CN114106015B - Near-infrared two-region emission aggregation-induced luminescent material, and preparation method and application thereof - Google Patents
Near-infrared two-region emission aggregation-induced luminescent material, and preparation method and application thereof Download PDFInfo
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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Abstract
The invention discloses a novel near-infrared two-region aggregation-induced luminescent material, a preparation method and application thereof, wherein the chemical structural general formula of the material is as follows:
r is independently selected from
And
one of them has D-pi-A-pi-D structure, 6,7-diphenyl- [1,2,5 in its molecular structure]Thiadiazole [3,4-g]Quinoxalines as strong electron acceptors, benzo [ c]Thiophene is used as an electron-rich donor and a pi-bridge on one hand, and is also used as a large steric hindrance group to increase a dihedral angle between thiophene and an acceptor unit on the other hand, so that the whole molecular skeleton is more distorted, the aggregation-induced emission characteristic of thiophene is ensured, and the absorption/emission wavelength can be prolonged under the action of a strong D-A (D-A) effect. The synthetic route of the invention is simple and the cost is low; the preparation method has good biocompatibility, fluorescence quantum yield for biological imaging and good photothermal conversion efficiency, and can be used for photothermal ablation tumor of multi-modal imaging navigation. In addition, the photothermal therapy can cause immunogenic death of cancer cells and induce immune stress reaction of organisms, and can be used for photothermal synergistic immunotherapy.
Description
Technical Field
The invention relates to the technical field of fluorescent molecular probes, in particular to a novel near-infrared two-region aggregation-induced luminescent material, and a preparation method and application thereof.
Background
Aggregation-induced emission molecules (AIEgens) have been widely used as a diagnostic integrated reagent as a future emerging, which mainly benefits from the realization of a balance between radiative transitions and non-radiative transitions in energy-annealing processes through a simple design. It is well known that propeller-like AIEgens are more likely to accumulate in a disordered manner in physiological environments, thereby effectively inhibiting intramolecular/intermolecular pi-pi accumulation, thereby enhancing fluorescence imaging (FLI) capabilities. On the other hand, the twisted rotor element can maintain local rotation/vibration even in a specific state, thereby facilitating dissipation of excited state energy through a non-radiative pathway, which can be used for photothermal imaging (PTI), photoacoustic imaging (PAI), and photothermal therapy (PTT).
Today, AIEgens have acceptable fluorescence Quantum Yield (QY) in the second near-infrared bio-window (NIR-II, 1000-1700 nm) for surgical navigation and excellent Photothermal Conversion Efficiency (PCE) for PTT is attractive due to higher tissue structure. NIR-II AIEgens of the D- π -A- π -D type structure, which contain a strong electron-rich donor (D) and a strong electron acceptor, are of interest because of their good photostability, as opposed to the extension of the degree of backbone conjugation to extend absorption/emission. Nevertheless, the design and synthesis of NIR-II AIEgens remains a challenge due to the limited choice of luminescent molecular donors available in comparison to the visible and NIR-I (700-900 nm) AIEgens which have been extensively studied.
Therefore, the prior art is still subject to further improvement.
Disclosure of Invention
The invention aims to solve the technical problems that the existing near-infrared two-region aggregation-induced emission molecular donor construction is limited in few choices and the maximum absorption wavelength is difficult to break through 800nm, and the existing near-infrared two-region aggregation-induced emission molecular material stock is enriched.
The technical scheme adopted by the invention for solving the technical problem is as follows: introduction of benzo [ c ] for the first time]Thiophene derivative as electron-rich donor element to construct new near infrared two-region polymerThe general formula of the chemical structure of the induced light-emitting material is as follows:
wherein, the near-infrared two-region aggregation-induced emission material is R independently selected from
To (3) is provided.
A method for preparing a novel near-infrared two-region aggregation-induced luminescent material based on benzo [ c ] thiophene electron donor derivatives comprises the following steps:
compound A, 4,9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Sequentially adding quinoxaline and palladium tetratriphenylphosphine into an ultra-dry toluene solvent, and stirring and refluxing overnight under the protection of inert gas to obtain a reaction solution; wherein the chemical structure general formula of the compound A is as follows:
r is independently selected from
To (3) is provided.
