CN101671427A - Water soluble fluorescent conjugated polymer and synthesis method thereof - Google Patents
Water soluble fluorescent conjugated polymer and synthesis method thereof Download PDFInfo
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- CN101671427A CN101671427A CN200910308614A CN200910308614A CN101671427A CN 101671427 A CN101671427 A CN 101671427A CN 200910308614 A CN200910308614 A CN 200910308614A CN 200910308614 A CN200910308614 A CN 200910308614A CN 101671427 A CN101671427 A CN 101671427A
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Abstract
The invention discloses a water soluble fluorescent conjugated polymer and a synthesis method thereof. The polymer has a conjugated main chain with hydrophobicity and ionic type functional group sidechains with hydrophilicity, wherein the ionic type functional group side chains with hydrophilicity are sulfonate and nitrobenzene; and the conjugated main chain introduces a single pyridine functional group. The invention introduces the single pyridine functional group at the conjugated main chain, thus being beneficial to aggregation of polymers, forming a three-dimensional structure and effectively improving the rigidity of the conjugated main chain; in addition, a pyridine ring can form complex with most of metallic ions so as to lead the polymeric molecule to have better quenching efficiency; further, the invention combines excellent optical performance of the conjugated polymer and water solubility of polyelectrolyte and provides a platform for designing a high-efficiency fluorescentprobe.
Description
Technical field
The present invention relates to a kind of water soluble fluorescent conjugated polymer and synthetic method thereof.
Background technology
In recent years, conjugated polymers gets more and more people's extensive concerning as a kind of novel chemistry and biological sensing material.Fields such as photodiode, solar cell, plastics laser and biosensor have been widely used at present.Soluble conjugated polymer is the conjugated polymers of ionic group functionalization, electrostatic interaction between the hydrophobic interaction of their conjugated main chain and the wetting ability ionic functional group makes them be self-assembled into various supramolecular structures easily in solution, and the space and the condition of design is provided for the selective action acceptor.Their ionic side chain, can be shifted quencher by electronics or energy by the quencher of some oppositely chargeds, the molecular wire character that also has conjugated polymers, electronics or energy can be on conjugated main chain fast transferring, delocalization very easily takes place in electronics or energy on whole polymer chain, its fluorescence can be very effective by the small molecules quencher of oppositely charged, can be widely used in biosensor (as detecting protein, DNA, carbohydrate and enzyme etc.) field.200610024113.0 disclose a kind of fluorescent sensing materials made of conjugated polymer, contained the electron-withdrawing group of sulphonate and nitrobenzene on the polymer lateral chain.It is mainly used in the detection to hydrogen peroxide, does not introduce pyridine functional groups in conjugated main chain; Usually pyridine functional groups can form coordination with most metal ions, in the design molecular structure, will connect two pyridines at present usually or connect three pyridine functional groups and receive in the molecular wire polymkeric substance, to realize the detection of multiple metal ion or the photoelectricity regulation and control of polymeric system.When pyridine functional groups and metal ion generation coordination, corresponding variation can take place in the light of molecular wire polymkeric substance or electrical property, when but various ions are had an effect with company's two pyridines and company's three pyridine molecular wire polymkeric substance, the poor specificity of response, selectivity is bad.
Summary of the invention
The object of the present invention is to provide a kind of kindliness that can increase conjugated main chain, improve the rigidity of conjugated main chain, and can make polymer molecule can have better quencher efficient, can effectively improve the signal of transmitter and optionally a kind of water soluble fluorescent conjugated polymer and synthetic method thereof.
Technical scheme of the present invention is:
Water soluble fluorescent conjugated polymer has hydrophobic conjugated main chain and hydrophilic ionic functional group side chain, and described hydrophilic ionic functional group side chain is sulfonate radical and nitrobenzene; Described conjugated main chain is introduced single pyridine functional groups, and its molecular structural formula is as follows:
A is a benzyne or to vinylbenzene support, B is pyridine, phenyl, pyrroles or thiophene in the formula in the formula.
