CN103773360A - Schiff base fluorescent polymer and preparation method thereof - Google Patents
Schiff base fluorescent polymer and preparation method thereof Download PDFInfo
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- CN103773360A CN103773360A CN201410006699.2A CN201410006699A CN103773360A CN 103773360 A CN103773360 A CN 103773360A CN 201410006699 A CN201410006699 A CN 201410006699A CN 103773360 A CN103773360 A CN 103773360A
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Abstract
The invention provides a Schiff base fluorescent polymer with a structure shown in a formula I and a preparation method thereof. The preparation method comprises the following steps: reducing 4-nitro polystyrene into 4-amino polystyrene, reacting 4,4-biformyl triphenylamine with 1,10-phenanthroline-5,6-diketone to synthesize a small molecule fluorescent compound II, and finally, carrying out a Schiff base reaction between the small molecule fluorescent compound II and the 4-amino polystyrene, cooling, washing and drying to prepare the Schiff base fluorescent polymer. The Schiff base fluorescent polymer can have high identification performance to DNA and metal ions and can be used as a polymer type fluorescence probe. (img file='DDA0000454216050000011.TIF' wi='1128' he='952' /).
Description
Technical field
The present invention relates to a kind of schiff bases fluorescent polymer and preparation method thereof, belong to fluorescent probe detection technique field.
Background technology
DNA is a kind of very important life genetic material, and detection analysis and fixation and recognition to its content have important application at aspects such as genomics, virusology, molecular biology, cytology.Therefore, recognition detection DNA is significant.The method that current detection DNA is conventional has: chromatography, spectrophotometry, microphotometry, immunoassay etc.
The detection of metal ion has great importance in human body and environment.Can be by the detection of metal ion, relevant enzyme catalysis, functions of hormones mechanism and the body metabolism process of researching human body, and then effectively find pathology, thus treat timely.For the detection of Metals in Environments ion, may identify some heavy metal ion, and then effectively it be implemented and is administered, prevent the injury to environment and human body.
Fluorescent method has the plurality of advantages such as convenient, fast, higher susceptibility in the detection of metal ion and DNA, but it is more that at present fluorescent method is used is organic molecule fluorescent probe, and the susceptibility of this class material light stability and detection all needs further to be improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of schiff bases fluorescent polymer.
The present invention also provides the preparation method of described schiff bases fluorescent polymer.
Technical scheme of the present invention is as follows:
A kind of schiff bases fluorescent polymer, has the structure of following formula I:
Wherein, polymerization degree n is 1000～1500.
Schiff bases fluorescent polymer of the present invention is to prepare by the schiff base reaction of 4-aminopolystyrene and micromolecular compound II.
A preparation method with the schiff bases fluorescent polymer of formula I structure, step is as follows:
Synthesizing of a, 4-aminopolystyrene
4-nitro polystyrene is placed in to flask, at 70～75 ℃, stirs, add sodium hydroxide and V-Brite B, reaction 3.5～4h, filters gained mixture, wash, be dried, and obtains 4-aminopolystyrene.
The mass ratio of described 4-nitro polystyrene and V-Brite B is 1:4～6, and the mass ratio of sodium hydroxide and V-Brite B is 1:0.25～0.4.
The preparation of b, small molecules fluorescent chemicals II
By 4,4 '-diformyl triphenylamine, 1,10-o-phenanthroline-5,6 diketone and glacial acetic acid add in there-necked flask, and magnetic is warming up to 110～120 ℃ under stirring, and adding in batches ammonium acetate, back flow reaction 2～3h, is cooled to room temperature, then be poured in the frozen water of 50～60mL, and with ammoniacal liquor regulate pH be 7～8, suction filtration, washing, dry, ethyl alcohol recrystallization, obtains small molecules fluorescent chemicals II;
Described 4,4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5, the mass ratio of 6 diketone is 1:1～1.1; 4,1:2.5～3.0 of 4 '-diformyl triphenylamine and ammonium acetate; 4, the mass ratio of 4 '-diformyl triphenylamine and glacial acetic acid is 1:65～70;
C, schiff bases fluorescent polymer I's is synthetic
Compound ii, dehydrated alcohol and anhydrous sodium sulphate are placed in to there-necked flask, be warming up to 75～80 ℃, after compound ii all dissolves, add the 4-aminopolystyrene with anhydrous alcohol solution, then add glacial acetic acid, reflux 5-6h, cooling, separate out yellow solid, suction filtration, and with absolute ethanol washing, dry, obtain schiff bases fluorescent polymer.
