CN105254853A - Water-dispersible hyperbranched conjugated polymer fluorescent nanoparticles as well as preparation method and application thereof - Google Patents
Water-dispersible hyperbranched conjugated polymer fluorescent nanoparticles as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to water-dispersible hyperbranched conjugated polymer fluorescent nanoparticles as well as a preparation method and an application thereof and aims to solve the technical problem of low sensitivity of conjugated polymers used currently during detection of nitro-aromatic compounds in a water phase. An internal hydrophobic cavity structure and a terminal hydrophilic structure of each nanoparticle are a hyperbranched conjugated polymer core part composed of conjugated structure units Ar1 and Ar2 and sodium oxypropyl sulfonate or sodium oxybutyl sulfonate generated through a reaction between terminal hydroxyl of precursors of the hyperbranched conjugated polymer fluorescent nanoparticles and 1,3-cyclopropane sultone or 1,4-cyclobutyl sultone respectively. The nanoparticles prepared with the method are effectively combined with TNT molecules through a hydrophobic enrichment function, and the detection sensitivity is remarkably improved. The quenching coefficient and the detection limit of the hyperbranched conjugated polymer fluorescent nanoparticles can be improved by several magnitudes in comparison with traditional linear conjugated polymers and nanoparticles of the traditional linear conjugated polymers, and the selective detection of TNT in an aqueous solution can be realized.
Description
Technical field
The present invention relates to a kind of nanoparticle, be specifically related to a kind of water-dispersion hyperbranched conjugated polymer fluorescent nano particles and its preparation method and application.
Background technology
Nitro arene explosive substance is as 2，4，6-trinitrotoluene (TNT), and 2，4，6-trinitrophenol (PA) etc. has high explosive, plays a significant role in national defense construction and military field.Meanwhile, these explosive substances are also utilized by terroristic organization and implement the attack of terrorism in recent years, constitute a serious threat, become one of safety problem of global concern to the country and people's life security.On the other hand, along with industrial development, current this kind of high toxic material is widely used in many industrial circles, its a large amount of use lack of standardization or as industrial waste discharge beyond standards, all can cause the severe contamination at air, soil and water source, be detrimental to health.Such as, TNT polluted source forms " pink water ", can cause anaemia, liver dysfunction, the various serious disease such as toxic gastritis and cataract after contact human body.EPA specifies that the content of TNT in tap water must not higher than 2ppb (10nM).Therefore, the novel method quick and precisely detecting nitro-aromatic developing highly sensitive and highly selective has become the focus of research both at home and abroad.
Present stage people have developed the method for various detection nitro arene explosive substance, as ion migration technology, and LC-MS analysis, Raman spectrum analysis, Electrochemical Detection, fluoroscopic examination etc.In these methods, fluoroscopic examination is due to higher sensitivity, and cost is low, does not need complex instrument, consuming time short, easy handling and realize portable inspectiont and real-time online and detect, and receives much concern.Especially in recent years, applying fluorescent conjugated polymer high-sensitivity detection explosive substance is one of study hotspot.This mainly shows higher absorbing ability and special " molecular wire effect " due to fluorescent sensing materials made of conjugated polymer, namely electronics or energy can in polymer conjugated main chain fast transferring, hundreds and thousands of times of ground amplify sensing response signals.The explosive substance molecularitys such as the TNT of conjugated polymers and electron deficiency, produce effective Photo-induced electron transfer, in conjunction with this " molecular wire effect ", its fluorescence by efficient cancellation, thus can have sensitiveer examine repair than small-molecule fluorescent probe.The current fluorescence sense system based on conjugated polymers is used for greatly the vapor detection of nitro-aromatic.But application conjugated polymers is not only reported seldom at aqueous phase detection nitro-aromatic, and detection sensitivity is lower.Its reason is that conjugated polymers is more weak with the nitro-aromatic molecular binding events such as TNT in water on the one hand, and the mechanism that conjugated polymer thin films detects nitro-aromatic steam under state of aggregation is difficult to be applicable in Liquid Detection.On the other hand, conjugated polymers low water solubility constrains the development that conjugated polymers detects for aqueous phase.Based on the importance detecting nitro-aromatic in aqueous phase, nearest Fang Yu etc. devise containing pyrene conjugated polymer thin films, can carry out TNT detection in aqueous phase; UllrichScherf etc. and Tang Benzhong etc. utilize the PA detected with the linear conjugated polymkeric substance of aggregation-induced emission character and hyperbranched conjugated polymer in aqueous phase respectively.However, most nitro-aromatics etc. are hydrophobic organic pollutants, and in water, concentration is very low, and application conjugated polymers realizes high-sensitivity detection and still has extreme difficulty.Therefore, design and development has superior water dispersibility, the fluorescent sensing materials made of conjugated polymer still challenging and significance of nitro-aromatic in highly sensitive and selective enumeration method aqueous phase.
