CN106220583B - Benzothiazole-triphenyl amine dyes and the preparation method and application thereof with AIE effects - Google Patents
Benzothiazole-triphenyl amine dyes and the preparation method and application thereof with AIE effects Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Abstract
The invention discloses the benzothiazole triphenyl amine dyes and the preparation method and application thereof with AIE effects.The preparation method of benzothiazole triphenyl amine dyes：By 2 acetonitrile of benzothiazole and 4 dissolution of benzaldehyde of diphenylamino in absolute ethyl alcohol, ammonium acetate, stirring at normal temperature reaction is added；Crude product is obtained by filtering, by recrystallization, obtains pure products benzothiazole triphenyl amine dyes.Benzothiazole triphenyl amine dyes aqueous solution of the present invention can be highly selective, highly sensitive, it is not interfered by other anion, detection limit is down to ppm ranks, the low method with the detection cyanide ion of simple operation of testing cost can overcome the problems such as of high cost, the complicated for operation and detection that cyanide ion detection field encounters is insensitive.
Description
Technical field：
The present invention relates to the detections of cyanide ion, more particularly to a kind of benzothiazole with AIE effects-triphen amine
Compound and preparation method thereof and a kind of application dyestuff detection cyanide ion method, this is that one kind can be water-soluble
The dyestuff of cyanide ion is rapidly and efficiently detected in liquid.
Technical background：
In fields such as drug, health products, food, environmental science and industrial productions, relate generally to the inspection to anion
It surveys.Wherein cyanide is the important source material of synthetic resin, medicine, pesticide, insecticide, chemical fertilizer etc., is widely used in each neck
In domain.But cyanide, as extremely toxic substance, micro cyanide ion can be with the ferric iron in internal cytochrome oxidase
In conjunction with to make cell lose the effect of transport oxygen, body anoxic being caused to cause poisoning even dead.The World Health Organization
It provides, the content of cyanide ion should be less than 1.9 μM of (World Health Organization Guidelines in normal water
For Drinking Water Quality (World Health Organization, Geneva) .2011.).Therefore it finds
Can be quick, efficiently, easily there is important answer in life science, environmental testing to the method that cyanide ion is detected
With.Up to the present, although it has already been proposed the method for a variety of detection cyanide ions, many methods need expensive
Instrument and complicated operation, such as atomic absorption spectrophotometry, flame spectrometry and ion-selective electrode etc., seriously constrain
These methods are promoted the use of.Therefore, it develops easy to operate, selectivity well and low-cost cyanide ion detection method has
Very important meaning.In recent years, in ion detection field, fluorescence method due to easy to operate, the reasons such as instrument is easy to get and become
The hot spot of research.
However fluoroscopic examination cyanide ion still has two main problems：Assemble fluorescent quenching effect (aggregation
Caused quenching, ACQ) and be difficult to be detected in aqueous solution.The designs such as Bin Chen synthesis series contains dicyan
Base fluorescent probe can detect cyanide ion (Chen B, Ding Y, Li X, et al.Chemical in dichloromethane solution
Communications, 2013,49 (86)：10136-10138.), this system be detect cyanide ion in organic solvent, and
It is unfavorable for practical application.What this loyalty of Tang tested that team proposed in 2001 has aggregation-induced emission effect (aggregation
Induced emission, AIE) fluorescent molecular for solve two above main problem provide new approaches.So-called aggregation lures
It refers to fluorescence not being shown under pure organic solution state, but have under coherent condition or solid state strong glimmering to lead luminescent effect
Light.The designs such as Yang little Dong have synthesized a kind of fluorescence probe with aggregation-induced emission effect of triphen amine, can be water-soluble
Cyanide ion is detected in liquid, while avoiding ACQ effects (Yang X, Chen X, Lu X, et al..Journal of
Materials Chemistry C, 2016,4 (2)：383-390.).Chinese invention patent application 2015107999552
(2016.2.17) discloses a kind of method detecting cyanide ion using triphen amine dyestuff.This method comprises the steps of：
(1) triphen amine dyestuff is dissolved in hydrophilic organic solvent, triphen amine dyestuff storing solution is prepared, takes triphen amine
Dyestuff storing solution obtains the aqueous dye solutions of amine containing triphen after being diluted with water；(2) detected sample is added dropwise, is 365nm in wavelength
Under light excitation, whether observation aqueous solution fluorescence is quenched, if solution fluorescence is quenched, illustrates in sample containing cyanide ion, Asia
Sulfate ion or ferric ion further pass through nuclear magnetic resonance spectroscopy supplementary globe, it is determined whether contain cyanide ion.But
There are a great defect, to be cyanide ion, sulfite ion or ferric ion can all be quenched the dyestuff to this method, also
Cyanide ion need to be determined whether by spectrum analyses such as nuclear-magnetisms, can increase testing cost.
