CN106397743B - A kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection - Google Patents
A kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection Download PDFInfo
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Abstract
The invention discloses a kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection, the structural formula of the polymer is as shown in Equation 1：Specific water soluble fluorescent conjugated polymer of the invention has good application as sensor in nitro-aromatic detection.The water soluble fluorescent conjugated polymer includes water soluble group, which includes two parts：A part is with carbazoles conjugated main chain existing for the pi-conjugated systems of π, ensures the optical property of polymer；Another part contains the water soluble group of polyhydroxy, so as to meet solubility of the polymer in water phase.Polymer chain can be dispersed substantially in aqueous environment, be conducive to analyte directly and polymer contact, realize the signal enlarge-effect of polymer.
Description
Technical field
Present invention relates particularly to a kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection.
Background technology
Soluble conjugated polymer received much attention in recent years as a kind of novel high polymer material.It can due to having
The characteristic being evenly dispersed in water phase makes soluble conjugated polymer in every field by extensive use.However at present
Report of the soluble conjugated polymer for nitro-aromatic in water to detect is seldom.
Nitro-aromatic compound (trinitrotoluene TNT, dinitrotoluene (DNT) DNT) is the important component of explosive, nitro
Aromatic hydrocarbons also has important harm to human body health.Therefore, the onthe technology of site test pair to microscratch amount nitro-aromatic is explored
The security of the lives and property of people and environmental protection have very important significance.It is quick-fried to gas phase nitro-aromatic in reality
The research of fried object is relatively more, fewer to the research in water phase.Explosive used in military base prepare, transport, deposit and
Very big pollution is caused to soil and water body, while as some industrial discharge sewage are to liquid such as seawater or underground water during use
Phase environment also results in some pollutions, when environmental pollution caused by explosive than it is more serious when, not only induce the danger of explosion at any time
Danger, and threaten to the existence of the mankind and animals and plants.Therefore research detects the detection method of microscratch amount nitro-aromatic in water
It is particularly urgent.
Fluorescence conjugated polymer can generate fluorescence signal enlarge-effect due to its unique molecular wire effect, into
To detect the very promising sensing material of nitro-aromatic.The fluorescence for nitro-aromatic explosive detection reported at present is total to
Conjugated polymer is mostly hydrophobic macromolecule, is generally used for the detection of gas phase nitro-aromatic, the detection for nitro-aromatic in water
It is difficult to meet.
Therefore, detection of the water-soluble fluorescent conjugated polymer for microscratch amount nitro-aromatic in water phase is developed, it is right
In environmental protection, reduce nitro-aromatic and have very important significance to the harm of the mankind.
Invention content
For the more than prior art, the object of the present invention is to provide a kind of water soluble fluorescent conjugated polymer in nitro-aromatic
Application in detection.
The present invention uses following technical scheme：
The present invention provides a kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection, its main feature is that：
The structural formula of the water soluble fluorescent conjugated polymer is as shown in Equation 1：
Wherein, n is the degree of polymerization of conjugated polymer, and the n is 20~30, preferably 25.
The present invention provides a kind of above-mentioned water soluble fluorescent conjugated polymer in the sensor for preparing detection nitro-aromatic
Application.The nitro-aromatic is dissolved in water phase.When detecting the nitro-aromatic in water phase as sensor, by water solubility altogether
Conjugated polymer adds in the water phase and carries out fluoroscopic examination.
Preferably, the nitro-aromatic includes nitrobenzene (NB), dinitrotoluene (DNT) (DNT), trinitrotoluene (TNT), hardship
Sour (PA) or other nitro-aromatics.
The preparation method of the above-mentioned water soluble fluorescent conjugated polymer of the present invention, includes the following steps：
(1) synthesis of monomer N
The structural formula of monomer M and diethanol amine reaction generation monomer N, the monomer M and monomer N are respectively such as 2 and 3 institute of formula
Show；
Wherein, X Cl, Br or I；
(2) synthesis of conjugated polymer P
Using triethanolamine, palladium and triphenylphosphine as additive, monomer N and to styrene occur polymerisation be total to
Conjugated polymer P, structural formula are as shown in Equation 1.
