WO2021088310A1

WO2021088310A1 - Preparation method for aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle, and preparation method for supramolecular photocatalytic assembly

Info

Publication number: WO2021088310A1
Application number: PCT/CN2020/083725
Authority: WO
Inventors: 田佳; 向德成; 张一帆
Original assignee: 东莞行渡科技有限公司
Priority date: 2019-11-05
Filing date: 2020-04-08
Publication date: 2021-05-14
Also published as: CN110804190B; CN110804190A

Abstract

A construction unit head-body-tail three-section amphiphilic molecule of an aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle, a preparation method for forming a water-phase ultra-uniform round micelle assembly by the construction unit, and a preparation method for a supramolecular photocatalytic assembly. According to the three-section amphiphilic molecule, an aromatic amide oligomer fragment is embedded into a conventional hydrophilic and hydrophobic molecule. The supramolecular photocatalytic assembly is prepared by carrying out a reaction on the prepared aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle and a catalyst in a water-phase sacrificial reagent. The aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle has extremely high chemical and structural stability in water, is ultra-uniform and monodisperse and has controllable particle size. The supramolecular photocatalytic assembly is suitable for producing hydrogen by reducing water phase protons under atmospheric atmosphere at normal temperature and normal pressure and selectively reducing carbon dioxide to prepare CO and CH₄ under normal temperature and normal pressure in a carbon dioxide atmosphere, and does not contain noble metals.

Description

Preparation method of hydrophilic-hydrophobic molecular self-assembled micelle embedded with arylamide fragment and supramolecular photocatalytic assembly

Technical field

The invention belongs to the technical field of organic visible light catalytic materials, and particularly relates to a preparation method of hydrophilic and hydrophobic molecular self-assembled micelles embedded in aramid fragments and supramolecular photocatalytic assemblies.

Background technique

The sun continuously provides heat to the earth and is the main source of light and heat on the earth. Up to now, it has delivered about 120,000 terawatts of electricity, which is expected to be 4000 times higher than the electricity required by human civilization in 2050. How to effectively use and store these energy is a subject that human beings have been exploring and researching continuously.

Storing solar energy in chemical fuels through carbon neutral strategies, such as splitting water into H ₂ and O ₂ or converting carbon dioxide into valuable organic compounds, provides potential solutions to the fossil fuel crisis. To achieve the goal of zero net greenhouse gas emissions, artificial photocatalysis to achieve this goal usually follows two main approaches: one is heterogeneous catalysis, which is usually represented by photoelectrochemical cells; the other is homogeneous catalysis, in which photosensitizers And the catalyst acts as a molecule in the solution. The above two approaches are different from nature. Natural plants use supramolecular assembly to convert photons into carbohydrates to achieve photosynthesis. Organisms use highly ordered combinations of light functional components in proteins to improve light capture efficiency. Provide the best catalytic environment. In the chloroplasts of plants, the cyclic polyporphyrin array in the light-harvesting complex exhibits an "antenna effect" to achieve precise excitation energy transfer during the photocatalytic process. The high stability, selectivity and efficiency of natural photocatalysis depend on the precise control of the orientation, distance and the delocalization of excited state electrons of the chromophore molecules and the metalloporphyrin catalytic center.

At present, it is extremely challenging to imitate the natural behavior of chloroplasts in plants and to precisely control the direction and distance between chromophores, electronic relay complexes and enzymes. In the past few decades, supramolecular self-assembly has been greatly developed in multiple scales and a wide range of fields. Self-assembly of chromophore molecules and fine-tuning of their catalytic properties through non-covalent interactions in water has become a promising strategy for mimicking natural photocatalytic systems.

However, the charge separation and transport characteristics of self-assembled structures have been studied for decades, and there are only few precedents for realizing integrated artificial systems, especially self-assembled hydrogel scaffolds, supramolecular metal-organic frameworks in natural lipid systems Assemble photosensitizer and catalyst together. Up to now, there are still few studies on artificial photosynthesis based on supramolecular assembly, and none of them can achieve CO2 reduction. Supramolecular usually refers to the combination of two or more molecules relying on intermolecular interaction to form a complex and organized aggregate, and maintain a certain integrity to make it have a clear microstructure and macroscopic characteristics. At present, the development of actual industrial applications of supramolecular photocatalytic materials is limited by low catalytic efficiency, high cost of noble metal catalytic components, photobleaching of photosensitizers, and low photocatalytic stability, and it is difficult to achieve further development.

Summary of the invention

technical problem

The technical problem to be solved by the present invention is to solve the above-mentioned shortcomings of the prior art, and provide a kind of hydrophilic and hydrophobic molecules embedded in aramid fragments with extremely high chemical and structural stability in water, ultra-uniform, monodisperse, and controllable particle size. Self-assembled micelles consist of inserting aramid oligomer fragments in traditional hydrophilic and hydrophobic molecules, and using the hydrophilic and hydrophobic molecules embedded in the aramid fragments to self-assemble micelles to prepare a supramolecular photocatalytic assembly, which is suitable for use in Atmospheric atmosphere, water-phase proton reduction under normal temperature and pressure to produce hydrogen, and under carbon dioxide atmosphere, normal temperature and pressure, selective reduction of carbon dioxide to produce CO and CH ₄ , constructing a photocatalytic system very similar to the "antenna effect" of natural photosynthesis. The photocatalytic system uses cationic porphyrin hydrophilic head groups as photosensitizers and anionic cobalt complexes as catalysts, and does not contain precious metals.

The solution to the problem

Technical solutions

In order to solve the above technical problems, the first aspect of the present invention has a technical solution: the hydrophilic and hydrophobic molecular self-assembled micelles embedded in the aramid fragments are formed by self-assembly of three-stage amphiphilic small molecule compounds in the water phase, and are characterized in that: The three-stage amphiphilic small molecule compound includes a head group, a neck connecting group, and a tail side chain group. The three-stage amphiphilic small molecule compound is embedded in an aramid oligomer fragment in a traditional hydrophilic and hydrophobic molecule. , Its general formula is:

In the general formula, X represents a water-soluble head group, Y represents a linking group containing hydrogen bonds, Z is a hydrophobic group, m is a positive integer selected from 0-100, and n is a positive integer selected from 1-100;

X is selected from any one of the following structures X1, X2, X3, X4, X5, X6:

X1 is selected from porphyrin structures with hydrophilic groups

X2 is selected from phthalocyanine structures with hydrophilic groups

In the structure of X1 and X2, A1 is selected from hydrophilic soluble groups with sulfonic acid group substituted benzene or carboxylic acid group substituted benzene, A2 is selected from amino substituted benzene (R1-NH3Ph-) or pyridine (R1-NC5H4-), A2 Where R1 is selected from C1-C5 alkyl or C1-C5 alkoxy; the counter ion of the head group is any one of organic cations, metal cations, organic anions or halogen anions, and the metal atom in the center of the head group M is selected from any one or several blends of metals that can coordinate with porphyrin;

X3 is selected from the linear polymer structure of hydrophilic group, including artificial synthetic polymer or natural water-soluble polymer, the artificial synthetic polymer is polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), poly Vinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, N-(2-hydroxypropyl) methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA) polyoxazoline, poly Any one of phosphate or polyphosphazene; the natural water-soluble polymer is xanthan gum, pectin, chitosan derivatives, dextran, carrageenan, guar gum, cellulose, fiber Any one of plain ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or starch-based derivatives;

X4 is selected from artificial synthetic polymers or natural water-soluble polymers, and the artificial synthetic polymers are polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylic acid (PAA), and polyvinyl pyrrolidone (PVP). Any one of acrylamide, N-(2-hydroxypropyl)methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA) polyoxazoline, polyphosphate or polyphosphazene; The natural water-soluble polymer is xanthan gum, pectin, chitosan derivatives, dextran, carrageenan, guar gum, cellulose, cellulose ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or any one of starch-based derivatives;

X5 is selected from the following polyelectrolyte structures with positive or negative charges, selected from any one of disodium polybenzenesulfonate, polyacrylic acid, and polyammonium salt, or any one of the following general structural formulas:

X6 is selected from dendritic polymer structures with hydrophilic groups, selected from polypropyleneimine dendrimers (PPI), poly(amidoamine) dendrimers (PAMAM), polyether dendrimers Any one of poly(arylene ether) dendrimers, polylysine dendrimers;

In the general formula, Y is selected from any one of natural amino acids, C1-C10 aliphatic chains, and linear _{aramid-(R2) n} NHC(O)-, and R2 is selected from substituted phenyl, five-membered or six-membered hetero One or a mixture of cyclic aromatic substituents, -(CH ₂ ) _n NHC(O)-, -(CH=CH) _n NHC(O)-, n is a positive integer from 1 to 100;

In the general formula, Z is selected from C5-C100 linear or branched alkyl, alkoxy, unsaturated aliphatic, polyvinyl, polypropylene, polybutadiene, polystyrene, polyvinyl chloride Any one of a polytetrafluoroethylene group, a polytetrafluoroethylene group, and a polymethacrylate group.

