Imidazolyl dimer receptor and preparation method thereof, photoelectric detector and biological light diagnosis and treatment nanoparticles

Abstract

The invention discloses an imidazolyl dimer receptor and a preparation method thereof, a photoelectric detector and a biological light diagnosis and treatment nanoparticle, the structural general formula of the imidazolyl dimer receptor is # imgabs0 #, R1 is # imgabs1 #, R2 is # imgabs2 # imgabs3 #, X1 and X2 are respectively and independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photoelectric functional materials, and in particular to an imidazole-based dimer receptor and a preparation method thereof, a photoelectric detector and bio-photodiagnostic nanoparticles. Background Art

[0002] Organic optoelectronic materials have attracted extensive attention due to their versatility and can be applied to solar cells, organic photodetectors, light-emitting diodes, transistors, biophototherapy and photocatalysis. Among them, organic photodetectors are known for their mechanical flexibility, making them suitable for flexible electronics and wearable devices. They have a wide spectral response, enabling them to cover a wide range of spectra, and some models have a fast response time, which is very suitable for high-speed response device applications. In addition, organic photodetectors are environmentally friendly and can be integrated with other organic electronic components to form an all-organic flexible system. In addition, phototherapy, as an emerging diagnosis and treatment mode, can achieve synergistic disease diagnosis and treatment under the excitation of light, with the advantages of non-invasiveness, spatiotemporal selectivity, high efficiency and few side effects. Among them, photodynamic therapy has made significant progress in the medical field, especially in tumor treatment, and it has become the fourth treatment method besides surgery, radiotherapy and chemotherapy. Photosensitizers play a vital role as the medium of light conversion. Organic optoelectronic materials have excellent application effects in fluorescence imaging-guided photodynamic therapy due to their unique optical properties, good biocompatibility, low toxicity and high structural diversity.

[0003] A dimer is a specific molecule composed of two identical units, which combines the characteristics of small molecules and polymers. This includes a clear molecular structure, precise molecular weight, excellent batch reproducibility, and good solution processing performance. However, limited by the number and type of dimer receptors, most of the current dimer receptors are based on perylene imide and ADA-type non-fullerene receptors represented by Y6. For the former, although it has good planarity, which gives it an obvious advantage in charge transport, the spectral absorption of this type of compound is relatively blue-shifted, and the poor light absorption capacity leads to insufficient utilization of sunlight, which limits its development; for the latter, although progress has been made in near-infrared absorption and the stability of organic solar cells has been effectively improved, its absorption is still not red-shifted enough, which limits its further development in the field of organic photodetectors and biophototherapy. In addition, the mainstream ADA-type dimer receptors do not participate in the stacking of the indenone end group at the bridging unit, which leads to a decrease in the charge transport performance of such materials.

[0004] Therefore, the existing technology still needs to be improved and innovated. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide an imidazole-based dimeric receptor and a preparation method thereof, a photodetector and a bio-photodiagnostic nanoparticle, aiming to solve the problem of poor charge transfer ability of the existing dimeric receptors.

[0006] The technical solution of the present invention is as follows:

[0007] In a first aspect of the present invention, an imidazole-based dimer receptor is provided, wherein the general structural formula of the imidazole-based dimer receptor is:

[0008] Among them, R1 is R2 is X1 and X2 are independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of the C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

[0009] Preferably, the structural formula of the imidazole-based dimer receptor is one of the following structural formulas:

[0010]

[0011] The second aspect of the present invention provides a method for preparing an imidazole-based dimer receptor, such as Figure 1 As shown, the preparation method comprises the following steps:

[0012] Will The first reactant is mixed with the first reaction solvent and stirred at a first temperature for a first time to obtain a structural formula of The first reaction product of

[0013] The first reaction product is mixed with the second reactant, the third reactant, and the second reaction solvent, and stirred at a second temperature for a second time to obtain a product having a structural formula of a second reaction product of

[0014] The second reaction product is The fourth reactant and the third reaction solvent are mixed, and stirred at a third temperature for a third time to obtain the imidazole-based dimer receptor;

[0015] Among them, the first reactant is sodium tert-butoxide, potassium tert-butoxide, sodium hydride or potassium carbonate, the second reactant is N,N-dimethylformamide, the third reactant is phosphorus oxychloride or phosphorus oxybromide, and the fourth reactant is pyridine, piperidine or sodium tert-butoxide; the first reaction solvent is N,N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone, the second reaction solvent is 1,2-dichloroethane, dichloromethane or chloroform, and the third reaction solvent is chloroform, dichloromethane, 1,2-dichloroethane or tetrahydrofuran.

[0016] Preferably, the The molar ratio with the first reactant is 2:1:(2-10);

[0017] The first temperature is 80-100° C., and the first time is 12-24 hours.

