CN103601873B - A kind of application containing the fluorescence conjugated polyelectrolyte of amphoteric side chain - Google Patents
A kind of application containing the fluorescence conjugated polyelectrolyte of amphoteric side chain Download PDFInfo
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Abstract
The invention discloses a kind of application containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, using it as fluorescence sense system, its application process comprise the steps: (1) will water and organic solvent make mixed solvent after mixing, the volumetric concentration of water is 0.1～99.9%; (2) in mixed solvent, add containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, its concentration in mixed solvent is 1～10 μ M; (3), under the optical excitation that is 400～430nm at wavelength, record intensity and the wavelength of this mixed solvent emission spectrum; Described organic solvent is the one in oxolane, methyl-sulfoxide or DMF. Of the present invention have different fluorescence radiation performances containing the fluorescence conjugated polyelectrolyte of amphoteric side chain in the water of different proportion and organic solvent mixed solvent, and predetermined substance is had to sensing response, therefore, can be used as the highly sensitive sensing system in the mixed solution of water and organic solvent, there is application prospect.
Description
Technical field
The present invention relates to a kind of fluorescence conjugated high molecular polymer and technology of preparing thereof, particularly a kind of containing amphoteric side chainFluorescence conjugated polyelectrolyte, preparation and application, belong to fluorescence chemical sensing material field.
Background technology
Aspect fluorescent sensing material, fluorescent small molecule has and grinds widely in the past as chemical sensor decadesStudy carefully, macromolecular material has many good qualities with respect to small molecule material, as the intensity of material, stability, adjustability of structure etc. ?In practical application, little molecule sensing material is final or will be embedded in polymer matrix, or by little molecular fluorescence group andSensing receiver is introduced polymer side chain, and high polymer main chain mainly plays a support.
Conjugated polymer is also sometimes referred to as conducting polymer or molecular wire, about the large portion of research of its photoluminescent propertyDividing is about electroluminescent material (LED). , there is being applied to the research of chemical sensor in recent years, representative is whereinThe Swager seminar of masschusetts, u.s.a science and engineering (MIT) institute, according to reports, they have succeeded in developing more detecting organic compounds and have pollutedThe conjugated polymer sensor systems of thing or biomolecule, the commercialization of a part wherein, and put application on market.
Conjugated polymer is mainly to utilize energy or the electronics can on whole conjugated polymer chain as fluorescent sensing materialWith delocalization and migration, thereby obtain the high sensitivity that general molecule does not have. Because what be subject in certain of macromolecular chain is micro-Little interference just likely affects the character of whole macromolecular chain, makes the signal that this interference obtains amplify (Acc.Chem.Res.1998,31,201-207; Chem.Rev.2000,100,2537-2574). In addition, by MOLECULE DESIGN, combination is differentHigh polymer main chain and sensing receive group and can obtain the output of the selectable signal of specific external interference.
Fluorescence conjugated polyelectrolyte is widely used in the fields such as water body environment detection and biological detection. Conjugated polyelectrolytes(CPEs) normally formed by oil loving polymer conjugated main chain and ionizable hydrophilic side-chains, because it has simultaneouslyThe character of ionization and molecular wire makes it at bio-sensing, electronics, and the application of photoelectronics aspect has had new possibility(Adv.Mater.2008,20,3793 – 3810). But, these polyelectrolyte due between its oil-soluble main chain mutually, mainly there is it in effect, ionizable side chain stretches to water environment in state of aggregation under water environment with the form of state of aggregationOutside and main polymer chain is gathered in inside. These conjugated polyelectrolytes are mainly to deposit with the form of state of aggregation in water body environment, intermolecular electron and energy transfer is strengthened, thereby affected its luminescent properties and sensing efficiency. Polyelectrolyte is owing to being total toBetween yoke main chain, there is very strong π-π*Interact, be difficult to afterwards destroy π-π in oven dry*Interaction and it is dissolved again, thereforeCan only be kept in solution, bring difficulty to storage and transport. The gathering of fluorescence conjugated polyelectrolyte to conjugated polymer certainlyThe fluorescence of body also has self-quenching effect, also just reduced conjugated polymer quantum efficiency (CHEM.COMMUN., 2002,446 – 447). Therefore, some researcher by adding surfactant or being introduced and propped up by synthetic method in systemThe hydrophilic side-chains of changing, the dissolubility again of improving conjugated polyelectrolytes with and luminescent properties (Chem.Commun.,2006,1983–1985；J.AM.CHEM.SOC.2006,128,4007-4016）。
Summary of the invention
It is simple that the object of the invention is to provide a kind of synthesis technique, in the mixed solution of water and organic solvent, has fluorescenceCan be adjustable, and the good application as fluorescence sense system containing the fluorescence conjugated polyelectrolyte of amphoteric side chain of dissolubility.