Summary of the invention
The present invention solves existing application conjugated polymers to detect the low technical problem of nitro-aromatic sensitivity at aqueous phase, and provides a kind of water-dispersion hyperbranched conjugated polymer fluorescent nano particles and its preparation method and application.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles, the method comprises the following steps: adopt A3 and B2 monomer, under the condition of alkali and palladium catalyst catalysis, Suzuki polycondensation is carried out in oil/water type miniemulsion, and carry out end capping with the end-capping reagent of hydroxyl, prepare and dispersible hyperbranched conjugated polymer fluorescent nano particles precursor hydroxy-end capped in organic phase, by William's nurse inferior ether building-up reactions, hydrophilic alkoxyl group sulfonate is introduced the end of hyperbranched conjugated polymer fluorescent nano particles precursor again, the water-dispersion hyperbranched conjugated polymer fluorescent nano particles of obtained inner hydrophobic cavity structure and hydrophilic end,
Described A3 and B2 monomer, is respectively and has Ar
1and Ar
2three boric acid ester monomers of structural unit and two bromine monomer, or be respectively there is Ar
1and Ar
2the tribromo monomer of structural unit and two boric acid ester monomer, its structure is as follows:
or
.
In technique scheme, described concrete steps of carrying out Suzuki polycondensation in oil/water type miniemulsion are: carry out under anaerobic, and water consumption is 45 ~ 135mL; Oil phase is toluene, and consumption is 2 ~ 10mL; Oil/water ratio is 1:15 ~ 45; Emulsifying agent is cetyl trimethylammonium bromide (CTAB), and consumption is 8 ~ 24mmol; Catalyzer is that four triphenylphosphines close palladium (Pd (PPh
3)
4), consumption is 0.1 ~ 0.8% of brominated monomer's mole dosage; Wet chemical concentration is 2mol/L, and consumption is 4 ~ 10 times of bromo functional groups mole dosage in monomer; Temperature of reaction is 80 ~ 90 DEG C, and the reaction times is 24 ~ 48h.
In technique scheme, the end-capping reagent of described hydroxyl is boric acid end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol and bromo end-capping reagent 4-bromophenol.
In technique scheme, described hyperbranched conjugated polymer fluorescent nano particles precursor is a kind of complete emulsifier-free, and can be dispersed in tetrahydrofuran (THF), methylene dichloride, chloroform or toluene, and diameter is the particle of 15 ~ 40 nanometers.
In technique scheme, described Ar
1structure is specific as follows:
Wherein, R
0the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
In technique scheme, the concrete steps of the inferior ether building-up reactions of described William's nurse are: carry out under anhydrous and oxygen-free, base catalysis condition, the terminal hydroxyl and 1 of described hyperbranched conjugated polymer fluorescent nano particles precursor, 3-ring propane sultone or 1,4-ring butyl sultone reacts, temperature of reaction is 85 DEG C, reaction times 24 ~ 60h, and described alkali is sodium tert-butoxide or NaH.
In technique scheme, described water-dispersion hyperbranched conjugated polymer fluorescent nano particles a kind ofly can be dispersed in water or DMF, and diameter is the particle of 15 ~ 40 nanometers.
In technique scheme, described Ar
2structure is specific as follows:
Wherein, R
1~ R
18the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
Apply the method that water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by above-mentioned preparation method detects nitro-aromatic in water, concrete steps are as follows:
Water-dispersion hyperbranched conjugated polymer fluorescent nano particles is configured to aqueous dispersions according to mass volume ratio, with luminoscope record fluorescent emission intensity I
0; The enriched sample storing solution of configuration nitro-aromatic in methyl alcohol or DMF, by serial dilution to the method configuration concentration gradient standard substance in the aqueous solution, fluorometric titration experiment is carried out to water-dispersion hyperbranched conjugated polymer fluorescent nano particles, under record different concns, fluorescence intensity I; By water-dispersion hyperbranched conjugated polymer fluorescent nano particles to before and after nitro-aromatic effect in the change of the fluorescence intensity at emission maximum place, with the fluorescence intensity I of initial nanoparticle blank solution
0with the ratio (I adding the fluorescence intensity I after nitro-aromatic
0/ I) as the function of nitro-aromatic concentration, make working curve, to nitro-aromatic detection by quantitative; According to Stern-Volmer equation: I
0/ I=Ksv [Q]+1, calculate cancellation constant, in formula, Ksv is Stern-Volmer cancellation constant, is calculated by the slope of above-mentioned working curve, the concentration that [Q] is nitro-aromatic.
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles obtained by above-mentioned preparation method, its structure is as follows:
Wherein, Ar
1, Ar
2for the conjugated structure unit component of described water-dispersion hyperbranched conjugated polymer fluorescent nano particles core, Ar
1, Ar
2between be singly-bound connect; ORSO
3na is the oxyalkyl sulfonate groups of described water-dispersion hyperbranched conjugated polymer fluorescent nano particles end, and wherein R is straight chain trimethylene or straight chain tetramethylene, Sauerstoffatom and Ar
1or Ar
2be connected with singly-bound conjugation by phenyl ring;
Described Ar
1for having phenyl ring derivative, triphenylamine derivative, triazole derivative, triphenyl-boron derivative, three also indene derivative, three also fluorenone derivatives or the three also carbazole derivative of the core conjugation branched structure unit of trifunctional;
Described Ar
2for having the benzene and its derivative of bifunctional conjugated structure unit, fluorenes and derivative, carbazole and derivative thereof, thiophene and derivatives, diazosulfide and derivative, dibenzothiophen and derivative thereof, sulphur sulfone and derivative, silicon fluorenes and derivative thereof, spiral shell fluorenes and derivative, triphenylamine and derivative thereof or tetraphenylethylene and derivative thereof.
