CN103773360B - Schiff base fluorescent polymer and preparation method thereof - Google Patents
Schiff base fluorescent polymer and preparation method thereof Download PDFInfo
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- CN103773360B CN103773360B CN201410006699.2A CN201410006699A CN103773360B CN 103773360 B CN103773360 B CN 103773360B CN 201410006699 A CN201410006699 A CN 201410006699A CN 103773360 B CN103773360 B CN 103773360B
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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, has important application to the detection analysis of its content and fixation and recognition in genomics, virusology, molecular biology, cytology etc.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 by the detection of metal ion, the relevant enzyme catalysis of researching human body, functions of hormones mechanism and body metabolism process, and then effectively find pathology, thus treat timely.For the detection of Metals in Environments ion, some heavy metal ion may be identified, and then effectively improvement be implemented to it, 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 at present the more of fluorescent method is organic molecule fluorescent probe, and the susceptibility of this kind of material light stability and detection all needs to be improved further.
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 prepared by the schiff base reaction of 4-aminopolystyrene and micromolecular compound II.
Have a preparation method for the schiff bases fluorescent polymer of formula I structure, step is as follows:
The synthesis of a, 4-aminopolystyrene
4-nitro polystyrene is placed in flask, stirs at 70 ~ 75 DEG C, add sodium hydroxide and V-Brite B, reaction 3.5 ~ 4h, gained mixture carried out filter, wash, dry, obtain 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 molecule fluorescent compound 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 DEG C under stirring, and adding ammonium acetate in batches, back flow reaction 2 ~ 3h, is cooled to room temperature, then be poured in the frozen water of 50 ~ 60mL, and regulate pH to be 7 ~ 8 with ammoniacal liquor, suction filtration, washing, drying, ethyl alcohol recrystallization, obtains small molecule fluorescent compound ii;
Described 4, the mass ratio of 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5,6 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;
The synthesis of c, schiff bases fluorescent polymer I
Compound ii, dehydrated alcohol and anhydrous sodium sulphate are placed in there-necked flask, be warming up to 75 ~ 80 DEG C, after compound ii all dissolves, add the 4-aminopolystyrene with anhydrous alcohol solution, then add glacial acetic acid, reflux 5-6h, cooling, separates out yellow solid, suction filtration, and with absolute ethanol washing, drying, 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, preferably, 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, preferably, the nitro of 4-described in step a polystyrene adds sodium hydroxide and V-Brite B, reaction times 4h under stirring at 75 DEG C, uses deionized water wash after reaction terminates.
According to the present invention, preferably, 4 described in step b, the mass ratio of 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5,6 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, preferably, described in step b add reactant after, react at being warming up to 115 DEG C.
According to the present invention, preferably, described in step b in batches to 1,10-o-phenanthroline-5,6 diketone and 4, add ammonium acetate in 4 '-diformyl triphenylamine reactant, be divided into 3-5 part by ammonium acetate, add 1 part at every turn, the feeding interval time is 5-8min.
According to the present invention, preferably, described in step b in batches to 1,10-o-phenanthroline-5,6 diketone and 4, after adding ammonium acetate in 4 '-diformyl triphenylamine reactant, back flow reaction 3h, and with ammoniacal liquor regulate pH be 7.
According to the present invention, preferably, the mass ratio of compound ii described in step c and dehydrated alcohol is 1:45; 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, preferably, after the reactant described in step c adds flask, react at being warming up to 75 DEG C.
According to the present invention, preferably, 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, preferably light stability and " molecular wire effect ", can realize the detection of trace, ultra-trace.Fluorescent polymer of the present invention has the incomparable advantage of small-molecule fluorescent probe.In the schiff bases fluorescent polymer synthesized in the present invention, containing adjacent, that electronegativity the is strong especially nitrogen groups taking phenanthroline as matrix in its probe structure, there is very strong suction electrical property, may have DNA and a certain ion of metal stronger in conjunction with recognition performance.And the polymer architecture itself formed, in probe identification, there is excellent performance.
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 molecule fluorescent compound ii;
Fig. 4 is the infared spectrum of small molecule fluorescent compound 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 thereto.