The technical solution used in the present invention is: provide a kind of containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, it has as followsStructure:
In formula: m is the degree of polymerization; R is OCnH2n+1Oleophylic side chain, wherein, the integer that n is 4～16; R ' is ammonium salt or sulphurOne in hydrochlorate ionic hydrophilic side chain. Described sulfonate ion type hydrophilic side chain is OCH2CH2CH2SO3 -Na+; Ammonium saltIonic hydrophilic side chain is OCH2CH2CH2N+(CH3)3Br-。
The invention provides a kind of preparation method containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, by oil-soluble monomer A and waterSoluble monomers B in molar ratio 1～1.12:1 mixes, in molar ratio, and the catalysis that to add with the ratio of monomer A be 1:0.05～0.08The cuprous iodide of agent tetrakis triphenylphosphine palladium and 1:0.05～0.08, after coupling reaction again under temperature is the condition of 20～50 DEG CDry processing, obtains a kind of containing the fluorescence conjugated polyelectrolyte of amphoteric side chain;
The structural formula of described oil-soluble monomer A is:
；
The structural formula of described water-soluble monomer B is:
；
The described structural formula containing the fluorescence conjugated polyelectrolyte of amphoteric side chain is:
In formula: m is the degree of polymerization; R is OCnH2n+1, wherein, be 4～16 integer; X is I or Br, R ' be sulfonate orOne in ammonium salt ionic hydrophilic side chain. Sulfonate ion type hydrophilic side chain in described water-soluble mono B isOCH2CH2CH2SO3 -Na+, ammonium salt ionic hydrophilic side chain is OCH2CH2CH2N+(CH3)3Br-。
The invention provides a kind of application containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, using it as fluorescence sense system,Its application process comprises the steps:
(1) will after water and organic solvent mixing, make mixed solvent, the volumetric concentration of water is 0.1～99.9%; Described hasMachine solvent is the one in oxolane, methyl-sulfoxide, DMF, methyl alcohol or dioxy six alkane;
(2) in mixed solvent, add containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, its concentration in mixed solvent is 1～10μM；
(3), under the optical excitation that is 400～430nm at wavelength, record intensity and the wavelength of this mixed solvent emission spectrum.
