CN114908127B - enzyme-TiO (TiO) utilization method 2 Method for catalyzing and synthesizing nanotube-quantum dot co-assembly - Google Patents
enzyme-TiO (TiO) utilization method 2 Method for catalyzing and synthesizing nanotube-quantum dot co-assembly Download PDFInfo
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- CN114908127B CN114908127B CN202210670679.XA CN202210670679A CN114908127B CN 114908127 B CN114908127 B CN 114908127B CN 202210670679 A CN202210670679 A CN 202210670679A CN 114908127 B CN114908127 B CN 114908127B
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- 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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- 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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Abstract
The invention relates to a method for preparing a catalyst by utilizing enzyme-TiO 2 The method for catalyzing and synthesizing the nanotube-quantum dot co-assembly comprises the following specific steps: using aldehyde ketone reductase as model, using cell disruption supernatant to form aldehyde ketone reductase protein assembly with the assistance of microwave, using TiO 2 The r-GQDs nanotube is used as a photocatalyst, the rhodium ligand is an electron transfer agent, and water is used as a hydrogen donor to regenerate the cofactor NADPH; and then, further combining photocatalysis with enzyme catalysis to realize catalytic synthesis of the medical key intermediate under infrared light. The invention takes water as a hydrogen donor to realize the regeneration of coenzyme factor, which is a negative carbon scheme and is green and sustainable; in the present invention, the enzyme-TiO is used 2 The nanotube-quantum dot co-assembly mode realizes the chemical reaction driven by infrared light, improves the light utilization rate, and is expected to contribute 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 synergistic catalytic synthesis method, in particular to a method for synthesizing a light-enzyme synergistic catalytic synthesis catalyst by utilizing enzyme-TiO 2 A method for catalyzing and synthesizing nanotube-quantum dot co-assembly.
Background
Catalysis is a hotspot in the research of 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 be combined with two or more types, so that a series reaction process is realized. Biological systems can rely on multiple enzymes with good compatibility and selectivity to catalyze and synthesize complex natural products and metabolites simultaneously. Oxidoreductase (oxidoreductase) accounts for about 25% of all enzymes, and can catalyze hydrogenation reduction of small carbon-based molecules to synthesize target products with high selectivity (100%) under mild conditions. However, the process of oxidoreductase-catalyzed hydrogenation of small carbon-based molecules typically requires expensive coenzymes as secondary substrates (reducing agents) to participate in the reaction. Thus, the search for a green, feasible and efficient method to achieve efficient regeneration of coenzymes is a hotspot and difficulty of general interest to researchers. The photocatalytic coenzyme regeneration process is most similar to the natural photosynthetic process, but as the related reaction substances (such as a sacrificial agent, an electronic conductor, a photocatalyst and the like) are mostly molecular scale, the energy consumption and the difficulty of the subsequent separation process are great, the photocatalytic coenzyme regeneration tends to develop into the construction of a highly integrated photocatalytic coenzyme regeneration system, the process of which is closer to the natural photoreaction, and the enzyme-coupled catalytic process is further coupled, so that the photo-enzyme coupled catalytic system with higher integration level is constructed. The chiral compound obtained by the photocatalysis and enzymatic reduction synergistic reaction system can be further converted into various bioactive molecules and valuable synthesis intermediates, which means that the method has wide application prospect in various fields including pharmacy. The reason why the photocatalysis and enzyme catalysis synergistic reaction system is successfully constructed is that: (1) Photochemical reactions generally occur at or near room temperature, consistent with enzymatic reaction conditions; (2) The photocatalytic reaction generally involves electron and energy transfer, and the resulting intermediates are stable to water and compatible with enzymatic reactions. And the photocatalysis and enzyme catalysis reactions are combined, so that the method can be completely used for asymmetric synthesis.