[0018] Preferably, the molar ratio of the first reaction product to the second reactant and the third reactant is 1:(2-10):(2-10);

[0019] The second temperature is 80-100° C., and the second time is 10-24 hours.

[0020] Preferably, the second reaction product is The molar ratio of the fourth reactant is 1:4:(10-100);

[0021] The third temperature is 60-80° C., and the third time is 12-24 hours.

[0022] According to a third aspect of the present invention, a photodetector is provided, wherein the photodetector comprises the above-mentioned imidazole-based dimer receptor.

[0023] Preferably, the photodetector comprises a substrate and an imidazole-based dimer receptor film deposited on the substrate, wherein the imidazole-based dimer receptor film is prepared by mixing the above-mentioned imidazole-based dimer receptor with a polymer donor and depositing the mixture on the substrate.

[0024] A fourth aspect of the present invention provides a biophotodiagnostic nanoparticle, wherein the biophotodiagnostic nanoparticle comprises the above-mentioned imidazole-based dimer receptor.

[0025] Preferably, the biophotodiagnostic nanoparticles are obtained by encapsulating the above-mentioned imidazole dimer receptor with hydrophilic polyethylene glycol.

[0026] Beneficial effects: The present invention provides an imidazole-based dimer receptor and a preparation method thereof, a photodetector and a bio-photodiagnostic nanoparticle. Compared with monomeric small molecules, the imidazole-based dimer receptor provided by the present invention has stronger intramolecular charge transfer and lower LUMO and HOMO energy levels, which is beneficial to the separation of excitons at the receptor interface, thereby increasing the current of the system. In addition, the optical detection device prepared based on the imidazole-based dimer receptor of the present invention has a higher external quantum efficiency value than the optical detection device based on monomeric small molecules, which indicates that the dimer receptor has better stacking, resulting in better charge transfer. In addition, the dark current of the dimer receptor device is also significantly lower than the dark current of the monomeric small molecule device, which leads to a significantly high specific detection rate value in the dimer receptor device, indicating that the imidazole-based dimer receptor is a good photodetector material.

[0027] In addition, the existing dimer receptors are based on perylene imide and ADA-type non-fullerene receptors represented by Y6. For the former, the spectral absorption of such compounds is relatively blue-shifted, and the poor light absorption capacity leads to insufficient utilization of sunlight, which limits its development; for the latter, although certain progress has been made in near-infrared absorption, and the stability of organic solar cells has been effectively improved, its absorption is still not red-shifted enough, which limits its further development in the field of organic photodetectors and biophototherapy. The imidazole-based dimer receptor provided by the present invention can make up for these shortcomings well. In addition, the current mainstream ADA-type dimer receptors do not participate in the stacking of the indane end groups at the bridging unit, which leads to a decrease in the charge transfer performance of such materials. The imidazole-based dimer receptor provided by the present invention connects the central cores through a flexible alkyl chain, thereby retaining the indane end groups with strong electron transfer ability, thereby achieving effective charge transport. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A synthetic route for the imidazole-based dimer receptor provided in an embodiment of the present invention;

[0029] Figure 2 The absorption spectra of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3 and H0 prepared in Comparative Example 1 in a dilute chloroform solution;

[0030] Figure 3 The absorption spectra of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3 and H0 prepared in Comparative Example 1 in the thin film;

[0031] Figure 4 Electrochemical cyclic voltammetry curves of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3, and H0 prepared in Comparative Example 1;

[0032] Figure 5 The external quantum efficiency curves of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3, and H0 prepared in Comparative Example 1;

[0033] Figure 6 The dark current curves of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3, and H0 prepared in Comparative Example 1;

[0034] Figure 7 Specific detection rate curves of H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3, and H0 prepared in Comparative Example 1;

[0035] Figure 8Fluorescence imaging images of H1 prepared in Comparative Example 2 of the present invention, H2-C6 prepared in Example 2, and H2-C6O2 prepared in Example 4;

[0036] Fig. 9 It is a photodynamic therapy diagram of H1 prepared in comparative example 2 of the present invention, H2-C6 prepared in example 2, and H2-C6O2 prepared in example 4;

[0037] Fig.10 Mouse fluorescence imaging images of H1 prepared in Comparative Example 2 of the present invention, H2-C6 prepared in Example 2, and H2-C6O2 prepared in Example 4;

[0038] Fig.11 This is a photodynamic therapy diagram of mice using the receptor material mentioned in Example 8 of the present invention. DETAILED DESCRIPTION

[0039] The present invention provides an imidazole-based dimer receptor and a preparation method thereof, a photodetector and a biophototherapy nanoparticle. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0040] The embodiment of the present invention provides an imidazole-based dimer receptor, and the general structural formula of the imidazole-based dimer receptor is:

[0041] Among them, R1 is R2 is X1 and X2 are independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of the C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

[0042] Compared with the prior art, the embodiments of the present invention firstly retain the indanone end groups, thereby realizing efficient electron transfer between end groups. Secondly, the embodiments of the present invention adopt a flexible connection mode of the central core head to head, which can effectively adjust the stacking of molecules, thereby further facilitating charge transport. By changing the different functional groups of the end groups and the length of the alkyl chain, the performance can be visually controlled.