A in formula is a benzyne, when B is phenyl or pyridine; Its molecular structural formula is as follows:
Structural formula (I)
Structural formula (II)
The molecular weight of structural formula (I) is 110000g/mol, and the polymerization degree is 105.36;
The molecular weight of structural formula (II) is 63000g/mol, and the polymerization degree is 100.96.
The synthetic method of above-mentioned water soluble fluorescent conjugated polymer may further comprise the steps:
(1) raw material 1,4-diynyl benzene and 2,6-diynyl pyridine and 1,4-two iodos-2,5-dipropoxy sodium sulfonate) two kinds or three kinds in the benzene are dissolved in the mixed solvent, according to (1,4-diynyl benzene: 2,6-diynyl pyridine: 1,4-two iodos-2,5-dipropoxy sodium sulfonate) benzene (mol ratio)=0～1: 1～1.2: 1.5～2.5; Select four triphenyl phosphorus palladiums for use: cuprous iodide=the composite catalyst consumption was 0.05～0.1 mole of reaction raw materials as composite catalyst in 1: 1, under nitrogen protection, at 50～85 ℃ of catalyzed reaction 20-30 of temperature hours;
(2) be cooled to room temperature after, centrifugal, remove insolubles;
(3) precipitation: upper solution slowly is added in the mixing solutions of a large amount of acetone and ether, high-speed stirring, to a large amount of burgundys precipitation occurring leaves standstill, the removal supernatant liquid, and lower floor carries out centrifugal treating;
(4) purifying: after with small amount of methanol solid being dissolved again, sedimentation twice in the mixing solutions of acetone and ether, obtains having the burgundy solid phase prod of one of above structural formula at last:
Described mixed solvent is a water: DMF: the mixed solvent of Diisopropylamine=2: 3: 1, should lead to the nitrogen deoxygenation 5-15 minute before using.
Acetone in the mixing solutions of described acetone and ether: ether=75: 50.
The present invention introduces single pyridine functional groups in conjugated main chain, the introducing of single pyridine functional groups, more help under the ad hoc structure, the coordination of ion and pyridine ring helps causing the reunion of molecular wire polymkeric substance and forming three-dimensional structure, thereby breaks the rigid state of linear conjugate main chain, increased the kindliness of main chain, effectively improved the rigidity of conjugated main chain, and pyridine ring can form title complex with most metal ions, make polymer molecule can have better quencher efficient; Simultaneously because the existence of sulfonate radical side chain, make conjugated polymers have good water-solubility, the present invention combines the excellent optical property and the water solubility of polyelectrolyte of traditional conjugated polymers, can detect the material of oppositely charged as fluorescent optical sensor in water-soluble.Have molecular wire character simultaneously, response signal is played amplification, fluorescent probe provides platform in order to design efficiently, and ion liquid adding makes polymkeric substance show different optical properties.
Embodiment
Embodiment 1:
The preparation of raw material:
A: preparing solvent: (water 5ml, dimethyl formamide 7.5ml, Diisopropylamine 2.5ml) mixes the back and lead to nitrogen deoxygenation ten minutes in solution;
B: in the 100ml three-necked flask, under the nitrogen protection, add 1,4-two iodos-2,5-dipropoxy sodium sulfonate) benzene 0.1342g (0.21mmol), 1,4-diynyl benzene 0.0120g (0.12mmol) g, 2,6-diynyl pyridine 0.0134g (0.1mmol), four triphenyl phosphorus palladium 12mg (10.0 μ mol), CuI, under 2mg (the 10.0 μ mol) nitrogen protection, add above-mentioned solvent with syringe again;
(1) polymerization: 65 ℃ of reactions 24 hours, solution was burgundy, under ultra violet lamp, bright blue-fluorescence is arranged;
(2) centrifugation impurity: centrifugal after being cooled to room temperature, remove insolubles;
(3) precipitation: solution slowly is added in acetone (75/50) mixed solution of 125ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating,
(4) purifying: after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, at last burgundy solid 0.0987g, be the have structural formula product P 1 of (I).
