CN118459750B - Artificial light capturing system based on covalent assembly and construction method thereof - Google Patents
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- 238000010276 construction Methods 0.000 title claims abstract description 9
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 30
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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Abstract
The invention is suitable for the technical field of high molecular compounds, and provides an artificial light capturing system based on a covalent assembly and a construction method thereof, wherein the construction method of the artificial light capturing system based on the covalent assembly comprises the following steps: step 1, synthesizing a fluorescence donor: step 2, synthesizing a fluorescent receptor: and 3, constructing an artificial light capturing system. In the invention, the fluorescein is coupled with the porphyrin ring through the alkyl chain, and has good light absorption performance in the ultraviolet-visible region of the solar spectrum, so that the conjugation of the fluorescein improves the light absorption energy; efficient FRET occurs between the fluorescein energy donor to the porphyrin energy acceptor, improving the fluorescence lifetime and fluorescence quantum yield of the porphyrin. The invention develops various artificial light and light capturing systems by utilizing a covalent assembly method, and provides new materials for biological optics and biological energy sources.
Description
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to an artificial light capturing system based on a covalent assembly and a construction method thereof.
Background
Photosynthesis is the basis of life and provides a material and energy basis for the survival and development of all living things on earth. Inspired by a natural light collecting system, the artificial light collecting system based on the artificial supermolecular material not only provides possibility for developing novel advanced functional materials and solving energy crisis, but also has important significance for further deep research and understanding of the complex structure and functional mechanism of the natural photosynthetic system. To date, scientists have focused their efforts on constructing a variety of artificial light collection systems, such as nanospheres, nanotubes, polymers, gels, nanoplatelets, nanoporous materials, and nanowires.
The natural light capturing antenna is integrated into the biological membrane, which resembles a polymer vesicle. The use of polymer vesicles as light collection platforms not only better mimics natural light capture platforms, but also provides a threshold-limiting structure for limited photochemical reactions in a closed environment. Compared with low molecular weight liposome, the polymer vesicle has the characteristics of high stability, permeability and easy functionalization, and has wide application in aspects of drug embedding, drug delivery, biomineralization, nanoreactors and the like, so that the polymer vesicle is widely focused by researchers when constructing an artificial light capturing system. The method for preparing the polymer vesicle comprises the methods of supermolecule self-assembly, template synthesis and the like. These methods have the disadvantage of complex synthesis, environmental pollution and cumbersome procedures, which motivate researchers to explore other methods to make polymer vesicles.
Fluorescein is one of the commonly used fluorescent molecules, which is readily soluble in water, has strong green fluorescence, and has a fluorescence quantum yield of 0.65 (ph=7, aqueous solution). Fluorescein has excellent physical and chemical properties, and can be used as a fluorescent probe and a diagnostic reagent in the fields of biology, medicine, pharmacy and the like. On the other hand, porphyrins have a strong light absorption capacity in the visible region, and the molecular structure can be conveniently optimized by adding different peripheral substitution color groups on the porphyrin ring to enhance their light capturing capacity. Porphyrin molecules are therefore widely used in photocatalysis, light capture devices and other biological systems. We therefore propose an artificial light capture system based on covalent assemblies and a method of constructing the same.