Described Ar
1structure can be specific as follows:
Wherein, R
0the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
Described Ar
2structure can be specific as follows:
Wherein, R
1~ R
18the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
The invention has the beneficial effects as follows:
1, the inner hydrophobic cavity structure of water-dispersion hyperbranched conjugated polymer fluorescent nano particles provided by the invention and terminal hydrophilic structure, be respectively above-mentioned conjugated structure unit Ar
1, Ar
2the hyperbranched conjugated polymer core formed, and the terminal hydroxyl of hyperbranched conjugated polymer nanoparticle precursor and 1,3-ring propane sultone or Isosorbide-5-Nitrae-ring butyl sultone react the oxygen propyl sulfonic acid sodium or oxygen-butyl sodium sulfonate that generate.
2, the invention provides the water-dispersion hyperbranched conjugated polymer fluorescent nano particles that preparation method obtains and there is hydrophilic end and hydrophobic interior cavity structure, by hydrophobic inrichment effectively in conjunction with TNT molecule, significantly improve detection sensitivity.Compared with traditional line style conjugated polymers and nanoparticle thereof, the cancellation constant of hyperbranched conjugated polymer fluorescent nano particles and detection limit can reach the raising on several order of magnitude.Meanwhile, the binding ability of nanoparticle to PA dies down, and can realize the selective enumeration method to TNT in the aqueous solution.
3, the method for hyperbranched conjugated polymer fluorescent nano particles precursor prepared of preparation method provided by the invention, emulsifying agent can remove completely, and after removing emulsifying agent, what nanoparticle energy was stable is dispersed in organic phase, overcomes the insoluble problem of hyperbranched conjugated polymer prepared by A3+B2 type conjugative monomer.Be conducive to realizing nanoparticle further Post functionalization reaction in organic phase simultaneously.
4, the hyperbranched conjugated polymer fluorescent nano particles precursor that prepared by preparation method provided by the invention has great amount of hydroxy group, with 1,3-ring propane sultone or 1, the reaction of 4-ring butyl sultone is efficient, thus effective by the end being connected to hyperbranched conjugated polymer of wetting ability sulfonate chain covalency, make stable being dispersed in aqueous phase of hyperbranched conjugated polymer fluorescent nano particles.
5, application water-dispersion hyperbranched conjugated polymer fluorescent nano particles of the present invention detects the method for nitro-aromatic in water, utilize its hydrophobic interior cavity structure, by hydrophobic inrichment, collect the TNT molecule that also enrichment is hydrophobic, and be limited in hydrophobic inside, transfer transport between effective enhancing TNT molecule and nanoparticle, produces efficient fluorescent quenching, realizes highly sensitive TNT and detects.Meanwhile, there is electrostatic repulsion with the PA that can dissociate positive charge in water in electronegative sulfonate end, reduces binding ability and the fluorescent quenching of its PA, can realize the selective enumeration method to TNT in the aqueous solution.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is prepared water-dispersion hyperbranched conjugated polymer fluorescent nano particles absorption and scattering spectrum in embodiment 1;
Fig. 2 is prepared water-dispersion hyperbranched conjugated polymer fluorescent nano particles transmission electron microscope image in embodiment 1;
Fig. 3 is prepared water-dispersion hyperbranched conjugated polymer fluorescent nano particles distribution of sizes histogram in embodiment 1;
Fig. 4 is that water-dispersion hyperbranched conjugated polymer fluorescent nano particles fluorescence spectrum prepared by embodiment 1 is with the change of TNT concentration;
Fig. 5 is the function of change ratio as TNT concentration of prepared water-dispersion hyperbranched conjugated polymer fluorescent nano particles fluorescence intensity in embodiment 1;
Fig. 6 is that the fluorescence intensity of prepared water-dispersion hyperbranched conjugated polymer fluorescent nano particles in embodiment 1 is to the response of different analyte.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
The preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles provided by the invention, concrete steps are as follows:
Step 1: under argon atmosphere, is dissolved completely in emulsifying agent in deoxygenation deionized water.Monomer A 3, B2, palladium catalyst are dissolved in the toluene of deoxygenation, transfer in the emulsifier solution of stirring.By reactor after 40 ~ 50 DEG C of sonic oscillation 5 ~ 20min, under whipped state, add the K that concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 5 ~ 10min.80 ~ 90 DEG C of oil baths that gained reaction miniemulsion is placed in, stirring reaction 24 ~ 48h.After adding boric acid end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol reactant 3 ~ 4h, add bromo end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with organic solvent.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in poor solvent, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, and this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor.
Step 2: under argon atmosphere, dissolves the DMF of excessive sodium tert-butoxide with 10 ~ 60mL drying, is warming up to 85 DEG C.By hyperbranched conjugated polymer fluorescent nano particles precursor dispersion hydroxy-end capped for 50 ~ 100mg in the tetrahydrofuran (THF) of 10 ~ 60mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, by excessive Isosorbide-5-Nitrae-ring butyl sultone or 1,3-ring propane sultone is dissolved in the DMF of 10 ~ 30mL drying, imports in dropping funnel with syringe, slowly be added drop-wise in reaction mixture, temperature of reaction is 85 DEG C, reaction times 24 ~ 60h.After cooling, add 20 ~ 50mL deionized water, and stir 30min.Gained suspension is centrifugal, isolated solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles.