While many materials are selective for light in the photocatalytic direction, e.g. TiO 2 Class materials generally absorb more strongly in the ultraviolet range than in the TiO range in recent years 2 There is also much research on materials in the direction of absorbing visible light. The structure of the photocatalyst is regulated on the molecular level, so that the photocatalytic efficiency can be improved, and guidance is provided for synthesizing 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 (titanium dioxide) 2 The movement of electrons and holes in semiconductor nanomaterials is mainly limited by one-dimensional quantum confinement. The main disadvantages of titanium dioxide are the rapid recombination of photogenerated electron-hole pairs and the narrow photoresponse, which greatly limit practical applications. Therefore, there have been many attempts to improve the photocatalytic activity of titanium dioxide by suppressing recombination of photogenerated electron-hole pairs and expanding light absorption into the visible region. Anti-stokes luminescent molecules and materials as new generation luminescent materials in the fields of energy, biology and medicineThe domain has received a great deal of attention. 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 them, the up-conversion process is most efficient because it involves a stable intermediate state.
One of the most promising methods in the future is to use renewable energy sources for low-cost power generation, solar energy is an endless energy source, and the position in renewable energy sources is very important. The proportion of infrared light in sunlight is up to 50%, and how to fully utilize the light energy is a research subject for future development.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing the enzyme-TiO 2 A method for catalyzing and synthesizing nanotube-quantum dot co-assembly. 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 coupling with enzyme catalysis by means of photocatalysis; in the NADPH regeneration system, water is used as a hydrogen donor to replace substances such as triethanolamine, ethylenediamine tetraacetic acid or glucose in the traditional regeneration method, so that the problems of impurity introduction and difficult separation in the catalysis process are solved; in addition, by enzyme-TiO 2 The nanotube-quantum dot co-assembly completes the photo-enzyme catalytic synthesis of 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 intermediate.
In order to achieve the above purpose, the invention adopts the following technical scheme:
enzyme-TiO (TiO) utilization method 2 The method for catalyzing and synthesizing the nanotube-quantum dot co-assembly comprises the following steps:
(1) Taking aldehyde ketone reductase as a model, and carrying out covalent crosslinking on the aldehyde ketone reductase by using a diyne crosslinking agent under the assistance of microwaves by using cell disruption supernatant to form an enzyme protein assembly;
(2) Utilizing the reduced graphene quantum dots and TiO 2 The nanotubes combine to form TiO 2 Composite material of r-GQDs；
(3) With TiO 2 The r-GQDs are used as a photocatalyst, rhodium ligand is an electron transfer agent, water is used as a hydrogen donor, and the regeneration of the cofactor NADPH is carried out under infrared light, so that a photo-enzyme catalytic system is established, and an enzyme-TiO is obtained 2 Nanotube-quantum dot co-assembled composite catalytic materials;
(4) By enzyme-TiO under infrared light 2 The nano tube-quantum dot co-assembly catalysis synthesizes a medical key intermediate.
Preferably, the cell disruption supernatant is prepared by the following method: e.coli is made into host for inducing aldehyde ketone reductase gene expression, and cell sediment is obtained by centrifugation, the rotation number of centrifugation is 7000-9000 rpm, the time is 4-8 min, and PBS buffer solution is used for washing the sediment; suspending the sediment in PBS and lysing 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 disruption adopts ice bath with the power of 300-500W, the disruption time is 8-13 min, and the disruption is set to be 3s for 7s every 10 s; the soluble and insoluble fractions after cell disruption were separated by centrifugation at 9000-12000 rpm for 10-20 min to obtain a cell disruption supernatant.
Preferably, the electron mediator rhodium ligand is rhodium trichloride-pentamethyl cyclopentadiene-dipropylenimine derivative, and the final concentration of rhodium ligand is 0.5 mM-3 mM.
Preferably, tiO in the photo-enzyme catalytic reaction system 2 The final concentration of the composite material of the r-GQDs 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 hours.
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 photo-enzyme catalysis process -2 Wavelength of infrared lamp>800nm。
Preferably, the diacetylene cross-linking agent is 5,6,11, 12-tetrahydrodibenzo [ a, e ]]CyclooctaneAlkene and dissolving the diacetylene cross-linking agent in isopropanol to a concentration of 0.5 mg.mL -1 ～1mg·mL -1 。
Preferably, the pharmaceutical 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 over 99.98%.