Disclosure of Invention
The invention aims to provide an artificial light capturing system based on a covalent assembly and a construction method thereof, and aims to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for constructing an artificial light capture system based on a covalent assembly, comprising the steps of:
step 1, synthesizing a fluorescence donor:
Placing 4-bromobutyric acid and thionyl chloride in a round-bottomed flask, and reacting at room temperature 4 h; dissolving fluorescein in 15 ml dry DMF, adding into the reaction after complete dissolution, slowly adding triethylamine into the reaction by using a syringe, reacting overnight at room temperature, removing DMF by using a rotary evaporator to obtain orange-yellow solid, purifying by silica gel chromatography to obtain transparent liquid, and changing the transparent liquid into white solid after drying, namely YGS-C 4; the same preparation method as YGS-C 4, respectively using 6-bromohexanoic acid and 8-bromooctanoic acid as starting molecules to synthesize fluorescence donors with different lengths, namely YGS-C 6 and YGS-C 8;
obtaining transparent liquid, and changing the transparent liquid into white solid after drying;
step 2, synthesizing a fluorescent receptor:
Dissolving 4-hydroxybenzaldehyde in 200 ml propionic acid, protecting with nitrogen and refluxing at 120 ℃; maintaining a reflux state, slowly dripping pyrrole into the mixed solution to obtain a black solution, and continuing nitrogen protection, and carrying out reflux reaction at 120 ℃ for 2 h; then cooled to room temperature, 120 ml propionic acid was removed by a rotary evaporator, 100ml ice absolute methanol was added to the remaining mixture, and the resulting solution was placed in a refrigerator 24 h; filtering and collecting blue filter residues, drying the blue filter residues in a vacuum drying oven at 50 ℃, and purifying by silica gel chromatography to obtain purple black solid, namely THPP;
step 3, constructing an artificial light capturing system:
dissolving THPP in 1ml DMF, adding potassium carbonate, and stirring at 90deg.C for 1 h; YGS-C 4 was dissolved in 1ml DMF and added to the reaction, followed by a continuous reflux reaction at 120℃for 12 h; after the reaction is finished, cooling to room temperature, dialyzing to remove unreacted monomers to obtain THPP-C 4 -YGS co-assembled vesicles; the same preparation method as that of the THPP-C 4 -YGS co-assembled vesicle is used for respectively reacting YGS-C 6 and YGS-C 8 with THPP to obtain the THPP-C 6 -YGS co-assembled vesicle and the THPP-C 8 -YGS co-assembled vesicle.
Further, the specific steps of the step 1 are as follows:
2ml, 1.72X10 -2 mol of 4-bromobutyric acid and 5ml, 6.88X10 -2 mol of thionyl chloride are placed in a round-bottomed flask, reacted at room temperature for 4h, and the excess thionyl chloride is removed by means of an oil pump; 1g, 3.01X10 -3 mol of fluorescein was dissolved in 15: 15ml dry DMF, added to the reaction after complete dissolution, 2.4 ml of 1.72X10. 10 -2 mol of triethylamine was slowly added to the reaction by syringe, reacted overnight at room temperature, DMF was removed by rotary evaporator to give an orange yellow solid which was purified by silica gel chromatography to give a clear liquid which became a white solid after drying.
Further, in the step1, dichloromethane and absolute methanol are used as eluent for chromatographic purification of silica gel, and the volume ratio of the dichloromethane to the absolute methanol is 20:1.
Further, the specific steps of the step 2 are as follows:
7.32 g, 5.99X10 -2 mol of 4-hydroxybenzaldehyde are dissolved in 200: 200 ml propionic acid, nitrogen is blanketed and refluxed at 120 ℃; maintaining a reflux state, dissolving 4.16 ml of 5.99X10 -2 mol of pyrrole in 40ml propionic acid, slowly dripping into the mixed solution to obtain a black solution, and continuing to carry out nitrogen protection and reflux reaction at 120 ℃ for 2 h; then cooled to room temperature, 120 ml propionic acid was removed by a rotary evaporator, 100ml ice absolute methanol was added to the remaining mixture, and the resulting solution was placed in a refrigerator 24h; and filtering and collecting the blue filter residue, drying the blue filter residue in a vacuum drying oven at 50 ℃, and purifying by silica gel chromatography to obtain a purple black solid, namely THPP.
Further, in the step2, dichloromethane and acetone are used as eluent for chromatographic purification of silica gel, and the volume ratio of the dichloromethane to the acetone is 5:1.
Further, the specific steps of the step 3 are as follows:
2mg, 2.95X10 -6 mol of THPP are dissolved in 1 ml DMF, 3.26 mg, 2.37X10 -5 mol of potassium carbonate are added and stirred at 90℃for 1 h; 18.56 mg, 2.95X10 -5 mol YGS-C4 were dissolved in 1 ml DMF and the reaction was added and the reflux reaction was continued at 120℃for 12 h; after the reaction, cooling to room temperature and dialyzing to remove unreacted monomers to obtain THPP-C 4 -YGS co-assembled vesicles.
Further, in the step 3, anhydrous methanol is used as a dialysis solvent.
An artificial light capture system based on a covalent assembly constructed according to the construction method described above.
Compared with the prior art, the invention has the beneficial effects that:
1. In the invention, the fluorescein is coupled with the porphyrin ring through the alkyl chain, and has good light absorption performance in the ultraviolet-visible region of the solar spectrum, so that the conjugation of the fluorescein improves the light absorption energy; efficient FRET occurs between the fluorescein energy donor to the porphyrin energy acceptor, improving the fluorescence lifetime and fluorescence quantum yield of the porphyrin.