The present invention prepares water-soluble monomer and oil-soluble monomer containing both sexes side by Sonogashira coupling reactionThe fluorescence conjugated polyelectrolyte of chain. Can synthesize different types of water-soluble and oil-soluble monomer by MOLECULE DESIGN, logicalCross the mutual combination between these monomers, prepare and there is the fluorescence conjugated polyelectrolyte of amphoteric side chain of different nature. In both sexesIn the fluorescence conjugated polyelectrolyte of side chain, introduce hydrophobic side chain, make the distance between conjugated main chain distant, at conjugated polyelectrolytesSolids accumulation state in, intermolecular π-π*Interact more weak, make these conjugated polyelectrolytes can also be very after oven dryGood dissolving, has overcome conjugated polyelectrolytes insoluble character after oven dry in the past. Although these conjugated polyelectrolytes are in waterHave good dissolubility, but can find out from the result of its fluorometric investigation, conjugated polyelectrolytes is in water or to assembleThe form of state exists. In conjugated polyelectrolytes, introduce oil-soluble side group, just can be molten by the mixing of water and organic solventAgent carrys out the fluorescent emission of telomerized polymer, and this has also overcome the low problem of polyelectrolyte luminous efficiency in the past. Containing amphoteric side chainFluorescence conjugated polyelectrolyte in, water miscible ionic group both as hydrophilic functional group be also simultaneously same metal ion andThe functional group of bio-molecular interaction; The introducing of oil-soluble side chain is mainly the deficiency that overcomes previous polyelectrolyte, as orderFront used similar polyelectrolyte is dried rear indissoluble solution and can only be kept in solution, brings the difficulty of storage and transport etc.The fluorescence conjugated polyelectrolyte of amphoteric side chain, in the mixed solvent (water and organic solvent) of different proportion, can be used for detecting individually defined thingThe fluorescence sense system of matter.
The present invention adopts oil-soluble monomer and water miscible monomer by the method for cross-couplings (Sonogashira), systemStandby polyphenylacetylene support (PPE) class conjugated polyelectrolytes simultaneously with hydrophilic side-chains and lipophile side chain, this containing both sexes sideThe fluorescence conjugated polyelectrolyte of chain has good dissolubility after drying, and therefore, the present invention compared with prior art, overcomesConjugated polyelectrolytes indissoluble solution after oven dry, and the difficult problem such as luminous efficiency is low, has facilitated to store and transport; Meanwhile, it is gone backCan regulate its luminescent properties by the method for mixed solvent (water and organic solvent), can be used as mixing at water and organic solventHighly sensitive sensing system in bonding solvent, provides a kind of new polyelectrolyte material, has application prospect.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance containing the fluorescence conjugated polyelectrolyte of amphoteric side chain of preparing by embodiment of the present invention technical schemeFigure;
Fig. 2 be prepare by embodiment of the present invention technical scheme containing the fluorescence conjugated polyelectrolyte of amphoteric side chain at different proportionWater and the mixed solvent of organic solvent in fluorescence property curve map;
Fig. 3 be prepare by embodiment of the present invention technical scheme containing the fluorescence conjugated polyelectrolyte of amphoteric side chain at different proportionWater and the mixed solvent of organic solvent in to Fe3+The curve map of quencher experiment.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment mono-:
The oil-soluble monomer that the present embodiment adopts is Isosorbide-5-Nitrae-diacetylene-2,5-docosane oxygen base benzene; What adopt is water-solubleProperty monomer is that Isosorbide-5-Nitrae-bis-are iodo-2,5-dipropoxy sulfonic acid benzene.
(1) Isosorbide-5-Nitrae-diacetylene-2, the synthesis step of 5-docosane oxygen base benzene is as follows:
Prepare Isosorbide-5-Nitrae-docosane oxygen base benzene
The DMF solution that contains hydroquinones (11g, 100mmol) and bromododecane (2.2 equivalent) is placed in to 500mlBe equipped with in single neck flask of condenser pipe, add wherein potassium hydroxide (250mmol). This mixed solution is stirred and slowly addedHot to 120 DEG C, stirring and refluxing after stable reaction. Finish, after reaction, reactant liquor to be cooled to room temperature, suction filtration is collected solids of sedimentation,The solid that collection is obtained obtains white solid with ethyl alcohol recrystallization, is placed in vacuum drying oven dry, obtain pure product Isosorbide-5-Nitrae-Docosane oxygen base benzene (productive rate 85%).