Described hyperbranched conjugated polymer fluorescent nano particles precursor is a kind of complete emulsifier-free, and can be dispersed in tetrahydrofuran (THF), methylene dichloride, chloroform or toluene, and diameter is the particle of 10 ~ 100 nanometers, is preferably 15 ~ 40nm.
Described water-dispersion hyperbranched conjugated polymer fluorescent nano particles a kind ofly can be dispersed in water or DMF, and diameter is the particle of 10 ~ 100 nanometers, is preferably 15 ~ 40nm.
Step of the present invention (1) described organic solvent is preferably methylene dichloride, chloroform or toluene, more preferably methylene dichloride; Described sedimentation solvent is preferably methyl alcohol, ethanol, acetone, ether or normal hexane, is preferably methyl alcohol; Described extraction solvent is preferably methyl alcohol, ethanol, acetone, ether or normal hexane, is more preferably methyl alcohol or acetone.
Step of the present invention (2) gained solid adopts supersound washing to be preferably placed in methyl alcohol successively, acetone, normal hexane or ether, and washs in tetrahydrofuran (THF), is more preferably and is placed in methyl alcohol successively, wash in acetone and tetrahydrofuran (THF).
Apply the method for nitro-aromatic in the water-dispersion hyperbranched conjugated polymer fluorescent nano particles high-sensitivity detection water of above-mentioned preparation in the present invention, concrete steps are as follows:
Water-dispersion hyperbranched conjugated polymer fluorescent nano particles is configured to aqueous dispersions according to mass volume ratio, with luminoscope record fluorescent emission intensity I
0; The enriched sample storing solution of configuration nitro-aromatic in methyl alcohol or DMF, by serial dilution to the method configuration concentration gradient standard substance in the aqueous solution, fluorometric titration experiment is carried out to water-dispersion hyperbranched conjugated polymer fluorescent nano particles, under record different concns, fluorescence intensity I; By water-dispersion hyperbranched conjugated polymer fluorescent nano particles to before and after nitro-aromatic effect in the change of the fluorescence intensity at emission maximum place, with the fluorescence intensity I of initial nanoparticle blank solution
0with the ratio (I adding the fluorescence intensity I after nitro-aromatic
0/ I) as the function of nitro-aromatic concentration, make working curve, to nitro-aromatic detection by quantitative; According to Stern-Volmer equation: I
0/ I=Ksv [Q]+1, calculate cancellation constant, in formula, Ksv is Stern-Volmer cancellation constant, is calculated by the slope of above-mentioned working curve, the concentration that [Q] is nitro-aromatic.
Described nitro-aromatic is preferably 2，4，6-trinitrotoluene (TNT), and 2,4-dinitrotoluene (DNT) (DNT), oil of mirbane (NB), 2,4,6-trinitrophenol (PA), is more preferably 2，4，6-trinitrotoluene (TNT).
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles aqueous dispersions of above-mentioned preparation, adds different analyte respectively, measures the fluorescence emission spectrum of water-dispersion hyperbranched conjugated polymer fluorescent nano particles to the selectivity of nitro-aromatic.
Embodiment 1
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles that preparation is conjugated structure unit with triphenylbenzene and fluorenes.Its synthetic route is as follows:
Wherein, monomer 1,3,5-tri-(4-(4,4,5,5 ,-tetramethyl--1,3,2-dioxaborolan) phenyl) benzene and the synthesis of 9,9-dihexyl-2,7-dibromo fluorenes reference literature method.
Step 1: under argon atmosphere, in the bottle with two necks of 250mL, is dissolved completely in CTAB5.82g (16mmol) in 90mL deoxygenation deionized water.Monomer 1,3,5-tri-(4-(4,4,5,5 ,-tetramethyl--1,3,2-dioxaborolan) phenyl) benzene 164mg (0.24mmol), 9,9-dihexyl-2,7-dibromo fluorenes 177mg (0.36mmol) and catalyst P d (PPh
3)
42mg is dissolved in the toluene of 6mL deoxygenation.The toluene solution syringe of monomer and catalyzer is transferred in the CTAB solution of stirring.Reactor is placed in the ultrasonic water bath of 50 DEG C, after sonic oscillation 20min, under whipped state, adds the K that 3mL concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 10min.Gained reaction miniemulsion is placed in the oil bath of 85 DEG C, stirring reaction 24h.Add end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol, after reaction 3 ~ 4h, add another end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with methylene dichloride.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in 200mL methyl alcohol, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, and this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor 156mg, yield: 82%.
Step 2: under argon atmosphere, in the 100mL there-necked flask that reflux condensing tube and dropping funnel are housed, dissolves the DMF of excessive sodium tert-butoxide (1.6g) with 60mL drying, is warming up to 85 DEG C.By hyperbranched conjugated polymer fluorescent nano particles precursor dispersion hydroxy-end capped for 100mg in the tetrahydrofuran (THF) of 60mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, excessive Isosorbide-5-Nitrae-ring butyl sultone (1.6mL) is dissolved in the DMF of 30mL drying, imports in dropping funnel with syringe, be slowly added drop-wise in reaction mixture, temperature of reaction 85 DEG C, continue stirring reaction 48h.After cooling, add 50mL deionized water, and stir 30min.Gained suspension is centrifugal, isolates solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles 105mg.