Firstly, carrying out covalent crosslinking on aldehyde ketone reductase by using a cyclooctyne crosslinking agent to form an enzyme protein assembly by using cell disruption supernatant under the assistance of microwaves; secondly, synthesizing TiO by a hydrothermal method 2 Synthesizing rhodium ligand by a chemical method, and characterizing the material by SEM, TEM, XRD and the like; finally, the infrared lamp is arranged below>800 nm) photocatalytic circulating NADPH systems are possible; forming enzyme-titanium dioxide nanotube-quantum dot co-assembly, and carrying out catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) under infrared light]And (3) phenethyl alcohol. In the method of the invention, water is used as hydrogen donor, tiO is used 2 The r-GQDs composite material is used as a photocatalyst, rhodium ligand is used as an electron transfer agent, and substrate 3, 5-bis (trifluoromethyl) acetophenone and isopropanol are used as substrate solvents to carry out photo-enzyme synergistic catalysis to synthesize a medical key intermediate.
The invention utilizes enzyme-TiO 2 The nanotube-quantum dot co-assembly achieves broad spectrum absorption and biocatalysis synthesis. Photo-enzyme coupling catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) under infrared light]Phenethyl alcohol has a catalytic yield of 84.18% and an ee value of over 99.98%. The research realizes the infrared light driven catalytic synthesis reaction, greatly improves the light utilization rate, expands the absorption band of the spectrum, realizes the green sustainable development, and is expected to contribute to the development of the green sustainable catalytic synthesis of fine chemicals and medical intermediates.
The invention has the beneficial effects that:
(1) The photocatalysis is carried out under mild conditions at room temperature by utilizing the photocatalysis regeneration cofactor NADPH, and can be combined with the enzyme catalytic reaction without influencing the activity of the enzyme;
(2) In the photocatalysis process, water is used as a hydrogen donor, so that byproducts introduced by using other organic reagents as the hydrogen donor are avoided, and the green, environment-friendly and sustainable development is realized;
(3) To improve the light utilization, tiO is used 2 The nanotube-quantum dot assembly expands the absorption band of light, and combines the light with enzyme catalysis to prove that the light is an advanced green sustainable catalyst, and realizes the catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) of an enzyme protein assembly under infrared spectrum]Phenethyl alcohol;
(4) By means of enzyme-TiO 2 The nanotube-quantum dot co-assembly realizes broad spectrum absorption and biocatalysis synthesis, greatly improves the light utilization rate, and has certain promotion effect on the development of green and sustainable catalysis synthesis of fine chemicals and medical intermediates.
Drawings
FIG. 1 is a schematic diagram of a photo-enzyme catalytic process;
FIG. 2 is a diagram of TiO 2 Characterization of the/r-GQDs composites (A, scanning electron microscope image; B, XRD image);
FIG. 3 is a Fourier transform infrared (FT-IR) characterization;
FIG. 4 shows the UV detection results of NADPH regeneration under IR;
FIG. 5 is a Photoluminescence (PL) spectrum;
FIG. 6 shows the results of HPLC spectral detection of reduction of 3,5-BTAP by photo-enzyme catalytic reaction.
Detailed Description
The present invention is further described with reference to the following specific examples, which are not intended to limit the scope of the invention, but are not intended to limit the scope of the invention in accordance with the prior art, and equivalents in the art to which the present invention pertains.
Example 1
Referring to FIG. 1, a method of using enzyme-TiO 2 The method for catalyzing and synthesizing the nanotube-quantum dot co-assembly comprises the following specific steps:
(1) E.coli is made into host for inducing aldehyde ketone reductase gene expression, and cell sediment is obtained by centrifugation, the rotation number of centrifugation is 7000-9000 rpm, the time is 4-8 min, and PBS buffer solution is used for washing the sediment; suspending the sediment in PBS and lysing 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 disruption adopts ice bath with the power of 300-500W, the disruption time is 8-13 min, and the disruption is set to be 3s for 7s every 10 s; the soluble and insoluble fractions after cell disruption were separated by centrifugation at 9000-12000 rpm for 10-20 min to obtain a cell disruption supernatant.
(2) The diacetylene cross-linking agent (5, 6,11, 12-tetrahydrodibenzo [ a, e)]Cyclooctene was dissolved in isopropanol at a concentration of 0.66 mg.mL -1 ) Suspending in 1mL AKR-114-189 cell disruption supernatant, placing the container containing the above mixture into a microwave reactor equipped with a cooling module, and irradiating at 10deg.C and 10W for 3min; the enzyme protein assembly is then separated by centrifugation to yield the aldehyde ketone reductase protein assembly.
