CN100358933C - Conjugated polymer fluorescent sensing material and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of chemical sensing materials, in particular to a class of conjugated polymer fluorescent sensing materials containing sulfonate and electron-withdrawing groups and a preparation method thereof. The invention uses aromatic compounds bonded by nitrobenzene through sulfonate as raw materials, and carries out organometallic catalytic reaction with various other aromatic compounds to synthesize a series of conjugated polymers. The polymer is a high-sensitivity high-molecular fluorescent sensing material, which is used for the detection of hydrogen peroxide. In addition, compared with the traditional detection method of hydrogen peroxide, the polymer is carried out by fluorescence recovery method, which greatly improves the detection sensitivity.

Description

Conjugated polymer fluorescent sensing material and preparation method thereof

technical field

The invention belongs to the technical field of chemical sensing materials, in particular to a class of conjugated polymer fluorescent sensing materials containing sulfonate and electron-withdrawing groups and a preparation method thereof.

Background technique

The aging of the body is a very complicated problem, but aging and the occurrence of certain diseases are related to the inability to eliminate some free radicals in the body in time, and there are many types of free radicals in the body, but the toxic oxygen source is mainly oxygen free radicals (Reactive Oxygen Species, ROS) or active oxygen mainly includes O ₂ ^- , O ₂ , -OH and H ₂ O ₂ , among which H ₂ O ₂ is the most important. This kind of living body produces ROS during the normal metabolic process. If it cannot be removed in time to restore the balance, it will cause peroxidative damage to the biofilm, and even cause damage to organelles and degradation and inactivation of DNA and proteins.

The detection of hydrogen peroxide has always been the focus of scientific research. The traditional detection methods are mainly divided into two methods: chemiluminescence detection and fluorescence detection. Due to the different detection mechanisms, fluorescence detection relies on its high sensitivity and convenient detection methods to get more research. . However, the main problem that currently plagues the detection of hydrogen peroxide is that all kinds of detection materials have always had the disadvantage of poor selectivity. This is mainly because the detection of hydrogen peroxide is generally carried out through its oxidative properties, while other active oxygen species are also relatively strong. Therefore, the specificity of the detection of hydrogen peroxide is problematic.

After 20 years of development, conjugated polymers have become a relatively mature and comprehensive interdisciplinary subject. Conjugated polymers have great potential commercial applications due to the combination of processability and flexibility of polymers, as well as inorganic semiconducting properties or metal conductivity. At present, conjugated polymers have also been greatly developed in the field of biological and chemical sensing. There have been a large number of reports on the use of conjugated polymers for ion detection, DNA and RNA detection. At the same time, fluorescent sensing materials of small molecular compounds with electron-withdrawing groups and fluorescent groups linked by sulfonate have been reported. Quenching, which restores the fluorescence of the fluorescent group by breaking the connected sulfonate group in the presence of hydrogen peroxide, and achieves the purpose of detection. For conjugated polymers, due to its higher sensitivity and responsiveness, it can It has a better application prospect for small molecule materials.

The present invention introduces nitrobenzene with a sulfonate group in the side chain through a conjugated polymer. In the presence of hydrogen peroxide, the sulfonate group is disconnected due to a strong electrophilic effect, thereby containing a strong electron-withdrawing group. The nitrobenzene detaches from the main chain of the conjugated polymer, which enhances the fluorescence of the main chain molecules that originally emit weak light when the electron-withdrawing group exists, and achieves the purpose of detection.

Contents of the invention

The purpose of the present invention is to propose a conjugated polymer material fluorescence sensor and its preparation method, and to propose the application of the conjugated polymer material in biological/chemical detection, especially in the detection of hydrogen peroxide.

The conjugated polymer fluorescent sensing material proposed by the invention has side chains containing sulfonate and nitrobenzene electron-withdrawing groups, and is synthesized by using an aromatic compound containing charge transport as a raw material through an organometallic catalyzed reaction. The molecular structure of this compound is as follows:

Wherein, _R1 is an alkoxy group, an alkyl group, a phenyl group or other aromatics and their derivative substituents, or a group with a water-soluble ionic group, etc., and k is an integer greater than or equal to 0;

_R2 is a nitrobenzene group, and m is an integer greater than or equal to 1;

Both X and Y can be one of 9,9-disubstituted fluorenyl, phenyl, thiophene, pyrrole, p-phenylene, phenylene, spirofluorene, naphthyl, anthracenyl, and their corresponding derivatives For any aromatic molecule, the degree of polymerization n can be any natural number.