Embodiment 1,
Schiff bases fluorescent polymer, molecular structural formula formula I as the aforementioned.Preparation method's step is as follows:
The synthesis of a, 4-aminopolystyrene: 1g4-nitro polystyrene is placed in flask, high-speed stirring at 75 DEG C, adds 16g sodium hydroxide and 5g V-Brite B, reaction 4h, gained mixture carried out filter, wash, dry, 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 molecule fluorescent compound 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 DEG C under stirring, and adds 8.5g ammonium acetate in batches; back flow reaction 3h, is cooled to room temperature, is then poured in the frozen water of 500mL; and regulate pH to be 7 with ammoniacal liquor; suction filtration, washing, dry; ethyl alcohol recrystallization, obtains small molecule fluorescent compound 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).
The synthesis of c, schiff bases fluorescent polymer I: 2.8g compound ii, 100mL dehydrated alcohol and 2.5g anhydrous sodium sulphate are placed in there-necked flask, slow intensification 75 DEG C, after compound ii all dissolves, add 2g4-aminopolystyrene (using anhydrous alcohol solution in advance), then add 25mL glacial acetic acid, reflux 5h, cooling, separates out yellow solid, suction filtration, and with absolute ethanol washing, drying, 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 according to claim 1, step is as follows:
The synthesis of a, 4-aminopolystyrene
4-nitro polystyrene is placed in flask, stirs at 70 ~ 75 DEG C, add sodium hydroxide and V-Brite B, reaction 3.5 ~ 4h, gained mixture carried out filter, wash, dry, obtain 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 molecule fluorescent compound 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 DEG C under stirring, and adding ammonium acetate in batches, back flow reaction 2 ~ 3h, is cooled to room temperature, then be poured in the frozen water of 50 ~ 60mL, and regulate pH to be 7 ~ 8 with ammoniacal liquor, suction filtration, washing, drying, ethyl alcohol recrystallization, obtains small molecule fluorescent compound ii;
Described 4, the mass ratio of 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5,6 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;
The synthesis of c, schiff bases fluorescent polymer I
Compound ii, dehydrated alcohol and anhydrous sodium sulphate are placed in there-necked flask, be warming up to 75 ~ 80 DEG C, after compound ii all dissolves, add the 4-aminopolystyrene with anhydrous alcohol solution, then add glacial acetic acid, reflux 5-6h, cooling, separates out yellow solid, suction filtration, and with absolute ethanol washing, drying, 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, it is characterized in that the mass ratio of the nitro polystyrene of 4-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, under it is characterized in that the nitro of 4-described in step a polystyrene stirs at 75 DEG C, adds sodium hydroxide and V-Brite B, reaction times 4h, uses deionized water wash after reaction terminates.
5. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, it is characterized in that 4 described in step b, the mass ratio of 4 '-diformyl triphenylamine and 1,10-o-phenanthroline-5,6 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, it is characterized in that described in step b by 4,4 '-diformyl triphenylamine; 1; 10-o-phenanthroline-5,6 diketone and glacial acetic acid add in there-necked flask, and magnetic reacts at being warming up to 115 DEG C under stirring.
7. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, it is characterized in that adding ammonium acetate in batches described in step b, be divided into 3-5 part by ammonium acetate, add 1 part at every turn, the feeding interval time is 5-8min.
8. the preparation method of schiff bases fluorescent polymer as claimed in claim 2, it is characterized in that described in step b add ammonium acetate in batches after, back flow reaction 3h, and regulate pH to be 7 with ammoniacal liquor.
9. schiff bases fluorescent polymer preparation method as claimed in claim 2, is characterized in that the mass ratio of compound ii described in step c and dehydrated alcohol is 1:45; 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, described in step c, compound ii, dehydrated alcohol and anhydrous sodium sulphate are placed in there-necked flask, react at being warming up to 75 DEG C; After compound ii all dissolves described in step c, add 4-aminopolystyrene, and then drip glacial acetic acid, reflux 5h.
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| 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 |
| 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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| CN101619032A (en) * | 2009-08-04 | 2010-01-06 | 中国科学院上海微***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 |
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| US20070072309A1 (en) * | 2005-09-29 | 2007-03-29 | General Electric Company | Analytical compositions including nanometer-sized transducers, methods to make thereof, and devices therefrom |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619032A (en) * | 2009-08-04 | 2010-01-06 | 中国科学院上海微***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 |
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| Polymer Composites》.2011,第20卷(第1-2期),9-12. * |
| Zhang Xian,等.Fluorescence of a New Phenanthrolin Derivative Sensitive to DNA.《Polymers & * |
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