Invention content
The object of the present invention is to provide a kind of benzothiazole-triphenyl amine dyes and preparation method thereof with AIE effects, should
Aqueous dye solutions can be highly selective, highly sensitive, is not interfered by other anion, and detection limit is down to ppm ranks, testing cost
The method of low and simple operation detection cyanide ion can overcome of high cost, the operation encountered in cyanide ion detection field
The problems such as complicated and detection is insensitive.
Another object of the present invention is to provide application of the benzothiazole-triphenyl amine dyes in detection cyanide ion.
The object of the invention is achieved through the following technical solutions：
A kind of benzothiazole-triphenyl amine dyes, structural formula are shown in (I)：
Benzothiazole-triphenyl amine dyes of the present invention are synthesized using method commonly used in the art, can be by benzothiazole -2- acetonitriles
It is obtained by the reaction with diphenylamino -4- benzaldehydes.
Synthetic method of the present invention is indicated by reaction formula (II)：
The preparation method of benzothiazole-triphenyl amine dyes of the present invention：By benzothiazole -2- acetonitriles and diphenylamino -4- benzene
Formaldehyde is dissolved in absolute ethyl alcohol, and ammonium acetate, stirring at normal temperature reaction is added；Crude product is obtained by filtering, by recrystallization, is obtained
Obtain pure products benzothiazole-triphenyl amine dyes.
Preferably, the molar ratio of the benzothiazole -2- acetonitriles and diphenylamino -4- benzaldehydes is 1:1-1.2；Often
0.5-l mL triethylamines are added in 10mmol benzothiazole -2- acetonitriles；Be added per 10mmol benzothiazole -2- acetonitriles 50-100mL without
Water-ethanol.
Preferably, the recrystallization is recrystallized by dichloromethane-absolute ethyl alcohol mixed solution.Further, it presses
It is calculated according to percent by volume, the content of dichloromethane is 5%-15% in the solution of recrystallization.
Preferably, the time of the stirring at normal temperature reaction is 20-30 hours.
Benzothiazole-triphenyl amine dyes of the present invention have AIE effects, and therefore, which can be entirely applied to
In water solution system, fluorescence spectrum has a hyperfluorescence peak at 580nm, and Chinese red fluorescence is shown under the excitation of 365nm light.Solution
Middle addition cyanide ion can be such that its fluorescence is quenched.
The present invention protects the benzothiazole-triphenyl amine dyes in the application of detection cyanide ion.Detection method is by following
Step forms：
1) benzothiazole-triphenyl amine dyes are dissolved in hydrophilic organic solvent, are prepared into dyestuff storing solution；With steaming
Dyestuff storing solution is diluted to aqueous dye solutions by distilled water；By volume percentage, hydrophilic organic solvent content is 0.1-10%,
A concentration of 5-20 μM of benzothiazole-triphenyl amine dyes in the aqueous dye solutions；
2) detected sample is added, is irradiated in the exciting light that wavelength is 365nm, observes the change in fluorescence situation of aqueous solution,
If fluorescence is quenched, cyanide ion is contained in solution to be measured, further by nmr spectrum assistant analysis, is confirmed whether
Contain cyanide ion.
Preferably, the hydrophilic organic solvent is second eyeball, THF, DMF or DMSO；Containing in aqueous dye solutions, by body
Product percentages, hydrophilic organic solvent content are 0.1%；Benzothiazole-triphenyl amine dyes of the aqueous dye solutions
A concentration of 5 μM.