[0043] In some embodiments, the imidazole-based dimerization receptor has the general structural formula:

[0044]

[0045] Among them, R1 is R2 is X1 and X2 are independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of the C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

[0046] In some embodiments, the structural formula of the imidazole-based dimer receptor is one of the following structural formulas:

[0047] In some embodiments, the preparation method comprises the following steps:

[0048] Will The first reactant is mixed with the first reaction solvent, and stirred at a first temperature for a first time to obtain the first reactant;

[0049] The first reactant is mixed with the second reactant, the third reactant, and the second reaction solvent, and stirred at a second temperature for a second time to obtain a structural formula of The second reactant;

[0050] The second reactant and The fourth reactant and the third reaction solvent are mixed, and stirred at a third temperature for a third time to obtain the imidazole-based dimer receptor;

[0051] Among them, the first reactant is sodium tert-butoxide, potassium tert-butoxide, sodium hydride or potassium carbonate, the second reactant is N,N-dimethylformamide, the third reactant is phosphorus oxychloride or phosphorus oxybromide, and the fourth reactant is pyridine, piperidine or sodium tert-butoxide; the first reaction solvent is N,N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone, the second reaction solvent is 1,2-dichloroethane, dichloromethane or chloroform, and the third reaction solvent is chloroform, dichloromethane, 1,2-dichloroethane or tetrahydrofuran.

[0052] In some embodiments, the first temperature is 80-100°C, the first time is 12-24h, the second temperature is 80-100°C, the second time is 10-24h, the third temperature is 60-80°C, and the third time is 12-24h.

[0053] In some embodiments, the structural formula of the imidazole-based dimer receptor is:

[0054] Insert a Z segment between two segments, where the Z segment can be etc. can be used for connecting fragments. R1 is R2 is X1 and X2 are independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of the C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

[0055] In some embodiments, in the structural formula of the above-mentioned imidazole-based dimer receptor, the molecules R1 and R2 can be exchanged.

[0056] According to a third aspect of the present invention, a photodetector is provided, wherein the photodetector comprises the above-mentioned imidazole-based dimer receptor.

[0057] In some embodiments, the photodetector includes a substrate and an imidazole-based dimer receptor film deposited on the substrate, wherein the imidazole-based dimer receptor film is prepared by mixing the above-mentioned imidazole-based dimer receptor with a polymer donor and depositing the mixture on the substrate.

[0058] A fourth aspect of the present invention provides a biophotodiagnostic nanoparticle, wherein the biophotodiagnostic nanoparticle comprises the above-mentioned imidazole-based dimer receptor.

[0059] In some embodiments, the biophotodiagnostic nanoparticles are obtained by encapsulating the above-mentioned imidazole dimer receptor with hydrophilic polyethylene glycol.

[0060] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments, and are only for illustrating the present invention but not limiting the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0061] Example 1

[0062] The preparation of the imidazole-based dimer receptor comprises the following steps:

[0063] (1) Synthesis of DBM-C4, the synthesis route is as follows:

[0064]

[0065] BM (600 mg) and 1,4-dibromobutane (55 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 30 mL of DMF (N, N-dimethylformamide) and 300 mg of sodium tert-butoxide were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 12 hours, cooled to room temperature, poured into 150 mL of water, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain a viscous solid DBM-C4. The solid was a crude product and was directly used in the next step after crude separation with a chromatography column.

[0066] (2) Synthesis of DBMCHO-C4, the synthetic route is as follows:

[0067]

[0068] The crude product DBM-C4 was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was dried to obtain a yellow solid. The solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain DBMCHO-C4 as a yellow solid (120.0 mg, two-step yield 19.6%).

[0069] 1 H NMR (400MHz, CDCl3) δ: 0.54-0.71 (m, 36H); 0.80-0.89 (m, 28H);

[0070] 0.91-1.04(m,28H);1.19-1.31(m,58H);1.36-1.48(m,12H);1.80-1.96(m,14H);2.20- 2.35(m,4H); 2.70(s,6H); 3.05-3.21(m,8H); 4.53-4.69(m,12H); 10.11-10.14(m,4H).

[0071] (3) Synthesis of H2-C4, the synthetic route is as follows:

[0072]

[0073] The obtained DBMCHO-C4 (120 mg) and IC-Cl (200 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (30 mL) and pyridine (0.6 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, and the obtained solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H2-C4 (140 mg, yield 77.0%).

