CN102516990B - 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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- CN102516990B CN102516990B CN 201110389116 CN201110389116A CN102516990B CN 102516990 B CN102516990 B CN 102516990B CN 201110389116 CN201110389116 CN 201110389116 CN 201110389116 A CN201110389116 A CN 201110389116A CN 102516990 B CN102516990 B CN 102516990B
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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 the application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator of a kind of PPV base polymer.
Background technology
In the preparation of oxygen sensor, as the fluorescence molecule of luminescence center, be the focus that people study always.Selecting suitable is vital for the fluorescence molecule by quencher to the performance of improving sensor.Fluorescence molecule commonly used has following several: 1. polycyclic aromatic hydrocarbons, as pyrene and pyrene two butyric acid; 2. organometallic complex, as the diimine ruthenium compound; 3. heterogeneous ring compound, as porphyrin.
In above three kinds of materials, organometallic complex especially transition metal complex is receiving much concern aspect luminous oxygen sensor.Up to the present, the main fluorescent indicator of selecting is that the lowest excited state 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 as Ru (II), Os (II), Pt (II) etc.; And part be all generally have bidentate or multiple tooth structure as dipyridyl, phenanthroline, phenylpyridine, porphyrin part etc.But, when adopting the transition metal complex assembling or preparing Luminescence based Oxygen Sensor, because this organometallic complex molecule is spontaneous, do not possess film-forming properties and adhesive ability a little less than, need make it compoundly could in substrate, disperse with substrate material by certain physics or chemical process, immobilized or film forming.Existing method mainly contains three kinds: (1) physisorphtion, it is the convenient method adopted the earliest, but due to the reactive force between fluorescence molecule and substrate material a little less than, the fluorescence molecule be adsorbed, easily by wash-out and peeling off, shortens and reduces the work-ing life of oxygen sensor and the application of stability limit sensor; (2) covalent linkage is legal, can effectively extend the work-ing life of sensor but have sensor or the preparation technology of probe is more complicated and may change its its optical physics chemical property due to fluorescence molecule and matrix generation chemical bonding, causing the problems such as oxygen quenching effect change; (3) entrapping method, by the fluorescent indicator physically trapping in porous matrix, the problem such as overcome fluorescence molecule by wash-out and easily peel off, but dispersity and the uniformity coefficient of fluorescence molecule are had relatively high expectations, the preparation technology of sensor or probe is more complicated.
Different from organometallic complex, organic polymer material has that good film-forming property, suppleness are high, the surface attachment ability strong, good weatherability and be difficult for the characteristics such as crystallization, in various fields, is used widely.Wherein, the organic polymer material of the large π key of tool one-dimentional structure and conjugation, because its prodigiosin band gap numerical value is suitable with visible light energy and electroluminescent intrinsic property, become the focus in current physics or Chemiluminescence Study field.Existing this base polymer mainly contains: polyphenylacetylene (PPV), substituting polythiophene, polyaniline, poly-to benzene, poly-fluorenes, polyvinyl carbazole etc.Wherein, Nature 347,539 (1990) wherein; The PPV of the reports such as US Patent 5189136 and derivative thereof have the luminescent quantum productive rate higher, at visible light wave range, have more by force absorb, be soluble in organic solvent, good film-forming property, stability is high and the good characteristic such as good weatherability, pay close attention to obtaining aspect the polymkeric substance electroluminescence widely, and be applied to the field such as electroluminescent display.Therefore, the performance requriements based on optical oxygen sensing to fluorescence molecule, PPV and the good Photophysics of hard and soft segmented copolymer thereof make it likely the candidate material as the quick indicator of a kind of oxygen.
The patent reports such as CN01120505.9, CN200410068054.8, CN200810057181.6 several high performance PPV materials, but, all for the material in the luminous fields such as electronic material, solar cell material, report and the patent of PPV class material for the optical oxygen sensing field not yet arranged.
The patent report such as CN03128980.0, CN200910205946.0 new optical oxygen sensing material, but be all matrix material, need to be doped in fixing carrier, its doping content is difficult to control, manufacture craft is loaded down with trivial details.
Summary of the invention
The invention provides the application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator of a kind of PPV base polymer, described PPV base polymer surface attachment ability is strong, oxygen quencher and good film-forming property, softness, thermally-stabilised good.