Preferably, the concentration of the cyanide ion is bent according to the work for measuring sample fluorescence titration cyanide ion to be tested
Line computation, the fluorescence intensity at 580nm calculate cyanide ion content from working curve；Sample fluorescence titration cyanogen root to be tested
The working curve of ion obtains by the following method：Compound concentration is the dyestuff acetonitrile solution of 1mM；Compound concentration is the four of 10mM
The aqueous solution of normal-butyl ammonium cyanide；Take 50 μ L dyestuffs acetonitrile solutions in 10mL volumetric flasks；Measure the tetra-n-butyl of different volumes
The aqueous solution of ammonium cyanide, is added in above-mentioned volumetric flask, and 10mL is diluted to distilled water, be configured to the cyanogen root containing various concentration from
Substandard tests solution.In the case where excitation wavelength is the test condition of 455nm, its fluorescence spectrum is obtained, it is at 580nm to obtain wavelength
Fluorescence intensity-cyanide ion concentration working curve.
The fluorescence spectrum of benzothiazole of the present invention-triphen amine dyestuff shows very strong fluorescence at 580nm
Peak, fluorescence color are Chinese red；After a certain amount of cyanide ion is added, fluorescence is quenched.Its principle is that cyanide ion can
Addition reaction occurs with the vinyl on dyestuff, influences the super of system and grip effect altogether, lead to fluorescent quenching.
Triphen amine dyestuff of the present invention has single-minded selectivity, and other anion such as HSO to cyanide ion4 –,
SO4 2–,HSO3 –,CH3COO–,Cl–,Br–,I–,F–,NO3 –And H2PO4 –The fluorescence of the dyestuff cannot all be quenched.Also, it is above-mentioned it is cloudy from
The presence of son will not cause any interference to the detection of cyanide ion.
Benzothiazole of the present invention-triphen amine dye structure and its application in detecting cyanide ion, do not have still at present
Document report.
Benzothiazole-triphenyl amine dyes of the present invention have selectivity well, have to cyanide ion single-minded glimmering
Photoresponse, other anion do not have the fluorescence of dyestuff any influence.Cyanide ion passes through affine addition reaction attack benzo
Vinyl in thiazole-triphen amine dye structure, destroys the conjugate planes of structure so that fluorescent quenching, and other anion
And there is no the nucleophilic additions to vinyl.Therefore the substance of patent 2015107999552, the benzothiazole-three are compared to
Aniline dyes has good selectivity to cyanide ion, can settle the cyanide ion in detection sample solution at one go, reduce behaviour
The step of making lowers testing cost.
Compared with the existing technology, the invention has the advantages that：
The benzothiazole-triphenyl amine dyes synthesis step is easy, and intramolecular conjugate planes are big, and fluorescence emission wavelengths are
580nm, fluorescence color are Chinese red, have very strong penetrability.The structure has AIE effects, can be in aqueous solution to cyanogen
Radical ion is detected, and can be widely applied in real life production.Using benzothiazole-triphenyl amine dyes, one is provided
Highly selective, the highly sensitive, low detection limits of kind, inexpensive cyanide ion detection method effectively solve existing cyanide ion
Detection method, as atomic absorption spectrophotometry, flame spectrometry, colorimetric method, electron probe microanalysis method and ion select
The problems such as electrode method etc., the testing cost brought is high, complicated for operation, and amount of samples is big and cannot continuously detect.
Description of the drawings
Fig. 1 is the fluorescence spectra of embodiment 1 dyestuff and various concentration anion.
Fig. 2 is the fluorescence spectra that embodiment 7 adds dyestuff after various concentration cyanide ion, and wherein dye strength is 5 μM.
Fig. 3 is that embodiment 7 adds cyanide ion and the fluorescence intensity at the 580nm of dyestuff after other anion, wherein contaminating
Expect a concentration of 5 μM, a concentration of 50 μM of cyanide ion, other anion concentrations are 50 μM.