Carry out structural characterization to the water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1 by infrared spectra and ultimate analysis, its infrared spectra is at 1000 ~ 1300cm
-1there is obvious-SO
3-absorption peak, has the element sulphur that content is 0.94% in ultimate analysis, can confirm the validity of water-dispersion hyperbranched conjugated polymer fluorescent nano particles structure and preparation method.
Static contact angle test is carried out to the water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1: the contact angle of hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor is 87.1 ± 2.5 °, and end is 41.7 ± 2.6 ° with the contact angle of the water-dispersion hyperbranched conjugated polymer fluorescent nano particles of wetting ability sulfonate, wetting ability improves greatly, and wetting ability is good.
Photophysics sign (Fig. 1) is carried out to the water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1.Water-dispersion hyperbranched conjugated polymer fluorescent nano particles maximum absorption is 340nm, and fluorescent emission is 419nm.
Carry out transmission electron microscope imaging representation (Fig. 2) to the water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1, mean diameter is about 25nm (Fig. 3).
Embodiment 2
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles that preparation is conjugated structure unit with triphenylamine and fluorenes.Its synthetic route is as follows:
Wherein, monomer three (4-bromophenyl) amine and the synthesis of 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane)-9,9-dihexyl fluorenes reference literature method.
Step 1: under argon atmosphere, in the bottle with two necks of 250mL, is dissolved completely in CTAB8.76g (24mmol) in 90mL deoxygenation deionized water.Two (4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane)-9,9-dihexyl fluorenes 181mg (0.36mmol), the catalyst P d (PPh of monomer three (4-bromophenyl) amine 164mg (0.24mmol), 2,7-
3)
42mg is dissolved in the toluene of 6mL deoxygenation.The toluene solution syringe of monomer and catalyzer is transferred in the CTAB solution of stirring.Reactor is placed in the ultrasonic water bath of 50 DEG C, after sonic oscillation 20min, under whipped state, adds the K that 3mL concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 10min.Gained reaction miniemulsion is placed in the oil bath of 85 DEG C, stirring reaction 24h.Add end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol, after reaction 3 ~ 4h, add another end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with methylene dichloride.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in 200mL methyl alcohol, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, and this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor 160mg, yield: 90%.
Step 2: under argon atmosphere, in the 100mL there-necked flask that reflux condensing tube and dropping funnel are housed, dissolves the DMF of excessive sodium tert-butoxide (0.8g) with 10mL drying, is warming up to 85 DEG C.By hyperbranched conjugated polymer fluorescent nano particles precursor dispersion hydroxy-end capped for 50mg in the tetrahydrofuran (THF) of 10mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, be dissolved in the DMF of 10mL drying by excessive Isosorbide-5-Nitrae-ring butyl sultone (0.8mL), import in dropping funnel with syringe, be slowly added drop-wise in reaction mixture, temperature of reaction is 85 DEG C, continues stirring reaction 24h.After cooling, add 20mL deionized water, and stir 30min.Gained suspension is centrifugal, isolates solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles 51mg.
Embodiment 3
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles that preparation is conjugated structure unit with trimerization indoles and spiral shell fluorenes.Its synthetic route is as follows:
Wherein, monomer 2,7-bis-bromo-2 ', 3 ', 6 ', 7 '-four octyloxy spiral shell fluorenes and 2,7,12-tri-(4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane)-N, N ', N " and-three hexyl trimerization indoles reference literature method synthesis.
Step 1: under argon atmosphere, in the bottle with two necks of 100mL, is dissolved completely in CTAB2.9g (8mmol) in 45mL deoxygenation deionized water.Monomer 2,7-bis-bromo-2 ', 3 ', 6 ', 7 '-four octyloxy spiral shell fluorenes 148.1mg (0.15mmol), 2,7,12-tri-(4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane)-N, N ', N "-three hexyl trimerization indoles 97.6mg (0.10mmol), catalyst P d (PPh
3)
41mg is dissolved in the toluene of 2mL deoxygenation.The toluene solution syringe of monomer and catalyzer is transferred in the CTAB solution of stirring.Reactor is placed in the ultrasonic water bath of 40 DEG C, after sonic oscillation 20min, under whipped state, adds the K that 0.6mL concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 10min.Gained reaction miniemulsion is placed in the oil bath of 90 DEG C, stirring reaction 48h.Add end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol, after reaction 3 ~ 4h, add another end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with methylene dichloride.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in 200mL methyl alcohol, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, and this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor 152mg, yield: 83%.