2. The invention develops a plurality of artificial light and light capturing systems, namely THPP-C 4-YGS, THPP-C6-YGS, THPP-C8 -YGS fluorescent-porphyrin FRET probes by utilizing a covalent assembly method.
3. The invention utilizes the covalent assembly to simulate the natural light capturing system and the arrangement structure of pigment in the natural protein assembly, so that the fluorescence donor and the fluorescence acceptor can transfer energy in the covalent assembly along the length Cheng Gaoxiao, and the light capturing efficiency is regulated and controlled by regulating and controlling the arrangement condition of the fluorescence donor and the fluorescence acceptor, thereby providing new materials for biological optics and biological energy.
Drawings
In fig. 1, (a) is a design drawing of covalent nanovesicles; (b) is a schematic representation of modulating covalent nanovesicles.
In fig. 2, (a) is the spectral overlap of THPP and YGS in MeOH; (b) The emission spectra of THPP-C 4-YGS、THPP-C6 -YGS and THPP-C 8 -YGS solutions; (c) Absorption spectra for THPP-C 4-YGS、THPP-C6 -YGS and THPP-C 8 -YGS solutions; (d) Ultraviolet absorption spectrum of THPP-C 4 -YGS; (e) Ultraviolet absorption spectrum of THPP-C 6 -YGS; (f) The ultraviolet absorption spectrum of THPP-C 8 -YGS.
Fig. 3 is a schematic diagram of an artificial light capture system.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
FRET is a dipole interaction between two fluorophores in close proximity that can provide detailed information on the nanoscale. The precondition for FRET is that there is good spectral overlap between the donor emission spectrum and the acceptor absorption spectrum, and that they are sufficiently close in space that non-radiative energy transfer from the donor fluorophore to the acceptor can occur. The efficiency of energy transfer is primarily dependent on the degree of overlap of the emission spectrum of the donor and the absorption spectrum of the acceptor, as well as the distance between the donor and acceptor molecules. As shown in FIG. 1, to meet the FRET requirement, we constructed covalent polymer vesicles based on a covalent assembly method using planar rigid building motifs fluorescein and porphyrin.
As can be seen from fig. 1, the light-captured nanovesicles are constructed based on a covalent self-assembly strategy, and the vesicles with uniform size and controllable fluorescence effect are obtained by regulating the donor-acceptor distance.
The invention provides a construction method of an artificial light capturing system based on a covalent assembly, which comprises the following steps:
step 1, synthesizing a fluorescence donor:
The starting molecules 4-bromobutyric acid (2 ml, 1.72X10 -2 mol) and thionyl chloride (5 ml, 6.88X10 -2 mol) were placed in a round-bottomed flask, reacted at room temperature for 4 h, and the excess thionyl chloride was removed with an oil pump. Fluorescein (1 g, 3.01X10 -3 mol) was dissolved in 15: 15 ml dry DMF, added to the reaction after complete dissolution, triethylamine (2.4 ml, 1.72X10 -2 mol) was slowly added to the reaction with a syringe, reacted overnight at room temperature, the DMF was removed by rotary evaporator to give an orange yellow solid, purified by silica gel chromatography, dichloromethane/absolute methanol (v/v=20:1) as eluent of silica gel chromatography to give a clear liquid which after drying turned into a white solid, YGS-C 4; the same preparation method as YGS-C 4, respectively using 6-bromohexanoic acid and 8-bromooctanoic acid as starting molecules to synthesize fluorescence donors with different lengths, namely YGS-C 6 and YGS-C 8;
step 2, synthesizing a fluorescent receptor:
4-hydroxybenzaldehyde (7.32 g, 5.99X10 -2 mol) was dissolved in 200: 200 ml propionic acid, nitrogen blanketed and refluxed at 120 ℃; 40 ml pyrrole (4.16 ml, 5.99X10. 10 -2 mol) propionic acid was slowly dropped into the above mixed solution while maintaining the reflux state to obtain a black solution, and the reflux reaction was continued at 120℃for 2 h under nitrogen protection.