Fig. 4 is that triphen amine aqueous dye solutions are separately added into when different type interferes anion in transmitted wave in embodiment 7
Fluorescence intensity figure at a length of 580nm.
Specific implementation mode
To more fully understand the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this hair
Bright embodiment is unlimited so.
Embodiment 1
1. the preparation method of benzothiazole-triphenyl amine dyes
Weigh 1.7422g benzothiazole -2- acetonitriles (10mmol) and 2.731g diphenylamino -4- benzaldehydes (10mmol) in
In the flask of 100mL, the absolute ethyl alcohol dissolving of 50mL is added, stirring at normal temperature is reacted for 24 hours under the catalysis of 0.5mL ammonium acetates.So
Crude product is obtained by filtering afterwards, is recrystallized by dichloromethane (5mL)-absolute ethyl alcohol (50mL) mixed solution, is obtained
Pure products 3.125g is in orange red solid.Yield 73%.
2. the characterization of compound
1H NMR(400MHz,CDCl3)δ(ppm):8.01(s,1H),7.94(d,1H),7.78(t,3H),7.39(t,
1H),7.25(m,5H),7.08(m,6H),6.93(d,2H).
13C NMR(100MHz,CDCl3)δ(ppm):163.91,153.75,151.58,146.18,145.98,134.79,
132.26,129.78,126.75,126.30,125.49,125.23,124.47,123.16,121.59,119.72,117.55,
100.71,77.43,77.12,76.80.
IR(cm-1,KBr):3750,3056,2360,2333,2205,1700,1566,1506,1482,1426,1331,
1295,1164,1069,980,914,819,754,724,700,617,587,533,498.
HR-MS(ESI):C28H19N3S m/z,429for[M+Na]+:452.1203.
Elemental analysis:calcd C,78.73；H,4.157；N,9.827；Found C,78.44；H,
4.20；N,9.95.
Mp:195.7-196.8℃
Above-mentioned Analysis of test results confirms that the compound of preparation synthesis is to obtain structure shown in chemical formula (I).
3. the AIE effects of benzothiazole-triphenylamine
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 11 parts of μ L dyestuffs acetonitrile solutions respectively, is separately added into not
Water and acetonitrile solution in proportion is diluted to 10mL, and the content of wherein distilled water is respectively 99.9%, 90%, 80%, 70%,
60%, 50%, 40%, 30%, 20%, 10%, 0.1%.
(2) Fig. 1 is the fluorescence spectra of dyestuff and various concentration anion.Aqueous dye solutions are observed under 365nm laser
Change in fluorescence, there is no fluorescence when distilled water solution content is few, only when it is 70% to distill water content to be higher than, solution is gradual
Fluorescent red-orange is presented and gradually increases, it can thus be appreciated that benzothiazole-triphenyl amine dyes have aggregation-induced emission effect
(AIE), it can apply in aqueous assay.Due to the fluorescence intensity difference of water content 99.9% and 90.0% solution not shadow
The application of the dyestuff in aqueous solution is rung, so it is 90.0-99.9% to use water content in the application detected to cyanide ion
(i.e. organic solvent content is 0.01-10%).
Embodiment 2
Cyanide ion is detected using dyestuff
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 2 parts of μ L dyestuffs acetonitrile solutions respectively, distilled water is all added
It is dilute to 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl cyaniding aqueous ammonium of 5mM, the sodium sulfite aqueous solution of a concentration of 5mM；
(3) in 2 parts of 10mL aqueous dye solutions distinguish the prepared tetra-n-butyl cyaniding aqueous ammonium of a dropping step (2) and
Each 0.l mL of sodium sulfite aqueous solution observe the change in fluorescence of aqueous dye solutions under the excitation of 365nm light after mixing.
The results show that after tetra-n-butyl cyaniding aqueous ammonium is added, the fluorescent quenching of aqueous dye solutions, and sulfurous acid is added
After the aqueous solution of sodium, the fluorescence of aqueous dye solutions remains unchanged.Thus illustrate that the dyestuff of the present invention shows specially cyanide ion
One selectivity and outstanding fluorescence identifying ability.The reality that cyanide ion is detected in complex sample solution of this advantageous dyestuff
Border is applied, and does not need other substances and detection to cyanide ion can be thus achieved.
