CN112175171A - Novel donor-acceptor polymer functionalized photoacoustic developer and preparation method thereof - Google Patents
Novel donor-acceptor polymer functionalized photoacoustic developer and preparation method thereof Download PDFInfo
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- CN112175171A CN112175171A CN202010991056.3A CN202010991056A CN112175171A CN 112175171 A CN112175171 A CN 112175171A CN 202010991056 A CN202010991056 A CN 202010991056A CN 112175171 A CN112175171 A CN 112175171A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
Abstract
The invention provides a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof, and relates to the technical field of organic synthesis and medical treatment. The developer is prepared from 2, 5-dibromothieno [3,2-b ] thiophene, 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde, 2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane), 3- (4-iodophenyl) -2-thio-4-thiazolidinone, p- (dimethylamino) phenylacetylene and any one of three click reagents of TCNQ, TCNE and F4-TCNQ; the synthesis process utilizes ultraviolet, laser and microwave integration technologies to help promote the accelerated click reaction, which also provides a new idea and a new scheme for the rapid control synthesis of similar compounds; the contrast agent provided by the invention has good biocompatibility, no toxic or side effect and good contrast effect; the preparation method of the contrast agent provided by the invention has simple steps and is convenient to operate.
Description
[ technical field ]: the invention belongs to the field of organic synthesis, and particularly relates to a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof.
[ technical background ]: cancer has become one of the major diseases threatening human life and health, and the in vivo, accurate and noninvasive diagnosis of cancer at cellular level has become the hot spot of scientific research. Photoacoustic Imaging is a nondestructive biophoton Imaging method based on optical absorption difference inside biological tissues and using ultrasound as a medium, and has the advantages of high resolution, high contrast, Deep penetration depth (up to 7cm), non-invasiveness and the like (Sheng Wang, Jing Lin, Tianfu Wang, et al. Recent Advances in Photonic Imaging for Deep-Tissue Biomedical Applications [ J ]. Theransotics, 2016,6(13): 2394-.
The photoacoustic imaging agent is a key component of photoacoustic imaging technology, and achieves the purpose of accurate diagnosis by accurately positioning the focus position. Currently, existing photoacoustic developers include many, and there are main problems that the compound itself does not reach the absorption range of near infrared light, the molar extinction coefficient is low, and the photoacoustic imaging resolution is low (Judith Weber, Paul C Beard, Sarah E Bohndiek. contrast agents for molecular photoacoustic imaging [ J ]. Nature America,2016,13(8): 639-. Therefore, the improvement of the 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde compound, so that the compound can be applied to the photoacoustic developer, and is a research difficulty and a hotspot of current scientific research work.
The invention provides a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof, and the technical route relates to a click principle and ultraviolet, microwave and Nd: YAG (neodymium-doped yttrium aluminum garnet, Nd: Y)3Al5O12) The solid pulse laser technology can effectively diversify the performance of the obtained product through the click action of different click reagents, and the ultraviolet, microwave and laser combined technology has more concentrated energy and no energy loss, thereby effectively improving the purity and yield of the product. The obtained product has good biological diversity, does not contain heavy metal elements, has no toxic or side effect on human bodies, and has novelty, novelty and practicability.
[ summary of the invention ]: the invention provides a novel donor-acceptor polymer functionalized compound, which is prepared by mixing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde, 2' - (9, 9-dioctadecyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 2, 5-dibromothieno [3,2-b ] thiophene to obtain a product, reacting the product with 3- (4-iodophenyl) -2-thio-4-thiazolidinone, reacting with p- (dimethylamino) phenylacetylene, and finally reacting with 7,7,8, 8-tetracyano-p-phenylenediquinone dimethane, namely TCNQ, Tetracyanoethylene abbreviated as TCNE and 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinone-dimethane abbreviated as F4-TCNQ are subjected to click chemistry modification to reach a near infrared absorption range, and absorption peaks at different positions can be obtained by adjusting the proportion of different click reagents, so that photoacoustic developers with different properties can be obtained.
[ technical solution ]: the invention provides a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof, and the structural general formula of the novel donor-acceptor polymer functionalized photoacoustic developer is as follows:
the preparation of the target product specifically comprises the following steps:
first, preparation of novel Donor-Acceptor polymers
50-500 mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 100-1000 mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 50-500 mg of 2, 5-dibromothieno [3,2-b ] borane at room temperature]Adding thiophene into a flask containing 1-20 mL of toluene and 1-30 mL of distilled water mixed solution in sequence, and then adding 1-30 mg of palladium-tetrakis (triphenylphosphine) Pd (PPh)3)4And 100 to 500mg of K2CO3As a catalyst; transferring the mixture into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 20-60 min of nitrogen with the flow rate of 0.1000-3.0000L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, heating the reaction system to 50-100 ℃, starting a reflux condensing device in the microwave reaction, plugging a rubber plug at the opening of a condensing pipe, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10-48 h; after cooling to room temperature, adding 10-50 mg of sodium diethyldithiocarbamate trihydrate and 1-10 mL of deionized water, and simultaneously turning on microwave and ultravioletAnd laser energy, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6.0 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 multiplied by 10 in power density6W/cm2The light spot of the laser focus is 1-2 mm below the liquid level, the wavelength of ultraviolet light is 365nm, and the illumination intensity is 5mW/cm2～5W/cm2Performing reflux reaction for 5-15 h at 50-100 ℃ under microwave frequency of 2450MHz and microwave power of 300-2100W; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 300-500 r/min, centrifuging and washing the product for 3-5 times by using deionized water and methanol respectively; extracting the collected crude product with 200mL of acetone in a Soxhlet extractor device for 3 days to remove any possible impurities, and finally drying the obtained solid at 50-80 ℃ for 2-8 h to obtain a target polymer M, wherein the structural formula of the target polymer M is as follows:
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 1-8 g of 2, 7-dibromocarbazole, 1-8 g of fresh potassium tert-butoxide, 1-5 g of 4-fluorobenzaldehyde and 20-100 mL of anhydrous N, N-dimethylformamide into a reaction kettle with 30-300 mL of polytetrafluoroethylene as a lining, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 80-200 ℃, the microwave frequency of 2450MHz, the microwave power of 300-1500W and the reaction time of 0.5-8.0 h, and stirring at the speed of 50-1000 r/min in the reaction kettle in the synthesis process; after cooling to room temperature, pouring the reaction mixture into stirred ice water and centrifuging, and purifying the collected crude product by column chromatography with the volume ratio of hexane to chloroform being 3:1 to obtain 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, wherein the chemical reaction formula of the step is as follows;