Embodiment 2:
Preparing solvent: water 5ml, DMF 7.5ml, Diisopropylamine 2.5ml, logical nitrogen deoxygenation ten minutes;
In the 100ml three-necked flask, under the nitrogen protection, add 1; 4-two iodos-2,5-dipropoxy sodium sulfonate) benzene 0.0663g (0.102mmol), 2; 6-diynyl pyridine 0.0127g (0.10mmol), under the nitrogen protection, four triphenyl phosphorus palladium 12mg (10.0 μ mol); CuI, 2mg (10.0 μ mol) adds solvent with syringe; 65 ℃ of reactions 24 hours; solution is burgundy, under ultra violet lamp, bright blue-fluorescence is arranged.After being cooled to room temperature, filter, remove insolubles, after the filtrate rotation is concentrated, slowly be added in acetone (75/50) mixed solution of 125ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating, after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, at last burgundy solid 0.0445g.Be the have structural formula product P 2 of (II).
Two kinds of polymkeric substance of P1 and P2 in the methanol solution and the aqueous solution maximum absorption band and maximum emission peak referring to table 1
Table 1
Embodiment 3:
Water 7.5ml, DMF 11.25ml, Diisopropylamine 3.75ml; logical nitrogen deoxygenation ten minutes; in the 100ml three-necked flask, under the nitrogen protection, add 1; 4-two iodos-2; 5-dipropoxy sodium sulfonate) benzene 0.2023g (0.31mmol), 1,4-diynyl benzene 0.0165 (0.16mmol) g; 2; 6-diynyl pyridine 0.0203g (0.16mmol), four triphenyl phosphorus palladium 17mg (15.0 μ mol), CuI; under 3mg (the 15.0 μ mol) nitrogen protection; solvent is added with syringe, and 65 ℃ of reactions 24 hours, solution was burgundy; under ultra violet lamp, bright blue-fluorescence is arranged.After being cooled to room temperature, centrifugal, remove insolubles, solution slowly is added in acetone (115/75) mixed solution of 190ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating, after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, gets burgundy solid 0.1895g at last.Be the have structural formula product P 1 of (I).
Embodiment 4:
Water 7.55ml; DMF 11.25ml, Diisopropylamine 3.75ml, logical nitrogen deoxygenation ten minutes; in the 100ml three-necked flask; under the nitrogen protection, add 1,4-two iodos-2; 5-dipropoxy sodium sulfonate) benzene 0.0996g (0.15mmol); 2,6-diynyl pyridine 0.0190g (0.15mmol) is under the nitrogen protection; four triphenyl phosphorus palladium 17mg (15.0 μ mol); CuI, 3mg (15.0 μ mol) adds solvent with syringe; 65 ℃ of reactions 24 hours; solution is burgundy, under ultra violet lamp, bright blue-fluorescence is arranged.After being cooled to room temperature, filter, remove insolubles, after the filtrate rotation is concentrated, slowly be added in acetone (115/75) mixed solution of 190ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating, after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, at last burgundy solid 0.0943g.Be the have structural formula product P 2 of (II).
Embodiment 5:
Water 10ml, DMF 15ml, Diisopropylamine 5ml; logical nitrogen deoxygenation ten minutes; in the 100ml three-necked flask, under the nitrogen protection, add 1; 4-two iodos-2; 5-dipropoxy sodium sulfonate) benzene 0.2573g (0.41mmol), 1,4-diynyl benzene 0.0211 (0.21mmol) g; 2; 6-diynyl pyridine 0.0203g (0.21mmol), four triphenyl phosphorus palladium 23mg (20.0 μ mol), CuI; under 4mg (the 15.0 μ mol) nitrogen protection; solvent is added with syringe, and 65 ℃ of reactions 24 hours, solution was burgundy; under ultra violet lamp, bright blue-fluorescence is arranged.After being cooled to room temperature, centrifugal, remove insolubles, solution slowly is added in acetone (115/75) mixed solution of 190ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating, after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, gets burgundy solid 0.1405g at last.Be the have structural formula product P 1 of (I).