The application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator of described PPV base polymer, the structure of described PPV base polymer is suc as formula (1a) or (1b):
In formula, R
1, R
2identical or different, be straight chain or the branched-chain alkyl of C5～C12, preferably R
1, R
2be n-pentyl, n-octyl, 3-ethylhexyl or dodecyl independently.
Above-mentioned PPV base polymer can be prepared by atom transfer radical polymerization (ATRP), and weight-average molecular weight is between 4000～15000, and the molecular-weight average here is the molecular-weight average of measuring by gel permeation chromatograph (GPC).
Can adopt the application method of existing fluorescent indicator at the concrete grammar of the oxygen sensor based on quenching of fluorescence using the PPV base polymer as fluorescent indicator, for example the PPV base polymer is dissolved in organic solvent to the application as fluorescent indicator in the oxygen sensor based on quenching of fluorescence.Organic solvent can comprise tetrahydrofuran (THF), methyl ethyl ketone, acetone, pimelinketone, ethylene glycol, trichloromethane, DMF, toluene, methyl ether, methylene dichloride, ethyl acetate, butylacetate etc.Preferred organic solvent has tetrahydrofuran (THF) and trichloromethane, more preferably trichloromethane.
Because PPV base polymer film forming properties of the present invention is good, therefore can also be by PPV base polymer film forming on substrate, the application as fluorescent indicator in the oxygen sensor based on 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 formation of film at surface on substrate then.The solvent used is generally can either molten this polymkeric substance, can after self volatilization, make again that polymkeric substance produces evenly, the organic solvent of flat film.Can adopt organic solvent described above.Described substrate can, for monocrystalline silicon piece, simple glass or silica glass, be preferably monocrystalline silicon piece.The method of PPV base polymer film forming on substrate can be adopted to the existing film of prior art, for example can, for gluing, glue spraying or vapour deposition process, be preferably vapour deposition process.
PPV base polymer of the present invention application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, described PPV base polymer surface attachment ability is strong, oxygen quencher 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 National Nature fund assistance (project approval number: 21075015).
The accompanying drawing explanation
Fig. 1 is the described PPV-CH of embodiment 1
2the quenching effect curve of OH in solution, wherein Fig. 1 a is the fluorescence spectrum figure under different oxygen volume percent; 1b is the Stern-Volmer relation curve;
Fig. 2 is the described PPV-CH of embodiment 1
2the quenching effect curve of OH in film, wherein Fig. 2 a is the fluorescence spectrum figure of different oxygen volume percent; 2b is the Stern-Volmer relation curve;
Fig. 3 is the quenching effect curve of the described PPV-b-PMMA of embodiment 2 in solution, and wherein Fig. 3 a is the fluorescence spectrum figure of different oxygen volume percent; 3b is the Stern-Volmer relation curve;
Fig. 4 is the quenching effect curve of the described PPV-b-PMMA of embodiment 2 in film, and wherein Fig. 4 a is the fluorescence spectrum figure of different oxygen volume percent; 4b is the Stern-Volmer relation curve.
Embodiment
Further illustrate the present invention below in conjunction with example, but embodiment does not limit the scope of the invention.
The synthetic Alpha-Methyl of embodiment 1, ω-(4-methylol-2,5-bis-octyloxyphenyl)-poly-(2,5-, bis-octyloxies-Isosorbide-5-Nitrae-phenylene vinylidene) (PPV-CH
2oH) (formula (1a))
By the 0.78g Alpha-Methyl, ω-(4-carboxaldehyde radicals-2,5-bis-octyloxyphenyl)-poly-(2,5-bis-octyloxies-Isosorbide-5-Nitrae-phenylene vinylidene) be dissolved in 50mL THF, dropwise splash in the 50mL dry THF suspension that contains the 0.70g lithium aluminum hydride, react careful the quenching 5 hours.Organic extraction, use anhydrous MgSO
4drying, suction filtration, concentrated, in cold methanol, precipitate, be placed in 20 ℃ of lower vacuum-dryings, obtain red powder shape solid.Record Mw=5655, Mn=4684, PD=1.21.