Among the above-mentioned compounds, typical compounds are as follows:

(1) _R1 is decyloxy, k=1, _R2 is 2,4-dinitrobenzene, m=1, Y is 9,9-disubstituted alkylfluorene, X is phenyl, and its structural formula is as follows :

(2) k=0, _R2 is p-nitrobenzene, m=2, Y is dihexyloxybenzyne, X is 9,9-diphenyl substituted fluorene, and its structural formula is as follows:

(3) k=0, R ₂ is 2,4-dinitrobenzene, m=2, Y is a diene structure containing a quaternary ammonium salt at the 1,4 position, X is 9,9-dipropane substituted fluorene, its The structural formula is as follows:

The synthetic method of the compound proposed by the present invention is as follows:

(1) Synthesis of 2,7-bisboronate-9,9'-dialkyl-fluorene monomer

Using 2,7-dibromofluorene as a template, add 2-3 times the amount of bromoalkyl under the condition of alkali catalysis to synthesize 9-position dialkyl substituted fluorene;

For the 9-position dialkyl substituted fluorene, use n-butyllithium to activate the bromine at the 2,7 position, and add triisopropyl borate to synthesize 2,7-bisboronate-9,9'-dialkyl- fluorene;

(2) Synthesis of sulfonate-containing nitrobenzene monomer

Using hydroquinone as a template, dihydroxydibromobenzene was prepared by reacting with 2 times the amount of liquid bromine;

Dihydroxydibromobenzene is added with 1 times amount of bromoalkane under the condition of potassium carbonate to carry out Williamson reaction to obtain monoalkoxy substituted dibromophenol.

For monoalkoxy substituted dibromophenol, use 2,6-lutidine and dichloromethane as solvents, add 1 times the amount of nitrosulfonyl chloride, and synthesize monomers containing nitrophenyl and sulfonate groups Dibromobenzene.

(3) Synthesis of polymers

Dibromobenzene containing nitrophenyl and sulfonate groups and 2,7-bisboronate-9,9'-dialkyl-fluorene in toluene solvent, using tetrakis-triphenylphosphopalladium as catalyst The Suzuki reaction is carried out, and the obtained product is subjected to step-by-step precipitation and dialysis membrane filtration to obtain a conjugated polymer of fluorene and aromatic groups connected by conjugation.

In the conjugated polymer of nitrobenzene with a sulfonate group in the side chain prepared by the present invention, in the presence of hydrogen peroxide, the sulfonate group will be disconnected due to strong electrophilic interaction, thus will contain strong electron-withdrawing polymers. The nitrobenzene of the base is separated from the main chain of the conjugated polymer, which enhances the fluorescence of the main chain molecules that originally emit weak light when the electron-withdrawing group exists, thus achieving the purpose of detection.

Therefore, the present invention also proposes the application of the above compounds in the detection of hydrogen peroxide. A hydrogen peroxide detector using the above compounds as detection substances is included.

The method for detecting hydrogen peroxide with any of the above-mentioned compounds as the detection object is as follows: use the corresponding solvent or aqueous solution to prepare the synthesized polymer and the substance to be tested into dilute solutions of 10 ^-4 ~ 10 ^-6 mol/L; The solution of the substance is added to the polymer solution, wherein the volume of the substance to be tested is less than 1% of the volume of the polymer solution; the ultraviolet absorption spectrum and the fluorescence emission spectrum of the polymer solution are measured in the presence of different substances to be tested; Under different concentrations of substances, the ultraviolet absorption spectrum and fluorescence emission spectrum of the polymer solution are obtained according to the change of fluorescence intensity.

Description of drawings

Fig. 1 is the fluorescence emission spectrum of the polymer synthesized in the present invention in the presence of different concentrations of hydrogen peroxide.

