CN102516990A - Application of polyphenylene vinylene (PPV) polymer serving as fluorescent indicator in oxygen sensor based on fluorescence quenching - Google Patents
Application of polyphenylene vinylene (PPV) polymer serving as fluorescent indicator in oxygen sensor based on fluorescence quenching Download PDFInfo
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- CN102516990A CN102516990A CN2011103891165A CN201110389116A CN102516990A CN 102516990 A CN102516990 A CN 102516990A CN 2011103891165 A CN2011103891165 A CN 2011103891165A CN 201110389116 A CN201110389116 A CN 201110389116A CN 102516990 A CN102516990 A CN 102516990A
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Abstract
The invention relates to application of polyphenylene vinylene (PPV) polymer serving as a fluorescent indicator in an oxygen sensor based on fluorescence quenching. The structure of the PPV polymer is shown as a formula (1a) or (1b), wherein R1 and R2 are identical or different and both are linear chain or branched paraffin of C5-C12, preferentially R1 and R2 are amyl group, n-octyl, 3-ethylhexyl or n-dodecyl. A detailed method for the PPV polymer to serve as the fluorescent indicator in the oxygen sensor based on the fluorescence quenching can adopt an application method of the existing fluorescent indicator, for example, an application method of the PPV polymer dissolved in organic solvent and used as the fluorescent indicator in the oxygen sensor based on the fluorescence quenching. The PPV polymer is strong in surface adhesive ability, good in oxygen quenching and film-processing capacity, soft and good in thermal stability. The polymer can not add other carriers and can form films on a substrate directly.
Description
Technical field
The present invention relates to a kind of PPV base polymer as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence.
Background technology
In the preparation of oxygen sensor, be the focus that people study as the fluorescence molecule of luminescence center always.Select that suitable to be used for by the fluorescence molecule of quencher be vital to the performance of improving transmitter.Fluorescence molecule commonly used has following several kinds: 1. polycyclic aromatic hydrocarbons, like pyrene and pyrene two butyric acid; 2. organometallic complex is like the diimine ruthenium compound; 3. heterogeneous ring compound is like porphyrin.
In above three kinds of materials, organometallic complex especially transition metal complex is receiving much concern aspect the luminous oxygen sensor.Up to the present, the main fluorescent indicator of selecting is that the lowest excited attitude is the transition metal complex of metal to part charge transfer (MLCT) excited state.Wherein central metallic ions mainly selects to have d
6Or d
8The transition metal of electronic configuration is like Ru (II), Os (II), Pt (II) etc.; And part generally all be have bidentate or multiple tooth structure like dipyridyl, phenanthroline, phenylpyridine, porphyrin part etc.But; When adopting transition metal complex assembling or preparation optical oxygen sensing device; Since this organometallic complex molecule is spontaneous do not possess film-forming properties and adhesive ability a little less than, need by certain physical or chemical process make it compoundly could disperse in the substrate with substrate material, immobilized or film forming.Existent method mainly contains three kinds: (1) physisorphtion; It is the convenient method that adopts the earliest; But since the reactive force between fluorescence molecule and substrate material a little less than; The fluorescence molecule that is adsorbed is prone to by wash-out and peels off, and shortens and reduce the work-ing life and the stability limit application of sensor of oxygen sensor; (2) covalent linkage is legal; Can effectively prolong the work-ing life of transmitter but have transmitter or the preparation technology of probe complicated with possibly change its its optical physics chemical property owing to fluorescence molecule and matrix generation chemically bonded, cause problems such as oxygen quenching effect change; (3) entrapping method, with the fluorescent indicator physically trapping in porous matrix, overcome fluorescence molecule by wash-out with problem such as be prone to peel off, but dispersity and the uniformity coefficient of fluorescence molecule are had relatively high expectations, the preparation technology of transmitter or probe is complicacy.