Embodiment 3
Cyanide ion is detected using dyestuff
(1) compound concentration is the dyestuff DMSO solution of 2mM, takes 50 2 parts of μ L dyestuffs DMSO solutions respectively, distilled water is all added
It is dilute to 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl cyaniding aqueous ammonium of 10mM, the sodium iodide aqueous solution of a concentration of 10mM；
(3) in 2 parts of 10mL aqueous dye solutions distinguish the prepared tetra-n-butyl cyaniding aqueous ammonium of a dropping step (2) and
Each 0.l mL of sodium iodide aqueous solution observe the change in fluorescence of aqueous dye solutions under the excitation of 365nm light after mixing.
The results show that after tetra-n-butyl cyaniding aqueous ammonium is added, the fluorescent quenching of aqueous dye solutions, and sodium iodide is added
Aqueous solution after, the fluorescence of aqueous dye solutions remains unchanged.This result shows that, dyestuff shows cyanide ion selective and glimmering
Light recognition capability.
Embodiment 4
Cyanide ion is detected using dyestuff
(1) compound concentration is the dyestuff THF solution of 2mM, takes 50 2 parts of μ L dyestuffs THF solutions respectively, it is dilute that distilled water is all added
To 10mL, 2 parts of aqueous dye solutions are obtained；
(2) compound concentration is the tetra-n-butyl cyaniding aqueous ammonium of 10mM, the aqueous sodium persulfate solution of a concentration of 10mM；
(3) in 2 parts of 10mL aqueous dye solutions distinguish the prepared tetra-n-butyl cyaniding aqueous ammonium of a dropping step (2) and
Each 0.l mL of aqueous sodium persulfate solution observe the change in fluorescence of aqueous dye solutions under the excitation of 365nm light after mixing.
The results show that after tetra-n-butyl cyaniding aqueous ammonium is added, the fluorescent quenching of aqueous dye solutions, and hydrogen sulfate is added
After the aqueous solution of sodium, the fluorescence of aqueous dye solutions remains unchanged.This result shows that, dyestuff to cyanide ion show selectivity and
Fluorescence identifying ability.
Embodiment 5
Cyanide ion is detected using dyestuff
(1) compound concentration is the dyestuff DMF solution of 3mM, takes 50 2 parts of μ L dyestuffs DMF solutions respectively, it is dilute that distilled water is all added
To 10mL, 2 parts of aqueous dye solutions are obtained；
(2) compound concentration is the tetra-n-butyl cyaniding aqueous ammonium of 15mM, the aqueous solution of sodium bisulfite of a concentration of 15mM；
(3) in 2 parts of 10mL aqueous dye solutions distinguish the prepared tetra-n-butyl cyaniding aqueous ammonium of a dropping step (2) and
Each 0.l mL of aqueous solution of sodium bisulfite observe the change in fluorescence of aqueous dye solutions under the excitation of 365nm light after mixing.
The results show that after tetra-n-butyl cyaniding aqueous ammonium is added, the fluorescent quenching of aqueous dye solutions, and sulfurous acid is added
After the aqueous solution of hydrogen sodium, the fluorescence of aqueous dye solutions remains unchanged.This result shows that, dyestuff shows selectivity to cyanide ion
With fluorescence identifying ability.
Embodiment 6
Cyanide ion is detected using dyestuff
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 2 parts of μ L dyestuffs acetonitrile solutions respectively, distilled water is all added
It is dilute to 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl cyaniding aqueous ammonium of 5mM, the sodium fluoride aqueous solution of a concentration of 5mM；
(3) the prepared tetra-n-butyl cyaniding aqueous ammonium of a dropping step (2) is distinguished in 2 parts of 10mL aqueous dye solutions
0.lmL, then a that sodium fluoride aqueous solution 0.l mL are added dropwise, distilled water 0.l mL are added dropwise in another, after mixing,
The change in fluorescence of the lower observation aqueous dye solutions of 365nm light excitation.