Detailed ways

In order to better understand the content of the present invention, the technical solutions of the present invention will be further described below through specific examples.

Embodiment 1, the preparation of the fluorene benzene system conjugated polymer containing sulfonate and electron-withdrawing group

1. Synthesis of 2,7-bisboronate-9,9'-dihexyl-fluorene monomer (monomer 1)

Add 2,7-dibromofluorene (6.61 g, 20.40 mmol) and a catalytic amount of tetrabutylammonium chloride into a 250 mL two-necked bottle, seal it, and perform anhydrous and oxygen-free treatment. Then inject 25-30mL dimethyl sulfoxide with a syringe, heat and stir. Then inject 45-55% sodium hydroxide aqueous solution and heat to 70-80°C, the solution changes from a colorless transparent solution to a purple-red solution. After stirring for 5-10 minutes, 1-hexyl bromide (7.41 g, 44.88 mol) was injected. The mixture was kept under reflux at 70-80°C overnight, and a large amount of white solids precipitated out. Cool to room temperature, add hydrochloric acid (2.0M) to adjust the pH value to neutral, the white solid disappears, and a large number of bubbles are generated. After the reaction is complete, add 80-100 mL of dichloromethane for extraction, wash with saturated brine and dry with anhydrous magnesium sulfate. After filtration and rotary evaporation to remove the solvent, it was separated by silica gel column chromatography (petroleum ether as the eluent) to obtain 2,7-dibromo-9,9'-dioctyl-fluorene as a light yellow viscous liquid.

Add 2,7-dibromo-9,9'-dihexyl-fluorene (8.96g, 18.20mmol) into a 500mL two-necked bottle, seal it, and perform anhydrous and oxygen-free treatment. Then inject 140-160 mL of tetrahydrofuran (after anhydrous and oxygen-free treatment) with a syringe, stir to dissolve, cool to -78°C, add 1.6M n-butyllithium (28.50 mL, 45.50 mmol), and stir for 50-80 minutes Afterwards, triisopropyl borate (21.16 mL, 0.09 mol) was injected and returned to room temperature, the solution changed from clear to white turbid solution, and stirred overnight. Then hydrochloric acid was added, the white turbidity disappeared, and the solution became clear again. Pour in a large amount of deionized water and ether, extract and separate the liquid. The organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate overnight. After removing the solvent by rotary evaporation, add 3 times the amount of 1,3-propanediol, and heat to 120-130°C in toluene solvent to react for 3-4 hours. After filtration, the solvent was removed by rotary evaporation, and then separated by column chromatography with petroleum ether and ethyl acetate. 2,7-Bisboronate-9,9'-dioctyl-fluorene was obtained as a pale yellow liquid.

2. Synthesis of 2,5-dibromo-4-decyloxy-1-(2,4-dinitrobenzenesulfonate)-benzene (monomer 2)

Sodium hydroxide (0.36g, 9.00mmol), 1,4-dibromohydroquinone (2.01g, 7.40mmol), brodecane (1.65g, 7.40mmol) were added to a 250mL reaction flask, sealed, and anhydrous Anaerobic treatment. Pour in 70-75mL of ethanol, heat to 60-65°C, slowly add brodecane (1.65g, 7.40mmol) dropwise into the system, and react the mixture under nitrogen atmosphere for 10-13 hours. The color of the system gradually became darker. After the reaction, the system was cooled, filtered, and washed with methanol. The filtrate was evaporated to remove the solvent under reduced pressure, and 80-100 mL of deionized water was added to the residue, acidified with hydrochloric acid, boiled for 1-1.5 hours, and cooled. The precipitate was filtered off, washed with water, dried, and passed through a silica gel column using petroleum ether: acetone = 5:1 as the eluent to obtain 2,5-dibromo-4-decyloxyphenol as a white solid product.