Step 2: under argon atmosphere, in the 100mL there-necked flask that reflux condensing tube and dropping funnel are housed, dissolves the DMF of excessive sodium tert-butoxide (0.8g) with 30mL drying, is warming up to 85 DEG C.Hyperbranched conjugated polymer nanoparticle precursor hydroxy-end capped for 50mg is dispersed in the tetrahydrofuran (THF) of 30mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, be dissolved in the DMF of 20mL drying by excessive Isosorbide-5-Nitrae-ring butyl sultone (0.8mL), import in dropping funnel with syringe, be slowly added drop-wise in reaction mixture, temperature of reaction is 85 DEG C, continues stirring reaction 60h.After cooling, add 20mL deionized water, and stir 30min.Gained suspension is centrifugal, isolates solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles 50mg.
Embodiment 4
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles that preparation is conjugated structure unit with triphenylamine and diazosulfide.Its synthetic route is as follows:
Wherein, monomer three (4-(4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane) phenyl) amine and two hexyloxy benzo [1,2,5] the thiadiazoles reference literature method synthesis of 4,7-bis-bromo-5,6-.
Step 1: under argon atmosphere, in the bottle with two necks of 250mL, is dissolved completely in CTAB8.76g (24mmol) in 90mL deoxygenation deionized water.Monomer three (4-(4,4,5,5-tetramethyl--1,3,2-dioxy pentaborane) phenyl) amine 149mg (0.24mmol), 4,7-bis-bromo-5,6-two hexyloxy benzo [1,2,5] thiadiazoles 177mg (0.36mmol), catalyst P d (PPh
3)
43.5mg is dissolved in the toluene of 6mL deoxygenation.The toluene solution syringe of monomer and catalyzer is transferred in the CTAB solution of stirring.Reactor is placed in the ultrasonic water bath of 50 DEG C, after sonic oscillation 5min, under whipped state, adds the K that 3mL concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 5min.Gained reaction miniemulsion is placed in the oil bath of 80 DEG C, stirring reaction 48h.Add end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol, after reaction 3 ~ 4h, add another end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with methylene dichloride.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in 200mL methyl alcohol, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor 150mg, yield: 84%.
Step 2: under argon atmosphere, in the 100mL there-necked flask that reflux condensing tube and dropping funnel are housed, dissolves the DMF of excessive sodium tert-butoxide (0.8g) with 30mL drying, is warming up to 85 DEG C.By hyperbranched conjugated polymer fluorescent nano particles precursor dispersion hydroxy-end capped for 50mg in the tetrahydrofuran (THF) of 30mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, excessive Isosorbide-5-Nitrae-ring butyl sultone (0.8mL) is dissolved in the DMF of 10mL drying, imports in dropping funnel with syringe, be slowly added drop-wise in reaction mixture, continue stirring reaction 48h.After cooling, add 40mL deionized water, and stir 30min.Gained suspension is centrifugal, isolates solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles 47mg.
Embodiment 5
The water-dispersion hyperbranched conjugated polymer fluorescent nano particles (end is oxygen propyl sulfonic acid sodium) that preparation is conjugated structure unit with triphenylbenzene and fluorenes.Its synthetic route is as follows:
Step 1: under argon atmosphere, in the bottle with two necks of 250mL, is dissolved completely in CTAB5.82g (16mmol) in 90mL deoxygenation deionized water.Monomer 1,3,5-tri-(4-(4,4,5,5 ,-tetramethyl--1,3,2-dioxaborolan) phenyl) benzene 164mg (0.24mmol), 9,9-dihexyl-2,7-dibromo fluorenes 177mg (0.36mmol) and catalyst P d (PPh
3)
42mg is dissolved in the toluene of 6mL deoxygenation.The toluene solution syringe of monomer and catalyzer is transferred in the CTAB solution of stirring.Reactor is placed in the ultrasonic water bath of 50 DEG C, after sonic oscillation 20min, under whipped state, adds the K that 3mL concentration is 2M
2cO
3the aqueous solution, then continue ultrasonic 10min.Gained reaction miniemulsion is placed in the oil bath of 85 DEG C, stirring reaction 24h.Add end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol, after reaction 3 ~ 4h, add another end-capping reagent 4-bromophenol and continue reaction 3 ~ 4h.After cooling, reaction emulsion is poured in the saturated NaCl aqueous solution of 200mL, repeatedly extracts with methylene dichloride.Merge organic phase, and concentrate with Rotary Evaporators, remove most of solvent.A small amount of surplus solution is deposited in 200mL methyl alcohol, and centrifugation goes out solid.Solid is placed in methyl alcohol supersound washing 20min, then centrifugation goes out solid, this operation repeats once.The apparatus,Soxhlet's extracting of gained solid, with methyl alcohol, acetone is each extracting of solvent 1 day, removes the emulsifying agent and unreacted monomer and end-capping reagent that remain.Finally, vacuum-drying 12h at 70 DEG C, obtains hydroxy-end capped hyperbranched conjugated polymer fluorescent nano particles precursor 156mg, yield: 82%.