Prepare Isosorbide-5-Nitrae-docosane oxygen base-2,5-diiodo-benzene
In being equipped with single neck flask of reflux condensing tube, 250ml joins following mixed solvent: 150ml glacial acetic acid, 1.5mlH2SO4And 15mlH2O, simultaneously by Isosorbide-5-Nitrae-docosane oxygen base benzene (6.4g), I2(4g) and Potassiumiodate (1.22g) be dissolved in above-mentioned mixedIn bonding solvent, then single neck flask is placed in to 120 DEG C of constant temperature oil bath agitating heating. After reaction finishes, cooling reactant liquor is to chamberTemperature, and to the NaS that adds 20% in reactant liquor2O4Solution is until the brown disappearance of iodine. Suction filtration is collected solid, and the solid obtaining is usedEthanol/Gossypol recrystallized from chloroform obtains white solid twice, is placed in vacuum drying oven dry, obtains pure product Isosorbide-5-Nitrae-docosane oxygenBase-2,5-diiodo-benzene.
Prepare Isosorbide-5-Nitrae-diacetylene-2,5-docosane oxygen base benzene
This step reaction needed is carried out under oxygen free condition, instrument 250ml three-neck flask, the condensation in course of reaction, usedPipe, vacuum stopper are dried and are put up device cooling under argon gas condition. By Isosorbide-5-Nitrae-docosane oxygen base-2,5-diiodo-benzene (3g) CuI(0.0409g) and (PPh3)2PdC12(0.1506g) under argon shield, join in flask, then system is carried out repeatedlyVacuumize logical argon gas operation, the diisopropylamine 60ml processing is joined in system under argon gas condition, this mixed liquor is in chamberTemperature stirs half an hour, and the trimethyl silicane ethyl-acetylene of 0.009456mol is added in 15 minutes with syringe under argon shieldIn reaction system. Then flask is placed in to 85 DEG C of constant temperature oil baths, reaction system is heated to stirring and refluxing. After reaction finishes,Question response liquid is cooled to room temperature dilution with toluene reactant liquor, and the silica gel column chromatography that this mixed liquor is grown by 4cm is fast collected liquidBody and with rotary evaporation except desolventizing, the solid obtaining is obtained to white pure solid product (product for twice with ethanol/Gossypol recrystallized from chloroformRate 92%) trimethyl silicon based acetenyl-2 of Isosorbide-5-Nitrae-bis-, 5-docosane oxygen base benzene. The product (2g) that above-mentioned reaction is obtained is dissolved in54mlTHF in the mono-neck flask of 250ml, then fast to the KOH and the 17ml methyl alcohol that add 1ml20% in reaction system simultaneously,After reaction finishes, add 54ml methyl alcohol to stir in reaction system 10 minutes, suction filtration is collected solid sediment, and the solid obtaining is heavyShallow lake thing obtains light yellow product twice with n-hexane recrystallization. Be placed in vacuum drying oven dryDry, obtain pure product Isosorbide-5-Nitrae-diacetylene-2,5-docosane oxygen base benzene. Its structural formula is:
In formula, R is OC12H25。
(2) Isosorbide-5-Nitrae-bis-are iodo-2, and the synthesis step of 5-dipropoxy sulfonic acid benzene is as follows:
Prepare Isosorbide-5-Nitrae-bis-(propoxyl group sulfonic acid) benzene
Under ar gas environment, hydroquinones (8.8g) is dissolved in NaOH solution in (10%) 100ml, will contains propane sulfonic acidThe dioxane solution of lactone (24.4g, 0.2mol) joins fast in above-mentioned solution, by this mixed solution under argon shieldUnder argon shield room temperature condition, stir 4 hours. Post processing: the frozen water liquid cooling filter cake ice acetone that but suction filtration obtains for reactant liquorDrip washing, finally collects white solid, is placed in vacuum drying oven dried overnight and obtains pure product Isosorbide-5-Nitrae-bis-(propoxyl group sulfonic acid) benzene.