In a 25mL reaction flask, 2,5-dibromo-4-decyloxyphenol (2.00g, 4.90mmol), 2,4-dinitrobenzenesulfonyl chloride (1.32g, 4.90mmol) were dissolved in dichloromethane 4 ～5mL, 2,6-Lutidine 4～5mL mixed solvent. After reacting overnight at room temperature, 20-25 mL of 2M hydrochloric acid solution was added, extracted twice with chloroform, the solvent was rotatably evaporated, and the eluent was passed through a silica gel column with petroleum ether: acetone = 5:1. The product 2,5-dibromo-4-decyloxy-1-(2,4-dinitrobenzenesulfonate)-benzene was obtained as a pale yellow solid.

3. Aggregation

2,7-Bisboronate-9,9'-dihexyl-fluorene (100.00mg, 0.20mmol) and 2,5-dibromo-4-decyloxy-1-(2,4-dinitro Benzenesulfonate group)-benzene (127.10mg, 0.20mmol) was mixed, then tetrakistriphenylphosphopalladium (Pd(PPh ₃ ) ₄ ) (7.01mg, 6.60μmol) was added, and the two-necked bottle was repeatedly vacuumed and Inflate with nitrogen three times, then add 10-12 mL of toluene deoxygenated by bubbling nitrogen gas and saturated ethanol solution of sodium carbonate that has also been deoxygenated, heat to 80°-90°C in an oil bath and react for 60-80 hours, then cool to At room temperature, the organic phase was separated, the aqueous phase was washed twice with toluene and the combined organic phase was washed three times with saturated brine. The reaction product was precipitated in methanol to give a yellow precipitate.

Example 2, Preparation of fluorenyne-benzene conjugated polymers containing sulfonate esters and electron-withdrawing groups

1. Synthesis of 1,4-dibromo-2,5-dihexyloxybenzene

Potassium carbonate (33.12 g, 0.24 mol), 1,4-dibromohydroquinone (10.72 g, 0.04 mol), and 300 mL of acetone were added to a 500 mL reaction flask, and the mixture was refluxed for about 25 to 30 minutes. Then, hexyl bromide (14.86 g, 0.09 mol) was added into the reaction flask, and reacted under reflux for 24 to 30 hours. The reaction mixture was filtered, and the filtrate was rotary evaporated to remove the solvent. The concentrated product was poured into water, extracted 2-3 times with ether, and the obtained organic layer was washed 2-3 times with aqueous solution and 2-3 times with saturated brine. The solution was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation to obtain a crude product. The crude product was recrystallized from ethanol to obtain white crystals.

2. Synthesis of 1,4-diethynyl-2,5-dihexyloxybenzene (monomer 1)

1,4-dibromo-2,5 dihexyloxybenzene (4.36g, 0.01mol), CuI (95.20g, 0.50mmol), PdCl ₂ (PPh ₃ ) ₂ (0.35g, 0.50mmol), dissolved in 40 ~45mL diisopropylamine. Trimethylsilyne (1.96 g, 0.02 mol) was added to the above solution. React under reflux conditions for 6-8 hours. The reaction mixture was spin-dried, the concentrate was poured into water, extracted with dichloromethane, the organic layer was washed 2-3 times with water, once with saturated brine and dried over anhydrous magnesium sulfate. The organic solvent was removed by rotary evaporation under reduced pressure, and the crude product was recrystallized from n-hexane to obtain white crystals. Add white crystals to a mixed solvent of tetrahydrofuran and methanol, add 5M aqueous sodium hydroxide solution, stir at room temperature for 4 hours, spin the solvent to dryness, and recrystallize the crude product from ethanol to obtain yellow crystals of 1,4-diethynyl-2,5 di Hexyloxybenzene.

3. Synthesis of 2,7-dibromo-9,9'-bis[4-(4-nitrobenzenesulfonate)-phenyl]fluorene (monomer 2)

Dissolve 2,7-dibromofluorenone (9.20g, 2.70mol), phenol (17.01g, 0.18mol) and methanesulfonic acid (7.81g, 0.08mol) in 35-40mL carbon tetrachloride, 70- Stir and react at 80°C for 40-50 hours. The system was cooled to room temperature, and the precipitate was filtered and washed with dichloromethane. The product 2,7-dibromo-9,9'-bis(4-phenolyl)fluorene was obtained as a white solid.