After the reaction is finished, adding a saturated potassium fluoride solution into the reaction solution, stirring for 2-4 h, extracting by using ethyl acetate, combining organic phases, drying, and carrying out reduced pressure concentration treatment to obtain a crude product;
and (3) purifying the crude product by silica gel column chromatography by using petroleum ether/tetrahydrofuran as an eluent to obtain the novel near-infrared two-region aggregation-induced emission material.
Optionally, in the preparation method of the novel near-infrared two-region aggregation-induced emission material, the temperature of stirring reflux is 115-125 ℃, and the time of stirring reflux is 10-14 h.
Optionally, in the preparation method of the novel near-infrared two-zone aggregation-induced emission material, the mass ratio of the compound A to 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline is 2.5 to 3.5:1.
optionally, in the preparation method of the novel near-infrared two-zone aggregation-induced emission material, 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline in the reaction solution is in a concentration of 1-2M.
Optionally, in the preparation method of the novel near-infrared two-zone aggregation-induced emission material, the mass ratio of 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline to palladium tetratriphenylphosphine is 10-20: 1.
optionally, the method for preparing the novel near-infrared two-region aggregation-induced emission material, wherein the step of quenching the reaction solution, extracting and combining organic phases, and then drying and concentrating under reduced pressure to obtain a crude product comprises:
adding a saturated potassium fluoride solution into the reaction solution to quench the reaction, and stirring for 2-4 h at room temperature;
extracting the reaction solution by using ethyl acetate, and combining organic phases in the extracted reaction solution;
and drying the reaction solution after the organic phase is combined by using anhydrous sodium sulfate, and carrying out reduced pressure concentration treatment on the dried reaction solution to obtain a crude product.
The application of the novel near-infrared two-region aggregation-induced emission material in preparing the photo-thermal synergistic immune diagnosis and treatment integrated reagent.
Has the beneficial effects that: the near-infrared two-zone aggregation-induced emission molecule is an aggregation-induced emission material with a novel D-pi-A-pi-D structure, and the material takes diphenylamine structure units with different substitutions as a first electron donor in a molecular system, takes benzo [ c ] thiophene as a second electron donor or a pi-bridge in the molecular system, and takes 6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline structure units as an electron acceptor to construct a novel photo-thermal material with near-infrared two-zone aggregation-induced emission property; the aggregation-induced emission material can cause immunogenic death of tumor cells under 808nm laser irradiation, and can effectively inhibit metastasis and recurrence of in-situ breast cancer by immune-photothermal synergistic treatment combined with the PD-L1 antibody.
Drawings
FIG. 1 is a synthesis scheme of a novel near-infrared two-region aggregation-induced emission molecule provided by an embodiment of the present invention;
FIG. 2 is the NMR spectrum of the near infrared two-region aggregation-induced emission molecule Alkoxy-BT-DPTQ prepared in example 1 of the present invention in tetrahydrofuran;
FIG. 3 is the nuclear magnetic resonance carbon spectrum of the near infrared two-region aggregation-induced emission molecule Alkoxy-BT-DPTQ prepared in example 1 of the present invention in tetrahydrofuran;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the near infrared two-region aggregation-induced emission molecule TPE-BT-DPTQ prepared in example 2 of the present invention in tetrahydrofuran;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of a near infrared two-region aggregation-induced emission molecule TPE-BT-DPTQ prepared in example 2 of the present invention in tetrahydrofuran;
FIG. 6 is the NMR hydrogen spectrum of the near infrared two-region aggregation induced emission molecule TPA-BT-DPTQ prepared in example 3 of the present invention in tetrahydrofuran;
FIG. 7 is the NMR carbon spectrum of the near infrared two-region aggregation inducing luminescent molecule TPA-BT-DPTQ prepared in example 3 of the present invention in tetrahydrofuran;
FIG. 8 is a graph of the UV absorption spectrum of a near infrared two-region aggregation induced emission molecule prepared in examples 1,2 and 3 of the present invention in tetrahydrofuran;
FIG. 9 is a fluorescence emission spectrum of a near infrared two-region aggregation induced emission molecule prepared in examples 1,2 and 3 of the present invention in tetrahydrofuran;
FIG. 10 is the experimental chart of the dark toxicity and photo-thermal killing effect of TPA-BT-DPTQ NPs as nanoparticles prepared from the NIR two-domain aggregation-induced emission molecules prepared in example 3 of the present invention on 4T1 cells;
FIG. 11 is a photo-thermal immunogenic death verification graph of 4T1 cells by TPA-BT-DPTQ NPs as nanoparticles prepared from the near infrared two-region aggregation-induced emission molecules prepared in example 3 of the present invention;
FIG. 12 is a graph of an experiment on the immunosuppression of far-end breast cancer caused by photothermal induced by the nanoparticle TPA-BT-DPTQ NPs prepared from the near-infrared two-region aggregation-induced emission molecules prepared in example 3 of the present invention;
FIG. 13 is a graph showing the effect of TPA-BT-DPTQ NPs as nanoparticles prepared from the NIR Biregion aggregation inducible luminescent molecules of example 3 of the present invention on photothermal combination immunotherapy;
FIG. 14 is a schematic view of photothermal therapy of the TPA-BT-DPTQ NPs nanoparticles prepared from the near-infrared two-region aggregation-induced emission molecules prepared in example 3 of the present invention for navigation of near-infrared two-region/photoacoustic/photothermal three-mode imaging.