As a further elaboration of the present invention:

Preferably, the three-stage amphiphilic small molecule compound has the following structure, wherein n is a positive integer from 1 to 100, and m is a positive integer from 10 to 200:

Preferably, the structure of the three-stage amphiphilic small molecule compound is:

The preparation of the three-stage amphiphilic small molecule compound includes the following steps:

S1, preparation of compound 3, to CHCl3, methyl p-aminobenzoate (compound 1), stearic acid (compound 2), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide salt The mixture of acid salts was added with 4-(dimethylamino)pyridine and stirred at room temperature for 24 hours. The formed precipitate was filtered, washed with CHCl3, and dried under vacuum to obtain a white solid. Then the obtained solid was suspended in a mixture of THF, MeOH, and H2O solution, LiOH·H2O was added and the reaction system was stirred under reflux for 24 hours. After the solvent was removed in vacuo, the obtained solid was washed with the solvent, and then with HCl aqueous solution and water Compound 3 is obtained after washing and drying;

S2. According to the method for preparing compound 3, compound 4 is prepared from the reaction of compound 3 and compound 1, with a yield of 87%, and it is a white solid;

S3. According to the method for preparing compound 3, compound 5 is prepared by the reaction of compound 4 and compound 1, with a yield of 81%, which is a white solid;

S4. Preparation of compound 7. The mixture of compound 5, compound 6 EDCI and DMAP was stirred in DMF at 60°C and kept at 24°C for 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the obtained red solid was used CHCl3 Wash three times to remove excess EDCI and DMAP, separate the precipitate, and use flash column chromatography (MeOH:MeCN:H2O 8:1:1) to purify the crude product, and evaporate the obtained components to dryness to obtain compound 7 , Is a red solid;

S5. In a 20 mL pressure vessel, dissolve compound 7 in water, add zinc acetate, stir the system under reflux for 5 hours, then add tetrabutylammonium iodide to exchange anions, stir the mixture at room temperature for 24 hours, and then The solvent was evaporated under reduced pressure until a green solid precipitate was formed, and the obtained green solid was further recrystallized from water to obtain a three-stage amphiphilic small molecule compound as a dark green solid.

Preferably, the washing solvent used in step S1 is one or more of water, hydrophilic alcohol solvent, tetrahydrofuran, acetone, dimethyl imide or dimethyl sulfoxide.

Preferably, the self-assembled micelles of the hydrophilic and hydrophobic molecules embedded in the aramid fragments are formed by the three-segment amphiphilic small molecule compound in the aqueous phase using the intermediate fragments to self-assemble between molecules through hydrogen bond interactions. Uniform, monodisperse, spherical micelles with controllable particle size.

The technical solution of the second aspect of the present invention is: a method for preparing self-assembled micelles of hydrophilic and hydrophobic molecules embedded with aramid fragments, including the following steps:

S1. Take 1mg～100mg three-stage amphiphilic small molecule compound in a glass sample bottle, add 1ml～100mL deionized water, ultrasonically disperse for 2min～20min, seal the tube and heat to 150 degrees Celsius to make the three-stage amphiphilic small molecule compound Disperse and dissolve to form a red solution;

S2. Take 5mg/mL～10mg/mL zinc acetate aqueous solution and add the equivalent to the above red solution;

S3. Heat until the above solution turns dark green, and further sonicate it for 2 to 20 minutes;

S4. The above mixture is allowed to stand for 10 hours to 24 hours to prepare self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments.

The technical solution of the third aspect of the present invention is: a preparation method of supramolecular photocatalytic assembly, said supramolecular photocatalytic assembly is prepared by the above-mentioned preparation of hydrophilic and hydrophobic molecular self-assembled micelles embedded in aramid fragments in the water phase The sacrificial reagent is prepared by reacting with a catalyst. The catalyst is a compound catalyst or a cobalt-based catalyst, and the catalyst has a charge opposite to the surface charge of the hydrophilic and hydrophobic molecular self-assembled micelle embedded in the arylamide fragment.

Preferably, the aqueous sacrificial reagent is any one or more of triethylamine, triethanolamine, ascorbic acid, sodium ascorbate reducing agent or oxidizing agent.

Preferably, the three-stage amphiphilic small molecule compound is applied to small molecule catalysis, polymer catalysis, enzyme catalysis, olefin polymerization, olefin cracking, petroleum cracking, photocatalysis, water splitting, nitrogen reduction, carbon monoxide, carbon dioxide reduction, water Oxidation, phenolic hydroxyl oxidation, alcohol oxidation, aldehyde oxidation, formaldehyde, benzene, ammonia, sulfur dioxide, carbon monoxide, nitrogen oxide oxidation reactions.

The technical solution of the fourth aspect of the present invention is: a water-phase self-assembled micelle and the photocatalytic assembly constructed therefrom, comprising the three-stage amphiphilic small molecule compound described in the technical solution of the first aspect and the third aspect The catalyst described in the technical solution and the sacrificial reagent described in the technical solution of the third aspect are combined with a solvent; wherein the solvent is one of water, alcohol solvents, carboxylic acid solvents, non-polar solvents, polar solvents, and ionic liquids. One or a combination of two or more. It is preferably pure water or methanol or ethanol.

Preferably, the alcohol solvent is one or a combination of two or more of methanol, ethanol, isopropanol, n-butanol, and tert-butanol.

Preferably, the carboxylic acid solvent is one or a combination of two or more of formic acid, acetic acid, propionic acid, and butyric acid.

Preferably, the non-polar solvent is one or a combination of two or more of n-hexane and cyclohexane.

Preferably, the polar solvent is one or a combination of two or more of dimethyl sulfoxide, dimethyl formamide, acetonitrile, and acetone.

Preferably, the solvent is a mixed solvent of water and other solvents, the ratio of the other solvents is 1% to 99%, and the other solvents are the alcohol solvents, carboxylic acid solvents, non-polar solvents, polar solvents, ionic liquids One or a combination of two or more. The proportion of the other solvent is preferably 1% to 50%, more preferably 1% to 10%.

Preferably, the weight percentage of the compound is 0.001% to 10%, preferably 0.001% to 1%, most preferably 0.001% to 0.1%, and the catalyst weight percentage is 0.001% to 5%, preferably 0.001% to 1% , Most preferably 0.001% to 0.1%, the weight percentage of the sacrificial reagent is 0.1% to 10%, preferably 1% to 10%, most preferably 1% to 5%, and the solvent percentage is 90% to 99.9%, preferably 95% % To 99.9%, most preferably 99% to 99.9%.