In a 25mL reaction flask, 2,7-dibromo-9,9'-bis(4-phenol)fluorene (2.01g, 3.92mmol), 4-nitrobenzenesulfonyl chloride (2.61g, 9.79mmol) were dissolved in di In a mixed solvent of 10-12 mL of methyl chloride and 10-12 mL of 2,6-lutidine. After reacting overnight at room temperature, 35-40 mL of 2M hydrochloric acid solution was added, extracted twice with chloroform, the solvent was rotary evaporated, and the eluent was passed through a silica gel column with petroleum ether: ethyl acetate = 2:1. The product 2,7-dibromo-9,9'-bis[4-(4-nitrosulfonate)-phenyl]fluorene was obtained as a pale yellow solid.

4. Aggregation

1,4-diethynyl-2,5 dibromobenzene (55.80 mg, 0.17 mmol) and 2,7-dibromo-9,9'-bis[4-(4-nitrosulfonate)- Phenyl]fluorene (150.01mg, 0.17mmol), after mixing, add tetrakistriphenylphosphorous palladium (Pd(PPh ₃ ) ₄ ) (8.50mg, 7.37μmol), cuprous iodide (5.75mg, 0.03mmol) and then pack Vacuumize and nitrogen-fill repeatedly into a two-necked bottle for three times, then add 5 mL of toluene deoxygenated by bubbling nitrogen gas and 2.5 mL of diisopropylamine solution that has also been deoxygenated, and heat to 65-70 °C in an oil bath to react After cooling to room temperature for 30 to 50 hours, the organic phase was separated, the water phase was washed 2 to 3 times with toluene, and the combined organic phases were washed 2 to 3 times with saturated brine. The reaction product was precipitated in methanol to give a yellow precipitate.

Example 3, Preparation of fluorene and water-soluble phenylene conjugated polymers containing sulfonate and electron-withdrawing groups

1. Synthesis of quaternary phosphorus salt monomer

Take 2,5-dihydroxy-diethyl terephthalate (10.1g, 39mmol) as raw material, use acetone as solvent, add (32g, 232mmol) potassium carbonate, reflux for 30-35 minutes, then add 16.4g 3- Dimethylamine-chloropropane hydrochloride, after stirring and refluxing for 60-72 hours, spin off acetone. Add water to dissolve and extract with ethyl acetate to obtain an organic layer. Then 2M hydrochloric acid was added until the aqueous layer was acidic. Remove the organic layer, add saturated potassium carbonate solution to the water layer until no bubbles occur, and the pH value should be neutral at this time. Ethyl acetate was added for extraction, the organic layer was washed with water, washed with salt and dried to obtain 21.9 g of viscous brown liquid 2,5-bis(3-dimethylamine-propyl)-diethyl terephthalate.

Add 5.2g of lithium aluminum hydride into 50-55mL of tetrahydrofuran, dissolve 15.0g of 2,5-bis(3-dimethylamine-propyl)-diethyl terephthalate in 200ml of tetrahydrofuran in an ice-water bath, and slowly drop Put it into the above system, heat and reflux for 2 to 3 hours after the dropwise addition, and after cooling to room temperature, add saturated sodium sulfate solution dropwise until no bubbles occur, add 200 ml of tetrahydrofuran to the obtained solid after filtration, and heat and reflux for 2 to 3 hours. The obtained filtrates were combined and spin-dried for recrystallization to obtain 11.1 g of a white solid. Add hydrogen chloride methanol solution to acidify, remove the solvent and recrystallize to obtain white crystals. Add the white crystals to 50-55 ml of thionyl chloride, stir at room temperature for 68-72 hours, remove the thionyl chloride and recrystallize to obtain 5.6 g of white crystals. Use DMF as a solvent, add the above white crystals, add triphenylphosphine after fully dissolving, react at 70-75°C for 20-24 hours, filter to obtain white powder, and recrystallize to obtain quaternary phosphorus salt monomer.

