified (>800nm,20mW·cm -2 ) Photocatalytic cycling of NADPH system is feasible, so enzyme-TiO is used 2 Nanotube-quantum dot co-assembly for catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl)]And (3) phenethyl alcohol. The reaction system is as follows: 750 μ M TiO 2 the/r-GQDs nanotube, 100mM PBS buffer (pH 7.0), 2mM NADP + 1mM of trichlororhodium-pentamethylcyclopentadiene-dipropargyl bipyridine complex (aqueous solution) and an aldehyde ketone reductase protein assembly, 50mM of a substrate 3, 5-bis (trifluoromethyl) acetophenone, wherein the total volume is 5ml, and the reaction is carried out for 10-24 hours under light. Infrared lamp (>800nm,20mW·cm -2 ) The reaction solution was directly irradiated, and then the reaction flask containing the reaction solution was placed on a magnetic stirrer. Because the infrared wavelength is relatively large, the damage to the enzyme structure caused by too high temperature is avoided by water bath and the irradiation distance of the infrared lamp is controlled, so that the enzyme inactivation influences the reaction catalysis effect.
Based on TiO 2 the/R-GQDs nanotube generates up-conversion to regenerate NADPH, a photo-enzyme catalytic system is established, and the catalytic performance of the AKR annular assembly on the synthesis of (R) -1-3',5' -BTPE is evaluated. FIG. 5 shows the HPLC spectroscopic detection results of infrared-driven chemical reaction photo-enzymatic reduction of 3,5-BTAP, showing that (R) -1-3',5' -BTPE was successfully synthesized in the photo-enzymatic system. Catalytic synthesis of (R) -3,5-BTPE by combining up-conversion process with enzyme catalysis, and TiO is used 2 The catalytic efficiency of the/r-GQDs nanotube material can reach 84.18%, which shows the feasibility of the whole catalytic system. And due to the presence of TiO 2 The nanotube and rhodium ligand catalytic system can also analyze and observe Ti-O-C bonds, induce interface charge transfer and drive infrared chemical reaction. Similarly, the enzyme-catalyzed reaction is further combined with enzyme catalysis to catalyze and synthesize (R) -3,5-BTPE, the HPLC is used for detecting the catalytic result, and the HPLC spectrum detection result of the 3,5-BTAP reduced by the photo-enzyme catalytic reaction is shown in FIG. 6, which can be seen in the process of repeated reactionThe catalytic result (conversion) of the composite material with the quantum dots reaches 84.18%, while the conversion rate of the composite material without the quantum dots is only 49.76%. In the catalytic process, water is used as hydrogen donor and TiO is used 2 the/r-GQDs nanotube material realizes up-conversion, the whole process reflects green, environment-friendly and sustainable development, and the material is a trend of future development.
In order to realize up-conversion and solve the problem of light utilization rate, the invention utilizes the reduced graphene quantum dots to combine the graphene quantum dots with TiO 2 The nanotubes are combined to form novel nanocomposites. Under infrared light, TiO material 2 the/r-GQDs nano-tube is used for the regeneration of NADPH, and the yield of the NADPH is 61.44 percent under proper conditions. Catalytic synthesis of aprepitant intermediate (R) -1- [3, 5-bis (trifluoromethyl) by means of photocatalysis in combination with enzyme catalysis]And (3) phenethyl alcohol. Meanwhile, TiO was found 2 Nanotubes also exhibited a non-negligible catalytic ability in the experiments of the regeneration of NADPH under infrared light. The analysis of a Fourier transform infrared instrument shows that when TiO is used 2 The connection of Ti-O-C detected in the nanotube and rhodium ligand induces ICT conversion, thereby realizing infrared light driven chemical reaction. Catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) by combination with enzyme catalysis]The yield of phenethyl alcohol was 84.18%, and its ee value exceeded 99.98%. Undeniably TiO 2 the/R-GQDs nanotube shows stronger utilization capability to infrared light as a photocatalyst, and catalyzes and synthesizes (R) -1- [3, 5-bis (trifluoromethyl)]The yield of the phenethyl alcohol is as high as 84.18%, and the ee value is over 99.98%. The project realizes the photo-enzyme catalytic synthesis driven by infrared light, improves the utilization rate of sunlight and achieves a green, economic and sustainable catalytic system.