In step (1), the preparation method of monomer M can be obtained according to method of the prior art.For product yield,
Preferably, the preparation method of the monomer M includes the following steps：
Using potassium hydroxide, tetrabutylammonium bromide as additive, 3,6- dihalo carbazoles and monohaloalkyl acetic acid ethyl reaction will
Product after reaction hydrolyzes generation monomer M under alkaline condition, and the structural formula of the monomer M is as shown in Equation 2.
Preferably, the reaction carries out in solvent DMF.
Preferably, 3, the 6- dihalos carbazole is 3,6- dibromo carbazoles, 3,6- dichloro carbazoles or 3,6- diiodocarbazol.
Preferably, the monohaloalkyl ethyl acetate is bromoacetate, ethyl chloroacetate or ethyl iodoacetate.
Preferably, the molar ratio of 3, the 6- dihalos carbazole and monohaloalkyl ethyl acetate is 1~2：2.
It is further preferred that the molar ratio of 3, the 6- dihalos carbazole, potassium hydroxide and tetrabutylammonium bromide is (4
~6)：(15~20)：(0.1~0.2).
Preferably, the reaction temperature of 3,6- dihalos carbazole and monohaloalkyl ethyl acetate is 80~90 DEG C, further preferably
It is 85 DEG C；Preferably, the reaction time is 19~21h, is further preferably 20h.
Preferably, hydrolysis generation monomer M, hydrolysis temperature are 80~90 DEG C under alkaline condition, are further preferably 85
℃；Preferably, hydrolysis time is 4~6h, is further preferably 5h.
It is further preferred that the preparation method of the monomer M includes step in detail below：
3,6- dihalos carbazole, potassium hydroxide, tetrabutylammonium bromide are dissolved in DMF respectively, after stirring, add in monohaloalkyl
Ethyl acetate after entire mixed solution heats at 80~90 DEG C and stirs 19~21h, is cooled to room temperature, and mixing is obtained by filtration
Filtrate；Sodium hydroxide is made into sodium hydrate aqueous solution, adds in filtrate, at 80~90 DEG C after 4~6h of heating stirring, will react
Solution pours into distilled water and filtrate is obtained by filtration；Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.
Solid product, as monomer M are obtained, yield is about 90% or so.
In the monomer M and diethanol amine reaction generation monomer N, it is preferred that the molar ratio of monomer M and diethanol amine
It is 1~2：2, it is further preferably 1：2；Preferably, the reaction temperature is 40~60 DEG C, and the time is 5~7h；It is further excellent
Choosing, the reaction temperature is 45 DEG C, time 6h.
The reaction carries out in solvent DMF, after reaction, extracts form with liquid separation, DMF is washed with water, and use second
Solution is obtained by extraction in acetoacetic ester, is finally purified with column tswett's chromatography methods, and monomer N is obtained after dry.Wherein, the column tswett's chromatography methods are adopted
Silicagel column, eluent are ethyl acetate and the mixed liquor of petroleum ether；Ethyl acetate：The volume of petroleum ether is preferably 10：1.
In step (2), it is preferred that the monomer N and be (1~2) to the molar ratio of styrene：(1~2), further
Preferably 1：1.
Preferably, the additive amount ratio of the monomer N, triethanolamine, palladium and triphenylphosphine is 1mmol：(0.3~
0.4)mL：(0.03~0.05) mmol:(0.1~0.3) mmol；It is further preferred that the monomer N, triethanolamine, palladium
Additive amount ratio with triphenylphosphine is 1mmol：0.35mL：0.04mmol:0.2mmol.
Preferably, the reaction temperature is 90~100 DEG C, and the reaction time is 5~7h；It is further preferred that the reaction
Temperature is 100 DEG C, reaction time 6h.
The polymerisation carries out in solvent DMF.
Preferably, the reaction is reacted under conditions of inert gas, it is further preferred that the inert gas is
Nitrogen.
After polymerisation, reaction solution is added in methanol solution, obtains the crude product containing conjugated polymer P.
Then DMF is respectively adopted and methanol is purified and (preferably purified twice, once refer to be purified using DMF and methanol), most
(extraction time preferably 23~25h) is extracted with dichloromethane afterwards, extra monomer is removed, obtains conjugated polymer P.