2. Synthesis of aldehyde-based monomers

Add 2,7-dibromofluorene (6.61 g, 20.40 mmol) and a catalytic amount of tetrabutylammonium chloride into a 250 mL two-necked bottle, seal it, and perform anhydrous and oxygen-free treatment. Then inject 25-30mL dimethyl sulfoxide with a syringe, heat and stir. Then inject 45-55% sodium hydroxide aqueous solution and heat to 70-80°C, the solution changes from a colorless transparent solution to a purple-red solution. After stirring for 5-10 minutes, 3-bromopropanol (6.23 g, 44.88 mol) was injected. The mixture was kept under reflux at 70-80°C overnight, and a large amount of white solids precipitated out. Cool to room temperature, add hydrochloric acid (2.0M) to adjust the pH value to neutral, the white solid disappears, and a large number of bubbles are generated. After the reaction is complete, add 80-100 mL of dichloromethane for extraction, wash with saturated brine and dry with anhydrous magnesium sulfate. After filtration and rotary evaporation to remove the solvent, the light yellow viscous liquid 2,7-dibromo-9,9'-di(3-hydroxypropyl ) fluorene.

In a 25mL reaction flask, 2,7-dibromo-9,9'-bis(3-hydroxypropyl)fluorene (2.00g, 4.54mmol), 2,4-dinitrobenzenesulfonyl chloride (1.32g, 4.90 mmol) was dissolved in a mixed solvent of 4-5 mL of dichloromethane and 4-5 mL of 2,6-lutidine. After reacting overnight at room temperature, 20-25 mL of 2M hydrochloric acid solution was added, extracted twice with chloroform, the solvent was rotatably evaporated, and the eluent was passed through a silica gel column with petroleum ether: acetone = 5:1. The product 2,7-dibromo-9,9'-bis[(2,4-nitrosulfonate)-propyl]fluorene was obtained as a pale yellow solid.

Take (10g, 11.1mmol) 2,7-dibromo-9,9'-bis[(2,4-nitrosulfonate)-propyl]fluorene as a raw material, add it to a two-necked bottle, seal it, Carry out anhydrous and oxygen-free treatment. Then inject 30-40 mL of tetrahydrofuran (after anhydrous and oxygen-free treatment) with a syringe, stir to dissolve, cool to -78°C, add 1.6M n-butyllithium (17.34 mL, 27.75 mmol), and stir for 50-80 minutes Afterwards, inject 10 mL of anhydrous DMF, return to room temperature, and stir overnight. Then hydrochloric acid was added for extraction and separation. The organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate overnight. After the solvent was removed by rotary evaporation, the solvent was removed by rotary evaporation, followed by column chromatography separation with petroleum ether and ethyl acetate to obtain a light yellow solid product.

3. Polymerization and quaternization

In a 50ml round bottom flask, add 0.8mmol of triphenylphosphine salt chloride monomer and 0.8mmol of nitrobenzaldehyde monomer, dissolve with 10ml of absolute ethanol and 10ml of anhydrous chloroform, stir well , adding 0.476 g of anhydrous sodium ethylate solution, the mixture was stirred for 12 hours and poured into 200 ml of methanol, the obtained precipitate was filtered, washed with water, extracted with a Soxhlet extractor for 3 days, and then dried to obtain a neutral polymer. Add 0.4mmol neutral polymer to a 50ml round bottom flask, add 20ml tetrahydrofuran to dissolve, then add 0.436g bromoethane and 5ml DMSO. Stir the solution at 50°C for 60-72 hours, spin off most of bromoethane and tetrahydrofuran, settle the polymer with acetone, centrifuge, and vacuum dry at 50°C to obtain the target polymer.

Detection of hydrogen peroxide

The polymer was formulated into a 1×10 ^-5 M aqueous solution, and 1.0 M hydrogen peroxide aqueous solution was added thereto. Add a small amount of hydrogen peroxide solution into the system with a micro syringe. At this time, the fluorescence of the polymer was significantly enhanced when the concentration of hydrogen peroxide was very small, observed by a fluorometer. Thus, it was demonstrated that the polymer can effectively detect hydrogen peroxide.