thirdly, preparing p- (diXylamino) phenylacetylene
Dissolving 1-15 g of p-iodoaniline and 5-20 g of halogenated hydrocarbon in 20-100 mL of polytetrafluoroethylene lining with the specification of N, N-dimethylformamide being 30-300 mL, then adding 1-15 g of potassium carbonate and 1-15 g of potassium iodide, mechanically stirring for 2-8 min, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature being 100-200 ℃, the microwave frequency being 2450MHz, the microwave power being 300-1500W, and the reaction time being 2-9 h, and stirring at the speed of 50-1000 r/min in the reaction kettle in the synthesis process; then centrifuging to remove the solid, and extracting with water to remove the N, N-dimethylformamide; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and then performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain N, N-dimethyl (X-base) -4-iodoaniline; the halogenated hydrocarbon is different according to n, when n is 1, the halogenated hydrocarbon can be methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenyl acetylene; when n is 4, the halogenated hydrocarbon can be bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n is 16, the halogenated hydrocarbon can be 1-bromohexadecane, and the obtained product is p- (hexacosanylamino) phenylacetylene;
dissolving 1-10 g of the N, N-dimethyl (X-base) -4-iodoaniline in 50-200 mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing nitrogen with a flow rate of 0.1-3.0L/min for 20-60 min to remove oxygen, and then adding 1-10 g of trimethylsilyl acetylene, 100-1000 mg of bis (triphenylphosphine) palladium dichloride and 100-800 mg of cuprous iodide; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, simultaneously starting microwave, ultraviolet irradiation and laser irradiation to enable a reaction system to irradiate for 0.1-48.0 h at the temperature of 30-100 ℃, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe opening by a rubber plug, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the set temperature; the laser parameters are wavelength 1.06 mu m, pulse width 1.2ms, spot diameter 0.2-6.0 mm and weightComplex frequency of 2-40 Hz, power density of 1.0X 106W/cm2The light spot of the laser focus is 1-2 mm below the liquid level; the ultraviolet wavelength is 365nm, and the illumination intensity is 5mW/cm2～5W/cm2The microwave frequency is 2450MHz, and the microwave power is 300-2100W; centrifuging at the speed of 5000-10000 r/min for 1-10 min to remove solids, performing rotary evaporation at the temperature of 40-80 ℃ at the pressure of-0.09 MPa and the rotating speed of 50-100 r/min for 10-120 min to remove a solvent, and performing further silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain N, N-diX-base-4- ((methylsilyl) ethynyl) aniline;
dissolving 1-8 g of the N, N-diXyl-4- ((methylsilyl) ethynyl) aniline described in the previous paragraph and 1-8 g of potassium carbonate in 30-100 mL of a solution of tetrahydrofuran and absolute ethanol in a volume ratio of 7:3, introducing nitrogen at a flow rate of 0.1-3.0L/min, and ultrasonically deoxidizing for 10-60 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 5mW/cm2～5W/cm2Irradiating for 1-720 min at room temperature; after the reaction is stopped, centrifuging at the speed of 5000-10000 r/min for 1-10 min to remove solids; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and performing dichloromethane column chromatography to obtain p- (diX-amino) phenylacetylene;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
Stirring 1-15 g of p-iodoaniline and 20-90 g of triethylamine in 10-50 mL of ethanol at room temperature under an ice bath condition, and then dropwise adding 5-20 g of carbon disulfide CS at a speed of 1-3 g/min2Then centrifuging to obtain a precipitate, and washing with deionized water and diethyl ether for 3-5 times respectively to obtain p-iodophenyl ammonium dithiocarbamate; adding 5-20 g of sodium chloroacetate and 10-30 g of chloroacetic acid into 30-100 ml of distilled water to prepare a solution, dropwise adding the obtained p-iodophenyl ammonium dithiocarbamate into the solution at a speed of 1-3 g/min, and stirring at room temperature until the solution becomes dark yellow; then uniformly mixing the mixture with 50-200 ml of hot hydrochloric acid with the temperature of 90-95 ℃, stirring for 3-10 min,colorless crystal precipitate is obtained; recrystallizing the precipitates in chloroform to obtain a dark yellow needle-shaped product, namely the target preparation 3- (4-iodophenyl) -2-sulfo-4-thiazolidone, wherein the chemical reaction formula of the step is as follows:
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 0.50-3.00 g of the target polymer M obtained in the step one and 50-400 mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 1-10 mL of acetic acid, then adding 0.01-3.00 g of ammonium acetate, carrying out water bath reflux reaction at 30-90 ℃ for 1-3 h, stirring at the speed of 300-700 r/min, then filtering out precipitates, washing with acetic acid and absolute ethyl alcohol for 3-5 times respectively to obtain the compound M in the patent drawing description1The structural formula is as follows:
0.5 to 3.0g of the compound M1Dissolving 100-250 mL of p- (dimethylamino) phenylacetylene in 50-150 mL of solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, introducing nitrogen with the flow rate of 0.1-3.0L/min for 20-60 min to remove oxygen, adding 80-250 mg of bis (triphenylphosphine) palladium dichloride and 30-150 mg of cuprous iodide, carrying out water bath reflux reaction at 30-90 ℃ for 8-12 h, centrifuging to remove solids, and eluting with solution with the volume ratio of dichloromethane to petroleum ether being 3:1 to obtain a compound M shown in the specification of the patent drawing2The structural formula is as follows:
100-400 mg of compound M2Dissolving the mixture in 5-50 mL of tetrahydrofuran, respectively adding 10-50 mg of a click reagent, then introducing nitrogen at the flow rate of 0.1-3.0L/min, and carrying out reaction at the temperature of 30-70 DEG CStirring in a water bath for 0.5-3.0 h; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and purifying the crude product by using a column chromatography with an eluent dichloromethane to obtain the target novel donor-acceptor polymer functionalized photoacoustic developer M3The structural formula is as follows:
the click reagent is any one of 7,7,8, 8-tetracyanoquinodimethane abbreviated as TCNQ, tetracyanoethylene abbreviated as TCNE and 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane abbreviated as F4-TCNQ, and the structural formula of the click reagent is as follows:
[ advantages and effects of the invention ]: the invention provides a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof, and the preparation method comprises the following beneficial effects: (1) the synthesis process of the invention utilizes ultraviolet, laser and microwave integration technology, has concentrated energy, no energy loss and secondary pollution problems, is beneficial to accelerating the reaction and improving the reaction rate and the product yield; (2) the patent technical route of the invention relates to a click chemical modification technology, which can enable a product to reach a near infrared absorption range, and absorption peaks at different positions can be obtained by adjusting the proportion of different click reagents, so that the diversity of product functions is increased; (3) the contrast agent has good biocompatibility, and the whole components of the contrast agent do not contain heavy metal elements, so the contrast agent has no toxic or side effect on human bodies.