Prepare Isosorbide-5-Nitrae-bis-iodo-2,5-bis-(propoxyl group sulfonic acid) benzene
By I2(3.86g) and KIO3(1.55g) be dissolved in 40ml glacial acetic acid, 3mlH2SO4And 30mlH2In the mixed solvent of O.Then product Isosorbide-5-Nitrae-bis-(propoxyl group sulfonic acid) benzene (5.77g) are also joined in above-mentioned mixed solution, by this reactant liquor at 60 DEG CLower stirring 12 hours. The post processing of this step reaction is: by cooling reactant liquor ice-water bath, suction filtration is collected solid also with a large amount of iceThe solid that ethanol drip washing obtains, collects white solid, and being placed in vacuum drying oven dried overnight, to obtain pure product Isosorbide-5-Nitrae-bis-iodo-2,5-bis-(propoxyl group sulfonic acid) benzene. Its structural formula is:
In formula, X is I; R ' is sulfonate ion type hydrophilic side chain OCH2CH2CH2SO3 -Na+。
(3) containing the preparation of the fluorescence conjugated polyelectrolyte of amphoteric side chain (PPESO3OR)
By Sonogashira coupling reaction, oil-soluble monomer and water-soluble monomer are made to side by cross-couplingChain both sexes conjugated polymer, in order to prevent that raw material from containing the self oxidation of alkynyl monomer, this step of conversion ratio that improves reaction is anti-In requisition for carrying out under anaerobic argon shield. Take respectively solid material oil-soluble monomer Isosorbide-5-Nitrae-diacetylene-2,5-22Alkoxy benzene 0.1g, water-soluble monomer Isosorbide-5-Nitrae-bis-are iodo-2,5-dipropoxy sulfonic acid benzene 0.1316g, catalyst four (triphenylphosphine)Palladium 11.6mg, cuprous iodide 1.9mg. After adding solid material and catalyst, system is carried out to the logical argon gas behaviour that vacuumizes repeatedlyDo, to remove as much as possible the oxygen of sneaking in system in reinforced process. React required solvent DMF(DMF), water, diisopropylamine leads to argon gas deoxygenation half an hour to it respectively, then by DMF: water: diisopropylamine is that 3:2:1 is mixedAfter closing, get 10ml and add in constant pressure funnel, system being vacuumized to logical argon gas operation, under stirring, mixed solvent is slowSlowly be added drop-wise in flask, flask be placed in to the constant temperature oil bath agitating heating system of 80 DEG C, react 24 hours. Will after reaction finishesReaction system cool to room temperature, the mixed liquor precipitation that reactant liquor is 10:40:50 with methanol/acetone/ether, centrifugation is collectedSediment, is dissolved in the processing of this liquid of 20ml water/methyl alcohol (7:3) 0.01g sodium thiosulfate again by the solid obtaining, and filters and receivesCollection filtrate, the mixed liquor precipitation by this filtrate with methanol/acetone/ether (10:40:50), centrifugation collecting precipitation thing, is placed inDry in vacuum drying oven, obtain product containing the fluorescence conjugated polyelectrolyte of amphoteric side chain (PPESO3OR), its oil loving side chain isOC12H25, hydrophilic side chain is OCH2CH2CH2SO3 -Na+。
Referring to accompanying drawing 1, it be the embodiment of the present invention provide containing the fluorescence conjugated polyelectrolyte of amphoteric side chain (PPESO3OR)Hydrogen nuclear magnetic spectrogram in deuterated dimethyl sulfoxide (DMSO); Can be seen by Fig. 1, wherein chemical shift is that 0ppm place is moltenThe peak of the reference material adding in agent, between 0.5～8.0ppm is the peak of hydrogen atom on phenyl ring in molecule. Oil-soluble and waterDissolubility side chain is present in chemical displacement value in this macromolecule between 0.8～4.5ppm, with institute in polymer molecule simultaneouslyMark hydrogen atom (referring to the product structure of preparation process reaction equation) corresponding as follows: A:4.2～4.0; D:42.～3.8;C:2.5～2.8；B:1.8～2.2；E:1.6～1.8；F:1.4～1.6；G:0.9～1.4；H:0.6～0.9。
The reaction equation of preparation process is:
(4) test of fluorescence radiation performance
Taking oxolane (THF) as organic solvent, the H of configuration different organic solvents ratio2O/THF mixed solvent: organicThe volumetric concentration of solvent is respectively 0%, 10%, and 50%, 90% and 99.9%.
