CN113024402B - Temperature-controlled supermolecule light capture system and preparation method and application thereof - Google Patents
Temperature-controlled supermolecule light capture system and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of supramolecular optical materials, and provides a temperature-controlled supramolecular optical capture system, and a preparation method and application thereof. The system is based on the supermolecule self-assembly of the P1 molecule, which comprises a hydrophobic end and a hydrophilic end with temperature response, is an amphiphilic molecule, can be self-assembled in a water phase and can respond to the temperature. The system of the invention comprehensively simulates the influence of temperature on photosynthesis; the assembly can load an energy receptor, the antenna ratio D/A can reach 1000/1, and the energy transfer efficiency and the antenna effect are both high; the light capture system constructed by P1 can be applied to photocatalytic reaction to convert light energy into chemical energy, can control the switch of a catalytic channel by using temperature, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of supramolecular optical materials, and particularly relates to an artificial temperature control supramolecular optical capture system for simulating photosynthesis as well as a preparation method and application thereof.
Background
The increasingly serious energy crisis becomes a core problem restricting the sustainable development of the current human society, and the solar energy has incomparable superiority as a substitute of fossil fuel. Photosynthesis is one of the most important photochemical events in nature, and is not only the basis on which life beings rely for survival, but also the most efficient pathway of solar energy conversion in nature. During photosynthesis, solar energy is first absorbed, then transferred to a reaction center, and finally converted into chemical energy by the reaction center. In the energy transfer process, the antenna pigment complex (complex of chlorophyll, carotene and the like and protein) forms a set of efficient System for collecting and transmitting Light energy, called Light-Harvesting System (LHS), and the ability of the antenna pigment complex to absorb Light and the efficiency of transferring Light energy to a reaction center directly determine whether the Light energy can be successfully converted into chemical energy.
Another very important phenomenon of photosynthesis is the close correlation with air temperature (temperature). For example, due to the influence of greenhouse effect, the temperature of subtropical and tropical regions gradually rises in summer and lasts for a long time, and high temperature is one of the main factors influencing the normal growth of plants. Photosynthesis, one of the most sensitive physiological responses of plants to high temperatures, is inhibited by high temperatures before other high temperature-induced nociceptive symptoms occur. When the air temperature is higher than the optimum temperature for photosynthesis, the photosynthetic rate obviously shows a trend of decreasing with increasing temperature, because the high temperature causes inactivation, denaturation and even destruction of related enzymes catalyzing dark reaction, and the high temperature also causes the structure of chloroplast to change and damage. High temperatures also affect the light trapping mechanism of LHC II associated with the substrate region. The combined action of these factors necessarily results in a dramatic decrease in the rate of photosynthesis. However, no temperature responsive artificial light harvesting system has emerged that mimics this mechanism. Therefore, the temperature variable is introduced into the artificial light capture system, which is not only helpful for further understanding the natural light capture mechanism, but also provides a new idea for developing a responsive artificial light capture system.
Disclosure of Invention
In order to fill the blank of the prior art, the invention provides a temperature-controlled supramolecular light capture system, a preparation method and application thereof, which can more comprehensively simulate the influence of temperature on photosynthesis (the light capture is inhibited due to high temperature in the nature).
The technical scheme provided by the invention is as follows:
a temperature controlled supramolecular light trapping system based on supramolecular self-assembly of P1 in aqueous phase, the chemical structural formula of P1 is as follows:
the invention also provides a preparation method of the temperature-controlled supramolecular optical capture system, which is characterized in that a compound A and a compound B are amidated to prepare P1:
and adding P1 into distilled water, and driving the mixture to perform self-assembly by hydrophilic and hydrophobic acting force to obtain the temperature-controlled supramolecular light capture system.
Further, the synthesis method of the compound A comprises the following steps: the compound is obtained by starting from 9-fluorenone and carrying out Wittig reaction, Suzuki reaction, demethylation and Gabriel reaction.
Further, the synthesis method of the compound B comprises the following steps: starting from diethylene glycol monomethyl ether, hydroxyl is firstly converted into OTs, then the OTs react with methyl gallate to generate ether, and the ether is obtained after demethylation and acyl chlorination.
Further, the preparation method of the P1 comprises the following steps:
in N2Adding DMAP and DCM solution of compound A into a flask under protection, carrying out ice bath, then dropwise adding DCM solution of compound B, and dropwise adding Et3N, stirring at room temperature for reaction overnight, stopping stirring after the reaction is completed, adding HCl for washing, washing with water, washing with saturated NaCl aqueous solution, combining organic phases, and anhydrous MgSO4The mixture is dried and then is dried,and (4) spin-drying by a rotary evaporator, performing column chromatography, and collecting a spin-dried product to obtain solid powder P1.