Drawings
FIG. 1 is a reaction scheme of the present invention.
FIG. 2 is a schematic structural diagram of a microwave, UV and laser combination apparatus used in the present invention, wherein the numbers in the diagram are respectively: reflux condensing unit, laser beam, microwave generating part, ultraviolet lamp and PTFE rack.
Detailed Description
The invention is described in further detail below with reference to figures 1-2 and the detailed description.
Example 1: preparation of a novel donor-acceptor Polymer functionalized photoacoustic imaging agent sample 1 with n-1 and the click reagent TCNE
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 1 was prepared using n ═ 1 and a click reagent as TCNE, as shown in fig. 1, and the specific preparation steps were as follows:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium and 276mg of K2CO3As a catalyst; transferring the mixture into a normal-pressure microwave reactor (as shown in figure 2) with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 30min of nitrogen with the flow rate of 1L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, heating a reaction system to 80 ℃, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe orifice with a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a set temperature, opening the microwave generator to heat when the temperature is lower than the set temperature, and carrying out reflux reaction for 10 hours; after cooling to room temperature, adding 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameter isWavelength of 1.06 μm, pulse width of 1.2ms, spot diameter of 0.5mm, repetition frequency of 20Hz, power density of 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 400r/min, centrifuging the product and washing the product for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing p- (dimethylamino) phenylacetylene
Dissolving 4.38g of p-iodoaniline and 4.26g of methyl iodide in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material to a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle to a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 120 ℃, the microwave frequency of 2450MHz, the microwave power of 1000W and the reaction time of 8h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 4.6g N, N-dimethyl (methyl) -4-iodoaniline with yield of 93%;
dissolving 4.45g of N, N-dimethyl (methyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen at a flow rate of 1L/min to remove oxygen, and then adding 1.77g of trimethylsilylacetylene, 828mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, simultaneously starting microwave, ultraviolet irradiation and laser irradiation to irradiate a reaction system at the temperature of 40 ℃ for 3 hours, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe opening by a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to heat when the temperature in the microwave reactor is lower than the set temperature; the laser parameters are wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.5mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level; the ultraviolet wavelength is 365nm, and the illumination intensity is 15mW/cm2Microwave frequency 2450MHz and microwave power 1000W; centrifuging at 8000r/min for 4min to remove solid, rotary evaporating at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 3.2g of N, N-dialkyl-4- ((trimethylsilyl) ethynyl) aniline with yield of 82%;
3g of N, N-dialkyl-4- ((trimethylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate are dissolved in 50mL of a solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, nitrogen gas with the flow rate of 1L/min is introduced, and oxygen is removed by ultrasound for 30 min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, and starting only ultraviolet irradiation and ultraviolet lightThe wavelength is 365nm, and the illumination intensity is 15mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 8000r/min for 4min to remove solid; performing rotary evaporation at 40 deg.C and 40 MPa for 100min to remove solvent, and performing dichloromethane column chromatography to obtain 1.93g of p- (dimethylamino) phenylacetylene with yield of 95%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; a solution was prepared by adding 11.6g of sodium chloroacetate and 18.9g of chloroacetic acid to 50ml of distilled water, and the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min to the solution and stirred at room temperature until it became deep yellow to obtain a product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h with stirring at a rate of 500r/min, filtering off the precipitate, washing with acetic acid and absolute ethanol for 3 times, respectively, to obtain 688mg of compound M1 with a yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mL of p- (dimethylamino) phenylacetylene in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen with a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 900mg of a compound M2 with a yield of 60%;
160mg of compound M2 was dissolved in 10mL of tetrahydrofuran, 26mg of TCNE was added, followed by introduction of nitrogen at a flow rate of 1L/min and stirring in a water bath at 30 ℃ for 1 hour; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 170mg of sample 1 of target novel donor-acceptor polymer functionalized photoacoustic developer with a yield of 99%.