Different with organometallic complex, organic polymer material has that good film-forming property, suppleness are high, the surface attachment ability is strong, good weatherability and be difficult for characteristics such as crystallization, is used widely in various fields.Wherein, the organic polymer material of the big π key of tool one-dimentional structure and conjugation because of suitable with visible light energy and the electroluminescent intrinsic property of its prodigiosin band gap numerical value, has become the focus in present physics or Chemiluminescence Study field.Existing this base polymer mainly contains: polyphenylacetylene (PPV), substituting polythiophene, polyaniline, gather benzene, gather fluorenes, polyvinyl carbazole etc.Wherein, Nature 347,539 (1990) wherein; The PPV of reports such as US Patent 5189136 and verivate thereof have the luminescent quantum productive rate higher, good characteristics such as absorbing, be soluble in organic solvent, good film-forming property, stable height and good weatherability arranged more by force at visible light wave range; Pay close attention to obtaining aspect the polymkeric substance electroluminescence widely, and be applied to field such as electroluminescent display.Therefore, based on the performance requriements of optical oxygen sensing to fluorescence molecule, the optical physics performance that PPV and hard and soft segmented copolymer thereof are good makes it might be as the candidate material of the quick indicator of a kind of oxygen.
Patent reports such as CN01120505.9, CN200410068054.8, CN200810057181.6 several kinds of high performance PPV materials; But all be used for the material in luminous fields such as electronic material, solar cell material, do not have PPV class material to be used for the report and the patent in optical oxygen sensing field as yet.
Patent report such as CN03128980.0, CN200910205946.0 new optical oxygen sensing material, but all be matrix material, need be doped in the fixed carrier, its doping content is difficult to control, manufacture craft is loaded down with trivial details.
Summary of the invention
The present invention provide a kind of PPV base polymer as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence, said PPV base polymer surface attachment ability is strong, oxygen quencher property and good film-forming property, softness, thermally-stabilised good.
Based on the application in the oxygen sensor of quenching of fluorescence, the structure of said PPV base polymer is suc as formula (1a) or (1b) as fluorescent indicator for said PPV base polymer:
In the formula, R
1, R
2Identical or different, be straight chain or the branched-chain alkyl of C5～C12, preferred R
1, R
2Be n-pentyl, n-octyl, 3-ethylhexyl or dodecyl independently.
Above-mentioned PPV base polymer can prepare through ATRP (ATRP), and weight-average molecular weight is between 4000～15000, and the molecular-weight average here is the molecular-weight average of measuring through gel permeation chromatograph (GPC).
The PPV base polymer can be adopted the application method of existing fluorescent indicator at the concrete grammar based on the oxygen sensor of quenching of fluorescence as fluorescent indicator; For example the PPV base polymer is dissolved in the organic solvent, as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence.Organic solvent can comprise THF, methyl ethyl ketone, acetone, pimelinketone, terepthaloyl moietie, trichloromethane, N, dinethylformamide, toluene, methyl ether, methylene dichloride, ETHYLE ACETATE, butylacetate etc.Preferred organic has THF and trichloromethane, more preferably trichloromethane.
Because PPV base polymer film forming properties according to the invention is good, therefore can also be with PPV base polymer film forming on substrate, as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence.Usually the PPV base polymer is dissolved in certain organic solvent, and by weight, polymer concentration is 1 * 10
-4～1 * 10
-6, direct film forming on substrate then.Employed solvent generally is to dissolve this polymkeric substance, can after self volatilizees, make polymkeric substance produce organic solvent even, flat film again.Can adopt like above-mentioned organic solvent.Said substrate can be preferably monocrystalline silicon piece for monocrystalline silicon piece, simple glass or silica glass.PPV base polymer film forming method on substrate can be adopted the existing film of prior art, for example can be preferably vapour deposition process for gluing, spray glue or vapour deposition process.
PPV base polymer according to the invention as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence; Said PPV base polymer surface attachment ability is strong, oxygen quencher property and good film-forming property, softness, thermally-stabilised good; This polymkeric substance does not add other carriers, directly film forming on substrate again.
Correlative study of the present invention is by country nature fund assistance (project approval number: 21075015).