The nuclear magnetic hydrogen spectrum of P1 is shown in FIG. 2, and the high resolution mass spectrum is shown in FIG. 3. P1 was added to distilled water and self-assembly occurred driven by hydrophilic and hydrophobic forces.
Further, the concentration of P1 in distilled water was greater than 132. mu.M.
Further, the concentration of HCl is 1 mol/L.
The invention also provides application of the temperature control supramolecular light capture system in photosynthesis simulation.
The invention also provides application of the temperature control supramolecular light capture system in catalyzing C-H alkylation reaction.
Further, preparing an aqueous solution of P1, and loading a hydrophobic dye Nile Red NiR by using an ultrasonic method; p1 is used as a donor (D), NiR is used as an acceptor (A), and the ratio of the molar ratio D/A of the donor to the acceptor is 100: 1-1000: 1.
The artificial light trapping system is based on the self-assembly of the P1 molecule as follows:
the first characteristic of P1 is that it is an amphiphilic molecule, the molecule of which contains a polyglycol ether chain part and is a hydrophilic end; also contains a bridging tetraphenylethylene group (BTPE), which is a hydrophobic end. Above the critical aggregation concentration (CAC, a value of 132. mu.M determined by light transmittance experiments), P1 will form spherical nano-assemblies driven by hydrophilic and hydrophobic forces, as shown in the following structure:
the second feature of P1 is the high number of triethylene glycol groups. At low temperature, O atoms in the groups and water form a hydrogen bond network, so that the O atoms and the water form a uniform phase; as the temperature increases, hydrogen bonds are broken and two-phase separation occurs, with turbidity appearing in the solution. This minimum temperature at which turbidity appears is called the "cloud point" and is also known as the minimum eutectic temperature (LCST). Thus P1 has a temperature response.
The third characteristic of P1 is that the contained hydrophobic end BTPE group has aggregation-induced emission (AIE), so that P1 does not generate aggregation-induced quenching (ACQ) due to micelle formation. Therefore, P1 forms an assembly and then very strong fluorescence appears, which provides a precondition for the construction of an artificial light capture system.
The hydrophobic dye nile red (NiR) was loaded by ultrasound. At this point, the BTPE group will act as an energy donor (D) and the NiR as an energy acceptor (A), since they are both in the confined space of the nanoparticle, enabling Fluorescence Resonance Energy Transfer (FRET). The light trapping performance of the system is studied, and the energy transfer efficiency (phi) is found when the acceptor ratio is very low (A/D is 0.1% -1%), which is equivalent to 1 energy acceptor is surrounded by 100 to 1000 donorsET) Can still reach 60% -85%, and meanwhile, the Antenna Effect (AE) reaches 48-90, which is superior to the previous report. The corresponding fluorescence spectra are shown in FIG. 4.
In addition, the light trapping system has temperature response performance, and the T of the light trapping system is determined by a light transmittance experimentcAt 46.8 c, see fig. 5. When the temperature of the system is from below TcRises above TcIn the meantime, the assembly of the compound P1 has a structural transition from "well-defined" to "discrete", the solution becomes turbid, and the energy transfer efficiency is greatly reduced. The control of the light capture process can be realized by controlling the temperature rise and fall, so that a reversible 'light capture switch' is successfully prepared.
The process of photosynthesis comprises light capture, energy transfer and catalytic reaction, and finally, light energy is converted into chemical energy; meanwhile, the whole process is closely influenced by the air temperature, and the photosynthesis can be inhibited by high temperature. This patent utilizes the excitation energy of artifical light capture collection to be applied to photocatalysis, has investigated the control of temperature to reaction process. First, a series of model reactions, such as C-H alkylation, dehalogenation, hydrogen evolution coupling and C (sp2) -P formation reactions, were selected and tested: comparative experiments were conducted with the conversion of the reactant R and the yield of the product P as evaluation indices. Then, the dosage of the photocatalyst (light capture system), the reaction time and the substrate concentration are optimized, and the optimal conversion rate and yield are all over 90 percent. Finally, a C-H alkylation is preferably selected as an optimal reaction model, and the optimal reaction model is used as a 'catalytic switch' through temperature regulation and control, so that the control of the reaction process is successfully realized: raising the temperature, disassembling the system, reducing the light capture capacity and interrupting the catalysis; conversely, the temperature is lowered below the cloud point, the catalyst channels reassemble, and the catalyst channels recover.