Example 2: preparation of a novel donor-acceptor Polymer functionalized photoacoustic imaging agent sample 2 with n-1 and the click reagent TCNQ
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 2 was prepared with n ═ 1 and the click reagent TCNQ, and the specific preparation steps were as follows:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium Pd (PPh3)4 and 276mg of K2CO3As a catalyst; transferring the mixture to a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 30min of nitrogen with the flow rate of 1L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, heating a reaction system to 80 ℃, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe orifice with a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10 hours; after cooling to room temperature, adding 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, and the ultraviolet lightThe wavelength is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 400r/min, centrifuging the product and washing the product for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing p- (dimethylamino) phenylacetylene
Dissolving 4.38g of p-iodoaniline and 4.26g of methyl iodide in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material to a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle to a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 120 ℃, the microwave frequency of 2450MHz, the microwave power of 1000W and the reaction time of 8h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 4.6g of N, N-dimethyl (methyl) -4-iodoaniline with yield of 93%;
dissolving 4.45g of N, N-dimethyl (methyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen at a flow rate of 1L/min to remove oxygen, and then adding 1.77g of trimethylsilylacetylene, 828mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, simultaneously starting microwave, ultraviolet irradiation and laser irradiation to irradiate a reaction system at the temperature of 40 ℃ for 3 hours, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe opening by a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to heat when the temperature in the microwave reactor is lower than the set temperature; the laser parameters are wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.5mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level; the ultraviolet wavelength is 365nm, and the illumination intensity is 15mW/cm2Microwave frequency 2450MHz and microwave power 1000W; centrifuging at 8000r/min for 4min to remove solid, rotary evaporating at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 3.2g of N, N-dialkyl-4- ((trimethylsilyl) ethynyl) aniline with yield of 82%;
3g of N, N-dialkyl-4- ((trimethylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate are dissolved in 50mL of a solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, nitrogen gas with the flow rate of 1L/min is introduced, and oxygen is removed by ultrasound for 30 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 10mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 9000r/min for 3min to remove solids; rotating at 40 deg.C under-0.09 MPa for 60r/minQuickly rotary-steaming for 120min to remove solvent, and performing dichloromethane column chromatography to obtain 1.93g of p- (dimethylamino) phenylacetylene with a yield of 95%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; a solution was prepared by adding 11.6g of sodium chloroacetate and 18.9g of chloroacetic acid to 50ml of distilled water, and the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min to the solution and stirred at room temperature until it became deep yellow to obtain a product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h, stirring at the speed of 500r/min, filtering out the precipitate, washing with acetic acid and absolute ethanol for 3 times respectively to obtain 688mg of compound M1 with the yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mg of p- (dimethylamino) phenylacetylene in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen with a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 900mg of a compound M2 with a yield of 60%;
150mg of compound M2 was dissolved in 10mL of tetrahydrofuran, 41mg of TCNQ was added, followed by introduction of nitrogen at a flow rate of 1L/min and stirring in a water bath at 50 ℃ for 2 hours; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 170mg of sample 2 of target novel donor-acceptor polymer functionalized photoacoustic developer in 99% yield.
Example 3: preparation of a novel donor-acceptor polymer functionalized photoacoustic imaging agent sample 3 with n-4 and the click reagent F4-TCNQ
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 3 was prepared with n-4 and the click reagent F4-TCNQ, and was prepared as follows:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium and 276mg of K2CO3As a catalyst; transferring the mixture to a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 30min of nitrogen with the flow rate of 1L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, heating a reaction system to 80 ℃, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe orifice with a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10 hours; after cooling to room temperature, adding 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature,pouring into a methanol solution stirred at the speed of 400r/min, centrifuging and washing for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing p- (dibutylamino) phenylacetylene
Dissolving 4.38g of p-iodoaniline and 4.11g of bromobutane in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material into a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 120 ℃, the microwave frequency of 2450MHz, the microwave power of 1000W and the reaction time of 8h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 6.16g of N, N-dimethyl (butyl) -4-iodoaniline with yield of 93%;
dissolving 5.63g of N, N-dimethyl (butyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing nitrogen at a flow rate of 1L/min for 30min to remove oxygen, and then adding 1.67g of trimethylsilylacetylene, 820mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then the flask is transferred into a microwave reactor with ultraviolet, Nd, YAG solid pulse laser, normal pressure and reflux, only laser irradiation is started, the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level and is irradiated for 200min at the temperature of 40 ℃; centrifuging at 9000r/min for 3min to remove solid, performing rotary evaporation at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 4.1g N, N-dialkyl-4- ((tributylsilyl) ethynyl) aniline with yield of 80%;
3g of N, N-dialkyl-4- ((tributylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate are dissolved in 50mL of a solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, nitrogen gas with the flow rate of 1L/min is introduced, and oxygen is removed by ultrasound for 30 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 10mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 9000r/min for 3min to remove solids; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and performing dichloromethane column chromatography to obtain 1.93g of p- (dibutylamino) phenylacetylene with a yield of 95%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; to 50ml of distilled water were added 11.6g of sodium chloroacetate and18.9g of chloroacetic acid were prepared as a solution to which the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min and stirred at room temperature until it became dark yellow to give product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h with stirring at a rate of 500r/min, filtering off the precipitate, washing with acetic acid and absolute ethanol for 3 times, respectively, to obtain 688mg of compound M1 with a yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mg of p- (dimethylamino) phenylacetylene in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen with a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 920mg of a compound M2 with a yield of 60%;
dissolving 165mg of compound M2 in 10mL of tetrahydrofuran, adding 55mg of F4-TCNQ respectively, introducing nitrogen at the flow rate of 1L/min, and stirring in a water bath at 70 ℃ for 2.5 h; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 180mg of target novel donor-acceptor polymer functionalized photoacoustic developer sample 3 with a yield of 99%.