Embodiment 6:
Water 10ml; DMF 15ml, Diisopropylamine 5ml, logical nitrogen deoxygenation ten minutes; in the 100ml three-necked flask; under the nitrogen protection, add 1,4-two iodos-2; 5-dipropoxy sodium sulfonate) benzene 0.1305g (0.20mmol); 2,6-diynyl pyridine 0.0267g (0.21mmol) is under the nitrogen protection; four triphenyl phosphorus palladium 23mg (20.0 μ mol); CuI, 4mg (10.0 μ mol) adds solvent with syringe; 65 ℃ of reactions 24 hours; solution is burgundy, under ultra violet lamp, bright blue-fluorescence is arranged.After being cooled to room temperature, filter, remove insolubles, after the filtrate rotation is concentrated, slowly be added in acetone (115/75) mixed solution of 190ml high-speed stirring, a large amount of burgundy precipitations occur, leave standstill, remove supernatant liquid, lower floor carries out centrifugal treating, after with small amount of methanol solid being dissolved again, sedimentation twice in the acetone mixing solutions, at last burgundy solid 0.0689g.Be the have structural formula product P 2 of (II).
Claims (5)
1. a water soluble fluorescent conjugated polymer is characterized in that, described polymkeric substance has hydrophobic conjugated main chain and hydrophilic ionic functional group side chain, and described hydrophilic ionic functional group side chain is sulfonate radical and nitrobenzene; Described conjugated main chain is introduced single pyridine functional groups, and the molecular structural formula of polymkeric substance is as follows:
A is a benzyne or to vinylbenzene support, B is pyridine, phenyl, pyrroles or thiophene in the formula in the formula.
2. water soluble fluorescent conjugated polymer according to claim 1 is characterized in that, the A in the described formula is a benzyne, and B is phenyl or pyridine; The molecular structural formula of polymkeric substance is as follows:
Structural formula (I)
Structural formula (II)
The molecular weight of structural formula (I) is 110000g/mol, and the polymerization degree is 105.36;
The molecular weight of structural formula (II) is 63000g/mol, and the polymerization degree is 100.96.
3. the synthetic method of the described water soluble fluorescent conjugated polymer of claim 2 is characterized in that, may further comprise the steps:
(1) raw material 1,4-diynyl benzene and 2,6-diynyl pyridine and 1,4-two iodos-2,5-dipropoxy sodium sulfonate) two kinds or three kinds in the benzene are dissolved in the mixed solvent, according to (1,4-diynyl benzene: 2,6-diynyl pyridine: 1,4-two iodos-2,5-dipropoxy sodium sulfonate) benzene (mol ratio)=0～1: 1～1.2: 1.5～2.5; Select four triphenyl phosphorus palladiums for use: cuprous iodide=the composite catalyst consumption was 0.05～0.1 mole of reaction raw materials as composite catalyst in 1: 1, under nitrogen protection, at 50～85 ℃ of catalyzed reaction 20-30 of temperature hours;
(2) be cooled to room temperature after, centrifugal, remove insolubles;
(3) precipitation: upper solution slowly is added in the mixing solutions of a large amount of acetone and ether, high-speed stirring, to a large amount of burgundys precipitation occurring leaves standstill, the removal supernatant liquid, and lower floor carries out centrifugal treating;
(4) purifying: after with small amount of methanol solid being dissolved again, sedimentation twice in the mixing solutions of acetone and ether, obtains having the burgundy solid phase prod of one of above structural formula at last.
4. according to the synthetic method of the described water soluble fluorescent conjugated polymer of claim 3, it is characterized in that described mixed solvent is a water: DMF: the mixed solvent of Diisopropylamine=2: 3: 1, should lead to the nitrogen deoxygenation 5-15 minute before using.