A technical solution in above-mentioned technical proposal has the advantages that：
(1) the specific water soluble fluorescent conjugated polymer of the present invention has well as sensor in nitro-aromatic detection
Application.The water soluble fluorescent conjugated polymer includes water soluble group, which includes two parts：One
It is with π-carbazoles conjugated main chain existing for pi-conjugated system to divide, and ensures the optical property of polymer；Another part contains polyhydroxy
The water soluble group of base, so as to meet solubility of the polymer in water phase.Polymer chain can be dispersed substantially in water phase
In environment, be conducive to analyte directly and polymer contact, realize the signal enlarge-effect of polymer.
(2) synthesis of the water soluble fluorescent conjugated polymer in application process of the invention, overcomes and is relied on polymer
The inorganic carrier of grafting water improves the hydrophilic defect of polymer sensor, which can be completely dissolved
In aqueous solution, excellent dissolubility can not only prevent from gathering phenomenon, while also substantially increase poly- between polymer chain
The fluorescence intensity of object is closed, at the same time, also avoids the self-quenching of polymer.The richness product effect of hydroxyl group on polymer chain,
Also improve the sensitivity that polymer detects nitro-aromatic in aqueous solution.
(3) present invention direct modified polymer in itself by way of, designed and synthesized out containing water soluble group
Water soluble fluorescent conjugated polymer, as the fluorescence detector of nitro-aromatic in water phase, be capable of substantially uniformity is dispersed in water phase
In, the fluorescence intensity of polymer is improved, the shortcomings that organic fluorescence polymer is not soluble in water is overcome, thoroughly realizes polymer
Sensor is in water to the signal enlarge-effect of " point contact, multiple spot respond " of nitro-aromatic.Simultaneously because polymer molecule
On the hydroxyl group that contains, not only increase the water solubility of polymer, while improve the sensitivity detected to nitro-aromatic.It pushes away
The development of water-soluble polymer sensor has been moved, the side such as underwater latent explosive and aqueous environment quality-monitoring is detected to hypersensitive
The application in face, has a very important role.
(4) preparation method of the water soluble fluorescent conjugated polymer in application process of the invention is simple, cost is relatively low, right
There is certain practical significance in the synthesis of water soluble fluorescence sensor, be suitble to large-scale promotion application.
Description of the drawings
Fig. 1：The preparation process of water soluble fluorescent conjugated polymer P in embodiment 1.
Fig. 2：Polymer P is in water to the fluorescence intensity change of the TNT of various concentration and DNT and quenching efficiency (ηEP)。
Fig. 3：Efficiency (a and c) and Stern-Volmer numerical value (b and d) are quenched to TNT and DNT concentration function change curves.
Fig. 4：Polymer is to fluorescent quenching research (TNT, DNT, picric acid PA, 1,4-benzoquinone BQ, the nitrobenzene of different analytes
NB, chlorobenzene chlorobenzene, benzene sulfonic acid benzenesulfonic acid, phenol phenol, toluene toluene, NaCl,
KOH and HCl).
Fig. 5：The nuclear magnetic spectrogram of monomer M.
Fig. 6：The nuclear magnetic spectrogram of monomer N.
Fig. 7：The nuclear magnetic spectrogram of water soluble fluorescent conjugated polymer P.
Specific embodiment
If reagent and instrument that the present invention uses can be obtained without specified otherwise by commercial sources.
A kind of preparation method of 1 water soluble fluorescent conjugated polymer of embodiment
Water soluble fluorescent conjugated polymer P preparation process is as shown in Figure 1：
(1) synthesis of monomer M
By 3,6- dibromos carbazole (1.63g, 5mmol), potassium hydroxide (1g, 17.8mmol), tetrabutylammonium bromide (0.05g,
It 0.155mmol) is dissolved in the DMF of 40mL respectively, after stirring 20min, adds in ethyl chloroacetate (1.23g, 10mmol), it is entire mixed
After conjunction solution heats at 85 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.By sodium hydroxide (0.8g,
5mL aqueous solutions 20mmol) are made into, adds in filtrate, at 85 DEG C after heating stirring 5h, reaction solution is poured into 400mL distilled water
And filtrate is obtained by filtration.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.Solid product M is obtained,
Yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H),7.519-7.582(q,4H),11.0
(s, 1H), as shown in Figure 5.