Example 4: preparation of a novel donor-acceptor polymer functionalized photoacoustic imaging agent sample 4 with n-4 and a click reagent as TCNE
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 4 was prepared with n-4 and the click reagent as TCNE, and the specific preparation steps were as follows:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium and 276mg of K2CO3As a catalyst; transferring the mixture to a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 30min of nitrogen with the flow rate of 1L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, heating a reaction system to 80 ℃, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe orifice with a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10 hours; after cooling to room temperature, adding 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 400r/min, centrifuging the product and washing the product for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing p- (dibutylamino) phenylacetylene
Dissolving 4.38g of p-iodoaniline and 4.11g of bromobutane in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material into a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 120 ℃, the microwave frequency of 2450MHz, the microwave power of 1000W and the reaction time of 8h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 6.16g N, N-dimethyl (butyl) -4-iodoaniline with yield of 93%;
dissolving 6.03g of N, N-dimethyl (butyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen at a flow rate of 1L/min to remove oxygen, and then adding 1.67g of trimethylsilylacetylene, 820mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then the flask is transferred into a microwave reactor with ultraviolet, Nd, YAG solid pulse laser, normal pressure and reflux, only laser irradiation is started, the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid levelIrradiating at 40 deg.C for 200 min; centrifuging at 9000r/min for 3min to remove solid, performing rotary evaporation at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 4.1g N, N-dialkyl-4- ((tributylsilyl) ethynyl) aniline with yield of 80%;
3g of N, N-dialkyl-4- ((tributylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate are dissolved in 50mL of a solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, nitrogen gas with the flow rate of 1L/min is introduced, and oxygen is removed by ultrasound for 30 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 10mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 9000r/min for 3min to remove solids; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and performing dichloromethane column chromatography to obtain 1.93g of p- (dibutylamino) phenylacetylene with a yield of 95%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; a solution was prepared by adding 11.6g of sodium chloroacetate and 18.9g of chloroacetic acid to 50ml of distilled water, and the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min to the solution and stirred at room temperature until it became deep yellow to obtain a product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h, stirring at the speed of 500r/min, filtering out the precipitate, washing with acetic acid and absolute ethanol for 3 times respectively to obtain 688mg of compound M1 with the yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mg of p- (dimethylamino) phenylacetylene in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen with a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 920mg of a compound M2 with a yield of 61%;
165mg of compound M2 was dissolved in 10mL of tetrahydrofuran, 26mg of TCNE was added, followed by introduction of nitrogen gas at a flow rate of 1L/min and stirring in a water bath at 30 ℃ for 1 hour; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 170mg of target novel donor-acceptor polymer functionalized photoacoustic developer sample 4 with a yield of 99%.
Example 5: preparation of a novel donor-acceptor polymer functionalized photoacoustic imaging agent sample 5 with n-16 and a click reagent as TCNQ
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 5 was prepared with n-16 and the click reagent TCNQ, using the following specific preparation steps:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium and 276mg of K2CO3As a catalyst; transferring the mixture into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and refluxing, and introducing the mixture at a flow speed of 30minRemoving oxygen by nitrogen of 1L/min, starting a microwave heating function, wherein the microwave frequency is 2450MHz, the microwave power is 1000W, the temperature of a reaction system is increased to 80 ℃, a reflux condensing device is started in the microwave reaction, the mouth of a condensing pipe is plugged by a rubber plug, when the temperature in a microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature, and the reflux reaction is carried out for 10 hours; after cooling to room temperature, adding 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameters are 1.06 μm in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0 × 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 400r/min, centrifuging the product and washing the product for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing 4-ethynyl-N, N-hexacosanylaniline
Dissolving 4.38g of p-iodoaniline and 9.16g of 1-bromohexadecane in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material into a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as 120 ℃ of heating temperature, 2450MHz of microwave frequency, 1000W of microwave power and 8 hours of reaction time, and stirring at the rate of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 12.41g N, N-dimethyl (hexadecyl) -4-iodoaniline with yield of 93%;
dissolving 11.35g of N, N-dimethyl (hexadecyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing nitrogen at a flow rate of 1L/min for 30min to remove oxygen, and then adding 1.67g of trimethylsilylacetylene, 820mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then the flask is transferred into a microwave reactor with ultraviolet, Nd, YAG solid pulse laser, normal pressure and reflux, only laser irradiation is started, the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level and is irradiated for 200min at the temperature of 40 ℃; centrifuging at 9000r/min for 3min to remove solid, performing rotary evaporation at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 9gN, N-dialkyl-4- ((hexadecylsilyl) ethynyl) aniline with yield of 83%;
7.7g of the N, N-dialkyl-4- ((hexadecylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate were dissolved in 50mL of a solution of tetrahydrofuran and absolute ethanol in a volume ratio of 7:3Introducing nitrogen with the flow rate of 1L/min and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 10mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 9000r/min for 3min to remove solids; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and performing dichloromethane column chromatography to obtain 6.24g of 4-ethynyl-N, N-hexacosanylaniline with a yield of 92%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; a solution was prepared by adding 11.6g of sodium chloroacetate and 18.9g of chloroacetic acid to 50ml of distilled water, and the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min to the solution and stirred at room temperature until it became deep yellow to obtain a product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h with stirring at a rate of 500r/min, filtering off the precipitate, washing with acetic acid and absolute ethanol for 3 times, respectively, to obtain 688mg of compound M1 with a yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mg of 4-ethynyl-N, N-hexacosanylaniline in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen at a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 1.5g of the compound M2, wherein the yield is 61%;
240mg of compound M2 was dissolved in 10mL of tetrahydrofuran, 41mg of TCNQ was added, followed by introduction of nitrogen at a flow rate of 1L/min, and stirring was carried out in a water bath at 50 ℃ for 1.5 hours; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 280mg of target novel donor-acceptor polymer functionalized photoacoustic developer sample 5 with a yield of 99%.