(3) Synthesis of dipropynyl bipyridine derivatives
To a mixture of the known compound 2,2 '-bipyridine-4, 4' -dimethanol (500 mg,2.3 mM) and NaH (276 mg,11.5 mM) in dry DMF (10 mL) was added propyne bromide (595 μl,6.9 mM) and the mixture was stirred at room temperature for 4 hours until TLC (n-hexane-EtOAc; 2:1) showed complete conversion of the starting material. MeOH was carefully added to neutralize excess NaH and the solvent was evaporated. The residue was dissolved in CH 2 Cl 2 (20 mL) and then H 2 O (20 mL) and brine (20 mL). The organic layer was separated, dried (Na 2 SO 4 ) Filtered and evaporated in vacuo. Purification by flash chromatography using n-hexane/EtOAc (3:1) as eluent afforded the pure compound. Subsequently, a small amount of the resulting pure compound was dissolved in deuterated chloroform and acetonitrile, respectively, and the compound was determined by nuclear magnetism and mass spectrometry.
Synthesis of rhodium ligands
[Cp*Rh(bipy)Cl]The Cl synthesis method comprises two steps: rhCl is added 3 ·H 2 The methanol mixture of O and one equivalent of 1,2,3,4, 5-pentamethylcyclopentadiene was refluxed under nitrogen at 65℃for 15 hours. At room temperature, thenThe solvent was 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 (bipropylenimine derivative) were added and the suspension was almost immediately removed to give a pale yellow solution. After 1h of reaction, the mixture was dried in a vacuum oven. [ Cp ] Rh (bipy) Cl]Cl is readily hydrolyzed to [ Cp ] Rh (bipy) (H 2 O)] 2+ The solution (100 mM) was prepared in water and stored at room temperature.
(4)TiO 2 Preparation of r-GQDs nanotubes
TiO 2 the/r-GQDs composite material is obtained by a hydrothermal method: 0.2g of TiO 2 And 40mL of r-GQDs suspension; the mixture was stirred continuously at room temperature for 4 hours to obtain a uniform suspension; collecting TiO by centrifugation 2 r-GQDs, washed three times with distilled water and dried under vacuum at 60℃overnight; tiO (titanium dioxide) 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) With TiO 2 The r-GQDs are used as a photocatalyst, rhodium ligand is an electron transfer agent, water is used as a hydrogen donor, and the regeneration of the cofactor NADPH is carried out under infrared light, so that a photo-enzyme catalytic system is established, and an enzyme-TiO is obtained 2 The nanotube-quantum dot co-assembled catalytic composite.
(6) enzyme-TiO 2 Nanotube-quantum dot co-assembly for catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl)]And detecting the phenylethanol and the catalytic result by using a high performance liquid chromatograph.
Example 2
By TiO 2 Up-conversion of/r-GQDs nanotubes to regenerate NADPH
Rhodium trichloride-pentamethylcyclopentadiene-dipropylene bipyridine complex (aqueous solution) and NADP + And TiO 2 The r-GQDs nanotube is prepared by preparing a reaction solution with a total volume of 25-50 mL by using pure water as a solvent. The total illumination time is 2 hours, sampling is carried out every 15 minutes, and the measurement of the absorbance value is carried out at 340nm by an ultraviolet spectrophotometer, and the total number is 8It is plotted as a trend line. Under the condition of ensuring that other experimental conditions are unchanged, respectively carrying out TiO in the experiment 2 R-GQDs nanotubes and NADP + Doubling, and exploring control of the strength of regenerating NADPH for the whole system.
TiO to be successfully synthesized 2 The r-GQDs nanotubes regenerate NADPH under infrared light. As shown in FIG. 3, when a normal amount of TiO is used 2 The absorbance at 340nm was not high for the/r-GQDs nanotubes and showed a tendency to slide down significantly after 105min, indicating that the amount of NADPH regenerated under this condition was small. Subsequently TiO 2 The amount of/r-GQDs nanotubes was tripled (TiO 2 after/r-GQDs) the regeneration of NADPH was continued to be attempted, which showed an increase in the amount of NADPH compared to that before the doubling (FIG. 4 d), increasing with time, reaching a maximum at 105 min. Consider probably NADP + Too small an amount to limit the overall photocatalytic reaction, thus NADP + After an increase in the amount of NADPH, there is a significant increase in the amount of NADPH (FIG. 4 a). Also, the maximum value was reached at 105min, and the yield of NADPH was 61.44% by comparison with the standard curve. At the same time, when TiO is used 2 When the nanotubes were subjected to NADPH regeneration experiments, NADPH absorption was still detectable at 340nm of UV (FIGS. 4 b-c).