The beneficial effects of the invention

Beneficial effect

The beneficial effects of the present invention are: First, the present invention synthesizes a series of hydrogen bond-enhanced new three-stage amphiphilic small molecule compounds, which are embedded in traditional hydrophilic and hydrophobic molecules with aramid oligomer fragments, and they use intermediate fragments. The molecules interact through hydrogen bonds to self-assemble into ultra-uniform micelles, which have extremely high chemical and structural stability in water, and have good uniformity, monodispersity, and colloidal stability in water, and their colloidal stability With the increase in the number of hydrogen bonds of the neck linking group, the increase in the interaction between small molecules is positively correlated, and the particle size can be precisely controlled by the length of the amphiphilic small molecule; second, supramolecular photocatalytic assembly can be It is suitable for hydrogen production by water-phase proton reduction in atmospheric atmosphere, normal temperature and pressure, and selective reduction of carbon dioxide to produce CO and CH4 in carbon dioxide atmosphere, normal temperature and pressure. It constructs a photocatalytic system that is very similar to the "antenna effect" of natural photosynthesis. Third, the photocatalytic system constructed by supramolecular photocatalytic assembly uses cationic porphyrin hydrophilic head groups as photosensitizers and anionic cobalt complexes as catalysts, and does not contain precious metals; fourth, due to the selective photocatalysis of the present invention Catalytic proton reduction to produce hydrogen, selective reduction of carbon dioxide to prepare CO and CH4 water phase ultra-uniform self-assembled micelles have nano-level spherical structure caused by the characteristics of controllable surface photosensitizer distance and large specific surface area, which is conducive to photosensitivity The delocalization of excited state electrons on the surface of the chemical agent and the collision probability of the catalyzed substrate on the surface of the catalyst greatly improve the reduction of hydrogen production of the supramolecular photocatalytic assembly and the selective reduction of carbon dioxide to produce CO and CH4 efficiency; Fifth, because the supramolecular photocatalytic assembly has a special multi-hydrogen bond for acceptor, it has excellent structural stability, and can be used as a new universal multifunctional water phase material platform, which is widely used Energy materials, catalysis, drug loading, bioimaging, semiconductor materials, display materials, molecular probe materials and many other fields.

Brief description of the drawings

Description of the drawings

Figure 1 is a molecular structure diagram of a three-stage amphiphilic small molecule compound of the present invention;

Fig. 2 is a schematic diagram of the molecular assembly of the three-stage amphiphilic small molecule compound induced by the quadruple hydrogen bond of the present invention;

Figure 3 is a diagram of the molecular structure of the catalyst of the present invention;

Figure 4a is a schematic diagram of the three-stage amphiphilic small molecule compound molecular water phase assembly spherical nanomicelle SPA-1 of the present invention;

Figure 4b is a schematic diagram of the photocatalytic water decomposition of the spherical nanomicelle SPA-1 of the present invention to produce hydrogen and CO2 reduction;

Figure 5 is a cryo-EM picture of the photocatalytic spherical nanomicelle SPA-1 aqueous solution of the present invention (the molecular concentration of the three-stage amphiphilic small molecule compound is 0.2mmol/L);

Figure 6 is a solid-phase transmission electron microscope picture of the photocatalytic spherical nanomicelle SPA-1 of the present invention;

Figure 7 is the dynamic light scattering particle size distribution of the photocatalytic spherical nanomicelle SPA-1 of the present invention (the molecular concentration of the three-stage amphiphilic small molecule compound is 0.2 mmol/L);

FIG. 8 is a diagram of the dynamic light scattering particle size distribution of the photocatalytic spherical nanomicelle SPA-1 under different concentrations of the present invention;

Figure 9 is the synchrotron radiation small-angle X-ray scattering curve of the photocatalytic spherical nanomicelle SPA-1 of the present invention (the molecular concentration of the three-stage amphiphilic small molecule compound is 5.0 mmol/L);

Fig. 10 is the ultraviolet-visible absorption spectrum of the three-stage amphiphilic small molecule compound molecule (0.02 mmol/L) in an aqueous solution of the present invention;

Figure 11 is the fluorescence emission spectrum of the three-stage amphiphilic small molecule compound molecule (0.02 mmol/L) in an aqueous solution of the present invention;

Fig. 12 is the ultraviolet-visible absorption spectrum of the three-stage amphiphilic small molecule compound molecule (0.02mmol/L) in the aqueous solution after different irradiation times of the present invention;

Fig. 13 is a cyclic voltammetric characteristic curve of a three-stage amphiphilic small molecule compound molecule (0.2 mmol/L) in an aqueous solution of the present invention;

Figure 14 is the reduction hydrogen production curve of the water-phase photocatalytic spherical nanomicelle SPA-1 of the present invention in an air atmosphere of 1 standard atmospheric pressure (including 0.2mmol/L three-stage amphiphilic small molecule compound molecules, 2μmol/L C7 molecule is used as a catalyst, and 20mmol/L ascorbic acid is used as a sacrificial reagent);

Figure 15 is the reduction CO production curve of the water-phase photocatalytic spherical nanomicelle SPA-1 of the present invention under 1 standard atmospheric pressure CO2 atmosphere (comprising 0.2mmol/L three-stage amphiphilic small molecule compound molecules, 2μmol/L C7 molecule is used as a catalyst, and 20mmol/L sodium ascorbate is used as a sacrificial reagent);

Fig. 16 is the reduction production curve of H2, CO, CH4 (comprising 0.2mmol/L three-stage amphiphilic small molecule compound molecules) of the water-phase photocatalytic spherical nanomicelle SPA-1 of the present invention under a CO2 atmosphere of 1 standard atmospheric pressure. 2μmol/L C7 molecule as a catalyst, 20mmol/L triethylamine hydrochloride as a sacrificial reagent);

Figure 17 is the reduction production curve of H2 and CH4 of the water-phase photocatalytic spherical nanomicelle SPA-1 of the present invention in a CO atmosphere of 1 standard atmospheric pressure (comprising 0.2mmol/L three-stage amphiphilic small molecule compound molecules, 2μmol/ The C7 molecule of L is used as a catalyst, and 20mmol/L triethylamine hydrochloride is used as a sacrificial reagent);

Figure 18 is the synchrotron radiation small-angle X-ray scattering curve of the photocatalytic spherical nanomicelle SPA-1 after illumination for different times in the present invention (the molecular concentration of the three-stage amphiphilic small molecule compound is 5.0 mmol/L);

Figure 19 is a characteristic gas chromatography curve of the photocatalytic spherical nanomicelle SPA-1 of the present invention reducing CO2 to produce CH4 and CO;

Figure 20 is the mass spectrometry analysis result of the photocatalytic spherical nanomicelle SPA-1 of the present invention producing 13CH4 and 13CO under an isotope-labeled 1 standard atmosphere 13CO2 atmosphere;

Figure 21 is the mass spectrometry analysis result of the photocatalytic spherical nanomicelle SPA-1 of the present invention producing 12CH4 and 12CO under 1 standard atmosphere of 12CO2;

Figure 22 is a schematic diagram of the centrifugal separation and ultrasonic dispersion of the photocatalytic spherical nanomicelle SPA-1 aqueous solution of the present invention;

FIG. 23 shows the recycling and catalytic effect of photocatalytic nanomicelles formed by molecular assembly of the three-stage amphiphilic small molecule compound of the present invention;

Figure 24 is a cryo-electron microscope picture of the spherical nanomicelle SPA-1 aqueous solution after the photocatalytic reaction is repeated 300 times (the molecular concentration of the three-stage amphiphilic small molecule compound is 0.2mmol/L);

Figure 25 is the result of small-angle X-ray scattering of the synchrotron radiation source of the spherical nanomicelle SPA-1 aqueous solution after the photocatalytic reaction is repeated 300 times in the present invention (the molecular concentration of the three-stage amphiphilic small molecule compound is 5 mmol/L);

Figure 26 shows the dynamic light scattering results of the spherical nanomicelle SPA-1 aqueous solution after the photocatalytic reaction is repeated 300 times (the concentration of the three-stage amphiphilic small molecule compound molecule is 5 mmol/L);

Figure 27 is the proton nuclear magnetic resonance spectrum of compound 3 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 28 is the carbon nuclear magnetic resonance spectrum of compound 3 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 29 is the proton nuclear magnetic resonance spectrum of compound 4 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 30 is a carbon nuclear magnetic resonance spectrum of compound 4 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 31 is the proton nuclear magnetic resonance spectrum of compound 5 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 32 is a carbon nuclear magnetic resonance spectrum of compound 5 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 33 is the proton nuclear magnetic resonance spectrum of compound 7 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 34 is a carbon nuclear magnetic resonance spectrum of compound 7 of the present invention in deuterated dimethyl sulfoxide (DMSO-d6);

Figure 35 is a high-resolution mass spectrum of compound 3 of the present invention;

Figure 36 is a high-resolution mass spectrum of compound 4 of the present invention;

Figure 37 is a high-resolution mass spectrum of compound 5 of the present invention;

Figure 38 is a high-resolution mass spectrum of compound 7 of the present invention;

Figure 39 is a high resolution mass spectrum of a three-segment amphiphilic small molecule compound of the compound of the present invention.