(2) synthesis of monomer N
After 2.8mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 6h is stirred at 45 DEG C.Reaction terminates
Afterwards, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column chromatogram chromatography method
(silica gel, ethyl acetate：Petroleum ether=10:1) purification obtains product, and be dried in vacuo at 60 DEG C, obtains white solid, as
Monomer N, yield 42.8%；1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q,
4H), 4.810 (s, 2H), 3.538 (t, 4H), 2.840 (t, 4H), as shown in Figure 6.
(3) synthesis of conjugated polymer P
By monomer N (0.47g, 1mmol), to styrene (0.13g, 1mmol), triethanolamine (0.35mL), palladium
(9.0mg, 0.04mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen, 100
At DEG C after heating stirring 6h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.Respectively with 5mL DMF and
250mL methanol purifies twice back and forth, finally with dichloromethane Soxhlet extraction for 24 hours, removes extra monomer, obtains orange solids,
That is conjugated polymer P, yield 85%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620-6.476(t,12H),
4.981 (s, 2H), 3.777 (s, 4H), 3.348 (s, 4H), as shown in Figure 7.FT-IR(KBr)：3383,3100,2950,
1700cm-1。
The measure of polymer P molecular weight：Since the magnitude relationship of polymer molecular weight is to molecular wire effect, and to fluorescence
The intensity at peak has an impact, and it is therefore necessary to survey the molecular weight of polymer.Due to containing a large amount of hydroxyl on polymer, it is impossible to use
Laser light scattering instrument measures the molecular weight of polymer P in tetrahydrofuran.The present invention is using to bromine cumene terminated polymer, so
Afterwards by, to the number ratio of the hydrogen of bromine cumene and polymer P, the molecular weight for estimating polymer P is about 1.1 on nuclear-magnetism ×
104, structural formula as indicated with 1, n 25.
A kind of preparation method of 2 water soluble fluorescent conjugated polymer of embodiment, includes the following steps：
(1) synthesis of monomer M
By 3,6- dichloros carbazole (1.1805g, 5mmol), potassium hydroxide (1g, 17.8mmol), tetrabutylammonium bromide
(0.05g, 0.155mmol) is dissolved in the DMF of 40mL respectively, after stirring 20min, addition bromoacetate (1.23g,
7.365mmol), after entire mixed solution heats at 85 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.It will
Sodium hydroxide (0.8g, 20mmol) is made into 5mL aqueous solutions, adds in filtrate, at 87 DEG C after heating stirring 5.5h, by reaction solution
It pours into 400mL distilled water and filtrate is obtained by filtration.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.
Obtain solid product-monomer M, yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H),
7.519-7.582(q,4H),11.0(s,1H)。
(2) synthesis of monomer N
After 2.8mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 6.5h is stirred at 42 DEG C.Reaction knot
Shu Hou, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column tswett's chromatography methods
(silica gel, ethyl acetate：Petroleum ether=10:1) purification obtains product, and be dried in vacuo at 60 DEG C, and obtained white solid is
Monomer N, yield 56.4%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q,4H),
4.810 (s, 2H), 3.538 (t, 4H), 2.840 (t, 4H).
(3) synthesis of conjugated polymer P
By monomer N (0.47g, 1mmol), to styrene (0.13g, 1mmol), triethanolamine (0.35mL), palladium
(9.0mg, 0.04mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen, 100
At DEG C after heating stirring 6.5h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.Respectively with 5mL DMF and
250mL methanol purifies twice back and forth, finally with dichloromethane Soxhlet extraction 24.5h, removes extra monomer, what is obtained is orange solid
Body, that is, conjugated polymer P, structural formula as indicated with 1, n 25.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620-
6.476(t,12H),4.981(s,2H),3.777(s,4H),3.348(s,4H).FT-IR(KBr)：3383,3100,2950,
1700cm-1。
A kind of preparation method of 3 water soluble fluorescent conjugated polymer of embodiment, includes the following steps：
(1) synthesis of monomer M
By 3,6- dibromos carbazole (1.793g, 5.5mmol), potassium hydroxide (1.124g, 20mmol), tetrabutylammonium bromide
(0.064g, 0.2mmol) is dissolved in the DMF of 40mL respectively, after stirring 20min, adds in ethyl chloroacetate (1.23g, 10mmol),
After entire mixed solution heats at 83 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.By sodium hydroxide
(0.8g, 20mmol) is made into 5mL aqueous solutions, adds in filtrate, at 85 DEG C after heating stirring 5h, reaction solution is poured into 400mL
Simultaneously filtrate is obtained by filtration in distilled water.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.What is obtained consolidates
Body product be monomer M, yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H),7.519-
7.582(q,4H),11.0(s,1H)。
(2) synthesis of monomer N
After 3mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 5h is stirred at 50 DEG C.Reaction terminates
Afterwards, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column tswett's chromatography methods (silicon
Glue, ethyl acetate：Petroleum ether=10:1) purification obtains product, and be dried in vacuo at 60 DEG C, and product is white solid-monomer
N,1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q,4H),4.810(s,2H),
3.538 (t, 4H), 2.840 (t, 4H).