[0074] 1 H NMR(400MHz, CDCl3)δ:0.71-0.78(m,28);0.80-0.90(m,24H);0.99-1.17(m,72H);1.27- 1.30(m,28H);1.38-1.43(m,8H);1.51-1.57(m,12H);1.87-1.94(m,4H);2.03(m,2H);2.1 2-2.14(m,2H);2.29(s,4H);2.88(s,6H);3.25-3.29(m,4H),4.63(s,4H);4.77(s,4H);4. 90(s,4H);7.67(s,2H);7.99(s,2H);8.53(s,2H);8.81(s,2H);8.92(s,2H);9.21(s,2H).

[0075] Example 2

[0076] The preparation of the imidazole-based dimer receptor comprises the following steps:

[0077] (1) Synthesis of DBM-C6, the synthesis route is as follows:

[0078]

[0079] BM (540 mg) and 1,6-dibromobutane (60 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 30 mL of DMF (N, N-dimethylformamide) and 300 mg of sodium tert-butoxide were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 12 hours, cooled to room temperature, poured into 150 mL of water, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain a viscous solid DBM-C6. The solid was a crude product and was directly used in the next step after crude separation with a chromatography column.

[0080] (2) Synthesis of DBMCHO-C6, the synthetic route is as follows:

[0081]

[0082] The crude product DBM-C6 was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was dried to obtain a yellow solid. The solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain DBMCHO-C6 as a yellow solid (160.0 mg, two-step yield 27.2%).

[0083] 1 H NMR(400MHz, CDCl3)δ:0.47-0.57(m,16H); 0.61-0.68(m,16H); 0.80-0.88(m,38H); 0.93-0.97(m,24H); 1.20-1.48(m,70H); 1.5 3-1.56(m,4H); 1.80-1.94(m,12H); 1.97-2.01(m,4H); 2.68(s,6H); 3.01-3.19(m,8H); 4.53-4.60(m,12H); 10.08-10.11(d,4H).

[0084] (3) Synthesis of H2-C6, the synthetic route is as follows:

[0085]

[0086] The obtained DBMCHO-C6 (80 mg) and IC-Cl (80 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (20 mL) and pyridine (0.5 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, and the obtained solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H2-C6 (60 mg, yield 52.9%).

[0087] 1H NMR (400MHz, CDCl3) δ: 0.69 (m, 22H); 0.78-0.81 (m, 18H); 0.86-1.19 (m, 80H); 1.27-1.28 (m, 32H); 1.37- 1.39(m,8H);1.48-1.58(m,8H);1.87-1.95(m,8H);2.03(s,4H);2.13(s,4H);2.24(s,4H);2.81(s,6H);

[0088] 3.24-3.28(m,4H); 4.60(s,4H); 4.77(s,4H); 4.94(s,4H); 7.33(s,2H); 7.98(s,2H); 8.75(s,2H); 8.80-8.81(d,4H); 9.20(s,2H).

[0089] Example 3

[0090] The preparation of the imidazole-based dimer receptor comprises the following steps:

[0091] (1) Synthesis of DBM-C8, the synthesis route is as follows:

[0092]

[0093] BM (600 mg) and 1,8-dibromobutane (65 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 30 mL of DMF (N, N-dimethylformamide) and 300 mg of sodium tert-butoxide were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 80 ° C for 12 hours, cooled to room temperature, poured into 150 mL of water, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain a viscous solid DBM-C8. The solid was a crude product and was directly used in the next step after crude separation with a chromatography column.

[0094] (2) Synthesis of DBMCHO-C8, the synthetic route is as follows:

[0095]

[0096] The crude product DBM-C8 was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was dried to obtain a yellow solid. The solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain DBMCHO-C6 as a yellow solid (110.0 mg, two-step yield 18%).

[0097] 1 H NMR(400MHz, CDCl3)δ:0.49-0.67(m,36H); 0.79-0.98(m,60H); 1.20-1.38(m,62H); 1.40-1.51(m,1 2H); 1.82-1.99(m,18H); 2.74(s,6H); 3.09-3.20(m,8H); 4.52-4.60(m,12H); 10.10-10.11(d,4H).

[0098] (3) Synthesis of H2-C8, the synthetic route is as follows:

[0099]

[0100] The obtained DBMCHO-C8 (110 mg) and IC-Cl (200 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (30 mL) and pyridine (0.6 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, and the obtained solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H2-C8 (120 mg, yield 72.0%).