Detailed Description
The preparation method and the biological application of the novel near-infrared two-region aggregation-induced luminescent material based on the benzo [ c ] thiophene electron donor derivative are further detailed below in order to make the purposes, technical schemes and advantages of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The multimode integrated optical diagnosis and treatment platform has obvious advantages due to simple composition, strong repeatability and the like, and is concerned with. Aggregation-induced emission molecules (AIEgens) allow a balance between radiative transitions (providing fluorescence imaging) and non-radiative transitions (providing photothermal therapy, photoacoustic/photothermal therapy) during energy withdrawal to be achieved with a simple design, and furthermore allow singlet oxygen to be generated for photodynamic therapy by energy exchange between singlet and oxygen.
Photothermal therapy (PTT) can convert absorbed light into heat, so that local high temperature of tumor tissue parts is achieved, thereby realizing efficient ablation of tumors. However, single mode PTT is highly light source dependent, and minute tumors outside the range of light source are prone to metastasis and recurrence. In addition, upregulated expression of Heat Shock Proteins (HSP) can enhance the thermotolerance of cancer cells, thereby reducing the efficiency of PTT. In recent years, more and more studies have found that photothermal agents can induce cell immunogenic death (ICD), and thus, by combining photothermal therapy and immunotherapy, tumor treatment can be effectively achieved and metastasis and recurrence of tumors can be suppressed.
In addition to its excellent imaging capabilities (for surgical navigation), AIEgens can generate heat for photothermal therapy/imaging and photoacoustic imaging due to the efficient rotation of the local rotors in their focused state. It is well known that a distorted molecular structure with a large dihedral angle is a key factor in imparting AIE properties to a fluorescent molecular illuminant. The currently reported multi-mode light diagnosis and treatment reagent based on AIEgens has the problems of insufficient penetration depth, short emission wavelength and the like. Given the relatively limited choice of A, the development of novel D/π -bridges with large steric hindrance is another viable option for the construction of AIEgens. Triphenylamine and its derivatives are often used as D, however its inherent properties limit further extension of the absorption/emission wavelength. The use of electron rich thiophene derivatives such as 3,4-Ethylxylylene Dioxythiophene (EDOT) and ortho alkylated thiophenes as D or pi-bridges not only extends the absorption/emission wavelength but also distorts the molecular backbone to inhibit pi-pi stacking to form aggregates. Despite substantial progress, the development of novel D/pi-bridges to differentiate and enrich NIR-II AIE theranostic agents remains worthy of further investigation.
In order to solve the above problems, embodiments of the present invention provide a novel near-infrared two-region aggregation-induced emission molecular material, wherein the chemical structural formula is:
wherein, the near-infrared two-region aggregation-induced emission material is R independently selected from
One kind of (1).
In this embodiment, the novel near-infrared two-region aggregation-induced emission material is an aggregation-induced emission material having a novel D-pi-a-pi-D structure, 6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline in the molecular structure thereof is used as a strong electron acceptor, benzo [ c ] thiophene is used as an electron-rich donor and a pi-bridge on the one hand, and is used as a large steric hindrance group to increase a dihedral angle between the benzo [ c ] thiophene and an acceptor element on the other hand, so that the overall molecular skeleton is more distorted, the aggregation-induced emission characteristic thereof is ensured, and the absorption and emission wavelengths can be prolonged by the strong D-a effect.