Description of drawings
Fig. 1 is embodiment 1 said PPV-CH
2The quenching effect curve of OH in solution, wherein Fig. 1 a is the fluorescence spectrum figure under the long-pending per-cent of Different Oxygen gas; 1b is the Stern-Volmer relation curve;
Fig. 2 is embodiment 1 said PPV-CH
2The quenching effect curve of OH in film, wherein Fig. 2 a is the fluorescence spectrum figure of the long-pending per-cent of Different Oxygen gas; 2b is the Stern-Volmer relation curve;
Fig. 3 is the quenching effect curves of embodiment 2 said PPV-b-PMMA in solution, and wherein Fig. 3 a is the fluorescence spectrum figure of the long-pending per-cent of Different Oxygen gas; 3b is the Stern-Volmer relation curve;
Fig. 4 is the quenching effect curves of embodiment 2 said PPV-b-PMMA in film, and wherein Fig. 4 a is the fluorescence spectrum figure of the long-pending per-cent of Different Oxygen gas; 4b is the Stern-Volmer relation curve.
Embodiment
To combine instance to further specify the present invention below, but embodiment does not limit protection scope of the present invention.
The synthetic Alpha-Methyl of embodiment 1, ω-(4-methylol-2,5-two octyloxyphenyl)-gather (2,5-two octyloxies-1,4-phenylene vinylidene) (PPV-CH
2OH) (formula (1a))
With the 0.78g Alpha-Methyl, ω-(4-carboxaldehyde radicals-2,5-two octyloxyphenyl)-gather (2; 5-two octyloxies-1, the 4-phenylene vinylidene) be dissolved among the 50mL THF, dropwise splash in the 50mL dry THF suspension-s that contains the 0.70g lithium aluminum hydride; Reacted careful the quenching 5 hours.Anhydrous MgSO is used in organic extraction
4Drying, suction filtration concentrates, and in cold methanol, precipitates, and places 20 ℃ of following vacuum-dryings, gets red powder shape solid.Record Mw=5655, Mn=4684, PD=1.21.
Reactor drum is roasting through taking out repeatedly, applying argon gas 3 times, with excluding air and water vapour.Add 0.020g CuBr, 0.065g bpy, 0.640g PPV macromole evocating agent, vacuumize repeatedly, applying argon gas 3 times, 30min is stirred in sealing.Add 1.45mL methyl-phenoxide, 1.45mL TEB 3K, stir half a hour, be warming up to 50 ℃ of reactions 1 hour.Use dissolved in chloroform,, concentrate, in methyl alcohol, precipitate, place 20 ℃ of following vacuum-dryings, get red powder shape solid through the neutral alumina post.Record Mw=14019, Mn=11857, PD=1.18.
Embodiment 3 is configured to 2 * 10 with embodiment 1 gained PPV-CH2OH
-4The chloroform soln of g/L; Get respectively with liquid-transfering gun in the volumetric flask of 1mL to three 10mL (being respectively applied for the fluorescence intensity of measurement in purity nitrogen, air and pure oxygen); Be diluted to 10mL; In volumetric flask, feed purity nitrogen (or pure oxygen), flow rate control is at 2mL/min, to discharge unnecessary oxygen (or nitrogen) in the solution.Repeatedly measure until measuring numerical value (＜0.5%) within error.Volume percent with oxygen is an X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.The result is as shown in Figure 1.
Embodiment 4 method for manufacturing thin film: with slide glass ultrasonic 20min in acetone, rinse well, use exsiccant N with deionized water
2Dry up.With PPV-CH
2OH is dissolved in chloroform and processes 2 * 10
-5G/L solution, solution is after the filtering head of 4.5 μ m filters, on the slide glass that spin coating is to handle well.The spin coater rotating speed is controlled at low speed 300rad/min, 10s, and high speed 2000rad/min, 30s, non-foaming through 100 ℃ of thermal treatments 2 hours in vacuum drying oven again, do not come off.Explain that film has higher thermotolerance, intensity and certain toughness.The slide glass that spin coating is good places special cuvette, and the ratio of control nitrogen and oxygen is tested its fluorescence intensity under different oxygen concentrations.Volume percent with oxygen is an X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.The result is as shown in Figure 2.
Embodiment 5 is configured to 2 * 10 with PPV-b-PMMA
-4The chloroform soln of g/L; Get respectively with liquid-transfering gun in the volumetric flask of 1mL to three 10mL (being respectively applied for the fluorescence intensity of measurement in purity nitrogen, air and pure oxygen); Be diluted to 10mL; In volumetric flask, feed purity nitrogen (or pure oxygen), flow rate control is at 2mL/min, to discharge unnecessary oxygen (or nitrogen) in the solution.Repeatedly measure until measuring numerical value (＜0.5%) within error.Volume percent with oxygen is an X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.The result is as shown in Figure 3.