The mass ratio of described compound ii and dehydrated alcohol is 1:40～50; The mass ratio of compound ii and anhydrous sodium sulphate is 1～1.1:1; The mass ratio of compound ii and 4-aminopolystyrene is 1.2～1.5:1; The mass ratio of compound ii and glacial acetic acid is 1:8～9.
Schiff bases fluorescent polymer synthetic route of the present invention is as follows:
According to the present invention, preferred, the mass ratio of the nitro polystyrene of 4-described in step a and V-Brite B is 1:5, and the mass ratio of sodium hydroxide and V-Brite B is 1:0.3.
According to the present invention, preferred, the nitro of 4-described in step a polystyrene, under 75 ℃ of stirrings, adds sodium hydroxide and V-Brite B, and reaction times 4h uses deionized water wash after reaction finishes.
According to the present invention, preferred, 4 described in step b, 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5, the mass ratio of 6 diketone is 1:1; 4, the mass ratio of 4 '-diformyl triphenylamine and ammonium acetate is 1:2.8; 4, the mass ratio of 4 '-diformyl triphenylamine and glacial acetic acid is 1:68.
According to the present invention, preferred, adding after reactant described in step b, is warming up at 115 ℃ and reacts.
According to the present invention, preferred, described in step b in batches to 1,10-o-phenanthroline-5,6 diketone and 4, add ammonium acetate in 4 '-diformyl triphenylamine reactant, are divided into 3-5 part by ammonium acetate, add 1 part at every turn, be 5-8min reinforced interval time.
According to the present invention, preferred, described in step b in batches to 1,10-o-phenanthroline-5,6 diketone and 4, add after ammonium acetate in 4 '-diformyl triphenylamine reactant, back flow reaction 3h, and with ammoniacal liquor adjusting pH be 7.
According to the present invention, preferred, the mass ratio of compound ii and dehydrated alcohol is 1:45 described in step c; The mass ratio of compound ii and anhydrous sodium sulphate is 1.1:1; The mass ratio of compound ii and 4-aminopolystyrene is 1.4:1; The mass ratio of compound ii and glacial acetic acid is 1:8.5.
According to the present invention, preferred, the reactant described in step c adds after flask, is warming up at 75 ℃ and reacts.
According to the present invention, preferred, after compound ii all dissolves described in step c, add 4-aminopolystyrene, and then drip glacial acetic acid, reflux 5h.
Fluorescent polymer of the present invention, owing to having large molar absorption coefficient, high fluorescence quantum yield, light stability and " molecular wire effect " preferably, can be realized the detection of trace, ultra-trace.Fluorescent polymer of the present invention has the incomparable advantage of small molecules fluorescent probe.In the present invention in synthetic schiff bases fluorescent polymer, in its probe structure, contain the nitrogen groups adjacent, that electronegativity is strong especially take phenanthroline as matrix, there is very strong suction electrical property, may there is stronger combination recognition performance to DNA and a certain ion of metal.And the polymer architecture itself forming, has good performance aspect probe identification.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra of intermediate 4-aminopolystyrene of the present invention;
Fig. 2 is the infared spectrum of intermediate 4-aminopolystyrene of the present invention;
Fig. 3 is the proton nmr spectra of small molecules fluorescent chemicals II;
Fig. 4 is the infared spectrum of small molecules fluorescent chemicals II;
Fig. 5 is the proton nmr spectra for schiff bases fluorescent polymer;
Fig. 6 is the infared spectrum of schiff bases fluorescent polymer.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail, but be not limited to this.
Schiff bases fluorescent polymer, molecular structural formula is formula I as the aforementioned.Preparation method's step is as follows:
Synthesizing of a, 4-aminopolystyrene: 1g4-nitro polystyrene is placed in to flask, high-speed stirring at 75 ℃, adds 16g sodium hydroxide and 5g V-Brite B, reaction 4h, gained mixture is filtered, washs, is dried, obtain 4-aminopolystyrene.（
1H?NMR:(DMSO,400MHz,TMS)δ(ppm):7.80(s,2H,-NH
2);6.99(m,4H);1.5(m,3H).IR(KBr)ν/cm
-1:3420cm
-1(-NH
2);2925,2855cm
-1(-CH
2);1612,1515,1453cm
-1(Ar–C=C);849cm
-1(Ar-C-H);
The preparation of b, small molecules fluorescent chemicals II: by 3.0g4,4 '-diformyl triphenylamine, 3.0g1,10-o-phenanthroline-5; 6 diketone and 215mL glacial acetic acid add in there-necked flask, and magnetic is slowly warming up to 115 ℃ under stirring, and adds in batches 8.5g ammonium acetate; back flow reaction 3h, is cooled to room temperature, is then poured in the frozen water of 500mL; and with ammoniacal liquor regulate pH be 7; suction filtration, washing, dry; ethyl alcohol recrystallization, obtains small molecules fluorescent chemicals II.