Step 2: under argon atmosphere, in the 100mL there-necked flask that reflux condensing tube and dropping funnel are housed, dissolves the DMF of excessive sodium tert-butoxide (0.8g) with 30mL drying, is warming up to 85 DEG C.By hyperbranched conjugated polymer fluorescent nano particles precursor dispersion hydroxy-end capped for 50mg in the tetrahydrofuran (THF) of 30mL drying, form the dispersion liquid of homogeneous transparent, import in dropping funnel with syringe, be slowly added drop-wise in sodium tert-butoxide solution, and maintain this temperature stirring reaction 2h.Then, excessive Isosorbide-5-Nitrae-ring propane sultone (0.6mL) is dissolved in the DMF of 20mL drying, imports in dropping funnel with syringe, be slowly added drop-wise in reaction mixture, continue stirring reaction 48h.After cooling, add 20mL deionized water, and stir 30min.Gained suspension is centrifugal, isolates solid.Gained solid adopts the method for supersound washing and centrifugation, is placed in methyl alcohol successively, centrifugation after supersound washing 20min in acetone and tetrahydrofuran (THF).Finally, vacuum-drying 12h at 70 DEG C, obtains water-dispersion hyperbranched conjugated polymer fluorescent nano particles 47mg.
Apply in water-dispersion hyperbranched conjugated polymer fluorescent nano particles high-sensitivity detection water of the present invention and detect nitro-aromatic.
Embodiment 6
Water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1 is configured to the aqueous dispersions of 5mg/L, and configures the TNT methanol solution of 0.1M, by the method for serial dilution, being configured to concentration is 1 × 10
-2m ~ 1 × 10
-5the TNT aqueous solution of M, then the amount of materialsing joins in the aqueous dispersions of the nanoparticle of 5mg/L, makes TNT concentration 1 × 10
-8m ~ 1 × 10
-5change in the scope of M, carry out fluorometric titration test.Excitation wavelength is 340nm, measures its fluorescence spectrum at 360 ~ 600nm and changes (Fig. 4).With do not add TNT nanoparticle blank solution fluorescence spectrum compared with, adding of TNT makes the fluorescence of nanoparticle there occurs cancellation, and the increase of fluorescence intensity TNT concentration and reducing gradually, shows that TNT has good fluorescent quenching performance to it.
Nanoparticle is adding the change ratio (I of fluorescence intensity at emission maximum 419nm place before and after TNT
0/ I) as the function of nitro-aromatic concentration, make working curve (Fig. 5).Be 1 × 10 in TNT concentration
-8m ~ 1 × 10
-5in the scope of M, there is good linear relationship, detect and be limited to 3.0 × 10
-9m, shows the TNT of water-dispersion hyperbranched conjugated polymer fluorescent nano particles of the present invention detection by quantitative low levels in aqueous phase.
According to Stern-Volmer Equation for Calculating cancellation constant (Fig. 6).Stern-Volmer equation is as follows: I
0/ I=Ksv [Q]+1, in formula, the concentration that [Q] is TNT, Ksv is Stern-Volmer cancellation constant, according to the above-mentioned working curve slope of calculating, can obtain cancellation constant Ksv=1.21 × 10
6m
-1, this value two orders of magnitude higher than the cancellation constant of TNT in the conjugated polymers nanoparticle detection aqueous phase of bibliographical information.Its result shows: water-dispersion hyperbranched conjugated polymer fluorescent nano particles of the present invention can utilize its hydrophobic interior cavity structure, by hydrophobic interaction enrichment TNT molecule, and high-sensitivity detection TNT in aqueous phase.
Embodiment 7
Water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by embodiment 1 is configured to the aqueous dispersions of 5mg/L, then in solution, adds TNT respectively, 2,4-dinitrotoluene (DNT) (DNT), 2，4，6-trinitrophenol (PA), oil of mirbane (NB), Nitromethane 99Min. (NM), toluene (Tol), chlorobenzene (CB), phenol (PhOH), its concentration is 1 × 10
-5m, is determined under various different analyte molecule exists situation, the fluorescence emission spectrum of water-dispersion hyperbranched conjugated polymer fluorescent nano particles.Only have the nitro-aromatic cancellation fluorescence of nanoparticle, and the fluorescence of nitroparaffins or non-nitro-aromatic not cancellation nanoparticle.By the ratio I to fluorescence intensity
0the monitoring of/I, the fluorescence of nanoparticle by nearly 13 times of TNT cancellation, by DNT cancellation 9 times, by NB cancellation 1.9 times, and only by PA cancellation 1.7 times.This shows that water-dispersion hyperbranched conjugated polymer fluorescent nano particles of the present invention has highly selective to nitro-aromatic in aqueous phase, especially reaches highly selective Detection results to TNT.