Synthetic 2,5-, bis-octyloxies of embodiment 2-Isosorbide-5-Nitrae-phenylene vinylidene-methyl methacrylate segmented copolymer (PPV-b-PMMA) (formula (1b))
Reactor is roasting through repeatedly taking out, applying argon gas 3 times, with excluding air and water vapour.Add 0.020g CuBr, 0.065g bpy, 0.640g PPV macromole evocating agent, repeatedly vacuumize, applying argon gas 3 times, sealing, stir 30min.Add 1.45mL methyl-phenoxide, 1.45mL methyl methacrylate, stir half an hour, be warming up to 50 ℃ of reactions 1 hour.With chloroform, dissolve, through neutral alumina column, concentrated, in methyl alcohol, precipitate, be placed in 20 ℃ of lower vacuum-dryings, obtain red powder shape solid.Record Mw=14019, Mn=11857, PD=1.18.
Embodiment 3 is configured to 2 * 10 by 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 and (be respectively used to measure the fluorescence intensity in purity nitrogen, air and pure oxygen), be diluted to 10mL, pass into purity nitrogen (or pure oxygen) in volumetric flask, flow rate control is at 2mL/min, to discharge unnecessary oxygen (or nitrogen) in solution.Repeatedly measure until measure numerical value (<0.5%) within error.The volume percent of oxygen of take is X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.Result as shown in Figure 1.
Embodiment 5 is configured to 2 * 10 by PPV-b-PMMA
-4the chloroform soln of g/L, get respectively with liquid-transfering gun in the volumetric flask of 1mL to three 10mL and (be respectively used to measure the fluorescence intensity in purity nitrogen, air and pure oxygen), be diluted to 10mL, pass into purity nitrogen (or pure oxygen) in volumetric flask, flow rate control is at 2mL/min, to discharge unnecessary oxygen (or nitrogen) in solution.Repeatedly measure until measure numerical value (<0.5%) within error.The volume percent of oxygen of take is X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.Result as shown in Figure 3.
Embodiment 6 method for manufacturing thin film: by slide glass ultrasonic 20min in acetone, rinse well with deionized water, with dry N
2dry up.PPV-b-PMMA is dissolved in to chloroform and makes 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, high speed 2000rad/min, 30s, more non-foaming through 100 ℃ of thermal treatments 2 hours in vacuum drying oven, do not come off.Illustrate that film has higher thermotolerance, intensity and certain toughness.By spin coating, good slide glass is placed in special cuvette, controls the ratio of nitrogen and oxygen, tests its fluorescence intensity under different oxygen concentrations.The volume percent of oxygen of take is X-coordinate, sensitivity (I
0/ I) be ordinate zou, make the Stern-Volmer relation curve.Result as shown in Figure 4.
Claims (9)
1.PPV base polymer is the application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, it is characterized in that, the structure of described PPV base polymer is suc as formula (1a) or (1b):
In formula, R
1, R
2identical or different, be straight chain or the branched-chain alkyl of C5～C12;
The weight-average molecular weight of described PPV base polymer is between 4000～15000.
2. PPV base polymer as claimed in claim 1 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, is characterized in that R
1, R
2be n-pentyl, n-octyl, 3-ethylhexyl or dodecyl independently.
3. PPV base polymer as claimed in claim 2 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, is characterized in that R
1, R
2be n-octyl.
4. PPV base polymer as described as any one in claim 1-3 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, it is characterized in that, the PPV base polymer is dissolved in to trichloromethane or tetrahydrofuran (THF), the application as fluorescent indicator in the oxygen sensor based on quenching of fluorescence.
5. PPV base polymer as described as any one in claim 1-3 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, it is characterized in that, by PPV base polymer film forming on substrate, the application as fluorescent indicator in the oxygen sensor based on quenching of fluorescence.
6. PPV base polymer as claimed in claim 5 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator is characterized in that described substrate is monocrystalline silicon piece, slide glass or silica glass.
7. PPV base polymer as claimed in claim 6 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator is characterized in that described substrate is slide glass.
8. PPV base polymer as described as any one in claim 5-7 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, is characterized in that, by the method for PPV base polymer film forming on substrate, is gluing, spin coating or vapour deposition process.
9. PPV base polymer as claimed in claim 8 application in the oxygen sensor based on quenching of fluorescence as fluorescent indicator, is characterized in that, by the method for PPV base polymer film forming on substrate, is spin-coating method.
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Citations (2)
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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