(3) synthesis of conjugated polymer P
By monomer N (0.564g, 1.2mmol), to styrene (0.13g, 1mmol), triethanolamine (0.40mL), palladium
(10.125mg, 0.045mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen,
At 100 DEG C after heating stirring 6h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.5mL DMF are used respectively
It is purified back and forth twice with 250mL methanol, finally with dichloromethane Soxhlet extraction 25h, removes extra monomer, obtain product as orange
Color solid-conjugated polymer P, structural formula as indicated with 1, n 25.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620-
6.476(t,12H),4.981(s,2H),3.777(s,4H),3.348(s,4H).FT-IR(KBr)：3383,3100,2950,
1700cm-1。
In order to better illustrate the effect of water-soluble polymer of the present invention, the water-soluble polymer sensitivities in embodiment 1
The application study of energy is as follows.
Detection of 4 polymer of embodiment to DNT in water and TNT
Polymer P in embodiment 1 can preferably be illustrated to TNT and DNT quenching effects by the variation of fluorescence spectrum
Size.This experiment has measured 1.0 × 10 by F-4600 sepectrophotofluorometers-5The polymer of g/L in water phase to TNT and
The fluorescence spectrum (such as Fig. 2) of DNT.As can be seen from Figure 2A, when a concentration of the 1.08 × 10 of TNT-4During mol/L, quenching efficiency reaches
To 84.5%；As TNT a concentration of 1.8 × 10-4During mol/L, the fluorescent quenching efficiency (1-I/I of polymer0) be when reaching balance
93%, from Fig. 2 B it is found that when a concentration of the 1.44 × 10 of DNT-4During mol/L, quenching efficiency reaches 80.5%；When the concentration of DNT
It is 2.3 × 10-4During mol/L, it is 91% that the fluorescent quenching efficiency of polymer, which reaches balance,.Apparent polymer is to TNT and DNT exhibitions
Good quenching performance is showed.As can be seen that the polymer P in embodiment 1 has preferable solubility in water phase, it can be complete
It is evenly distributed in water phase entirely, so as to have higher quenching effect to two kinds of nitro-aromatics.
The measure of the detection limit of embodiment 5
Since explosive causes the fields such as ocean, underground water huge environmental pollution, biotic environment and people are directly endangered
Class health.TNT is again mainly one of most common explosive, and the byproduct (DNT) of simultaneously synthesizing TNT is often existed simultaneously with TNT,
Therefore TNT and DNT is selected to be detected as the representative of NACs to its fluorescence sensitivity here.
Solubility under TNT and DNT room temperature in water is 130mg/L (i.e. 5.7 × 10-4) and 300mg/L (i.e. 1.6 mol/L
×10-3mol/L).A concentration of 5mg/L that national regulation industrial wastewater allows the maximum emission of NACs, and allow surface water most
Height contains a concentration of 0.5mg/L of nitro-aromatic.Detection limit (LOD) is key index whether measurement sensor is sensitive.Therefore it needs
It calculates polymer to limit the detection of two kinds of nitro-aromatics, so as to obtain polymer in aqueous solution to TNT and DNT high sensitivities
Low physical quantity.