Example 6: preparation of a novel donor-acceptor polymer functionalized photoacoustic imaging agent sample 6 with n-16 and a click reagent of F4-TCNQ
A new donor-acceptor polymer functionalized photoacoustic imaging agent sample 6 was prepared with n-16 and the click reagent F4-TCNQ, using the following specific preparation steps:
first, preparation of novel Donor-Acceptor polymers
215mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 600mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 150mg of 2, 5-dibromothieno [3,2-b ] borane were mixed at room temperature]Thiophene was sequentially added to a flask containing a mixed solution of 4mL of toluene and 2mL of distilled water, followed by addition of 10mg of tetrakis (triphenylphosphine) palladium and 276mg of K2CO3As a catalyst; transferring the mixture to a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 30min of nitrogen with the flow rate of 1L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz and the microwave power is 1000W, heating a reaction system to 80 ℃, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe orifice with a rubber plug, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10 hours; after cooling to room temperature, 22.5mg sodium diethyldithiocarbamate trihydrate and 1mL deionized water are added, and microwave, ultraviolet and laser energy are turned on simultaneously, whereinThe laser parameters are wavelength 1.06 μm, pulse width 1.2ms, spot diameter 0.5mm, repetition frequency 20Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 2mm below the liquid level, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 15mW/cm2The microwave frequency is 2450MHz, the microwave power is 1000W, and the reaction system is refluxed and reacted for 5 hours at the temperature of 80 ℃; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 400r/min, centrifuging the product and washing the product for 3 times by using deionized water and methanol respectively; the collected crude product was extracted with 200mL of acetone in a soxhlet extractor apparatus for 3 days to remove any possible impurities, and finally the resulting solid was dried at 60 ℃ for 8h to give the target polymer M in 860mg yield, 82%;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 3.25g of 2, 7-dibromocarbazole, 1.10g of fresh potassium tert-butoxide, 1.27g of 4-fluorobenzaldehyde and 40mL of anhydrous N, N-dimethylformamide into a reaction kettle with a polytetrafluoroethylene lining of 100mL, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 110 ℃, the microwave frequency of 2450MHz, the microwave power of 900W and the reaction time of 6h, and stirring at the speed of 500r/min in the reaction kettle in the synthesis process; the product was then cooled to room temperature, poured into stirred ice water and centrifuged, and the collected crude product was purified by column chromatography with a volume ratio of hexane to chloroform of 3:1 to give 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde in a yield of 1.3g and a yield of 30%;
thirdly, preparing 4-ethynyl-N, N-hexacosanylaniline
Dissolving 4.38g of p-iodoaniline and 9.16g of 1-bromohexadecane in a flask containing 65mL of N, N-dimethylformamide, then adding 8.28g of potassium carbonate and 9.96g of potassium iodide, then transferring the mixed material into a reaction kettle with 150mL of polytetrafluoroethylene as an inner liner, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as 120 ℃ of heating temperature, 2450MHz of microwave frequency, 1000W of microwave power and 8 hours of reaction time, and stirring at the rate of 500r/min in the reaction kettle in the synthesis process; after the reaction is finished, cooling to room temperature, centrifuging to remove solids, and extracting with water to remove N, N-dimethylformamide; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 12.41g N, N-dimethyl (hexadecyl) -4-iodoaniline with yield of 93%;
dissolving 11.35g of N, N-dimethyl (hexadecyl) 4-iodoaniline obtained in the previous step in 80mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing nitrogen at a flow rate of 1L/min for 30min to remove oxygen, and then adding 1.67g of trimethylsilylacetylene, 820mg of bis (triphenylphosphine) palladium dichloride and 240mg of cuprous iodide; then the flask is transferred into a microwave reactor with ultraviolet, Nd, YAG solid pulse laser, normal pressure and reflux, only laser irradiation is started, the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.5mm in spot diameter, 20Hz in repetition frequency and 1.0X 10 in power density6W/cm2The light spot of the laser focus is 2mm below the liquid level and is irradiated for 200min at the temperature of 40 ℃; centrifuging at 9000r/min for 3min to remove solid, performing rotary evaporation at-0.09 MPa at 40 deg.C and 60r/min for 120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether at volume ratio of 1:6 as eluent to obtain 9gN, N-dialkyl-4- ((hexadecylsilyl) ethynyl) aniline with yield of 83%;
dissolving 7.7g of N, N-dialkyl-4- ((hexadecylsilyl) ethynyl) aniline of the previous step and 2g of potassium carbonate in 50mL of a solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing nitrogen at a flow rate of 1L/min, and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 10mW/cm2Irradiating at room temperature for 100 min; after the reaction is stopped, centrifuging at the speed of 9000r/min for 3min to remove solids; performing rotary evaporation at 40 deg.C and 40 MPa for 120min at 60r/min for removing solvent, and performing dichloromethane column chromatography to obtain 6.24g of 4-ethynyl-N, N-hexacosanylaniline with a yield of 92%;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
10.7g of p-iodoaniline and 50.5g of triethylamine are stirred in 20mL of ethanol at room temperature under ice-bath conditions, and 15.2g of carbon disulfide CS are added dropwise at a rate of 2g/min2Then centrifuging to obtain a precipitate, and washing for 3 times by using deionized water and diethyl ether respectively to obtain p-iodophenyl ammonium dithiocarbamate; a solution was prepared by adding 11.6g of sodium chloroacetate and 18.9g of chloroacetic acid to 50ml of distilled water, and the obtained ammonium p-iodophenyldithiocarbamate was added dropwise at a rate of 1g/min to the solution and stirred at room temperature until it became deep yellow to obtain a product D; then mixing the precipitate with 140ml of hot hydrochloric acid at 90 ℃, and stirring for 5min to obtain colorless crystal precipitate; these precipitates were recrystallized from chloroform to give 50g of 3- (4-iodophenyl) -2-thioxo-4-thiazolidinone with a yield of 74.6%;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 1.4g of the polymer of step A with 170mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 3mL of acetic acid, adding 0.15g of ammonium acetate, carrying out reflux reaction at room temperature for 2h with stirring at a rate of 500r/min, filtering off the precipitate, washing with acetic acid and absolute ethanol for 3 times, respectively, to obtain 688mg of compound M1 with a yield of 90%;
dissolving 1.5g of the product in the compound M1 and 145mL of p- (dimethylamino) phenylacetylene in 100mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing 30min of nitrogen with a flow rate of 1L/min to remove oxygen, adding 140.4mg of bis (triphenylphosphine) palladium dichloride and 40mg of cuprous iodide, carrying out reflux reaction in a water bath at 40 ℃ for 12h, centrifuging to remove solids, and eluting with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:3 to obtain 1.5g of the compound M2 with a yield of 61%;
dissolving 240mg of compound M2 in 10mL of tetrahydrofuran, adding 55mg of F4-TCNQ respectively, introducing nitrogen at the flow rate of 1L/min, and stirring for 3 hours in a water bath at 70 ℃; the solvent was removed by rotary evaporation at-0.09 MPa, 40 ℃ and 60r/min for 120min and the crude product was purified by column chromatography with an eluent dichloromethane to give 280mg of target novel donor-acceptor polymer functionalized photoacoustic developer sample 6 with a yield of 99%.