Based on the same inventive concept, the invention also provides a preparation method of the novel near-infrared two-region aggregation-induced emission molecule, which comprises the following steps:
s1, mixing the compound A, 4,9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Sequentially adding quinoxaline and palladium tetratriphenylphosphine into an ultra-dry toluene solvent, and stirring and refluxing overnight under the protection of inert gas to obtain a reaction solution; wherein the chemical structure general formula of the compound A is as follows:
as shown in fig. 1, which is a synthesis route diagram of a novel near-infrared two-region aggregation-induced emission molecule in the embodiment of the present invention, a compound a, 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline and tetratriphenylphosphine palladium are sequentially added to an ultra-dry toluene solvent, and stirring and refluxing are performed under the protection of an inert gas overnight to obtain a reaction solution; wherein the reaction solution contains a near-infrared two-region aggregation-induced emission material.
In a specific embodiment, the temperature of the stirring reflux is 115-125 ℃, the time of the stirring reflux is 10-14 h, and the mass ratio of the compound A to the 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline is 2.5-3.5: 1; the concentration of 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline in the reaction solution is 1-2M; 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline and tetrakistriphenylphosphine palladium at a mass ratio of 10-20: 1; under the reaction condition and the reactant proportion, the near-infrared two-region aggregation-induced luminescent material with stable performance can be prepared.
S2, adding a saturated potassium fluoride solution into the reaction solution, stirring for 2-4 hours, extracting by using ethyl acetate, combining organic phases, drying, and carrying out reduced pressure concentration treatment to obtain a crude product;
in this example, after the reaction, the reaction solution was first quenched with a saturated potassium fluoride solution, then extracted with ethyl acetate to remove a part of impurities, and the organic phases in the extracted reaction solution were combined, then the reaction solution after the organic phase was combined was dried with anhydrous sodium sulfate, and the dried reaction solution was concentrated under reduced pressure to obtain a crude product.
And S3, purifying the crude product by using petroleum ether/tetrahydrofuran as an eluent through silica gel column chromatography to obtain the novel near-infrared two-region aggregation-induced emission material.
In this example, after obtaining the crude product, the crude product was purified by silica gel column chromatography using petroleum ether/tetrahydrofuran as an eluent to obtain a pure novel near-infrared two-region aggregation-induced emission material. Wherein the volume ratio of the petroleum ether to the tetrahydrofuran is 100: 1. the crude product obtained is eluted by using petroleum ether/tetrahydrofuran as an eluent, and impurities which cannot be removed by extraction, such as reaction raw materials and the like, are removed.
Based on the same inventive concept, the invention also provides application of the novel near-infrared two-region aggregation-induced emission material in a photo-thermal synergetic immune diagnosis and treatment integrated reagent. The novel near-infrared two-region aggregation-induced emission material has good photo-thermal conversion efficiency, can cause immunogenic death of cells when 4T1 cells are subjected to photo-thermal killing, releases Tumor Associated Antigen (TAA) and Damage Associated Molecular Pattern (DAMP), further stimulates the 4T1 cells to generate immune stress, improves the treatment effect, and can effectively inhibit the transfer and recurrence of in-situ breast cancer through immune-photo-thermal synergistic treatment combined with a PD-L1 antibody. Has very important research significance for improving the treatment effect of the breast cancer.
The invention is further illustrated by the following specific examples.
Example 1
As shown in FIG. 1, at N 2 Under the protection of (2), 360mg of compound A (wherein R is
) 100mg of 4, 9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Quinoxaline and 23mg of palladium tetratriphenylphosphine are sequentially added into an anhydrous toluene solution, stirring and refluxing are carried out for 12h at 110 ℃, saturated potassium fluoride solution is added to quench the reaction solution after the reaction is completed, then ethyl acetate is used for extraction, organic phases in the extracted reaction solution are combined, then anhydrous sodium sulfate is used for drying the reaction solution after the organic phases are combined, the dried reaction solution is subjected to reduced pressure concentration treatment, and petroleum ether/tetrahydrofuran (100). The NMR hydrogen spectrum and NMR carbon spectrum of Alkoxy-BT-DPTQ in tetrahydrofuran are shown in figure 2 and figure 3. Its ultraviolet absorption spectrum in tetrahydrofuran is shown in fig. 8.