[0101] 1 H NMR (400MHz, CDCl3) δ: 0.63-0.73(m,32H); 0.80-0.89(m,26H); 0.93-1.00(m,28H); 1.11-1.31(m,70H); 1.35(m,4H); 1.47-1.67(m,20H);

[0102] 1.86-1.89(m,4H); 2.00-2.04(m,8H); 2.80(s,6H); 3.21-3.25(m,4H); 4.59(s,4H); 4.72-4.74(d,4H) ); 4.82-4.84(d,4H); 7.69(s,2H); 7.95(s,2H); 8.73(s,2H); 8.78(s,2H); 8.91(s,2H); 9.17(s,2H).

[0103] Example 4

[0104] The preparation of the imidazole-based dimer receptor comprises the following steps:

[0105] (1) Synthesis of DBM-C6O2, the synthesis route is as follows:

[0106]

[0107] BM (600mg) and bromo-triethylene glycol-bromo (60mg) are added to a drying round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling 3 times with argon, DMF (N, N-dimethylformamide) 30mL and sodium tert-butoxide 300mg are added to the round-bottom flask successively. The above reaction mixture is stirred at 80 ℃ for 12 hours, cooled to room temperature, poured into 150mL water, and extracted with ethyl acetate. After the organic layer is washed with brine, it is dried over anhydrous magnesium sulfate, filtered, and the filtrate is spin-dried to obtain a sticky solid DBM-C8. The solid is a crude product, which is directly used in the next step reaction after being roughly separated by a chromatography column.

[0108] (2) Synthesis of DBMCHO-C6O2, the synthesis route is as follows:

[0109]

[0110] The crude product DBM-C6O2 was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was dried to obtain a yellow solid. The solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain DBMCHO-C6O2 as a yellow solid (120.0 mg, two-step yield 18.1%).

[0111] 1H NMR(400MHz, CDCl3)δ:0.48-0.70(m,38H);0.71-0.99(m,78H);1.16-1.25(m,22H);1.32-1.38(m,12H);1.40-1.49(m,8H);1 .73-1.94(m,18H); 2.70-2.76(m,6H); 3.11-3.22(m,8H); 3.36(m,4H); 3.93-3.97(m,4H); 4.53-4.80(m,12H); 10.11(s,4H).

[0112] (3) Synthesis of H2-C6O2, the synthesis route is as follows:

[0113]

[0114] The obtained DBMCHO-C6O2 (60 mg) and IC-Cl (100 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (30 mL) and pyridine (0.6 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, and the obtained solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H2-C6O2 (50 mg, yield 59.1%).

[0115] 1 H NMR(400MHz, CDCl3)δ:0.61-0.69(m,32H);0.82-1.10(m,68H);1.19-1.23 (d,54H);1.43-1.56(m,12H);1.72(m,4H);1.82-1.84(m,4H);1.99(s,4H); 2.80-2.93(m,8H);3.20(s,4H),3.49(s,4H);4.04(s,4H);4.70-4.80(m,12 H);7.84(s,2H);7.95(s,2H);8.76-8.78(d,4H);9.02(s,2H);9.14(s,2H).

[0116] Comparative Example 1

[0117] The preparation of the dimeric receptor comprises the following steps:

[0118] (1) Synthesis of BMCHO-CH3, the synthetic route is as follows:

[0119]

[0120] BM-CH3 (200 mg) was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain a yellow solid. The yellow solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain BMCHO-CH3 (145 mg, yield 69.0%) as a yellow solid.

[0121] 1 H NMR (400MHz, CDCl3) δ: 0.51-0.66(m,18H); 0.67-1.12(m,32H); 1.21-1.31(m,24H); 1.36-1.56(m,8H); 1.75-2.13(m,6H); 2.74-3.13(m,4H);

[0122] 3.21(s,3H); 4.36(s,3H); 4.61-4.73(m,4H); 10.13(s,2H).

[0123] (2) Synthesis of H0, the synthetic route is as follows:

[0124]

[0125] The BMCHO-CH3 (70 mg) and IC-Cl (50 mg) prepared above were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (30 mL) and pyridine (0.4 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, the solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H0 (70 mg, yield 81.8%).

[0126] 1 H NMR(400MHz, CDCl3)δ:0.51-0.66(m,18H); 0.67-1.12(m,32H); 1.21-1.31(m,24H); 1.33-1.38(m,4H); 1.39-1.53(m,4H); 1.82-1.92(m,4H);

[0127] 1.93-1.89(m,2H);2.74(s,3H);3.12-3.24(m,4H);4.36(s,3H);4.61- 4.73(m,4H);7.93-7.95(d,2H);8.77-8.79(d,2H);9.14-9.15(d,2H).