Invention embodiment

Implementation of the present invention

The structural principle and working principle of the present invention will be further described in detail below in conjunction with the accompanying drawings.

One of the objectives of the present invention is to provide a three-segment amphiphilic molecule for building a self-assembled micellar assembly of hydrophilic and hydrophobic molecules embedded with aramid fragments, that is, a head-body-tail three-segment water-soluble amphiphilic molecule Design ideas.

The self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments are formed by self-assembly of three-stage amphiphilic small molecule compounds in the water phase. The three-stage amphiphilic small molecule compounds include a head group, a neck connecting group and The tail side chain group, the three-segment amphiphilic small molecule compound is embedded in the aramid oligomer fragment in the traditional hydrophilic and hydrophobic molecule, and its general formula is:

In the general formula, X represents a water-soluble head group, Y represents a linking group containing hydrogen bonds, Z is a hydrophobic group, m is a positive integer selected from 0-100, and n is a positive integer selected from 1-100

X is selected from any one of the following structures X1, X2, X3, X4, X5, X6:

X1 is selected from porphyrin structures with hydrophilic groups

X2 is selected from phthalocyanine structures with hydrophilic groups

In the structure of X1 and X2, A1 is selected from hydrophilic soluble groups with sulfonic acid group substituted benzene or carboxylic acid group substituted benzene, A2 is selected from amino substituted benzene (R1-NH3Ph-) or pyridine (R1-NC5H4-), A2 Where R1 is selected from C1-C5 alkyl or C1-C5 alkoxy; the counter ion of the head group is any one of organic cations, metal cations, organic anions or halogen anions, and the metal atom in the center of the head group M is selected from any one or several blends of metals capable of coordinating with porphyrin; X3 is selected from linear polymer structures with hydrophilic groups, including artificial synthetic polymers or natural water-soluble polymers. Synthetic polymers are polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, N-(2-hydroxypropyl)methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA), polyoxazoline, polyphosphate or polyphosphazene; the natural water-soluble polymer is xanthan gum, pectin, chitosan Sugar derivatives, dextran, carrageenan, guar gum, cellulose, cellulose ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or starch-based derivatives Any kind

The three-stage amphiphilic small molecule compound has the following structure, wherein n is a positive integer from 1 to 100, and m is a positive integer from 10 to 200:

The water-phase ultra-uniform assembly in this embodiment is a round micelle, and its building unit head-neck-tail three-stage water-soluble amphiphilic molecule has the following structure: H-N-T. The N part can be a collection of multi-level structures, such as N1, N2, N3...

The head group (H) part of the building unit molecule constituting the aqueous ultra-uniform circular micelle assembly has the following structure:

It can be a porphyrin structure with a hydrophilic group, where A is a hydrophilic soluble group, and N is the N part of the head-neck-tail (H-N-T) three-part formula:

It can be a phthalocyanine structure with a hydrophilic group, where A is a hydrophilic soluble group, and N is the N part of the head-neck-tail (H-N-T) three-part formula:

It can be a linear polymer structure with hydrophilic groups:

Such as synthetic polymers, such as polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, N-(2-hydroxypropyl)methyl Acrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA) polyoxazoline, polyphosphate, polyphosphazene, etc., or natural water-soluble polymers such as xanthan gum, pectin, chitosan derived Substances, dextran, carrageenan, guar gum, cellulose, cellulose ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or starch-based derivatives, etc.

Can be polyelectrolyte structure:

Such as disodium polybenzene sulfonate, polyacrylic acid, etc.

It can be a dendritic polymer structure with hydrophilic groups:

Such as polypropyleneimine dendrimer (PPI), poly(amidoamine) dendrimer (PAMAM), polyether dendrimer, polyarylether dendrimer, polylysine dendrimer Wait,

Wherein S is a water-soluble group, B is the connection fulcrum, C is the main connection point, 1-3 is the algebra, which can be 1-n.

The neck base (N) part of the building unit molecule constituting the aqueous ultra-uniform circular micelle assembly has the following structure:

The aramid group is an essential group, and n is a positive integer greater than 0 and less than 100. Among them, the neck groups of the building unit molecules that make up the water phase ultra-uniform circular micellar assembly mainly include linear arylamides, unsaturated amino acids and saturated amino acids; at the same time, the neck group (N) part can also include other linking groups The linking group may be amino, carbonyl, —S—, alkene, alkyne or one or more of the following groups or no linking group, n is a positive integer greater than 0 and less than 100.

The tail (T) part of the building unit molecule constituting the water phase ultra-uniform circular micelle assembly can be a saturated or unsaturated long-chain alkane structure.

The second objective of the present invention is to provide a method for preparing the above-mentioned three-stage amphiphilic molecule of the building unit molecule to form an aqueous phase ultra-uniform circular micelle assembly:

1) Take 1-100 mg of the amphiphilic three-segment small molecule compound prepared in Example 1 into a glass sample bottle, add 1-100 mL deionized water, and ultrasonically disperse for 2-20 minutes. Appropriate heating can promote the formation of small molecules by dispersing and dissolving. Red solution.

2) Take 5-10 mg/mL zinc acetate aqueous solution and add it to the above small molecule solution in an equivalent amount.

3) Heat until the above solution turns dark green, and further sonicate for 2-20 minutes.

4) The mixture is allowed to stand for 10-24 hours to obtain an ultra-uniform, monodisperse, 8-20nm-scale spherical micelle assembly.

The spherical micelle prepared according to the above method has good monodispersity in water, colloidal stability, and its colloidal stability is positively correlated with the increase in the number of hydrogen bonds of the neck linking group, which leads to the enhancement of the interaction between small molecules, and The particle size can be precisely controlled by the length of the amphiphilic small molecule. Through high-resolution cryo-transmission electron microscope, synchrotron radiation source X-ray small-angle scattering, solution dynamic light scattering, concentration-dependent solution phase dynamic light scattering, and Zeta potential test and other related characterization methods proved that the spherical micelle size is 8-20nm and has Good monodispersity and colloidal stability.

It is used to assemble the head-neck-tail three-stage water-soluble amphiphilic molecule for assembling water-phase ultra-uniform circular micelles. The assembled monomer structure of the water-phase ultra-uniform assembly of the water-phase ultra-uniform monomer structure. The three-stage monomer structure has two ends Asymmetric amphiphilic substituents use intermediate fragments to self-assemble between molecules through hydrogen bond interactions, thereby obtaining the water phase of the present invention for selective photocatalytic proton reduction to produce hydrogen, CO2 reduction to produce CO, and CH4 Ultra-uniform self-assembled micelles, the ultra-uniform self-assembled micelles (about 20 nanometers in diameter) have extremely high specific surface area and photocatalytic hydrogen production effect; therefore, this water-phase ultra-uniform self-assembled micelles can be used as excellent Artificially imitate the natural photocatalytic system; and, due to the selective photocatalytic proton reduction of the present invention to produce hydrogen, CO2 reduction to produce CO, and CH4, the water phase ultra-uniform self-assembled micelles have a nano-level spherical structure caused by the surface The characteristics of the photosensitizer’s controllable distance and large specific surface area are conducive to the delocalization of the excited electrons of the photosensitizer on the surface and the collision probability of the catalyzed substrate on the catalyst surface, thereby greatly improving the recovery of the self-assembled micelles. The original production of hydrogen, CO2 reduction to produce CO and CH4. Therefore, the head-body-tail three-stage water-soluble amphiphilic water phase super-uniform self-assembled micelle of the present invention can be used as a good selective photocatalytic proton reduction to produce hydrogen and CO2 reduction to produce CO. And the artificial imitation of natural photocatalytic system for producing CH4.