1H?NMR:(DMSO,400MHz,TMS)δ(ppm):13.73(s,1H);9.83(s,1H);9.03(d,J=3.6Hz,2H);8.91(t,J=6.2Hz,2H);8.28(d,J=8.4Hz,2H);7.81-7.86(m,4H);7.24-7.58(m,7H);7.07(d,J=8.4Hz,2H).IR(KBr)ν/cm
-1:2931cm
-1(Ar,-N-H);2738cm
-1(CHO,-C-H);1697cm
-1(CHO,-C=O);1585,1450cm
-1(Ar,-C=C);1317cm
-1(Ar,-C-N)；827,760cm
-1(Ar,-C-H).
C, schiff bases fluorescent polymer I's is synthetic: 2.8g compound ii, 100mL dehydrated alcohol and 2.5g anhydrous sodium sulphate are placed in to there-necked flask, slowly heat up 75 ℃, after compound ii all dissolves, add 2g4-aminopolystyrene (using in advance anhydrous alcohol solution), then add 25mL glacial acetic acid, reflux 5h, cooling, separate out yellow solid, suction filtration, and with absolute ethanol washing, dry, obtain schiff bases fluorescent polymer.
1H?NMR(DMSO,400Hz)δ(ppm):13.70(s,1H);9.01(m,4H);8.24(m,2H);7.79(d,J=8.0Hz,8H);7.06-7.48(m,11H);6.8(s,4H);2.28(m,2H);1.15(m,1H).IR(KBr)ν/cm
-1:3019cm
-1(=C-H);2923cm
-1(Ar,-N-H)；1600cm
-1(C=N);1518,1466cm
-1(Ar,-C=C);857,746,693cm
-1(Ar,-C-H)。
Claims (10)
1. a schiff bases fluorescent polymer, has the structure of following formula I:
Wherein, polymerization degree n is 1000～1500.
2. the preparation method of schiff bases fluorescent polymer claimed in claim 1, step is as follows:
Synthesizing of a, 4-aminopolystyrene
4-nitro polystyrene is placed in to flask, at 70～75 ℃, stirs, add sodium hydroxide and V-Brite B, reaction 3.5～4h, filters gained mixture, wash, be dried, and obtains 4-aminopolystyrene;
The mass ratio of described 4-nitro polystyrene and V-Brite B is 1:4～6, and the mass ratio of sodium hydroxide and V-Brite B is 1:0.25～0.4;
The preparation of b, small molecules fluorescent chemicals II
By 4,4 '-diformyl triphenylamine, 1,10-o-phenanthroline-5,6 diketone and glacial acetic acid add in there-necked flask, and magnetic is warming up to 110～120 ℃ under stirring, and adding in batches ammonium acetate, back flow reaction 2～3h, is cooled to room temperature, then be poured in the frozen water of 50～60mL, and with ammoniacal liquor regulate pH be 7～8, suction filtration, washing, dry, ethyl alcohol recrystallization, obtains small molecules fluorescent chemicals II;
Described 4,4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5, the mass ratio of 6 diketone is 1:1～1.1; 4,1:2.5～3.0 of 4 '-diformyl triphenylamine and ammonium acetate; 4, the mass ratio of 4 '-diformyl triphenylamine and glacial acetic acid is 1:65～70;
C, schiff bases fluorescent polymer I's is synthetic
Compound ii, dehydrated alcohol and anhydrous sodium sulphate are placed in to there-necked flask, be warming up to 75～80 ℃, after compound ii all dissolves, add the 4-aminopolystyrene with anhydrous alcohol solution, then add glacial acetic acid, reflux 5-6h, cooling, separate out yellow solid, suction filtration, and with absolute ethanol washing, dry, obtain schiff bases fluorescent polymer;
The mass ratio of described compound ii and dehydrated alcohol is 1:40～50; The mass ratio of compound ii and anhydrous sodium sulphate is 1～1.1:1; The mass ratio of compound ii and 4-aminopolystyrene is 1.2～1.5:1; The mass ratio of compound ii and glacial acetic acid is 1:8～9.
3. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, the mass ratio that it is characterized in that 4-nitro polystyrene described in step a and V-Brite B is 1:5, the mass ratio of sodium hydroxide and V-Brite B is 1:0.3.
4. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, is characterized in that the polystyrene of 4-nitro described in step a, under 75 ℃ of stirrings, adds sodium hydroxide and V-Brite B, and reaction times 4h uses deionized water wash after reaction finishes.
5. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, is characterized in that 4 described in step b, 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5, and the mass ratio of 6 diketone is 1:1; 4, the mass ratio of 4 '-diformyl triphenylamine and ammonium acetate is 1:2.8; 4, the mass ratio of 4 '-diformyl triphenylamine and glacial acetic acid is 1:68.
6. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, is characterized in that adding after reactant described in step b, is warming up at 115 ℃ and reacts.
7. the preparation method of schiff bases fluorescent polymer as claimed in claim 2; it is characterized in that described in step b in batches to 1; 10-o-phenanthroline-5; 6 diketone and 4; in 4 '-diformyl triphenylamine reactant, add ammonium acetate; be divided into 3-5 part by ammonium acetate, add 1 part at every turn, be 5-8min reinforced interval time.
8. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, it is characterized in that described in step b in batches to 1,10-o-phenanthroline-5; 6 diketone and 4; in 4 '-diformyl triphenylamine reactant, add after ammonium acetate, back flow reaction 3h, and with ammoniacal liquor regulate pH be 7.
9. schiff bases fluorescent polymer preparation method as claimed in claim 2, is characterized in that the mass ratio of compound ii and dehydrated alcohol is 1:45 described in step c; The mass ratio of compound ii and anhydrous sodium sulphate is 1.1:1; The mass ratio of compound ii and 4-aminopolystyrene is 1.4:1; The mass ratio of compound ii and glacial acetic acid is 1:8.5.
10. schiff bases fluorescent polymer preparation method as claimed in claim 2, is characterized in that the reactant described in step c adds after flask, is warming up at 75 ℃ and reacts; After compound ii all dissolves described in step c, add 4-aminopolystyrene, and then drip glacial acetic acid, reflux 5h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866907A (en) * | 2017-03-07 | 2017-06-20 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
| CN110746423A (en) * | 2019-11-11 | 2020-02-04 | 福建医科大学 | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070072309A1 (en) * | 2005-09-29 | 2007-03-29 | General Electric Company | Analytical compositions including nanometer-sized transducers, methods to make thereof, and devices therefrom |
| CN101619032A (en) * | 2009-08-04 | 2010-01-06 | 中国科学院上海微系统与信息技术研究所 | Schiff base compound and method for detecting aniline compound thereof |
| CN101735217A (en) * | 2009-12-15 | 2010-06-16 | 广东药学院 | Application of imidazole [4,5-f][1,10] phenanthroline and derivative thereof to preparation of antineoplastic drug |
| CN102250091A (en) * | 2011-05-20 | 2011-11-23 | 上海大学 | Fluorine-containing fluorescent compounds and preparation method thereof |
| CN102604412A (en) * | 2012-01-17 | 2012-07-25 | 北京师范大学 | Bis-carbazole group containing dye for dye-sensitized solar cells and preparation method of bis-carbazole group containing dye |
-
2014
- 2014-01-07 CN CN201410006699.2A patent/CN103773360B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070072309A1 (en) * | 2005-09-29 | 2007-03-29 | General Electric Company | Analytical compositions including nanometer-sized transducers, methods to make thereof, and devices therefrom |
| CN101619032A (en) * | 2009-08-04 | 2010-01-06 | 中国科学院上海微系统与信息技术研究所 | Schiff base compound and method for detecting aniline compound thereof |
| CN101735217A (en) * | 2009-12-15 | 2010-06-16 | 广东药学院 | Application of imidazole [4,5-f][1,10] phenanthroline and derivative thereof to preparation of antineoplastic drug |
| CN102250091A (en) * | 2011-05-20 | 2011-11-23 | 上海大学 | Fluorine-containing fluorescent compounds and preparation method thereof |
| CN102604412A (en) * | 2012-01-17 | 2012-07-25 | 北京师范大学 | Bis-carbazole group containing dye for dye-sensitized solar cells and preparation method of bis-carbazole group containing dye |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG XIAN，等: "Fluorescence of a New Phenanthrolin Derivative Sensitive to DNA", 《POLYMERS & POLYMER COMPOSITES》, vol. 20, no. 12, 16 May 2011 (2011-05-16), pages 9 - 12 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866907A (en) * | 2017-03-07 | 2017-06-20 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
| CN106866907B (en) * | 2017-03-07 | 2018-12-04 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
| CN110746423A (en) * | 2019-11-11 | 2020-02-04 | 福建医科大学 | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions |
| CN110746423B (en) * | 2019-11-11 | 2022-03-18 | 福建医科大学 | Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions |
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