The invention takes aldehyde ketone reductase as a model, utilizes cell disruption supernatant to form aldehyde ketone reductase protein assemblies under the assistance of microwaves, and takes TiO as raw material 2 the/r-GQDs nanotube is used as a photocatalyst, a rhodium ligand is used as an electron transfer agent, and water is used as a hydrogen donor to regenerate a cofactor NADPH; then, the catalytic synthesis of the medicine key intermediate under infrared light is realized by means of the further combination of photocatalysis and enzyme catalysis, and the catalytic synthesis of the enzyme protein assembly under infrared spectrum (R) -1- [3, 5-bis (trifluoromethyl)]And (3) phenethyl alcohol.The method takes water as a hydrogen donor to realize the regeneration of the coenzyme factor, which is a carbon-negative scheme and is green and sustainable; in the present invention, the enzyme-TiO 2 The nanotube-quantum dot co-assembly mode realizes chemical reaction driven by infrared light, improves the light utilization rate, and is expected to make a contribution to the development of green sustainable catalytic synthesis of fine chemicals and medical intermediates.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention and are not to be construed as limiting the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. Use of enzyme-TiO 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps:
(1) taking aldehyde ketone reductase as a model, carrying out covalent crosslinking on the aldehyde ketone reductase by using a diacetylene crosslinking agent under the assistance of microwaves by using cell disruption supernatant to form an enzyme protein assembly;
(2) by using reduced graphene quantum dots and TiO 2 Nanotube bonding to form TiO 2 a/r-GQDs composite material;
(3) with TiO 2 The regeneration of cofactor NADPH is carried out under infrared light by taking/r-GQDs as photocatalyst, rhodium ligand as electron transfer agent and water as hydrogen donor, and a photo-enzyme catalytic system is established to obtain enzyme-TiO 2 The nanotube-quantum dot co-assembly composite catalytic material;
(4) passing enzyme-TiO under infrared light 2 The nanotube-quantum dot co-assembly is used for catalytically synthesizing a medical key intermediate.
2. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized in that the cell disruption supernatant is prepared by the following methodPreparing to obtain: making escherichia coli become a host for inducing aldehyde ketone reductase gene expression, centrifuging to obtain cell sediment, wherein the centrifugation revolution is 7000-9000 rpm, the centrifugation time is 4-8 min, and washing the sediment by using PBS (phosphate buffer solution); resuspending the precipitate in PBS and cracking the cells by ultrasonic treatment, wherein the addition amount of the PBS is 1/6-1/4 of the volume of the original bacterial liquid, the concentration of the PBS is 0.02M, the pH is 7.0, the ultrasonic crushing adopts an ice bath, the power is 300-500W, the crushing time is 8-13 min, and the crushing time is 3s and 7s are stopped every 10 s; and (3) centrifugally separating the soluble and insoluble parts after cell disruption, wherein the rotational speed of centrifugation is 9000-12000 rpm, and the time is 10-20 min, so as to separate and obtain cell disruption supernatant.
3. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: the rhodium ligand of the electron transfer agent is rhodium trichloride-pentamethylcyclopentadiene-dipropynyl bipyridine derivative, and the final concentration of the rhodium ligand is 0.5 mM-3 mM.
4. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: TiO in photo-enzyme catalytic reaction system 2 The final concentration of the/r-GQDs composite material is 0.5 mg/mL -1 ～5mg·mL -1 。
5. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: the microwave temperature is 5-25 ℃, the power is 5-40W, and the time is 1-5 min.
6. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: the temperature of the photo-enzyme catalysis is 20-40 ℃, and the time is 10-24 h.
7. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: photo-enzyme catalyzed processIn the process, the intensity of the infrared light is 20-80 mW cm -2 Wavelength of infrared lamp>800nm。
8. The method of claim 1 using enzyme-TiO 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: the diyne cross-linking agent is 5,6,11, 12-tetrahydrodibenzo [ a, e]Cyclooctene, and a diyne crosslinking agent were dissolved in isopropanol to give a concentration of 0.5 mg/mL -1 ～1mg·mL -1 。
9. The method according to claim 1, wherein the enzyme-TiO is used 2 The method for the catalytic synthesis of the nanotube-quantum dot co-assembly is characterized by comprising the following steps: the key intermediate of the medicine is aprepitant intermediate (R) -1- [3, 5-bis (trifluoromethyl)]Phenyl ethanol, and the (R) -1- [3, 5-bis (trifluoromethyl) is synthesized by the photo-enzyme coupling catalysis under the infrared light]The catalytic yield of the phenethyl alcohol is 84.18%, and the ee value exceeds 99.98%.
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