The spherical micelle water phase ultra-uniform assembly prepared according to the above method has related applications of selective photocatalytic proton reduction to produce hydrogen, CO2 reduction to produce CO and CH4.

When the spherical micelle water phase ultra-uniform assembly prepared according to the above method is used for selective photocatalytic proton reduction to produce hydrogen, small catalyst molecules with opposite charges to the surface charge of the assembly must be added for mixing.

When the spherical micelle water phase ultra-uniform assembly prepared according to the above method is used for selective photocatalytic proton reduction to produce hydrogen, the water phase sacrificial reagent can be triethylamine, triethanolamine, ascorbic acid, sodium ascorbate, etc. Agent or oxidant.

One of the objectives of this embodiment is to provide a three-segment amphiphilic molecule for building a self-assembled micellar assembly of hydrophilic and hydrophobic molecules embedded with aramid fragments. The present invention is a self-assembled micelle of hydrophilic and hydrophobic molecules embedded with aramid fragments. Its building unit head-neck-tail (HNT) three-stage water-soluble amphiphilic molecule has the following structure. Among them, the head group (H) part is a porphyrin structure with a hydrophilic group:

Wherein: X is one of X1, X2, X3 or X4; said X1, X2, X3 or X4 represents four types of porphyrin derivatives with different symmetrical substituents in the head group. X1 represents a para-methyl substituted pyridine substituent; X2 represents a para-trimethylamino-substituted phenyl group; X3 represents a para-carboxyl substituted phenyl group; X4 represents a para-sulfonic acid group substituted phenyl.

The neck group (N) part mainly includes three types of linear arylamides, unsaturated amino acids and saturated amino acids, and has any one of the following structures:

Among them, the tail (T) part of the building unit molecule that composes the water phase ultra-uniform circular micellar assembly mainly includes straight-chain alkanes, unsaturated olefin chains and long ether chains, with the following structures:

The central metal of the head group (H) part of the porphyrin molecule of the building unit molecule constituting the water phase ultra-uniform circular micelle assembly is one or more of zinc, iron, cobalt, and nickel, and a counter ion It is one or a blend of chlorine, bromine and iodide anions.

The connecting group of the neck-base part of the building unit molecule constituting the water phase ultra-uniform circular micelle assembly is a linear aramid oligomer fragment, or a condensation fragment of aramid and linear aliphatic or unsaturated amino acids, The order and proportion can be arbitrarily matched. The neck connecting group can also introduce a charged group such as polyelectrolyte.

As shown in Figures 1 to 39, the synthetic route of the three-stage amphiphilic small molecule compound (TD-1) in this example is as follows:

Prepare a head-neck-tail three-stage water-soluble amphiphilic molecule with the following molecular formula:

Step 1, the preparation method of compound 3, add CHCl3 (150 ml), methyl p-aminobenzoate (compound 1) (0.50 g, 3.3 mmol), stearic acid (compound 2) (0.94 g, 3.3 mmol), 1 -Ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI, 0.78 g, 4.0 mmol) was added to 4-(dimethylamino) pyridine (DMAP, 0.49 g, 4.0 mmol) and stirred at room temperature for 24 hours. The formed precipitate was filtered, washed with CHCl3 (20 mL), and dried under vacuum to obtain a white solid. Then the obtained solid was suspended in a mixture of THF/MeOH/H2O (4:2:1) solution, LiOH·H2O (0.72 g, 17.0 mmol) was added and the reaction system was stirred under reflux for 24 hours. After the solvent is removed in vacuo, the solid obtained is washed with a solvent (20 ml). The solvent can be water or a hydrophilic solvent such as methanol, ethanol, isopropanol and other alcoholic solvents, tetrahydrofuran, acetone, dimethylimide, dimethyl One or several combinations of sulfoxides. In this embodiment, water is used as the solvent, and then washed with 1M HCl aqueous solution (20 mL) and water (20 mL), and dried to obtain compound 3. The test results are shown in Figure 27, Figure 28, and Figure 35.

Step 2. According to the method described in compound 3, compound 4 was prepared by the reaction of

compound

3 and 1, with a yield of 87%, and it was a white solid. The test results are shown in Figure 29, Figure 30, and Figure 36.

Step 3. According to the method described in compound 3, compound 5 was prepared from the reaction of

compound

4 and 1, with a yield of 81%, and it was a white solid. The test results are shown in Figure 31, Figure 32, and Figure 37.

Step 4. Preparation of compound 7. A mixture of compound 5 (27.2 mg, 0.096 mmol), compound 6 (50.0 mg, 0.064 mmol), EDCI (18.3 mg, 0.096 mmol) and DMAP (13.0 mg, 0.096 mmol) in DMF (5 mL) at 60°C Stir. It was kept at 24°C for 24 hours, and after cooling to room temperature, the solvent was removed under reduced pressure. The obtained red solid was washed three times with CHCl3 (1 mL) to remove excess EDCI and DMAP. The precipitate was separated, and the crude product was purified using flash column chromatography (MeOH:MeCN:H2O 8:1:1). The obtained components were evaporated to dryness to obtain compound 7 as a red solid (44 mg, 67%). (For the preparation of compound 6, refer to Bryden, F.; Boyle, R.W., A Mild, Facile. Synlett. 2013, 24, 1978.) The test results are shown in Figure 33, Figure 34, and Figure 38.

Step 5. In a 20 mL pressure vessel, dissolve compound 7 (100 mg, 0.095 mmol) in water (5 mL), add zinc acetate (69 mg, 0.45 mmol), stir the system under reflux for 5 hours, and then add tetrabutylene Ammonium iodide (252 mg, 0.91 mmol) exchanges anions. The mixture was stirred at room temperature for 24 hours, and then the solvent was evaporated under reduced pressure until a green solid precipitate formed, and the obtained green solid was further recrystallized from water to obtain the compound three-stage amphiphilic small molecule. The structure is shown in Figure 1, which is dark green Solid (60 mg, 74%). The test results are shown in Figure 33, Figure 34, and Figure 39.

The amphiphilic three-segment small molecules prepared according to the above embodiments can spontaneously assemble in the water phase to form ultra-uniform, monodisperse, spherical micelles with a scale of 8-20 nm.

The second purpose of this embodiment is to provide a method for preparing the above-mentioned three-segment amphiphilic molecule of the building unit molecule to form an aqueous ultra-uniform circular micelle assembly. In this example, the three-stage amphiphilic small molecule compound formed super-uniform spherical nanomicelle SPA-1 is characterized as follows:

Step 6. Use the amphiphilic three-segment small molecule three-segment amphiphilic small molecule compound prepared by the method described in steps 1 to 5 of the above embodiment. Take 1 mg of compound 1 in a glass sample bottle, add 1 mL of deionized water, and ultrasonically disperse After 10 minutes, the tube is sealed and heated to 150 degrees Celsius to promote the dispersion and dissolution of small molecules to form a green solution. The prepared solution is heated until it becomes dark green, and is further sonicated for 2-20 minutes to obtain a clear and transparent photocatalytic nanomicelle SPA-1 aqueous solution.

Step 7, take out 10 microliters of the clear and transparent mixture obtained in step 6 and drop it on the copper mesh, and observe under the Talos high-resolution cryo-transmission electron microscope after the solvent evaporates. Using a Gatan 626 cryogenic transfer holder (Gatan, USA), 3 microliters of SPA-1 aqueous solution was deposited on a copper TEM grid with porous carbon support membrane (Electron Microscopy Sciences), and fixed with tweezers mounted on Vitrobot. The sample is sucked dry in a 90-100% humidity environment and put into a liquid ethane reservoir, which is cooled with liquid nitrogen. The vitrified sample is transferred to liquid nitrogen in a nitrogen environment, and then transferred to a Gatan 626 cryostat using a low temperature transfer stage. The photomicrograph is recorded on a 4,096×4,096 pixel Tietz CCD camera at the nominal magnification (Figure 5).