5. according to the synthetic method of the described water soluble fluorescent conjugated polymer of claim 3, it is characterized in that acetone in the mixing solutions of described acetone and ether: ether=75: 50.
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Cited By (8)
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| CN101892045A (en) * | 2010-06-02 | 2010-11-24 | 苏州大学 | Fluorescence conjugated polyelectrolytes with amphoteric side chain, preparation method and application |
| CN102585171A (en) * | 2011-12-31 | 2012-07-18 | 华中科技大学 | Ether chain substituted conjugate polycationic electrolyte material and application thereof |
| CN103232591A (en) * | 2013-05-09 | 2013-08-07 | 上海大学 | Conductive polymer for solar cell conductive films and synthesis method thereof |
| CN104448061A (en) * | 2014-11-20 | 2015-03-25 | 四川大学 | Simple method for connecting acrylate copolymer with fluorescent functional groups |
| CN105115945A (en) * | 2015-06-26 | 2015-12-02 | 安徽师范大学 | gamma-globulin detection method |
| CN108976394A (en) * | 2018-08-02 | 2018-12-11 | 湖南师范大学 | Conjugated polymer, synthetic method and the method for detecting Etimicin concentration with it |
| CN110563636A (en) * | 2019-09-11 | 2019-12-13 | 湖南师范大学 | conjugated polymer containing pyrene-pyridine group and synthetic method and application thereof |
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| CN1275989C (en) * | 2004-07-22 | 2006-09-20 | 复旦大学 | Water-soluble poly-p-phenylene ethynylene and synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101892045A (en) * | 2010-06-02 | 2010-11-24 | 苏州大学 | Fluorescence conjugated polyelectrolytes with amphoteric side chain, preparation method and application |
| CN101892045B (en) * | 2010-06-02 | 2014-04-16 | 苏州大学 | Fluorescence conjugated polyelectrolytes with amphoteric side chain, preparation method and application |
| CN102585171A (en) * | 2011-12-31 | 2012-07-18 | 华中科技大学 | Ether chain substituted conjugate polycationic electrolyte material and application thereof |
| CN102585171B (en) * | 2011-12-31 | 2013-06-26 | 华中科技大学 | Ether chain substituted conjugate polycationic electrolyte material and application thereof |
| CN103232591A (en) * | 2013-05-09 | 2013-08-07 | 上海大学 | Conductive polymer for solar cell conductive films and synthesis method thereof |
| CN104448061A (en) * | 2014-11-20 | 2015-03-25 | 四川大学 | Simple method for connecting acrylate copolymer with fluorescent functional groups |
| CN105115945A (en) * | 2015-06-26 | 2015-12-02 | 安徽师范大学 | gamma-globulin detection method |
| CN105115945B (en) * | 2015-06-26 | 2018-01-19 | 安徽师范大学 | The detection method of gamma Globulin |
| CN108976394A (en) * | 2018-08-02 | 2018-12-11 | 湖南师范大学 | Conjugated polymer, synthetic method and the method for detecting Etimicin concentration with it |
| CN110563636A (en) * | 2019-09-11 | 2019-12-13 | 湖南师范大学 | conjugated polymer containing pyrene-pyridine group and synthetic method and application thereof |
| CN110563636B (en) * | 2019-09-11 | 2020-12-08 | 湖南师范大学 | Conjugated polymer containing pyrene-pyridine group and synthetic method and application thereof |
| CN111057054A (en) * | 2019-12-02 | 2020-04-24 | 武汉工程大学 | Dibromo monomer and preparation method thereof, water-soluble random copolymer and preparation method thereof, and fluorescent sensor |
| CN111057054B (en) * | 2019-12-02 | 2021-07-23 | 武汉工程大学 | Dibromo monomer and preparation method thereof, water-soluble random copolymer and preparation method thereof, and fluorescent sensor |
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