Example 2
As shown in FIG. 1, at N 2 Under the protection of (2), 437mg of compound A (wherein R is
) 100mg of 4, 9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Quinoxaline and 23mg of palladium tetratriphenylphosphine are sequentially added into an anhydrous toluene solution, stirring and refluxing are carried out for 12h at 110 ℃, saturated potassium fluoride solution is added to quench the reaction solution after the reaction is completed, then ethyl acetate is used for extraction, organic phases in the extracted reaction solution are combined, then anhydrous sodium sulfate is used for drying the reaction solution after the organic phases are combined, the dried reaction solution is subjected to reduced pressure concentration treatment, and petroleum ether/tetrahydrofuran (50). The nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum of the TPE-BT-DPTQ in tetrahydrofuran are shown in figures 4 and 5. The ultraviolet absorption spectrum in tetrahydrofuran is shown in figure 8.
Example 3
As shown in FIG. 1, at N 2 394mg of Compound A (wherein R is
) 100mg of 4, 9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Quinoxaline and 23mg of palladium tetratriphenylphosphine are sequentially added into an anhydrous toluene solution, stirring and refluxing are carried out for 12h at 110 ℃, saturated potassium fluoride solution is added to quench the reaction solution after the reaction is completed, then ethyl acetate is used for extraction, organic phases in the extracted reaction solution are combined, then anhydrous sodium sulfate is used for drying the reaction solution after the organic phases are combined, the dried reaction solution is subjected to reduced pressure concentration treatment, and petroleum ether/tetrahydrofuran (10). The hydrogen and carbon nuclear magnetic resonance spectra of TPA-BT-DPTQ in tetrahydrofuran are shown in FIG. 6 and FIG. 7. Its ultraviolet absorption spectrum in tetrahydrofuran is shown in fig. 8.
As shown in fig. 9, fig. 9 is a fluorescence emission spectrum of the novel near-infrared two-region aggregation-induced emission molecule prepared in examples 1-3 in a tetrahydrofuran/water mixed solvent, and it can be seen from fig. 9 that the synthesized molecules all have aggregation-induced emission properties.
As shown in fig. 10, fig. 10 is a graph illustrating dark toxicity and photo-thermal killing effect of nanoparticles prepared from the near-infrared two-region aggregation-induced emission molecule prepared in example 3 of the present invention on 4T1 cells; as can be seen from FIG. 10, TPA-BT-DPTQ NPs still have low cell dark toxicity in the 20uM range and have excellent ability to kill 4T1 cells by light and heat.
As shown in FIG. 11, FIG. 11 is a graph showing the verification of the photo-thermal induced immunogenic death of 4T1 cells by the nanoparticle TPA-BT-DPTQ NPs prepared from the near-infrared two-region aggregation-induced emission molecules prepared in example 3 of the present invention. From FIG. 11, it can be seen that the overheating induced by TPA-BT-DPTQ NPs can kill 4T1 cells and cause the over-expression of calreticulin.
As shown in fig. 12, fig. 12 is an experimental graph of immunosuppression of far-end breast cancer caused by photothermal induced by the nanoparticle TPA-BT-DPTQ NPs prepared from the near-infrared two-region aggregation-induced emission molecule prepared in example 3 of the present invention; it can be seen from FIG. 12 that the overheating caused by TPA-BT-DPTQ NPs can achieve effective inhibition of distant tumors by activating the immune system.
As shown in fig. 13 to 14, fig. 13 is an experimental graph of the effect of the nanoparticle TPA-BT-DPTQ NPs prepared from the near-infrared two-region aggregation-induced emission molecule prepared in example 3 of the present invention for photothermal combination immunotherapy; from FIG. 13, it can be seen that the photothermal therapy mediated by TPA-BT-DPTQ NPs and the immunotherapy mediated by PD-L1 antibody can better realize the treatment of in situ breast cancer, and can effectively inhibit the metastasis and recurrence of cancer cells.