Then cooled to room temperature, 120 ml propionic acid was removed by a rotary evaporator, 100ml ice absolute methanol was added to the remaining mixture, and the resulting solution was placed in a refrigerator 24. 24 h. The blue filter residue was collected by filtration and dried in a vacuum oven at 50 ℃, purified by silica gel chromatography, dichloromethane/acetone (v/v=5:1) as eluent of silica gel chromatography purification to give a purple-black solid, namely Tetrahydroxyporphyrin (THPP).
Step 3, constructing an artificial light capturing system: according to the supermolecule assembly principle, a covalent assembly method is utilized to synthesize a covalent polymer system, which comprises the following specific steps:
THPP (2 mg, 2.95X10 -6 mol) was dissolved in 1ml DMF, potassium carbonate (3.26 mg, 2.37X10 -5 mol) was added and stirred at 90℃for 1 h; YGS-C 4（18.56 mg,2.95×10-5 mol) was dissolved in 1ml DMF and added to the reaction, and the reflux reaction was continued at 120℃for 12 h. After the reaction, cooling to room temperature, taking absolute methanol as a dialysis solvent, and dialyzing to remove unreacted monomers to obtain the THPP-C 4 -YGS co-assembled vesicle. The same preparation method as that of the THPP-C 4 -YGS co-assembled vesicle is used for respectively reacting YGS-C 6 and YGS-C 8 with THPP to obtain the THPP-C 6 -YGS co-assembled vesicle and the THPP-C 8 -YGS co-assembled vesicle.
In the embodiment of the invention, spectrum identification is carried out; as can be seen from FIG. 2, the fluorescein can emit stronger fluorescence when excited at 454 nm, and the corresponding maximum emission peak is 475-600 nm. It can be seen that the emission band of fluorescein has a significant spectral overlap with the Soret and Q bands of THPP. This spectral overlap satisfies the precondition for energy transfer interactions between fluorescein and THPP. In this case, the fluorescein in THPP-C 4 -YGS acts as an "antenna" to absorb light energy. THPP is then excited by efficient FRET using the short distance between the fluorescein donor and THPP acceptor.
The synthetic route of the fluorescence-porphyrin FRET probe of THPP-C 4-YGS, THPP-C6-YGS, THPP-C8 -YGS is as follows:
Example 1, characterization of morphology of artificial light capture system:
in order to evaluate the morphological characteristics of the covalent polymer, porphyrin is taken as an acceptor, the appearance of the covalent polymer under different donor conditions is respectively measured under the same condition, and the assembling structure of the covalent polymer is studied by using a TEM, AFM and other methods.
SEM: a drop of stock solution was dropped onto the wafer and air dried. SEM images were taken using JEOL JSM 6700F equipment.
TEM: samples were prepared by dropping a drop of stock solution onto a 300 mesh carbon coated copper grid and air-drying. TEM images were taken with a JEOL1011 transmission electron microscope at an accelerating voltage of 200 kV.
Results:
These FRET probes were studied by Scanning Electron Microscopy (SEM), transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM) methods. In this study, SEM and AFM images confirm the spherical morphology of FRET probes (a, d, e, f in fig. 2). TEM image of THPP-C 4 -YGS as shown in FIG. 2b shows a vesicle with a diameter of 300: 300 nm. Dynamic Light Scattering (DLS) measurements showed that the aggregates formed had monodispersity (c in FIG. 2) with an average aqueous kinetic diameter (Dh) between 300 and 400 nm. The THPP-C 4 -YGS vesicles observed in the AFM image had an average diameter of about 370: 370 nm and an average height of about 100: 100 nm (f in FIG. 2). Statistical analysis of TEM images shows that the average diameter of the vesicles is slightly smaller than Dh of DLS. This may be due to shrinkage of the vesicles during TEM sample preparation.
Example 2, fluorescence properties of artificial light capture system:
in order to study the fluorescence properties of covalent polymers, covalent polymers of donor and acceptor with different distances are designed and constructed, and the influence of the arrangement, position and distance of fluorescence donors and fluorescence acceptors on the fluorescence efficiency of an artificial light capturing system is studied.
Photophysical properties of the co-assembled vesicles were determined by uv-vis absorption, steady state fluorescence and time resolved fluorescence. These co-assembled vesicles were studied by Scanning Electron Microscopy (SEM), transmission Electron Microscopy (TEM), atomic Force Microscopy (AFM) and Dynamic Light Scattering (DLS). Fluorescence spectra were obtained by scanning from 200 nm to 900 nm using a fluorescence spectrophotometer 5301 PC equipped with a 150W xenon lamp.