[0128] Comparative Example 2

[0129] The preparation of the dimeric receptor comprises the following steps:

[0130] (1) Synthesis of BMCHO, the synthetic route is as follows:

[0131]

[0132] BM (150 mg) was added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, 1,2-dichloroethane (20 mL), DMF (5 mL) and phosphorus oxychloride (1 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 80 ° C for 10 hours, cooled to room temperature, poured into 150 mL of water, and extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain a yellow solid. The yellow solid was further purified by silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain BMCHO (130.0 mg, yield 82.4%) as a yellow solid.

[0133] 1 H NMR(400MHz, CDCl3)δ:0.47-0.67(m,18H); 0.79-0.87(m,16H); 0.90-1.02(m,12H); 1.23-1.32(m,32H); 1.35-1.43(m,4H); 1.81-1.96(m,6H); 2.82(s,3H); 3.10-3.14(m,4H); 4.55-4.60(m,4H); 10.11(s,2H).

[0134] (2) Synthesis of H1, the synthetic route is as follows:

[0135]

[0136] BMCHO (70 mg) and IC-Cl (80 mg) were added to a dried round-bottom flask equipped with a magnetic stirring bar. After evacuation and refilling with argon three times, chloroform (20 mL) and pyridine (0.5 mL) were added to the round-bottom flask in sequence. The above reaction mixture was stirred at 60 ° C for 12 hours. After cooling to room temperature, the reaction mixture was concentrated to about 10 mL and methanol (100 mL) was added. Filter, and the solid was further purified by flash silica gel column chromatography (petroleum ether: dichloromethane = 1: 1 to 2: 1) to obtain a black solid H1 (70 mg, yield 70.0%).

[0137] 1 H NMR (400MHz, CDCl3) δ: 0.66 (s, 16H); 0.87-1.01 (m, 40H); 1.26 (s, 18H); 1.35 (s, 4H); 1.50 (m, 4H); 1.8 7(s,4H); 2.01(s,2H); 2.86(s,3H); 3.22(s,4H); 4.71(s,4H); 7.95(s,2H); 8.80(s,2H); 9.17(s,2H).

[0138] Performance testing experiment

[0139] UV tests were performed on H2-C4 prepared in Example 1 of the present invention, H2-C8 prepared in Example 3, and H0 prepared in Comparative Example 1:

[0140] The absorption spectra of H0, H2-C4 and H2-C8 in chloroform solution and in thin film state were measured by UV-visible spectrophotometer, and the optical band gap was calculated using the empirical formula (E g opt =1240 / λ onset film ), where λ onset film is the absorption edge of the absorption spectrum of the acceptor material in the film, Figure 2 The absorption spectra of H0, H2-C4 and H2-C8 in dilute chloroform solution are shown in Figure 2. Figure 2 It can be seen that in dilute solutions, the absorption spectrum shows an obvious red shift from monomeric small molecules to dimeric receptors, and the molar absorption coefficient is significantly enhanced, which indicates that dimeric receptors have stronger intramolecular charge transfer than monomeric small molecules. Figure 3 The absorption spectra of H0, H2-C4 and H2-C8 solid films show that from monomeric small molecules to dimeric receptors, the maximum absorption peaks are similar, but the absorption edge of the dimeric receptor is redder than that of the monomeric small molecules, indicating stronger aggregation. The corresponding data are listed in Table 1.

[0141] The H2-C4 prepared in Example 1 of the present invention, the H2-C8 prepared in Example 3, and the H0 prepared in Comparative Example 1 were subjected to electrochemical tests, including the measurement of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of H0, H2-C4, and H2-C8, as well as the band gap (E g ec ) calculation:

[0142] Dissolve H0, H2-C4 and H2-C8 in chloroform to prepare a solution with a concentration of 1 mg / mL, and drip it on the working electrode (drip diameter is 2 mm). Use 0.1M Bu4NPF6 acetonitrile solution as electrolyte, platinum wire as counter electrode, Ag / Ag + The reference electrode and ferrocene were used as the standard. The redox potential was measured by electrochemical cyclic voltammetry, and the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and the band gap (E g ec ).

[0143] E HOMO = -Eox + [(-4.8) + 0.34] (eV), E LUMO =-E red +[(-4.8)+0.34](eV)

[0144] Among them, the electrochemical cyclic voltammetry curves of H0, H2-C4 and H2-C8 are as follows: Figure 4 As shown in the figure. The energy levels of monomeric small molecules and dimeric receptors are significantly different. Dimeric receptors have lower LUMO and HOMO energy levels, which is conducive to the separation of excitons at the donor-receptor interface, thereby increasing the current of the system. At the same time, the electrochemical band gap E calculated by electrochemical tests g ec The optical band gap E calculated from UV absorption g opt The specific data are listed in Table 1.