The product of the present embodiment step (3) is joined above-mentioned containing the fluorescence conjugated polyelectrolyte of amphoteric side chain (PPESO3OR)The H of different proportion2In O/THF mixed solvent, the concentration of conjugated polyelectrolytes is 1 μ M(repetitive), be 400 at wavelength～Under the optical excitation of 430nm, record intensity and the wavelength of each mixed solution emission spectrum.
Referring to accompanying drawing 2, it be the present embodiment provide containing the fluorescence conjugated polyelectrolyte of amphoteric side chain (R ' beOCH2CH2CH2SO3 -Na+, R is OC12H25) at the H of different proportion2Fluorescence radiation wavelength in O/THF and the song of fluorescence intensityLine chart; From figure, can draw, polymer has by state of aggregation in these mixed solvents---non-state of aggregation---state of aggregationChange procedure. In water He in organic solvent, be coherent condition, show as lower fluorescence intensity and longer emission wavelength. AndWhen in the mixed solvent of suitable water and organic solvent, the fluorescent emission of system is non-state of aggregation form.
(5) to Fe3+The test of sensing response
Taking oxolane (THF) as organic solvent, the H of configuration different organic solvents ratio2O/THF mixed solvent: organicThe volumetric concentration of solvent is respectively 0%, 10%, and 20%, 30%, 40%, 50%, 90% and 99.9%. The present embodiment step (3) is obtainedProduct (PPESO3OR) join the H of above-mentioned different proportion2In O/THF mixed solvent, the concentration of conjugated polyelectrolytes is 1 μ M(repetitive), makes mixed solution; In different mixed solutions, add respectively 1～10 μ MFe3+, be 400 at wavelength～Under the optical excitation of 430nm, record the intensity of emission spectra of each mixed solution, obtain the sensing effect of different systems.
Referring to accompanying drawing 3, it is at mixed solvent H containing the fluorescence conjugated polyelectrolyte of amphoteric side chain2In O/THF to Fe3+'sThe curve map of quencher experiment, I in figure0/ I is the initial fluorescence intensity (I of system0) with add fluorescence intensity (I) after quencherRatio. From figure, can draw, in the time that the oxolane ratio in system is 30%, sensing effect is best, and water ratio is large simultaneouslyThe sensing effect of the system that system is large compared with oxolane ratio will be got well, and it affects factor and may be: initial glimmering light intensity, energyThe speed of migration, connects an easy degree contacting with sulfonic acid. Result shows, Fe3+When concentration is lower, (when < 2 μ M), containsTHF has reaction quickly in 0～10% system to the cancellation of ion, the highest containing having in 20～30%THF systemSensitivity.
Claims (1)
1. containing an application for the fluorescence conjugated polyelectrolyte of amphoteric side chain, it is characterized in that: described fluorescence conjugated containing amphoteric side chainPolyelectrolyte has following structure:
In formula: m is the degree of polymerization; R is OCnH2n+1Oleophylic side chain, wherein, the integer that n is 4～16; R ' is ammonium salt or sulfonateOne in ionic hydrophilic side chain, described sulfonate ion type hydrophilic side chain is OCH2CH2CH2SO3 -Na+; Ammonium salt ionType hydrophilic side chain is OCH2CH2CH2N+(CH3)3Br-; Using it as fluorescence sense system, its application process comprises the steps:
(1) will after water and organic solvent mixing, make mixed solvent, the volumetric concentration of water is 0.1～99.9%;
(2) in mixed solvent, add containing the fluorescence conjugated polyelectrolyte of amphoteric side chain, its concentration in mixed solvent is 1～10μM；
(3), under the optical excitation that is 400～430nm at wavelength, record intensity and the wavelength of this mixed solvent emission spectrum;
Described organic solvent is the one in oxolane, methyl-sulfoxide or DMF.
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