Table 1 shows photophysical data of THPP, YGS, THPP-C 4-YGS、THPP-C6 -YGS and THPP-C 8 -YGS.
Results:
table 1 shows that fluorescence-porphyrin FRET probes containing four fluorescein donor chromophores (YGS, THPP-C 4-YGS、THPP-C6-YGS、THPP-C8 -YGS) and one porphyrin ring acceptor chromophore (THPP) were tested for fluorescence spectra and UV absorbance properties under anhydrous methanol conditions. We speculate that under light irradiation, the energy transfer of the fluorescein donor to the porphyrin acceptor occurs due to the overlap of the emission spectrum of fluorescein with the excitation of the porphyrin moiety, and THPP-C 4-YGS、THPP-C6-YGS、THPP-C8 -YGS porphyrin produces a long-lived photoexcited state. The results indicate that THPP-C 4 -YGS porphyrin probe exhibited fluorescence lifetime (τ ave) of 8.813 ns, higher than the control porphyrins THPP-C 6-YGS (τave = 5.721 ns) and THPP-C 8-YGS (τave =3.937 ns. The energy transfer was shown to have a distance dependence, with increasing flexible chains, the fluorescence lifetime of THPP-C 4-YGS、THPP-C6 -YGS and THPP-C 8 -YGS gradually decreasing.
Example 3, mechanism analysis of artificial light capture system:
And (3) researching the structure of the artificial light capturing system, researching the relation between the fluorescent molecular structure and the light capturing efficiency, and pushing out the mechanism of the artificial light capturing system. The method mainly analyzes the influence of the positions, the arrangement and the distances of the fluorescence donors and the fluorescence acceptors of the artificial light capturing system on the light capturing efficiency, analyzes the energy transfer characteristics of the fluorescence donors and the fluorescence acceptors in linear structures and multidimensional structures, and finally summarizes and deduces related mechanisms.
Results:
table 1 shows that FRET effects are dependent on the spectral overlap of the donor acceptor and the donor acceptor distance, and that by modulating the donor acceptor distance it was found that the change in donor acceptor distance significantly affects the quantum yield of the assembly. The THPP-C 4-YGS、THPP-C6-YGS、THPP-C8 -YGS quantum yield is calculated by regulating the donor-acceptor distance, and the result shows that the calculated porphyrin photoluminescence quantum yield is consistent with the fluorescence lifetime rule of the porphyrin photoluminescence quantum yield.
In addition, as can be seen from fig. 3, in a low dimensional array, the proximity of the donor or acceptor is defective, resulting in a blockage of energy transfer. In high-dimensional arrays, however, the donor or acceptor can transfer energy through different paths, and energy transfer blockage is not easy to occur.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.
Claims (8)
1. A method for constructing an artificial light capture system based on a covalent assembly, comprising the steps of:
step 1, synthesizing a fluorescence donor:
Placing 4-bromobutyric acid and thionyl chloride in a round-bottomed flask, and reacting at room temperature 4 h; dissolving fluorescein in 15 ml dry DMF, adding into the reaction after complete dissolution, slowly adding triethylamine into the reaction by using a syringe, reacting overnight at room temperature, removing DMF by using a rotary evaporator to obtain orange-yellow solid, purifying by silica gel chromatography to obtain transparent liquid, and changing the transparent liquid into white solid after drying, namely YGS-C 4; the same preparation method as YGS-C 4, respectively using 6-bromohexanoic acid and 8-bromooctanoic acid as starting molecules to synthesize fluorescence donors with different lengths, namely YGS-C 6 and YGS-C 8;
step 2, synthesizing a fluorescent receptor:
Dissolving 4-hydroxybenzaldehyde in 200 ml propionic acid, protecting with nitrogen and refluxing at 120 ℃; maintaining a reflux state, slowly dripping pyrrole into the mixed solution to obtain a black solution, and continuing nitrogen protection, and carrying out reflux reaction at 120 ℃ for 2 h; then cooled to room temperature, 120 ml propionic acid was removed by a rotary evaporator, 100ml ice absolute methanol was added to the remaining mixture, and the resulting solution was placed in a refrigerator 24 h; filtering and collecting blue filter residues, drying the blue filter residues in a vacuum drying oven at 50 ℃, and purifying by silica gel chromatography to obtain purple black solid, namely THPP;