[0145] Table 1

[0146]

[0147]

[0148] The H2-C4 prepared in Example 1 of the present invention, the H2-C8 prepared in Example 3, and the H0 prepared in Comparative Example 1 were used as receptors in the bulk heterojunction structure and prepared into optical probe devices for performance testing:

[0149] The preparation and measurement process of organic optical detector devices (OPDs) is as follows: First, the glass substrate coated with indium tin oxide (ITO) was thoroughly cleaned with detergent, deionized water, acetone and isopropanol in sequence, and each solvent was ultrasonically treated for 15 minutes, followed by drying in an oven at 80°C. Next, the ITO glass substrate was placed in a UV-ozone environment for 25 minutes, and then spin-coated with a PEDOT:PSS solution and heat-treated at 150°C for 10 minutes. The concentration of the mixed solution of PBDB-TF and the acceptor material in the embodiment of the present invention (ratio of 1:1.2) for spin coating was 11 mg / mL, with chloroform as the solvent. 30 minutes before spin coating, 0.5% by volume of chloronaphthalene (CN) was added to the mixed solution as an additive. The mixed solution was stirred overnight at room temperature in a glove box. The active layer was formed into a mixed film by spin coating at a speed of 3000 rpm for 30 seconds. Afterwards, a PNDIT-F3N solution (0.5 mg / mL in methanol) was spin-coated as an interfacial layer, and a 100 nm layer of silver (Ag) was evaporated through a 0.045 cm2 shadow mask to precisely define the active area of ​​the device. Finally, the structure of the integrated device was ITO / PEDOT:PSS / PBDB-TF:acceptor

[0150] / PNDIT-F3N / Ag. A solar simulator (Enlitech.Inc) equipped with an AM 1.5G filter was used as the light source, generating 100 mW / cm 2 The light intensity is used to illuminate the optical detector device. The light intensity is calibrated by a 2 cm × 2 cm calibrated silicon solar cell and a KG-5 visible light filter. In order to accurately define the photoactive area, a shadow mask is placed on the device. The external quantum efficiency curves of the H0, H2-C4 and H2-C8 bulk heterojunction optical detector devices are tested by the solar cell-photodetector response measurement system, and the dark current of the device is measured by the Keithley 4200 source, and the specific detection rate (Dsh*) at different voltages is calculated. The result data is shown in Table 2. Figure 5 , Figure 6 and Figure 7 The external quantum efficiency curves, dark current curves and specific detection rate curves of H0, H2-C4 and H2-C8 bulk heterojunction photodetector devices are shown respectively. The results show that the photodetector device based on the dimeric receptor has a higher external quantum efficiency value than the photodetector device based on the monomer small molecule, which indicates that the dimeric receptor has better stacking, resulting in better charge transfer. In addition, the dark current of the device based on the dimeric receptor is also significantly lower than that of the device based on the monomer small molecule, which leads to a significantly high specific detection rate value in the dimeric receptor device, indicating that the imidazole-based dimeric receptor is a good photodetector material.

[0151] Table 2

[0152]

[0153] H1 prepared in comparative example 2 of the present invention, H2-C6 prepared in example 2, and H2-C6O2 prepared in example 4 were prepared into nanoparticles, and then photodynamic therapy and other related performance tests were performed.

[0154] The preparation and measurement methods of nanoparticles are as follows: 0.5 mg of sample and 5 mg of amphiphilic block polymer DSPE-PEG5000 are dissolved in 2 mL of tetrahydrofuran solvent, and ultrasonicated for 3-5 minutes until completely dissolved. Subsequently, 18 mL of deionized water is poured into the above tetrahydrofuran mixed solution under ultrasonic conditions, and ultrasonication is continued for 10 minutes, followed by stirring at 40°C for 24 hours to remove tetrahydrofuran. The nanoparticle solution (NPs) is filtered using a 220 nm filter membrane to remove impurities with large particle sizes. Use a 50KD ultrafiltration centrifuge tube for centrifugation to enrich the solution into a high-concentration nanoparticle solution to remove free amphiphilic block polymers, and finally the high-concentration solution is diluted to 20 mL to obtain a nanoparticle mother solution (25 μg·mL -1 ) and stored in a 4°C refrigerator. In the fluorescence performance test experiment, 25 μg mL -1 Take 2.5 mL of the nanoparticle solution and place it in a quartz dish with light passing through four sides, and collect the spectral information with the help of a fluorescence spectrometer. Figure 8 As shown in the figure, the fluorescence intensity of the dimeric receptor is significantly enhanced compared to that of the monomer. The DPBF probe was used to measure the fluorescence intensity at 0.3 W cm -2 The total amount of active oxygen generated by the nanoparticles under 808 nm laser irradiation. As the amount of active oxygen generated under laser irradiation gradually increases, DPBF will be degraded, which is manifested as a decrease in the absorption value of the absorption spectrum. First, weigh the DPBF solid and prepare it with DMSO to 1 mg mL -1 10 μL of DPBF solution was taken and mixed with 90 μL of three nanoparticle solutions in a 96-well plate. In addition, ICG was selected as a reference substance. Then, at different laser irradiation time points, the absorption spectra of each mixed solution at 350nm to 500nm were tested using an ELISA instrument, and the highest point absorption value was normalized to obtain the degradation curve of DPBF. Fig. 9 As shown in the figure, the degradation rate of DPBF by dimer-based nanoparticles under light excitation is faster than that of monomer nanoparticles, indicating that dimers can produce more reactive oxygen molecules and have better photodynamic effects. Therefore, the best performance H2-C6 dimer nanoparticles were selected to perform photodynamic therapy tests on mouse tumor models. 3 The mice with subcutaneous tumors were divided into 4 groups. The control group did not receive any treatment, and the laser group was only irradiated with 808 nm laser (0.3 W cm-2 , 15min), the H2-C6 NPs group was injected with only 100 μg of H2-C6 dimer nanoparticles, and the H2-C6 NPs+ group was irradiated with 808 nm laser (0.3 W cm -2 , 15min). The optimal enrichment time point was obtained by near-infrared second-zone fluorescence imaging of mice, such as Fig.10 As shown in the figure, the fluorescence intensity of the tumor reached a peak at 36 hours. After the mice were treated with laser photodynamic therapy at 36 hours, the tumor size data was collected every two days and a growth curve was drawn to compare the treatment effect. Fig.11 As shown, compared with the other three groups without photodynamic therapy, the tumor growth of mice in the H2-C6 NPs+ group was significantly inhibited, indicating that the imidazole dimer receptor is a very potential photodynamic therapy material.