Claims (2)
1. The invention provides a novel donor-acceptor polymer functionalized photoacoustic developer and a preparation method thereof, and the structural general formula of the novel donor-acceptor polymer functionalized photoacoustic developer is as follows:
q is 1:1, n is an integer of 1-16;
the preparation of the target product specifically comprises the following steps:
first, preparation of novel Donor-Acceptor polymers
50-500 mg of 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, 100-1000 mg of 2,2' - (9, 9-dihexyl-9H-fluorene-2, 7-diyl) bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) and 50-500 mg of 2, 5-dibromothieno [3,2-b ] borane at room temperature]Adding thiophene into a flask containing 1-20 mL of toluene and 1-30 mL of distilled water mixed solution in sequence, and then adding 1-30 mg of palladium-tetrakis (triphenylphosphine) Pd (PPh)3)4And 100 to 500mg of K2CO3As a catalyst; transferring the mixture into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, introducing 20-60 min of nitrogen with the flow rate of 0.1000-3.0000L/min to remove oxygen, starting a microwave heating function, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, heating the reaction system to 50-100 ℃, starting a reflux condensing device in the microwave reaction, plugging a rubber plug at the opening of a condensing pipe, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, opening the microwave generator to heat when the temperature is lower than the preset temperature, and carrying out reflux reaction for 10-48 h; after cooling to room temperature, adding 10-50 mg of sodium diethyldithiocarbamate trihydrate and 1-10 mL of deionized water, and simultaneously starting microwave, ultraviolet and laser energy, wherein the laser parameters are 1.06 mu m in wavelength, 1.2ms in pulse width, 0.2-6.0 mm in spot diameter, 2-40 Hz in repetition frequency and 1.0 in power density×106W/cm2The light spot of the laser focus is 1-2 mm below the liquid level, the wavelength of ultraviolet light is 365nm, and the illumination intensity is 5mW/cm2～5W/cm2Performing reflux reaction for 5-15 h at 50-100 ℃ under microwave frequency of 2450MHz and microwave power of 300-2100W; after the reaction is finished, cooling the product to room temperature, pouring the product into a methanol solution stirred at the speed of 300-500 r/min, centrifuging and washing the product for 3-5 times by using deionized water and methanol respectively; extracting the collected crude product with 200mL of acetone in a Soxhlet extractor device for 3 days to remove any possible impurities, and finally drying the obtained solid at 50-80 ℃ for 2-8 h to obtain a target polymer M, wherein the structural formula of the target polymer M is as follows:
a target polymer M;
secondly, preparing 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde
Transferring a mixed material containing 1-8 g of 2, 7-dibromocarbazole, 1-8 g of fresh potassium tert-butoxide, 1-5 g of 4-fluorobenzaldehyde and 20-100 mL of anhydrous N, N-dimethylformamide into a reaction kettle with 30-300 mL of polytetrafluoroethylene as a lining, sealing, transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature of 80-200 ℃, the microwave frequency of 2450MHz, the microwave power of 300-1500W and the reaction time of 0.5-8.0 h, and stirring at the speed of 50-1000 r/min in the reaction kettle in the synthesis process; after cooling to room temperature, pouring the reaction mixture into stirred ice water and centrifuging, and purifying the collected crude product by column chromatography with the volume ratio of hexane to chloroform being 3:1 to obtain 4- (2, 7-dibromo-9H-carbazol-9-yl) benzaldehyde, wherein the chemical reaction formula of the step is as follows;
a chemical reaction formula in the preparation process of 4- (2, 7-dibromo-9H-carbazole-9-yl) benzaldehyde;
thirdly, preparing p- (diXylamino) phenylacetylene
Dissolving 1-15 g of p-iodoaniline and 5-20 g of halogenated hydrocarbon in 20-100 mL of polytetrafluoroethylene lining with the specification of N, N-dimethylformamide being 30-300 mL, then adding 1-15 g of potassium carbonate and 1-15 g of potassium iodide, mechanically stirring for 2-8 min, sealing, then transferring the reaction kettle into a microwave hydrothermal synthesizer, setting the conditions of the synthesizer as the heating temperature being 100-200 ℃, the microwave frequency being 2450MHz, the microwave power being 300-1500W, and the reaction time being 2-9 h, and stirring at the speed of 50-1000 r/min in the reaction kettle in the synthesis process; then centrifuging to remove the solid, and extracting with water to remove the N, N-dimethylformamide; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and then performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain N, N-dimethyl (X-base) -4-iodoaniline; the halogenated hydrocarbon is different according to n, when n is 1, the halogenated hydrocarbon can be methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenyl acetylene; when n is 4, the halogenated hydrocarbon can be bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n is 16, the halogenated hydrocarbon can be 1-bromohexadecane, and the obtained product is p- (hexacosanylamino) phenylacetylene;