step 3, constructing an artificial light capturing system:
Dissolving THPP in 1ml DMF, adding potassium carbonate, and stirring at 90deg.C for 1 h; YGS-C 4 was dissolved in 1ml DMF and added to the reaction, followed by a continuous reflux reaction at 120℃for 12 h; after the reaction is finished, cooling to room temperature, dialyzing to remove unreacted monomers to obtain THPP-C 4 -YGS co-assembled vesicles; the preparation method is the same as that of the THPP-C 4 -YGS co-assembled vesicle, and the THPP-C 6 -YGS co-assembled vesicle and the THPP-C 8 -YGS co-assembled vesicle are obtained by respectively utilizing the YGS-C 6 and the YGS-C 8 to react with the THPP;
The synthetic route of the fluorescence-porphyrin FRET probe of THPP-C 4-YGS, THPP-C6-YGS, THPP-C8 -YGS is as follows:
。
2. the method for constructing an artificial light capturing system based on a covalent assembly according to claim 1, wherein the specific steps of step 1 are as follows:
2 ml, 1.72X10 -2 mol of 4-bromobutyric acid and 5 ml, 6.88X10 -2 mol of thionyl chloride are placed in a round-bottomed flask, reacted at room temperature for 4 h, and the excess thionyl chloride is removed by means of an oil pump; 1 g, 3.01X10 -3 mol of fluorescein was dissolved in 15: 15 ml dry DMF, added to the reaction after complete dissolution, 2.4 ml of 1.72X10. 10 -2 mol of triethylamine was slowly added to the reaction by syringe, reacted overnight at room temperature, DMF was removed by rotary evaporator to give an orange yellow solid which was purified by silica gel chromatography to give a clear liquid which became a white solid after drying.
3. The method for constructing an artificial light trapping system based on a covalent assembly according to claim 2, wherein in the step 1, dichloromethane and absolute methanol are used as eluent for chromatographic purification of silica gel, and the volume ratio of dichloromethane to absolute methanol is 20:1.
4. The method for constructing an artificial light capturing system based on a covalent assembly according to claim 1, wherein the specific steps of the step 2 are as follows:
7.32 g, 5.99X10 -2 mol of 4-hydroxybenzaldehyde are dissolved in 200: 200 ml propionic acid, nitrogen is blanketed and refluxed at 120 ℃; maintaining a reflux state, dissolving 4.16 ml of 5.99X10 -2 mol of pyrrole in 40ml propionic acid, slowly dripping into the mixed solution to obtain a black solution, and continuing to carry out nitrogen protection and reflux reaction at 120 ℃ for 2 h; then cooled to room temperature, 120 ml propionic acid was removed by a rotary evaporator, 100ml ice absolute methanol was added to the remaining mixture, and the resulting solution was placed in a refrigerator 24h; and filtering and collecting the blue filter residue, drying the blue filter residue in a vacuum drying oven at 50 ℃, and purifying by silica gel chromatography to obtain a purple black solid, namely THPP.
5. The method of constructing an artificial light trapping system based on a covalent assembly according to claim 4, wherein in the step 2, dichloromethane and acetone are used as eluent for chromatographic purification of silica gel, and the volume ratio of dichloromethane to acetone is 5:1.
6. The method for constructing an artificial light capturing system based on a covalent assembly according to claim 1, wherein the specific steps of the step 3 are as follows:
2mg, 2.95X10 -6 mol of THPP are dissolved in 1 ml DMF, 3.26 mg, 2.37X10 -5 mol of potassium carbonate are added and stirred at 90℃for 1 h; 18.56 mg, 2.95X10 -5 mol YGS-C4 were dissolved in 1 ml DMF and the reaction was added and the reflux reaction was continued at 120℃for 12 h; after the reaction, cooling to room temperature and dialyzing to remove unreacted monomers to obtain THPP-C 4 -YGS co-assembled vesicles.
7. The method of constructing an artificial light harvesting system based on a covalent assembly according to claim 6, wherein in step 3, anhydrous methanol is used as a dialysis solvent.
8. A covalent assembly-based artificial light harvesting system constructed according to the construction method of any one of claims 1-7.
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