Example 3
enzyme-TiO 2 Nanotube-quantum dot co-assembly for catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) under infrared light]Phenethyl alcohol
Based on the previous experiment, the infrared lamp is defined>800nm,20mW·cm -2 ) Photocatalytic cycling of NADPH systems is possible, so that an 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 mu M TiO 2 R-GQDs nanotubes, 100mM PBS buffer (pH 7.0), 2mM NADP + 1mM rhodium chloride-penta methyl cyclopentadiene-dipropylenimine complex (aqueous solution) and aldehyde ketone reductase protein assembly, 50mM substrate 3, 5-bis (trifluoromethyl) acetophenone, total volume 5ml, the reaction was carried out under light for 10-24 hours. Infrared lamp>800nm,20mW·cm -2 ) The reaction liquid is directly irradiated to the reaction liquid,the reaction flask containing the reaction solution was then placed on a magnetic stirrer. Because the infrared wavelength is relatively large, the enzyme structure is prevented from being damaged due to the fact that the temperature is too high by water bath and controlling the irradiation distance of the infrared lamp, so that the catalytic effect of the reaction is influenced by enzyme deactivation.
TiO-based 2 The R-GQDs nanotube is up-converted to regenerate NADPH, a photo-enzyme catalytic system is established, and the catalytic performance of the AKR cyclic assembly body for synthesizing (R) -1-3',5' -BTPE is evaluated. FIG. 5 shows the HPLC spectral detection results of infrared-driven chemical reaction photo-enzyme catalytic reduction 3,5-BTAP, showing successful synthesis of (R) -1-3',5' -BTPE in a photo-enzyme system. Up-conversion process and enzyme catalysis combined catalysis synthesis of (R) -3,5-BTPE using TiO 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 Ti-O-C bonds can be observed in the nano tube and rhodium ligand catalytic system by analysis, and interfacial charge transfer is induced, so that infrared chemical reaction is driven. The (R) -3,5-BTPE is also synthesized by combining with enzyme catalysis, and the HPLC detection result is used for detecting the catalysis result, and the HPLC spectrum detection result of the photo-enzyme catalysis reaction for reducing 3,5-BTAP is shown in figure 6, so that the catalysis result (conversion rate) of adding quantum dots into the composite material reaches 84.18 percent, and the conversion rate of not adding quantum dots is only 49.76 percent. In the catalytic process, water is used as hydrogen donor and TiO is used 2 The r-GQDs nanotube material realizes up-conversion, and the whole process shows green, environment-friendly and sustainable trend in the future.
In order to realize up-conversion and solve the problem of light utilization rate, the invention uses the reduced graphene quantum dots to combine with TiO 2 The nanotubes combine to form novel nanocomposite materials. Under infrared light, tiO material 2 The r-GQDs nanotubes were used for NADPH regeneration with a yield of 61.44% NADPH under the appropriate 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. At the same time, tiO was found 2 Nanotubes also show a non-negligible catalytic capacity in the regeneration experiments of NADPH under infrared light. Analysis by Fourier transform infrared instrument finds that when TiO 2 The detection of Ti-O-C linkages in the nanotubes and rhodium ligands induces ICT transformations, thereby effecting infrared light driven chemical reactions. Catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) by combination with enzyme catalysis]The yield of phenethyl alcohol was 84.18% and the ee value exceeded 99.98%. Undeniable is TiO 2 The R-GQDs nano tube as a photocatalyst has stronger utilization capability for infrared light, and the nano tube catalyzes and synthesizes (R) -1- [3, 5-bis (trifluoromethyl)]The yield of the phenethyl alcohol is up to 84.18%, and the ee value is also over 99.98%. The project realizes the photo-enzyme catalytic synthesis driven by infrared light, improves the sunlight utilization rate, and achieves a green economical sustainable catalytic system.