The results show that after tetra-n-butyl cyaniding aqueous ammonium and sodium fluoride aqueous solution are added simultaneously, aqueous dye solutions it is glimmering
Optical quenching, this quenching effects same with positive tetrabutyl cyaniding aqueous ammonium is individually added into.This result shows that, fluorine ion is to cyanogen root
The detection identification of ion does not interfere with, and dyestuff shows selectivity and fluorescence identifying ability to cyanide ion.
Embodiment 7
Below by taking the dyestuff of chemical formula (I) as an example, illustrate benzothiazole-triphen amine dyestuff can be applicable to detection cyanogen root from
Son, the fluorescence probe as detection cyanide ion.
1. fluorescent detection dye is to the selectivity of cyanide ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 11 parts of μ L dyestuffs acetonitrile solutions, is all diluted with distilled water
To 10mL, 11 parts of aqueous dye solutions are obtained.
(2) NaHSO that compound concentration is 5mM respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl ammonium cyanide, KI,
NaNO3,NaH2PO4,Na2SO4,NaHSO4With the aqueous solution of NaF.
(3) 11 parts of 10mL aqueous dye solutions are taken, NaHSO is added dropwise respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl cyaniding
Ammonium, KI, NaNO3,NaH2PO4,Na2SO4,NaHSO4With the aqueous solution of NaF dye is observed under the excitation of 365nm light after mixing
Expect the change in fluorescence of aqueous solution.
As a result, it has been found that the fluorescence color of aqueous dye solutions script is Chinese red, after tetra-n-butyl cyaniding aqueous ammonium is added,
The fluorescent quenching of three aqueous dye solutions；And NaHSO is added3,CH3COONa,KBr,NaCl,KI,NaNO3,NaH2PO4,Na2SO4,
NaHSO4It is held essentially constant with the fluorescence color of the aqueous solution of NaF, aqueous dye solutions.Therefore the dyestuff shows cyanide ion
Go out selectivity and fluorescence identifying ability.
The fluorescence spectra for detecting above-mentioned solution is as shown in Figure 2.As a result, it has been found that cyanide ion, the fluorescence light of solution is added
Fluorescence peak in spectrum at 580nm disappears；And other anion are added, the fluorescence intensity change of solution is smaller.Therefore, the dyestuff pair
Cyanide ion shows good selectivity.
2. the working curve of fluorescence titration cyanide ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM；Compound concentration is the aqueous solution of the tetra-n-butyl ammonium cyanide of 5mM；
(2) take 50 μ L dyestuffs acetonitrile solutions in 10mL volumetric flasks；Measure the water of the tetra-n-butyl ammonium cyanide of different volumes
Solution, is added in above-mentioned volumetric flask, and 10mL is diluted to distilled water, is configured to the cyanide ion standard testing containing various concentration
Solution.In the case where excitation wavelength is the test condition of 455nm, its fluorescence spectrum is obtained, it is strong for the fluorescence at 580nm to obtain wavelength
The working curve of degree-cyanide ion concentration.Test result is shown in attached drawing 3；Triphen amine is calculated with nonlinear least square method
The binding constant of dyestuff and cyanide ion is 5.88*107M-1。
3. cyanide ion Concentration Testing
Using the working curve of above-mentioned preparation, replace laying in sample to be tested (prepared by our unit laboratory) addition molten
Liquid measures fluorescence intensity at 580nm, cyanide ion content is calculated from working curve, at 5 μM or less.
4. detection cyanide ion experiment coexists in interfering ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 11 parts of μ L dyestuffs acetonitrile solutions, is all diluted with distilled water
To 10mL, 11 parts of aqueous dye solutions are obtained.
(2) NaHSO that compound concentration is 5mM respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl ammonium cyanide, KI,
NaNO3,NaH2PO4,Na2SO4,NaHSO4With the aqueous solution of NaF.