Embodiment 6 method for manufacturing thin film: with slide glass ultrasonic 20min in acetone, rinse well, use exsiccant N with deionized water
2Dry up.PPV-b-PMMA is dissolved in chloroform processes 2 * 10
-5G/L solution, solution is after the filtering head of 4.5 μ m filters, on the slide glass that spin coating is to handle well.The spin coater rotating speed is controlled at low speed 300rad/min, 10s, and high speed 2000rad/min, 30s, non-foaming through 100 ℃ of thermal treatments 2 hours in vacuum drying oven again, do not come off.Explain that film has higher thermotolerance, intensity and certain toughness.The slide glass that spin coating is good places special cuvette, and the ratio of control nitrogen and oxygen is tested its fluorescence intensity under different oxygen concentrations.Volume percent with oxygen is an X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.The result is as shown in Figure 4.
Claims (10)
1.PPV base polymer based on the application in the oxygen sensor of quenching of fluorescence, is characterized in that as fluorescent indicator the structure of said PPV base polymer is suc as formula (1a) or (1b):
In the formula, R
1, R
2Identical or different, be straight chain or the branched-chain alkyl of C5～C12.
2. PPV base polymer as claimed in claim 1 based on the application in the oxygen sensor of quenching of fluorescence, is characterized in that R as fluorescent indicator
1, R
2Be n-pentyl, n-octyl, 3-ethylhexyl or dodecyl independently.
3. PPV base polymer as claimed in claim 2 based on the application in the oxygen sensor of quenching of fluorescence, is characterized in that R as fluorescent indicator
1, R
2Be n-octyl.
Like each described PPV base polymer among the claim 1-3 as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence; It is characterized in that; The PPV base polymer is dissolved in trichloromethane or THF, as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence.
Like each described PPV base polymer among the claim 1-3 as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence; It is characterized in that; With PPV base polymer film forming on substrate, as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence.
6. PPV base polymer as claimed in claim 5 based on the application in the oxygen sensor of quenching of fluorescence, is characterized in that as fluorescent indicator said substrate is monocrystalline silicon piece, slide glass or silica glass.
7. PPV base polymer as claimed in claim 6 based on the application in the oxygen sensor of quenching of fluorescence, is characterized in that as fluorescent indicator said substrate is a slide glass.
Like each described PPV base polymer among the claim 5-7 as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence, it is characterized in that, be gluing, spin coating or vapour deposition process with PPV base polymer film forming method on substrate.
9. PPV base polymer as claimed in claim 8, is characterized in that based on the application in the oxygen sensor of quenching of fluorescence as fluorescent indicator, is spin-coating method with PPV base polymer film forming method on substrate.
Like each described PPV base polymer among the claim 1-9 as fluorescent indicator based on the application in the oxygen sensor of quenching of fluorescence, it is characterized in that the weight-average molecular weight of said PPV base polymer is 4000～15000.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969238A (en) * | 2014-05-21 | 2014-08-06 | 东南大学 | Ultrasensitive oxygen sensor and preparation method thereof |
| CN103981700A (en) * | 2014-05-07 | 2014-08-13 | 苏州大学 | Polyvinyl alcohol fluorescence fiber film, and making method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6979543B2 (en) * | 1999-05-05 | 2005-12-27 | The Regents Of The University Of California | Method for detecting biological agents |
| CN1712940A (en) * | 2005-08-02 | 2005-12-28 | 武汉大学 | Production of fluorescent sensor based on soluble conjugated polymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6979543B2 (en) * | 1999-05-05 | 2005-12-27 | The Regents Of The University Of California | Method for detecting biological agents |
| CN1712940A (en) * | 2005-08-02 | 2005-12-28 | 武汉大学 | Production of fluorescent sensor based on soluble conjugated polymer |
Non-Patent Citations (7)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981700A (en) * | 2014-05-07 | 2014-08-13 | 苏州大学 | Polyvinyl alcohol fluorescence fiber film, and making method and application thereof |
| CN103969238A (en) * | 2014-05-21 | 2014-08-06 | 东南大学 | Ultrasensitive oxygen sensor and preparation method thereof |
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Granted publication date: 20131218 Termination date: 20171130 |