Through the preparation method, the beneficial effects of the invention are embodied in that:
1. through elaborate design, an artificial supramolecular light capture system with temperature response is developed, and the influence of temperature on photosynthesis (the light capture is inhibited due to high temperature in the nature) is simulated more comprehensively; the system of the invention has reversible temperature response and can be cycled for 2-50 times.
2. The P1 molecule comprises a hydrophobic end and a hydrophilic end (a polyethylene glycol ether chain) with temperature response, is an amphiphilic molecule, has the function of a diabrotica, can be subjected to self-assembly in an aqueous phase and can respond to temperature;
3. the P1 adopts AIE group as hydrophobic end, so that P1 has fluorescence emission capability after being assembled into regular assembly nanospheres, the luminous capability is reduced after the assembly, and the design requirement of 'heating induction disassembly and inhibition of light capture capability' is perfectly met;
4. the assembly of P1 can load an energy receptor, the antenna ratio D/A can reach 1000/1, and the energy transfer efficiency and the antenna effect are both high;
5. the temperature-controlled light capture system constructed by P1 can be applied to photocatalytic reaction to convert light energy into chemical energy.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic view of the present invention;
FIG. 2 shows NMR of P1 compound1H NMR) spectrum.
FIG. 3 is a high resolution mass spectrum of compound P1, [ M + NH ]4 +]+＝1674.8637。
FIG. 4 is a graph of energy transfer fluorescence spectra.
FIG. 5 is a graph showing the temperature response of the system measured in the light transmittance experiment, wherein (a) is a cloud point measurement graph and (b) is a temperature response cycle graph.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
Example 1
(1) Synthesis of P1: in N2Adding DMAP and DCM solution of compound A into a flask under protection, carrying out ice bath, then dropwise adding DCM solution of compound B, and dropwise adding Et3N, the reaction was stirred at room temperature overnight. After the reaction is completed, stopping stirring, adding 1M HCl for washing, washing with water, washing with saturated NaCl aqueous solution, combining organic phases, and anhydrous MgSO4Drying, rotary drying by a rotary evaporator, performing column chromatography, and collecting a rotary-dried product to obtain solid powder P1 with the yield of 98%. The nuclear magnetic characterization of compound P1 is shown in fig. 2, and the high resolution mass spectrometry characterization is shown in fig. 3.
(2) The P1 molecule is self-assembled in distilled water driven by hydrophilic and hydrophobic forces, the light transmittance experiment determines that the critical aggregation concentration of P1 is 132 μ M, and above the critical aggregation concentration, P1 assembles into a spherical micelle structure.
(3) The P1 molecule has a temperature response due to its polyethylene glycol ether chain, and a 1mM aqueous solution of P1 was prepared, and the cloud point temperature T under these conditions was measured by a light transmittance experimentcAt 46.8 c, see fig. 5. The temperature response in the step is reversible and can be cycled for 2-50 times.
(4) Preparing a 1mM aqueous solution of P1, loading a hydrophobic dye Nile red NiR by an ultrasonic method, using a BTPE group as an energy donor (D) and a NiR group as an energy acceptor (A), preparing a donor-acceptor solution with a donor-acceptor molar ratio D/A of 100:1, and measuring a fluorescence spectrum to obtain phiETAt 85%, AE 48, see fig. 4.
(5) Preparing a 1mM aqueous solution of P1, loading a hydrophobic dye Nile red NiR by an ultrasonic method, taking a BTPE group as an energy donor (D) and the NiR as an energy acceptor (A), preparing a solution with a donor-acceptor molar ratio D/A of 100:1, wherein D/A is the molar ratio of the BTPE group to the NiR, and catalyzing C-H alkylation reaction by using the donor-acceptor solution, wherein the conversion rate and the yield are 95% and 90% respectively. The temperature of the system is increased to 48 ℃, the solution becomes turbid, the conversion rate and the yield are respectively reduced to 35 percent and 5 percent, the temperature is increased successfully to inhibit the catalytic channel, the conversion from the light energy to the chemical energy is hindered, and the high-grade bionics of the photosynthesis is realized.
Example 2:
step (1), step (2) and step (3) are the same as in example 1.
(4) Preparing 1mM aqueous solution of P1, loading NiR by ultrasonic method, preparing donor-acceptor solution with D/A ═ 200:1, measuring fluorescence spectrum to obtain phiET80% and AE 61.
(5) A1 mM aqueous solution of P1 was prepared, and NiR was loaded by sonication to prepare a donor/acceptor solution with D/A ═ 200:1, which catalyzes the C-H alkylation reaction with 93% and 90% conversion and yield, respectively. The temperature of the system is increased to 48 ℃, the solution becomes turbid, the conversion rate and the yield are respectively reduced to 31 percent and 4 percent, the catalytic channel is successfully inhibited by increasing the temperature, the conversion from the light energy to the chemical energy is hindered, and the high-grade bionics of the photosynthesis is realized.