[0155] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. An imidazole-based dimer receptor, characterized in that: The general structural formula of the imidazole-based dimer receptor is: Among them, R1 is R2 is X1 and X2 are independently selected from H, F, Cl, Br, I, NO2, CF3, CH3 or OCH3, Y is selected from one of the C1-C10 alkane chains, and n is 0, 1, 2, 3, 4, 5 or 6.

2. The imidazole-based dimer receptor according to claim 1, characterized in that The structural formula of the imidazole-based dimer receptor is one of the following structural formulas:

3. A method for preparing the imidazole-based dimer receptor according to claim 1, characterized in that: The preparation method comprises the following steps: Will The first reactant is mixed with the first reaction solvent and stirred at a first temperature for a first time to obtain a structural formula of The first reaction product of The first reaction product is mixed with the second reactant, the third reactant, and the second reaction solvent, and stirred at a second temperature for a second time to obtain a product having a structural formula of a second reaction product of The second reaction product is The fourth reactant and the third reaction solvent are mixed, and stirred at a third temperature for a third time to obtain the imidazole-based dimer receptor; Among them, the first reactant is sodium tert-butoxide, potassium tert-butoxide, sodium hydride or potassium carbonate, the second reactant is N,N-dimethylformamide, the third reactant is phosphorus oxychloride or phosphorus oxybromide, and the fourth reactant is pyridine, piperidine or sodium tert-butoxide; the first reaction solvent is N,N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone, the second reaction solvent is 1,2-dichloroethane, dichloromethane or chloroform, and the third reaction solvent is chloroform, dichloromethane, 1,2-dichloroethane or tetrahydrofuran.

4. The method for preparing the imidazole-based dimer receptor according to claim 3, characterized in that: Said The molar ratio with the first reactant is 2:1:(2-10); The first temperature is 80-100° C., and the first time is 12-24 hours.

5. The method for preparing the imidazole-based dimer receptor according to claim 3, characterized in that: The molar ratio of the first reaction product to the second reactant and the third reactant is 1:(2-10):(2-10); The second temperature is 80-100° C., and the second time is 10-24 hours.

6. The method for preparing the imidazole-based dimer receptor according to claim 3, characterized in that: The second reaction product The molar ratio of the fourth reactant is 1:4:(10-100); The third temperature is 60-80° C., and the third time is 12-24 hours.

7. A photoelectric detector, characterized in that: The photodetector comprises the imidazolyl dimer receptor according to claim 1.

8. The photodetector according to claim 7, characterized in that: The photodetector comprises a substrate and an imidazole-based dimer receptor film deposited on the substrate. The imidazole-based dimer receptor film is prepared by mixing the imidazole-based dimer receptor according to claim 1 with a polymer donor and then depositing the mixture on the substrate.

9. A bio-phototherapy nanoparticle, characterized in that: The biophotodiagnostic nanoparticles include the imidazole-based dimer receptor according to claim 1.

10. The biophotodiagnostic nanoparticle according to claim 8, characterized in that: The biophotodiagnostic nanoparticles are obtained by encapsulating the imidazole dimer receptor described in claim 1 with hydrophilic polyethylene glycol.

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