dissolving 1-10 g of the N, N-dimethyl (X-base) -4-iodoaniline in 50-200 mL of a solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, introducing nitrogen with a flow rate of 0.1-3.0L/min for 20-60 min to remove oxygen, and then adding 1-10 g of trimethylsilyl acetylene, 100-1000 mg of bis (triphenylphosphine) palladium dichloride and 100-800 mg of cuprous iodide; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, simultaneously starting microwave, ultraviolet irradiation and laser irradiation to enable a reaction system to irradiate for 0.1-48.0 h at the temperature of 30-100 ℃, wherein the microwave frequency is 2450MHz, the microwave power is 300-1000W, starting a reflux condensing device in the microwave reaction, plugging a condenser pipe opening by a rubber plug, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the set temperature; laser parameters of wavelength 106 μm, pulse width 1.2ms, spot diameter 0.2-6.0 mm, repetition frequency 2-40 Hz, power density 1.0 × 106W/cm2The light spot of the laser focus is 1-2 mm below the liquid level; the ultraviolet wavelength is 365nm, and the illumination intensity is 5mW/cm2～5W/cm2The microwave frequency is 2450MHz, and the microwave power is 300-2100W; centrifuging at the speed of 5000-10000 r/min for 1-10 min to remove solids, performing rotary evaporation at the temperature of 40-80 ℃ at the pressure of-0.09 MPa and the rotating speed of 50-100 r/min for 10-120 min to remove a solvent, and performing further silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain N, N-diX-base-4- ((methylsilyl) ethynyl) aniline;
dissolving 1-8 g of the N, N-diXyl-4- ((methylsilyl) ethynyl) aniline described in the previous paragraph and 1-8 g of potassium carbonate in 30-100 mL of a solution of tetrahydrofuran and absolute ethanol in a volume ratio of 7:3, introducing nitrogen at a flow rate of 0.1-3.0L/min, and ultrasonically deoxidizing for 10-60 min; transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, and starting only ultraviolet irradiation with the ultraviolet wavelength of 365nm and the irradiation intensity of 5mW/cm2～5W/cm2Irradiating for 1-720 min at room temperature; after the reaction is stopped, centrifuging at the speed of 5000-10000 r/min for 1-10 min to remove solids; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and performing dichloromethane column chromatography to obtain p- (diX-amino) phenylacetylene;
fourthly, preparation of 3- (4-iodophenyl) -2-thio-4-thiazolidinone
Stirring 1-15 g of p-iodoaniline and 20-90 g of triethylamine in 10-50 mL of ethanol at room temperature under an ice bath condition, and then dropwise adding 5-20 g of carbon disulfide CS at a speed of 1-3 g/min2Then centrifuging to obtain a precipitate, and washing with deionized water and diethyl ether for 3-5 times respectively to obtain p-iodophenyl ammonium dithiocarbamate; adding 5-20 g of sodium chloroacetate and 10-30 g of chloroacetic acid into 30-100 ml of distilled water to prepare a solution, dropwise adding the obtained p-iodophenyl ammonium dithiocarbamate into the solution at a speed of 1-3 g/min, and stirring at room temperature until the solution becomes dark yellow; then mixing the mixture with 50-200 ml of water at 90-95 DEG CUniformly mixing the hot hydrochloric acid, and stirring for 3-10 min to obtain colorless crystal precipitate; recrystallizing the precipitates in chloroform to obtain a dark yellow needle-shaped product, namely the target preparation 3- (4-iodophenyl) -2-sulfo-4-thiazolidone, wherein the chemical reaction formula of the step is as follows:
a chemical reaction formula of a preparation process of the 3- (4-iodophenyl) -2-thio-4-thiazolidone;
fifth, preparation of target novel Donor-Acceptor Polymer functionalized photoacoustic imaging Agents
Dissolving 0.50-3.00 g of the target polymer M obtained in the step one and 50-400 mg of 3- (4-iodophenyl) -2-thio-4-thiazolidinone in 1-10 mL of acetic acid, then adding 0.01-3.00 g of ammonium acetate, carrying out water bath reflux reaction at 30-90 ℃ for 1-3 h, stirring at the speed of 300-700 r/min, then filtering out precipitates, washing with acetic acid and absolute ethyl alcohol for 3-5 times respectively to obtain the compound M in the patent drawing description1The structural formula is as follows:
compound M1；
0.5 to 3.0g of the compound M1Dissolving 100-250 mL of p- (dimethylamino) phenylacetylene in 50-150 mL of solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, introducing nitrogen with the flow rate of 0.1-3.0L/min for 20-60 min to remove oxygen, adding 80-250 mg of bis (triphenylphosphine) palladium dichloride and 30-150 mg of cuprous iodide, carrying out water bath reflux reaction at 30-90 ℃ for 8-12 h, centrifuging to remove solids, and eluting with solution with the volume ratio of dichloromethane to petroleum ether being 3:1 to obtain a compound M shown in the specification of the patent drawing2The structural formula is as follows:
compound M2；
100-400 mg of compound M2Dissolving in 5-50 mL of tetrahydrofuran, respectively adding 10-50 mg of a click reagent, then introducing nitrogen at the flow rate of 0.1-3.0L/min, and stirring for 0.5-3.0 h in a water bath at the temperature of 30-70 ℃; performing rotary evaporation for 10-120 min at the rotating speed of 50-100 r/min at the temperature of 40-80 ℃ and the pressure of-0.09 MPa to remove the solvent, and purifying the crude product by using a column chromatography with an eluent dichloromethane to obtain the target novel donor-acceptor polymer functionalized photoacoustic developer M3The structural formula is as follows:
developer M3。
2. The novel donor-acceptor polymer functionalized photoacoustic imaging agent and the method for preparing the same according to claim 1, wherein: the click reagent is any one of 7,7,8, 8-tetracyanoquinodimethane abbreviated as TCNQ, tetracyanoethylene abbreviated as TCNE and 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane abbreviated as F4-TCNQ, and the structural formula of the click reagent is as follows:
tetracyanoethylene abbreviated as TCNE
7,7,8, 8-tetracyanoterephthalquinodimethane abbreviated as TCNQ
2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane abbreviated as F4-TCNQ.
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