The invention takes aldehyde ketone reductase as a model, utilizes cell disruption supernatant to form aldehyde ketone reductase protein assembly under the assistance of microwaves, and uses TiO 2 The r-GQDs nanotube is used as a photocatalyst, the rhodium ligand is an electron transfer agent, and water is used as a hydrogen donor to regenerate the cofactor NADPH; subsequently, the photocatalysis and enzyme catalysis are combined to realize the catalytic synthesis of a pharmaceutical key intermediate under infrared light, and the catalytic synthesis of (R) -1- [3, 5-bis (trifluoromethyl) of the enzyme protein assembly under infrared spectrum is realized]And (3) phenethyl alcohol. The invention takes water as a hydrogen donor to realize the regeneration of coenzyme factor, which is a negative carbon scheme and is green and sustainable; in the present invention, the enzyme-TiO is used 2 The nanotube-quantum dot co-assembly mode realizes the chemical reaction driven by infrared light, improves the light utilization rate, and is expected to contribute to the development of green sustainable catalytic synthesis of fine chemicals and medical intermediates.
The above-described embodiments are merely illustrative of preferred aspects of the invention and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the scope of the described embodiments. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (2)
1. enzyme-TiO (TiO) utilization method 2 The method for catalyzing and synthesizing the nanotube-quantum dot co-assembly is characterized by comprising the following steps of:
(1) Taking aldehyde ketone reductase as a model, and carrying out covalent crosslinking on the aldehyde ketone reductase by using a diyne crosslinking agent under the assistance of microwaves by using cell disruption supernatant to form an enzyme protein assembly;
(2) Utilizing the reduced graphene quantum dots and TiO 2 The nanotubes combine to form TiO 2 r-GQDs composites;
(3) With TiO 2 The r-GQDs are used as a photocatalyst, rhodium ligand is an electron transfer agent, water is used as a hydrogen donor, and the regeneration of the cofactor NADPH is carried out under infrared light, so that a photo-enzyme catalytic system is established, and an enzyme-TiO is obtained 2 Nanotube-quantum dot co-assembled composite catalytic materials;
(4) By enzyme-TiO under infrared light 2 The nanotube-quantum dot co-assembled catalytic synthesis of a pharmaceutical key intermediate;
in the photo-enzyme catalysis process, the infrared light intensity is 20-80 mW cm -2 Wavelength of infrared lamp>800 nm；
The key medical 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 over 99.98%;
the microwave temperature is 5-25 ℃, the power is 5-40W, and the time is 1-5 min; the diacetylene cross-linking agent is 5,6,11, 12-tetrahydrodibenzo [ a, e ]]Cyclooctene, and dissolving the diacetylene cross-linking agent in isopropanol to a concentration of 0.5 mg.mL -1 ～1mg·mL -1 ；
The electron transfer agent rhodium ligand is rhodium trichloride-pentamethyl cyclopentadiene-dipropylenimine derivative, and the final concentration of the rhodium ligand is 0.5-mM-3 mM;
TiO in photo-enzyme catalytic reaction system 2 The final concentration of the composite material of the r-GQDs is 0.5 mg.mL -1 ～5 mg·mL -1 ；
The temperature of the photo-enzyme catalysis is 20-40 ℃ and the time is 10-24 h.
2. The enzyme-TiO according to claim 1 2 The method for catalyzing and synthesizing the nanotube-quantum dot co-assembly is characterized in that cell disruption supernatant is prepared by the following method: e.coli is made into host for inducing aldehyde ketone reductase gene expression, and cell sediment is obtained by centrifugation, the rotation number of centrifugation is 7000-9000 rpm, the time is 4-8 min, and PBS buffer solution is used for washing the sediment; suspending the sediment in PBS and lysing 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 disruption adopts ice bath with the power of 300-500W, the disruption time is 8-13 min, and the disruption is set to be 3s for 7s every 10 s; the soluble and insoluble fractions after cell disruption were separated by centrifugation at 9000-12000 rpm for 10-20 min to obtain a cell disruption supernatant.
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| CN101857887A (en) * | 2010-06-13 | 2010-10-13 | 江南大学 | Method for preparing optically pure aryl alcohol with cell-free extracts of recombinant strains by catalytic asymmetric conversion |
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