Step 8, using a JEM-2100-FEG transmission electron microscope (JEOL, Japan) at 200 KeV to obtain a solid phase TEM image Figure 6. As shown in Figure 5 and Figure 6, SPA-1 is an ultra-uniform spherical nanomicelle with a size between 14 and 16 nanometers and has excellent monodispersity and colloidal stability in water. After high-resolution cryo-transmission electron microscope, synchrotron radiation source X-ray small-angle scattering, solution dynamic light scattering, concentration-dependent solution phase dynamic light scattering, and Zeta potential tests, spherical micelles have good monodispersity and colloidal stability in water. Its colloidal stability is positively correlated with the increase in the number of hydrogen bonds of the neck linking group leading to the enhancement of the interaction between small molecules, and the particle size can be precisely controlled by the length of the amphiphilic small molecule.

Step 9. Take out 2 ml of the clear and transparent mixed solution (1 mg/mL) obtained in Step 6, and add it to a quartz cuvette, perform a solution phase dynamic light scattering test, and obtain FIG. 7. The spherical micelles of SPA-1 have an average hydrated particle size of 15.7 nm and a dispersibility index (PDI) of 1.01.

Step 10: Take out 2 ml of the clear and transparent mixed solution (1 mg/mL) obtained in Step 6, dilute to different concentrations, add to a quartz cuvette, and perform concentration-related solution phase dynamic light scattering to obtain Figure 8. The particle size of SPA-1 micelles can be maintained at different concentrations.

In

step

11, 100 microliters of the clear and transparent mixed solution (1 mg/mL) obtained in step 6 is taken out, and added to a quartz capillary tube, and X-ray small-angle scattering is performed with a synchrotron radiation source to obtain FIG. 9. By using the core-shell model in the Irena 2.63 software, the average particle size of SPA-1 is 14.1±1.1 nanometers.

Step 12: Take out 2 ml of the clear and transparent mixed solution (1 mg/mL) obtained in Step 6, and perform an ultraviolet-visible absorption spectrum test to obtain FIG. 10.

In step 13, take out 2 ml of the clear and transparent mixed solution (1 mg/mL) obtained in step 6, and perform a fluorescence emission spectrum test to obtain FIG. 11.

In step 14, take out 2 ml of the clear and transparent mixed solution (1 mg/mL) obtained in step 6, and irradiate it with a 500w photoreactor for different periods of time, and then perform an ultraviolet-visible absorption spectrum test to obtain FIG. 12.

Step 15, cyclic voltammetric oxidation-reduction potential test, performed in a 20mL custom glass vial with 0.2M Na2 SO4 aqueous solution at 25°C. Use BioLogic VMP3 workstation to record electrochemical response. In a typical three-electrode test system, 2mm diameter gold, platinum foil (Beantown Chemical, 99.99%) and Ag/AgCl/KCl (saturated aqueous solution) are used as working electrode, counter electrode and reference electrode, respectively. The working electrode was cleaned by polishing with 0.05 μm polished alumina and then sonicating. The scan rate is 100mV/s. In this work, E(relative to NHE)=E(relative to Ag/AgCl)+0.197V was used to convert all the potentials measured for the Ag/AgCl electrode into the normal hydrogen electrode (NHE) scale. The cyclic volt-ampere characteristic curve obtained is shown in Figure 13.

The third purpose of this embodiment is to provide the application of the three-stage amphiphilic molecular water phase ultra-uniform assembly in selective photocatalytic proton reduction to produce hydrogen, CO2 reduction to produce CO, and CH4. Mix the ultra-uniform, monodisperse, and controllable water-phase assembly formed by the three-stage amphiphile in the water-phase assembly with the small catalyst molecule in Figure 3 with the opposite charge to the surface of the assembly. Preparation of water phase supramolecular photocatalytic assembly. The supramolecular photocatalytic assembly may be suitable for hydrogen production by water-phase proton reduction in atmospheric atmosphere, normal temperature and normal pressure, and selective reduction of CO2 to prepare CO and CH4 in CO2 atmosphere, normal temperature and normal pressure. And the entire photocatalytic assembly does not contain any precious metals. According to different requirements, the aqueous sacrificial reagent can be a reducing agent or an oxidizing agent such as triethylamine, triethanolamine, ascorbic acid, and sodium ascorbate.

In this example, the photocatalytic reaction activity test of the water-phase photocatalytic assembly SPA-1 is as follows:

In step 16, the spherical micelle water phase ultra-uniform assembly obtained in step 6 is subjected to selective photocatalytic reduction to produce hydrogen. Photocatalytic hydrogen production is carried out in an externally illuminated reaction vessel with a magnetic stirrer. Samples for photocatalytic hydrogen production were prepared in 8 mL septum-sealed glass vials. Make up each sample to 1.0 mL volume of aqueous solution. The sample usually contains 0.2 mM ZnPAAs and 0.002 mM cobalt catalyst. The solution was irradiated with a 500W solid-state light source with a wavelength>400nm filter. After the reaction, the gas in the headspace of the vial was analyzed by GC to determine the amount of gas generated.

Step 17, analyze the amount of gas obtained in step 12 for photocatalytic hydrogen production. The yield of electrochemical experiments was analyzed by GC in an SRI 8610C GC system equipped with a 72×1/8 inch S.S. molecular sieve packed column and a thermal conductivity detector. Check the production of H2, CO and CH4 respectively. Thermal conductivity detector (TCD) is mainly used to quantify H2 concentration, and flame ionization detector (FID) with methanator is used for quantitative analysis of CO and other alkanes content. Ultra-high-purity CO2 (purchased from AirGas) is used as the carrier gas for CO and CH4 detection, and ultra-high-purity nitrogen (AirGas) is used for H2 detection. Initially, the GC system was calibrated for H2, CO and CH4. Obtain Figure 14-17.

Step 18, referring to step 11, take out the solution with different illumination time after the photoreaction and perform the synchrotron radiation source small-angle X-ray scattering to detect the stability of the reaction SPA-1 to obtain Figure 18.

Step 19, in order to confirm that the CO and CH4 products are from CO2, the isotope 13 CO2 (Sigma Aldrich) is used as the atmosphere gas for the visible light irradiation experiment, and GC-mass spectrometry is used for gas detection. The 13C-labeled samples were analyzed on Agilent 7890A gas chromatograph (GC) and Agilent 5975C mass spectrometer (MS). A DB-5MS column (60m×0.25mm×2.5μm) was used for analysis. The injection port and the GC column oven are set at 100°C. The transmission line, source and MS were set at 270°C, 230°C and 150°C, respectively. The MS is in full scan mode, and the m/z scan range is 14-50amu. Use an air-tight syringe to manually inject the sample. Inject air as the instrument background. Figure 19-21 were obtained.

Recycling stability test of the photocatalytic nanomicelle SPA-1 after the photocatalytic reaction of the water-phase photocatalytic assembly SPA-1

Step 20: Take out 2 mL of the solution after participating in the photoreaction, and use a high-speed centrifuge with a centrifugal speed of 15,000 rpm for 5 minutes, and it is found that the SPA-1 spherical nanomicelles can be centrifuged.

In step 21, the SPA-1 micelles centrifuged in step 20 are ultrasonically dispersed for 2-10 minutes (35kHz, 160W) to obtain a uniformly dispersed aqueous solution of SPA-1. See Figure 22.

Step 22, repeat steps 20 and 21, and perform a photocatalytic test on the recycled SPA-1 aqueous solution (repeat step 17) and detect the catalytic effect to obtain Figure 23.

Step 23: Observe the SPA-1 aqueous solution subjected to the photoreactivity test after repeated centrifugal separation 300 times (refer to step 7) to obtain Figure 24.

Step 24: Perform the small-angle X-ray scattering test of the synchrotron radiation source with the SPA-1 aqueous solution subjected to the photoreaction test after repeated centrifugal separation 300 times (refer to step 11) to obtain FIG. 25.

In step 25, the SPA-1 aqueous solution subjected to the light reaction test after repeated centrifugal separation 300 times is subjected to a dynamic light scattering test (refer to step 10) to obtain FIG. 26.