Claims (5)

1, a kind of fluorescent sensing materials made of conjugated polymer is characterized in that containing on the polymer lateral chain sulphonate and nitrobenzene electron-withdrawing group, and molecular structural formula is as follows:

Wherein, R ₁Be alkoxyl group, alkyl, phenyl and derivative substituting group thereof; Or having the group of water soluble ion base, k gets the integer more than or equal to 0;

R ₂Be the nitrobenzene group, m gets the integer more than or equal to 1;

X, Y be, 9,9-two replace fluorenyls, phenyl, thiophene, pyrroles, to vinylbenzene support, benzyne, spiral fluorenes, naphthyl, anthryl, with and corresponding derivative in a kind of any aromatic molecule, polymerization degree n is the natural number greater than 1.

2. fluorescent sensing materials made of conjugated polymer according to claim 1 is characterized in that for following 3 kinds a kind of:

(1) R ₁Be oxygen base in the last of the ten Heavenly stems, k=1, R ₂Be 2, the 4-dinitrobenzene, m=1, Y are 9,9-two substituted alkyl fluorenes, X is a phenyl, its structural formula is as follows:

(2) k=0, R ₂Be p-nitrophenyl, m=2, Y are two hexyloxy benzynes, and X is 9,9-phenylbenzene substituted fluorene, and its structural formula is as follows:

(3) k=0, R ₂Be 2,4-dinitrobenzene, m=2, Y are 1,4 diene structure that contains quaternary amine, and X is 9,9-two propane substituted fluorenes, and its structural formula is as follows:

3, a kind of synthetic method of fluorescent sensing materials made of conjugated polymer as claimed in claim 1 is characterized in that concrete steps are as follows:

The two boric acid esters-9 of (one) 2,7-, 9 '-dialkyl group-fluorenes is monomeric synthetic

With 2,7-two bromo fluorenes are masterplate, add 2-3 and doubly measure synthetic 9 fluorenes that two alkyl replace of bromo alkyl under the base catalysis condition;

The fluorenes that 9 two alkyl are replaced adds triisopropyl boric acid ester Synthetic 2, the two boric acid esters-9 of 7-, 9 '-dialkyl group-fluorenes with the bromine in 2,7 of the n-Butyl Lithium activation;

(2) it is monomeric synthetic to contain sulfonate group oil of mirbane

With the Resorcinol is masterplate, makes the dihydroxyl dibromobenzene by the liquid bromine reaction with 2 times of amounts;

The dibromo Resorcinol adds 1 times of amount under the salt of wormwood condition bromoalkane carries out the Williamson reaction, obtains the dibromobenzene that monoalkoxy and monohydroxy replace;

The dibromo hydroxybenzene that monoalkoxy is replaced is with 2, and 6-lutidine and methylene dichloride are made solvent, the nitro SULPHURYL CHLORIDE that adding 1-2 doubly measures, and synthon contains the dibromobenzene of nitrophenyl and sulfonate group;

(3) polymkeric substance is synthetic

The dibromobenzene and 2 that will contain nitrophenyl and sulfonate group, the two boric acid esters-9 of 7-, 9 '-dialkyl group-fluorenes is in toluene solvant, carry out the Suzuki reaction with four-triphenyl phosphorus palladium as catalyzer, products therefrom obtains with the fluorenes of conjugation connection and the conjugated polymers of aromatic group through precipitation and dialysis membrane filtration step by step.

4. serve as the hydrogen peroxide detector that detects thing with the described fluorescent sensing materials made of conjugated polymer of claim 1.

5. serve as the hydrogen peroxide detection method that detects thing with the described fluorescent sensing materials made of conjugated polymer of claim 1, it is characterized in that concrete steps are as follows:

With the corresponding solvent or the aqueous solution synthetic polymkeric substance and test substance are made into 10 respectively ^-4～10 ^-6The dilute solution of mol/L;

The solution of test substance is joined in the polymers soln, and wherein the test substance liquor capacity is below 1% of polymers soln volume;

Be determined at different test substances and have down the ultra-violet absorption spectrum of polymers soln and fluorescence emission spectrum;

Measure under the test substance different concns state, the ultra-violet absorption spectrum of polymers soln and fluorescence emission spectrum according to the variation of fluorescence intensity, obtain detected result.

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