Example 3:
step (1), step (2) and step (3) are the same as in example 1.
(4) Preparing 1mM aqueous solution of P1, loading NiR by ultrasonic method, preparing donor-acceptor solution with D/A being 500:1, measuring fluorescence spectrum to obtain phiET60% and AE 78.
(5) A1 mM aqueous solution of P1 was prepared, and NiR was loaded by sonication to prepare a donor/acceptor solution with D/A of 500:1, which was used to catalyze C-H alkylation reactions with 90% and 86% conversion and yield, respectively. The temperature of the system is increased to 48 ℃, the solution becomes turbid, the conversion rate and the yield are respectively reduced to 20 percent and 3 percent, the catalytic channel is successfully inhibited by increasing the temperature, the conversion from the light energy to the chemical energy is hindered, and the high-grade bionics of the photosynthesis is realized.
Example 4:
step (1), step (2) and step (3) are the same as in example 1.
(4) A1 mM aqueous solution of P1 was prepared, NiR was supported by an ultrasonic method, a donor/acceptor solution was prepared with D/A1000: 1, and fluorescence spectrum was measuredTo get phiET60% and 90% AE.
(5) A1 mM aqueous solution of P1 was prepared, NiR was loaded by sonication to prepare a donor/acceptor solution with D/A ═ 1000:1, which catalyzes the C-H alkylation reaction with 84% and 80% conversion and yield, respectively. The temperature of the system is increased to 48 ℃, the solution becomes turbid, the conversion rate and the yield are respectively reduced to 15 percent and 0.6 percent, the temperature is increased to successfully inhibit a catalytic channel, the conversion from light energy to chemical energy is hindered, and the high-grade bionics of photosynthesis is realized.
Although the embodiments of the present invention have been specifically described in the above examples, it will be understood by those skilled in the art that these are for illustration only and that various changes or modifications of the technical solution of the present invention and its embodiments may be made without departing from the spirit and scope of the present invention. The scope of the invention may be defined by the following claims.
Claims (10)
1. A temperature-controlled supramolecular light capture system is characterized in that the temperature-controlled supramolecular light capture system is based on supramolecular self-assembly of P1 in an aqueous phase, and the chemical structural formula of P1 is as follows:
2. the method of claim 1, wherein P1 is prepared by amidation of compound A and compound B,
and adding P1 into distilled water, and driving the mixture to perform self-assembly by hydrophilic and hydrophobic acting force to obtain the temperature-controlled supramolecular light capture system.
3. The method for preparing a temperature controlled supramolecular optical trapping system as claimed in claim 2, wherein the synthesis of compound a is: the compound is obtained by starting from 9-fluorenone and carrying out Wittig reaction, Suzuki reaction, demethylation and Gabriel reaction.
4. The method for preparing a temperature controlled supramolecular optical trapping system as claimed in claim 2, wherein the synthesis of compound B is: starting from diethylene glycol monomethyl ether, hydroxyl is firstly converted into OTs, then the OTs react with methyl gallate to generate ether, and the ether is obtained after demethylation and acyl chlorination.
5. The method for preparing a temperature controlled supramolecular light trapping system as claimed in claim 2, wherein said method for preparing P1 comprises the steps of:
in N2Adding DMAP and DCM solution of compound A into a flask under protection, carrying out ice bath, then dropwise adding DCM solution of compound B, and dropwise adding Et3N, stirring at room temperature for reaction overnight, stopping stirring after the reaction is completed, adding HCl for washing, washing with water, washing with saturated NaCl aqueous solution, combining organic phases, and anhydrous MgSO4Drying, rotary drying with rotary evaporator, performing column chromatography, and collecting the product to obtain solid powder P1.
6. The method of preparing temperature controlled supramolecular light trapping systems as claimed in claim 2, wherein the concentration of P1 in distilled water is greater than 132 μ Μ.
7. The method of preparing temperature controlled supramolecular optical trapping system of claim 5, wherein the concentration of HCl is 1 mol/L.
8. Use of the temperature controlled supramolecular light capture system of claim 1 to simulate photosynthesis.
9. Use of the temperature controlled supramolecular light trapping system of claim 1 for catalyzing C-H alkylation reactions.
10. The application of the composition as claimed in claim 8 or 9, wherein an aqueous solution of P1 is prepared, a hydrophobic dye Nile Red NiR is loaded by an ultrasonic method, P1 is used as a donor D, the NiR is used as an acceptor A, and the ratio of the molar ratio of the donor to the acceptor D/A is 100: 1-1000: 1.
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