That Fig. 3 a and 3c are represented respectively is fluorescent quenching rate (η EP=1-I/ of the polymer with the TNT and DNT of various concentration
I0) curve.As can be seen that with the increase of TNT and DNT concentration in water phase, it is quenched always, quenching rate η EP numerical value is increasing.
These results have reacted concentration dependent of the fluorescent quenching to TNT or DNT well.
Quenching process can be represented (1) by Stern-Volmer equations
I0/ I=1+Ksv [Q] (1)
I0Represent maximum fluorescence intensity, I represent when gas DNT either the fluorescence intensity Q in the presence of TNT represent DNT or
The concentration of TNT.Slope represent Stern-Volmer constant (Ksv) of the film to two kinds of gas, the Stern to DNT and TNT-
Volmer constants are respectively 42000M-1And 24000M-1。
Polymer passes through equation C to the detection limit (LOD) of DNT in aqueous solution and TNTL=3S/Ksv is obtained, CLRepresent be
The numerical value of detection limit (LOD), what S was represented is the standard deviation of polymer fluorescent intensity in 15 water blanks measured.It is poly-
It is 7.4 × 10 respectively to the detection limit of TNT and DNT to close object–7Mol/L and 1.1 × 10–6mol/L.It can obtain, in embodiment 1
Water-soluble polymer it is higher to the detection sensitivity of nitro-aromatic in water.
6 water-soluble polymer of embodiment is to the selectivity of different determinands
According to the quenching mechanism of fluorescent conjugated polymer, between the substance of electron deficient and the polymer of supplied for electronic, due to hair
Raw electronics transfer, may result in the fluorescent quenching of conjugated polymer.Fig. 4 show common chemical substance (such as TNT, DNT,
Picric acid PA, 1,4-benzoquinone BQ, nitrobenzene NB, chlorobenzene, benzene sulfonic acid, phenol, toluene) to the fluorescent quenching of water-soluble polymer, it removes
Except this, many inorganic chaff interferents (NaCl, KOH and HCl) are also put into wherein.Fig. 4 shows, TNT, DNT, nitrobenzene and bitter taste
Acid has polymer apparent quenching effect, and quenching rate is 95%, 91%, 86% and 69% respectively.1,4-benzoquinone and benzene sulfonic acid pair
Polymer has small quenching effect, however, other organic matters (chlorobenzene, phenol, toluene) and inorganic chaff interferent (such as HCl,
NaCl and KOH etc.) to polymer almost without response.
Polymer is mainly derived from the response difference of nitro-aromatic and chaff interferent the electron-withdrawing ability of determinand and with gathering
Close the electron orbit matching degree of object.There is higher electronics rail between carbazole polymer and TNT, DNT, nitrobenzene and picric acid
Road matches, while TNT, there are three nitryl group, electron-withdrawing ability is eager to excel than DNT, therefore caused quenching efficiency (95%) is more than
DNT (91%), as nitrobenzene NB, only there are one electron withdrawing group, therefore caused quenching efficiency (86%) is lower than DNT.
For picric acid PA, although there are three nitryl group, the electron repulsion effect of hydroxyl weakens the suction of PA on molecular structure
Electronic capability causes quenching rate (69%) slightly lower.For benzoquinones BQ, although electron-withdrawing ability is strong, fluorescent quenching rate is low.It is former
Because being that quinones has poor binding constant (K with polymerb), it is low so as to cause quenching rate.In contrast, benzene and its derivative
(chlorobenzene, benzene sulfonic acid, phenol, toluene) quenching rate is low may be weak related with their electron-withdrawing ability.For inorganic matter (NaCl,
KOH, HCl) interference, fluorescence intensity do not have any variation.Inorganic matter does not have matched electron orbit to receive electricity
Son causes polymer to quench.These results indicate that the polymer P in embodiment 1 has higher quenching effect to nitro-aromatic
And selectivity.