In conclusion, the invention discloses a benzo [ c ] based material]A preparation method of a novel near-infrared two-region aggregation-induced emission material of a thiophene electron donor derivative and biological application thereof are disclosed, wherein the chemical structural general formula of a novel near-infrared two-region aggregation-induced emission molecule is as follows:
wherein, the near-infrared two-region aggregation-induced emission material and R are independently selected from
One kind of (1). The novel near-infrared region II provided by the embodiment of the invention is an aggregation-induced emission material with a novel D-pi-A-pi-D structure, and 6,7-diphenyl- [1,2,5 in the molecular structure]Thiadiazole [3,4-g]Quinoxalines as strong electron acceptors, benzo [ c]Thiophene is used as an electron-rich donor and a pi-bridge on one hand, and is used as a large steric hindrance group to increase a dihedral angle between thiophene and an acceptor element on the other hand, so that the whole molecular skeleton is more distorted, the aggregation-induced emission characteristic of thiophene is ensured, and the absorption and emission wavelength can be prolonged under the action of strong D-A. In addition, the prepared TPA-BT-DPTQ NPs have excellent photothermal conversion efficiency, can cause immunogenic death of cells under 808nm laser irradiation, and cause immune stress reactionFurther combined with the PD-L1 antibody mediated immunotherapy, the composition can effectively inhibit the metastasis and recurrence of the in situ breast cancer.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A novel near-infrared two-region aggregation-induced emission material is characterized by comprising the following structural general formula:
wherein R is independently selected from
One kind of (1).
2. A method for preparing a novel near-infrared two-region aggregation induced emission material as claimed in claim 1, wherein the method comprises:
compound A, 4,9-dibromo-6,7-diphenyl- [1,2,5]Thiadiazole [3,4-g]Quinoxaline and palladium tetratriphenylphosphine are added into a toluene solvent, and stirring reflux is carried out overnight under the protection of inert gas to obtain a reaction solution; the chemical structural general formula of the compound A is as follows:
r is independently selected from
One of (1);
adding a saturated potassium fluoride solution into the reaction solution and stirring for 2-4 hours to obtain a crude product;
and purifying the crude product to obtain the novel near-infrared two-region aggregation-induced luminescent material.
3. The method for preparing the novel near-infrared two-region aggregation-induced emission material as claimed in claim 2, wherein the temperature of the stirring reflux is 115-125 ℃, and the time of the stirring reflux is 10-14 h.
4. The method for preparing a novel near-infrared two-zone aggregation-induced emission material as claimed in claim 2, wherein the mass ratio of the compound A to 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline is 2.5-3.5: 1.
5. the method for preparing a novel near-infrared two-zone aggregation-induced emission material according to claim 2, wherein the concentration of 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline in the reaction solution is 1-2M.
6. The method for preparing a novel near-infrared two-zone aggregation-induced emission material as claimed in claim 2, wherein the mass ratio of 4,9-dibromo-6,7-diphenyl- [1,2,5] thiadiazole [3,4-g ] quinoxaline to the tetratriphenylphosphine palladium is 10-20: 1.
7. the method for preparing a novel near-infrared two-region aggregation-induced emission material as claimed in claim 2, wherein the step of adding a saturated potassium fluoride solution to the reaction solution and stirring for 2-4 hours to obtain a crude product comprises:
adding a saturated potassium fluoride solution into the reaction solution to quench the reaction, and stirring for 2-4 h at room temperature;
extracting the stirred reaction solution, and combining organic phases in the extracted reaction solution;
and drying the reaction solution after the organic phase is combined by using anhydrous sodium sulfate, and carrying out reduced pressure concentration treatment on the dried reaction solution to obtain a crude product.
8. The method according to claim 2, wherein the step of purifying the crude product to obtain the new near-infrared two-region aggregation-induced emission material comprises:
and (3) purifying the crude product by silica gel column chromatography by using a mixed solution of petroleum ether and tetrahydrofuran as an eluent to obtain the novel near-infrared two-region aggregation-induced emission material.
9. The method for preparing a novel near-infrared two-region aggregation-induced emission material according to claim 8, wherein the volume ratio of petroleum ether to tetrahydrofuran in the eluent is 100: 1.
10. the use of the novel near-infrared two-region aggregation-induced emission material as defined in claim 1 in the preparation of a photothermal synergistic immunodiagnostic integrated reagent.
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