Result of study shows, water-dispersion hyperbranched conjugated polymer fluorescent nano particles prepared by the present invention can have High sensitivity and optionally detect to the nitro-aromatic in aqueous phase.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. the preparation method of a water-dispersion hyperbranched conjugated polymer fluorescent nano particles, it is characterized in that, the method comprises the following steps: adopt A3 and B2 monomer, under the condition of alkali and palladium catalyst catalysis, Suzuki polycondensation is carried out in oil/water type miniemulsion, and carry out end capping with the end-capping reagent of hydroxyl, prepare and dispersible hyperbranched conjugated polymer fluorescent nano particles precursor hydroxy-end capped in organic phase, by William's nurse inferior ether building-up reactions, hydrophilic alkoxyl group sulfonate is introduced the end of hyperbranched conjugated polymer fluorescent nano particles precursor again, the water-dispersion hyperbranched conjugated polymer fluorescent nano particles of obtained inner hydrophobic cavity structure and hydrophilic end,
Described A3 and B2 monomer, is respectively and has Ar
1and Ar
2three boric acid ester monomers of structural unit and two bromine monomer, or be respectively there is Ar
1and Ar
2the tribromo monomer of structural unit and two boric acid ester monomer, its structure is as follows:
Described Ar
1for having phenyl ring derivative, triphenylamine derivative, triazole derivative, triphenyl-boron derivative, three also indene derivative, three also fluorenone derivatives or the three also carbazole derivative of the core conjugation branched structure unit of trifunctional;
Described Ar
2for having the benzene and its derivative of bifunctional conjugated structure unit, fluorenes and derivative, carbazole and derivative thereof, thiophene and derivatives, diazosulfide and derivative, dibenzothiophen and derivative thereof, sulphur sulfone and derivative, silicon fluorenes and derivative thereof, spiral shell fluorenes and derivative, triphenylamine and derivative thereof or tetraphenylethylene and derivative thereof.
2. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, it is characterized in that, described concrete steps of carrying out Suzuki polycondensation in oil/water type miniemulsion are: carry out under anaerobic, and water consumption is 45 ~ 135mL; Oil phase is toluene, and consumption is 2 ~ 10mL; Oil/water ratio is 1:15 ~ 45; Emulsifying agent is cetyl trimethylammonium bromide (CTAB), and consumption is 8 ~ 24mmol; Catalyzer is that four triphenylphosphines close palladium (Pd (PPh
3)
4), consumption is 0.1 ~ 0.8% of brominated monomer's mole dosage; Wet chemical concentration is 2mol/L, and consumption is 4 ~ 10 times of bromo functional groups mole dosage in monomer; Temperature of reaction is 80 ~ 90 DEG C, and the reaction times is 24 ~ 48h.
3. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, it is characterized in that, the end-capping reagent of described hydroxyl is boric acid end-capping reagent 4-(4,4,5,5-4 methyl-[1,3,2] dioxaborolan-2-base) phenol and bromo end-capping reagent 4-bromophenol.
4. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, it is characterized in that, described hyperbranched conjugated polymer fluorescent nano particles precursor is a kind of complete emulsifier-free, and can be dispersed in tetrahydrofuran (THF), methylene dichloride, chloroform or toluene, diameter is the particle of 15 ~ 40 nanometers.
5. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, is characterized in that, described Ar
1structure is specific as follows:
Wherein, R
0the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
6. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, it is characterized in that, the concrete steps of the inferior ether building-up reactions of described William's nurse are: carry out under anhydrous and oxygen-free, base catalysis condition, the terminal hydroxyl and 1 of described hyperbranched conjugated polymer fluorescent nano particles precursor, 3-ring propane sultone or Isosorbide-5-Nitrae-ring butyl sultone reaction, temperature of reaction is 85 DEG C, reaction times 24 ~ 60h, described alkali is sodium tert-butoxide or NaH.
7. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, it is characterized in that, described water-dispersion hyperbranched conjugated polymer fluorescent nano particles a kind ofly can be dispersed in water or DMF, and diameter is the particle of 15 ~ 40 nanometers.
8. the preparation method of water-dispersion hyperbranched conjugated polymer fluorescent nano particles according to claim 1, is characterized in that, described Ar
2structure is specific as follows:
Wherein, R
1~ R
18the alkyl or the alkoxyl group that are selected from H or C1 ~ C30.
9. the water-dispersion hyperbranched conjugated polymer fluorescent nano particles that described in application rights requirement 1 prepared by preparation method detects the method for nitro-aromatic in water, and it is characterized in that, concrete steps are as follows:
Water-dispersion hyperbranched conjugated polymer fluorescent nano particles is configured to aqueous dispersions according to mass volume ratio, with luminoscope record fluorescent emission intensity I
0; The enriched sample storing solution of configuration nitro-aromatic in methyl alcohol or DMF, by serial dilution to the method configuration concentration gradient standard substance in the aqueous solution, fluorometric titration experiment is carried out to water-dispersion hyperbranched conjugated polymer fluorescent nano particles, under record different concns, fluorescence intensity I; By water-dispersion hyperbranched conjugated polymer fluorescent nano particles to before and after nitro-aromatic effect in the change of the fluorescence intensity at emission maximum place, with the fluorescence intensity I of initial nanoparticle blank solution
0with the ratio (I adding the fluorescence intensity I after nitro-aromatic
0/ I) as the function of nitro-aromatic concentration, make working curve, to nitro-aromatic detection by quantitative; According to Stern-Volmer equation: I
0/ I=Ksv [Q]+1, calculate cancellation constant, in formula, Ksv is Stern-Volmer cancellation constant, is calculated by the slope of above-mentioned working curve, the concentration that [Q] is nitro-aromatic.
10. a water-dispersion hyperbranched conjugated polymer fluorescent nano particles, is characterized in that, is obtained by the preparation method of the water-dispersion hyperbranched conjugated polymer fluorescent nano particles described in claim 1-8 any one.
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| CN105949444A (en) * | 2016-05-16 | 2016-09-21 | 江西农业大学 | Preparation method of Fe<3+> fluorescent film sensor device based on dispersible hyperbranched conjugated polymer nano-particles |
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