Conclusion：
Pass through above example, it can be deduced that：The present invention has the fluorescent conjugated polymer of water soluble group, as water phase
The fluorescence detector of middle nitro-aromatic can be uniformly dispersed in water phase, and it is not soluble in water to overcome organic fluorescence polymer
Shortcoming thoroughly realizes polymer sensor and amplifies effect to the signal of " point contact, multiple spot respond " of nitro-aromatic in water
It should.Simultaneously because the hydroxyl group contained on polymer molecule can generate hydrogen bond between nitro-aromatic, have to nitro-aromatic
Enrichment so as to reduce the detection limit to nitro-aromatic, improves the sensitivity detected to nitro-aromatic.The present invention pushes
The development of water-soluble polymer sensor detects underwater latent explosive and aqueous environment quality-monitoring etc. to hypersensitive
Application, have a very important role.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (16)
1. a kind of application of water soluble fluorescent conjugated polymer in nitro-aromatic detection, it is characterized in that, the water soluble fluorescence
The structural formula of conjugated polymer is as shown in Equation 1：
Wherein, n is 20~30.
2. application as described in claim 1, it is characterized in that：The water soluble fluorescent conjugated polymer is preparing detection nitro virtue
Application in the sensor of hydrocarbon.
3. application as described in claim 1, it is characterized in that：The nitro-aromatic includes nitrobenzene (NB), dinitrotoluene (DNT)
(DNT), trinitrotoluene (TNT), picric acid (PA) or other nitro-aromatics.
4. application as described in claim 1, it is characterized in that, the preparation method of water soluble fluorescent conjugated polymer includes following step
Suddenly：
(1) synthesis of monomer N
The structural formula of monomer M and diethanol amine reaction generation monomer N, the monomer M and monomer N are respectively as shown in formula 2 and formula 3；
Wherein, X Cl, Br or I；
(2) synthesis of conjugated polymer P
Using triethanolamine, palladium and triphenylphosphine as additive, monomer N and polymerisation occurs to styrene to obtain conjugation poly-
Close object P.
5. application as claimed in claim 4, it is characterized in that：In step (1), the preparation method of the monomer M includes following step
Suddenly：Using potassium hydroxide, tetrabutylammonium bromide as additive, 3,6- dihalo carbazoles and monohaloalkyl acetic acid ethyl reaction will react
Product afterwards hydrolyzes generation monomer M under alkaline condition.
6. application as claimed in claim 5, it is characterized in that：3, the 6- dihalos carbazole be 3,6- dibromo carbazoles, 3,6- bis-
Chlorine carbazole or 3,6- diiodocarbazols；The monohaloalkyl ethyl acetate is bromoacetate, ethyl chloroacetate or ethyl iodoacetate.
7. application as claimed in claim 6, it is characterized in that：Mole of the 3,6- dihalos carbazole and monohaloalkyl ethyl acetate
Ratio is 1~2：2.
8. application as claimed in claim 6, it is characterized in that：The 3,6- dihalos carbazole, potassium hydroxide and tetrabutyl phosphonium bromide
The molar ratio of ammonium is (4~6)：(15~20)：(0.1~0.2).
9. application as claimed in claim 6, it is characterized in that：Hydrolysis generation monomer M under alkaline condition, hydrolysis temperature for 80~
90 DEG C, hydrolysis time is 4~6h.
10. application as claimed in claim 4, it is characterized in that：In step (1), the molar ratio of monomer M and diethanol amine is 1
~2：2；The reaction temperature is 40~60 DEG C, and the time is 5~7h.
11. application as claimed in claim 10, it is characterized in that：The reaction temperature is 45 DEG C, time 6h.
12. application as claimed in claim 4, it is characterized in that：In step (1), the reaction carries out in solvent DMF, reaction
After, form is extracted with liquid separation, DMF is washed with water, and be extracted with ethyl acetate to obtain solution, is finally carried with column tswett's chromatography methods
It is pure, obtain monomer N after dry.
13. application as claimed in claim 4, it is characterized in that：In step (2), the monomer N and the molar ratio to styrene
For (1~2)：(1~2).
14. application as claimed in claim 3, it is characterized in that：The monomer N, triethanolamine, palladium and triphenylphosphine add
Dosage ratio is 1mmol：(0.3~0.4) mL：(0.03~0.05) mmol:(0.1~0.3) mmol.
15. application as claimed in claim 4, it is characterized in that：In step (2), the reaction temperature is 90~100 DEG C, reaction
Time is 5~7h；The reaction is reacted under conditions of inert gas.
16. application as claimed in claim 15, it is characterized in that：The inert gas is nitrogen.
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