The preparation method of the amphiphilic small molecule organic compound of the present invention identifies the structure of the new type of compound through nuclear magnetic resonance, high-resolution mass spectrometry, ultraviolet-visible absorption spectroscopy, and fluorescence spectroscopy. The inventors further used coordination and water-phase self-assembly strategies to successfully prepare an ultra-uniform, monodisperse, and particle-controllable micellar assembly structure that is stable in the water phase. This type of assembly structure has not been reported at home and abroad. The inventor further passed the synchrotron radiation source small-angle X-ray scattering, wide-angle X-ray scattering, dynamic light scattering, cryo-transmission electron microscope, high-resolution field emission microscope, cyclic voltammetry characteristic curve test, ultraviolet-visible absorption spectrum, fluorescence luminescence spectrum, transient state Experiments such as electronic absorption spectroscopy, transient fluorescence emission spectroscopy, and laser confocal have carried out property tests on the SPA water phase assembly materials. It is found that this type of material is easy to synthesize and prepare, and has ultra-uniform particle size and water phase monodispersion. It can form an ultra-uniform particle size structure by self-installation in the water phase, and can achieve particle size monodispersity without template agents and particle size control equipment. At the same time, the material has good modifierability, which makes it possible to give it rich functions. Because the structure has special multiple hydrogen bonds for acceptors, it has excellent structural stability. It can be used as a new universal multifunctional water phase material platform and widely used in many fields such as energy materials, catalysis, drug loading, bioimaging, semiconductor materials, display materials, molecular probe materials and so on.

The above are only preferred embodiments of the present invention, and any minor modifications, equivalent changes and modifications made to the above embodiments based on the technical solutions of the present invention fall within the scope of the technical solutions of the present invention.

Industrial applicability

The present invention is a preparation method of self-assembled micelles of hydrophilic and hydrophobic molecules embedded in aramid fragments and supramolecular photocatalytic assembly. The present invention synthesizes a series of new three-stage amphiphilic small molecule compounds with enhanced hydrogen bond. In water molecules, arylamide oligomer fragments are embedded. They use the intermediate fragments to interact through hydrogen bonds between the molecules to self-assemble into ultra-uniform micelles. They have extremely high chemical and structural stability in water, and have high chemical and structural stability in water. Good uniformity, monodispersity, colloidal stability, its colloidal stability increases with the number of hydrogen bonds of the neck linking group, which leads to a positive correlation between the interaction of small molecules, and the particle size can be determined by the size of the amphiphilic small molecule. The length is precisely controlled; the supramolecular photocatalytic assembly is suitable for the reduction of water-phase protons to produce hydrogen in the atmosphere, normal temperature and pressure, and the selective reduction of carbon dioxide to produce CO and CH4 in a carbon dioxide atmosphere, normal temperature and normal pressure. The photocatalytic system is very similar to the "antenna effect" of natural photosynthesis; the photocatalytic system constructed by supramolecular photocatalytic assembly uses cationic porphyrin hydrophilic head group as photosensitizer and anionic cobalt complex as catalyst, and does not contain precious metals; The water-phase ultra-uniform self-assembled micelle of the selective photocatalytic proton reduction to produce hydrogen and the selective reduction of carbon dioxide to prepare CO and CH4 of the present invention has a nano-level spherical structure, which results in a controllable surface photosensitizer distance and a large specific surface area. The characteristic of this is conducive to the delocalization of the excited state electrons of the photosensitizer on the surface and the collision probability of the catalyzed substrate on the surface of the catalyst, thereby greatly improving the reduction of hydrogen production and the selective reduction of carbon dioxide of the supramolecular photocatalytic assembly Preparation efficiency of CO and CH4; supramolecular photocatalytic assembly has special multi-hydrogen bond donor and acceptor, which makes it have excellent structural stability, and can be used as a new type of universal multifunctional water phase material platform. It is used in many fields such as energy materials, catalysis, drug loading, bioimaging, semiconductor materials, display materials, molecular probe materials and so on. Therefore, the present invention has industrial applicability.

Claims

The self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments are formed by self-assembly of three-stage amphiphilic small molecule compounds in the water phase, and are characterized in that: the three-stage amphiphilic small molecule compounds include a head group and a neck The linking group and the tail side chain group, the three-segment amphiphilic small molecule compound is embedded in the aramid oligomer fragment in the traditional hydrophilic and hydrophobic molecule, and its general formula is:

In the general formula, X represents a water-soluble head group, Y represents a linking group containing hydrogen bonds, Z is a hydrophobic group, m is a positive integer selected from 0-100, and n is a positive integer selected from 1-100;

X is selected from any one of the following structures X1, X2, X3, X4, X5, X6:

X1 is selected from porphyrin structures with hydrophilic groups

X2 is selected from phthalocyanine structures with hydrophilic groups

In the structure of X1 and X2, A1 is selected from hydrophilic soluble groups with sulfonic acid group substituted benzene or carboxylic acid group substituted benzene, A2 is selected from amino substituted benzene (R1-NH3Ph-) or pyridine (R1-NC5H4-), A2 Where R1 is selected from C1-C5 alkyl or C1-C5 alkoxy; the counter ion of the head group is any one of organic cations, metal cations, organic anions or halogen anions, and the metal atom in the center of the head group M is selected from any one or several blends of metals that can coordinate with porphyrin;

X3 is selected from the linear polymer structure of hydrophilic group, including artificial synthetic polymer or natural water-soluble polymer, the artificial synthetic polymer is polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), poly Vinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, N-(2-hydroxypropyl)methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA) polyoxazoline, poly Any one of phosphate or polyphosphazene; the natural water-soluble polymer is xanthan gum, pectin, chitosan derivatives, dextran, carrageenan, guar gum, cellulose, fiber Any one of plain ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or starch-based derivatives;

X4 is selected from artificial synthetic polymers or natural water-soluble polymers, and the artificial synthetic polymers are polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylic acid (PAA), and polyvinyl pyrrolidone (PVP). Any one of acrylamide, N-(2-hydroxypropyl)methacrylamide (HPMA), divinyl ether-maleic anhydride (DIVEMA) polyoxazoline, polyphosphate or polyphosphazene; The natural water-soluble polymer is xanthan gum, pectin, chitosan derivatives, dextran, carrageenan, guar gum, cellulose, cellulose ether, sodium carboxymethyl cellulose, hyaluronic acid (HA), albumin, starch or any one of starch-based derivatives;

X5 is selected from the following polyelectrolyte structures with positive or negative charges, selected from any one of disodium polybenzenesulfonate, polyacrylic acid, and polyammonium salt, or any one of the following general structural formulas:

X6 is selected from dendritic polymer structures with hydrophilic groups, selected from polypropyleneimine dendrimers (PPI), poly(amidoamine) dendrimers (PAMAM), polyether dendrimers Any one of poly(arylene ether) dendrimers, polylysine dendrimers;

In the general formula, Y is selected from any one of natural amino acids, C1-C10 aliphatic chains, and linear aromatic amides -(R2) n NHC(O)-, and R2 is selected from substituted phenyl, five-membered or six-membered hetero One or a mixture of cyclic aromatic substituents, -(CH 2 ) n NHC(O)-, -(CH=CH) n NHC(O)-, n is a positive integer from 1 to 100;

In the general formula, Z is selected from C5-C100 linear or branched alkyl, alkoxy, unsaturated aliphatic, polyvinyl, polypropylene, polybutadiene, polystyrene, polyvinyl chloride Any one of a polytetrafluoroethylene group, a polytetrafluoroethylene group, and a polymethacrylate group.
The self-assembled micelle of hydrophilic and hydrophobic molecules embedded with aramid fragments according to claim 1, wherein the three-stage amphiphilic small molecule compound has the following structure, wherein n is a positive integer from 1 to 100, m Positive integer from 10-200:
The self-assembled micelle of hydrophilic and hydrophobic molecules embedded with arylamide fragments according to claim 2, wherein the structure of the three-stage amphiphilic small molecule compound is:
The self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments according to any one of claims 1 to 3, wherein the preparation of the three-stage amphiphilic small molecule compound comprises the following steps:

S1, prepare compound 3, add CHCl 3, methyl p-aminobenzoate (compound 1), stearic acid (compound 2), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide The mixture of hydrochloride salt was added with 4-(dimethylamino)pyridine and stirred at room temperature for 24 hours. The formed precipitate was filtered, washed with CHCl 3, and dried under vacuum to obtain a white solid. Then the obtained solid was suspended in a mixture of THF, MeOH, and H2O solution, LiOH·H2O was added and the reaction system was stirred under reflux for 24 hours. After the solvent was removed in vacuo, the obtained solid was washed with the solvent, and then with HCl aqueous solution and water Compound 3 is obtained after washing and drying;

S2. According to the method for preparing compound 3, compound 4 is prepared from the reaction of compound 3 and compound 1, with a yield of 87%, and it is a white solid;

S3. According to the method for preparing compound 3, compound 5 is prepared by the reaction of compound 4 and compound 1, with a yield of 81%, which is a white solid;

S4. Preparation of compound 7. The mixture of compound 5, compound 6 EDCI and DMAP was stirred in DMF at 60°C and kept at 24°C for 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the obtained red solid was treated with CHCl 3 Wash three times to remove excess EDCI and DMAP, separate the precipitate, and use flash column chromatography (MeOH:MeCN:H2O 8:1:1) to purify the crude product, and evaporate the obtained components to dryness to obtain the compound 7. It is a red solid;

S5. In a 20 mL pressure vessel, dissolve compound 7 in water, add zinc acetate, stir the system under reflux for 5 hours, then add tetrabutylammonium iodide to exchange anions, stir the mixture at room temperature for 24 hours, and then The solvent was evaporated under reduced pressure until a green solid precipitate was formed, and the obtained green solid was further recrystallized from water to obtain a three-stage amphiphilic small molecule compound as a dark green solid.
The self-assembled micelles of hydrophilic and hydrophobic molecules embedded in aramid fragments according to claim 4, wherein the washing solvent used in step S1 is water, hydrophilic alcohol solvents, tetrahydrofuran, acetone, dimethylimide or One or more of dimethyl sulfoxide.
The self-assembled micelles of hydrophilic and hydrophobic molecules embedded in aramid fragments according to claim 5, characterized in that: the self-assembled micelles of hydrophilic and hydrophobic molecules embedded in arylamide fragments are the three-stage amphiphilic small molecule compound in In the water phase, uniform, monodisperse spherical micelles with controllable particle size are formed by self-assembly of the intermediate fragments between molecules through hydrogen bond interactions.
A method for preparing self-assembled micelles of hydrophilic and hydrophobic molecules embedded with aramid fragments according to claim 6, characterized in that it comprises the following steps:

S1. Take 1mg～100mg three-stage amphiphilic small molecule compound in a glass sample bottle, add 1ml～100mL deionized water, ultrasonically disperse for 2min～20min, seal the tube and heat to 150 degrees Celsius to make the three-stage amphiphilic small molecule compound Disperse and dissolve to form a red solution;

S2. Take 5mg/mL～10mg/mL zinc acetate aqueous solution and add the equivalent to the above red solution;

S3. Heat until the above solution turns dark green, and further sonicate it for 2 to 20 minutes;

S4. The above mixture is allowed to stand for 10 hours to 24 hours to prepare self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments.
A preparation method of supramolecular photocatalytic assembly, characterized in that: said supramolecular photocatalytic assembly is prepared by claim 6 of the hydrophilic and hydrophobic molecular self-assembled micelles embedded in aramid fragments in an aqueous sacrificial reagent Prepared by a catalyst reaction, the catalyst is an oxidized metal nanocatalyst (such as TiO2, ZnO, CdS, WO3, Fe2O3, PbS, SnO2, ZnS, SrTiO3, SiO2, etc.), a duplex catalyst or a metalloporphyrin-based catalyst, a metal bipyridyl (Or terpyridyl) catalysts, metal pyridoxime-based catalysts, carbon dots, quantum dots, metal nanoparticles (such as gold nanoparticles, platinum nanoparticles, etc.), graphene-based catalysts, and the catalysts are not charged, or It has the same or opposite charge as the surface charge of the hydrophilic and hydrophobic molecule self-assembled micelle embedded in the arylamide fragment.
The method for preparing supramolecular photocatalytic assembly according to claim 8, wherein the aqueous sacrificial reagent is methanol, ethanol, isopropanol, tert-butanol, n-butanol, alcohol derivatives, phenol Hydroxy derivatives, triethylamine, triethanolamine, ascorbic acid, sodium ascorbate, ethylenediaminetetraacetic acid, dimethylaniline, oxalic acid and its derivatives, thioacid derivatives, triphenylphosphorus reducing agent or acidic medium oxidant (Example: hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate), alkaline medium oxidizer (example: sodium hypochlorite, sodium percarbonate, sodium perborate, perboric acid Potassium), neutral oxidants (e.g. bromine, iodine), high-valent non-metallic compounds such as HNO3, NaClO3, NaClO, high-valent metal salts such as KMnO4, Na2Cr2O3, K2Cr2O7, high-valent metal oxides such as MnO2, CrO3, organic peroxyacid oxidants Any one or several.
The self-assembled micelles of hydrophilic and hydrophobic molecules embedded with arylamide fragments according to claim 1, wherein the three-stage amphiphilic small molecule compound is applied to small molecule catalysis, polymer catalysis, enzyme catalysis, olefin polymerization, Olefin cracking, petroleum cracking, photocatalysis, water decomposition, nitrogen reduction, carbon monoxide, carbon dioxide reduction, water oxidation, phenolic hydroxyl oxidation, alcohol oxidation, aldehyde oxidation, formaldehyde, benzene, ammonia, sulfur dioxide, carbon monoxide, nitrogen oxide oxidation reactions .
An aqueous self-assembled micelle and a photocatalytic assembly constructed by the same, characterized in that it is composed of the three-stage amphiphilic small molecule compound according to claim 1, the catalyst according to claim 8, and the photocatalytic assembly according to claim 9. The sacrificial reagent is combined with a solvent; wherein the solvent is one or a combination of water, alcohol solvents, carboxylic acid solvents, non-polar solvents, polar solvents, and ionic liquids.
The aqueous self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 11, wherein the alcohol solvent is one of methanol, ethanol, isopropanol, n-butanol, and tert-butanol. One or a combination of two or more.
The aqueous self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 11, wherein the carboxylic acid solvent is one or a combination of formic acid, acetic acid, propionic acid, and butyric acid .
The aqueous self-assembled micelle and the photocatalytic assembly constructed by the water-phase self-assembled micelle according to claim 11, wherein the non-polar solvent is one or a combination of two or more of n-hexane and cyclohexane.
The water-phase self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 11, wherein the polar solvent is one of dimethyl sulfoxide, dimethyl formamide, acetonitrile, and acetone. One or a combination of two or more.
The water-phase self-assembled micelle and the photocatalytic assembly constructed by the water-phase self-assembled micelle according to claim 11, wherein the solvent is a mixed solvent of water and other solvents, and the proportion of other solvents is 1% to 99%. The solvent is one or a combination of the alcohol solvents, carboxylic acid solvents, non-polar solvents, polar solvents, and ionic liquids.
The aqueous self-assembled micelle and the photocatalytic assembly constructed by the water-phase self-assembled micelle according to claim 16, wherein the proportion of the other solvent is 1% to 50%, preferably 1% to 10%.
The water-phase self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 11, wherein the weight percentage of the compound of claim 1 is 0.001% to 10%, and the weight percentage of the catalyst in claim 8 The content is 0.001% to 5%, the weight percentage of the sacrificial reagent in claim 9 is 0.1% to 10%, and the solvent content is 90% to 99.9%.
The water-phase self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 18, wherein the weight percentage of the compound of claim 1 is 0.001% to 1%, and the weight percentage of the catalyst in claim 8 The content is 0.001% to 1%, the weight percentage of the sacrificial reagent in claim 9 is 1% to 10%, and the solvent content is 95% to 99.9%.
The water-phase self-assembled micelle and the photocatalytic assembly constructed thereof according to claim 19, wherein the weight percentage of the compound of claim 1 is 0.001% to 0.1%, and the weight percentage of the catalyst in claim 8 The content is 0.001% to 0.1%, the weight percentage of the sacrificial reagent in claim 9 is 1% to 5%, and the solvent content is 99% to 99.9%.