(3) 11 parts of 10mL triphen amines aqueous dye solutions are taken, the tetra-n-butyl cyaniding aqueous ammonium of 0.l mL is separately added into,
Then the NaHSO of 0.l mL is added dropwise respectively3,CH3COONa,KBr,NaCl,KI,NaNO3,NaH2PO4,Na2SO4,NaHSO4And NaF
Aqueous solution, after mixing, excitation wavelength be 455nm test condition under, obtain its fluorescence spectrum, obtain every part of solution
It is the fluorescence intensity at 580nm in launch wavelength.Test result such as Fig. 4.
By Fig. 4, it is apparent that influence of other anion to the detection of cyanide ion can be ignored.
Benzothiazole-triphenyl amine dyes with AIE effects efficiently can detect cyanogen root very in aqueous solution in the present invention
Ion, detection limit is low, up to ppm ranks, has highly selective and sensitivity, is not interfered substantially by other anion, grasps
Make simply, testing cost is low.
Cyanide ion is destroyed by the vinyl in affine addition reaction attack benzothiazole-triphen amine dye structure
The conjugate planes of structure so that fluorescent quenching, and other anion and there is no nucleophilic additions to vinyl.Show the present invention
Dyestuff single-minded selectivity and outstanding fluorescence identifying ability are shown to cyanide ion, can be applied to the water-soluble of complex sample
Cyanide ion is detected in liquid, it is easy to operate, it is at low cost.
Claims (4)
1. benzothiazole-triphenyl amine dyes are in the application of detection cyanide ion, which is characterized in that the benzothiazole-triphen
The structural formula of amine dyestuff is lower formula (I)：
2. benzothiazole-triphenyl amine dyes according to claim 1 are in the application of detection cyanide ion, it is characterised in that：
Detection method comprises the steps of：
1) benzothiazole-triphenyl amine dyes are dissolved in hydrophilic organic solvent, are prepared into dyestuff storing solution；It will with distilled water
Dyestuff storing solution is diluted to aqueous dye solutions；By volume percentage, hydrophilic organic solvent content is 0.1-10%, the dyestuff
A concentration of 5-20 μM of benzothiazole-triphenyl amine dyes in aqueous solution；
2) detected sample is added, is irradiated in the exciting light that wavelength is 365nm, the change in fluorescence situation of aqueous solution is observed, if glimmering
Light is quenched, and cyanide ion is contained in solution to be measured, further by nmr spectrum assistant analysis, be confirmed whether containing
Cyanide ion.
3. benzothiazole-triphenyl amine dyes according to claim 2 are in the application of detection cyanide ion, it is characterised in that：
The hydrophilic organic solvent is acetonitrile, THF, DMF or DMSO；It is hydrophilic by volume percentage containing in aqueous dye solutions
Property organic solvent content be 0.1%；A concentration of 5 μM of benzothiazole-triphenyl amine dyes of the aqueous dye solutions.
4. benzothiazole-triphenyl amine dyes according to claim 1 are in the application of detection cyanide ion, it is characterised in that：
The concentration of the cyanide ion is calculated according to the working curve for measuring sample fluorescence titration cyanide ion to be tested, in 580nm
Locate fluorescence intensity, cyanide ion content is calculated from working curve；The working curve of sample fluorescence titration cyanide ion to be tested
It obtains by the following method：Compound concentration is the dyestuff acetonitrile solution of 1mM；Compound concentration is the tetra-n-butyl ammonium cyanide of 10mM
Aqueous solution；Take 50 μ L dyestuffs acetonitrile solutions in 10mL volumetric flasks；The aqueous solution of the tetra-n-butyl ammonium cyanide of different volumes is measured,
It is added in above-mentioned volumetric flask, 10mL is diluted to distilled water, be configured to the cyanide ion standard test solution containing various concentration；
In the case where excitation wavelength is the test condition of 455nm, its fluorescence spectrum is obtained, it is fluorescence intensity-cyanogen root at 580nm to obtain wavelength
The working curve of ion concentration.
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| CN106189343B (en) * | 2016-07-20 | 2017-06-13 | 南方医科大学 | A kind of acetonitrile class dyestuff of benzothiazole 2 and its application |
| CN107118587B (en) * | 2017-04-06 | 2019-01-18 | 大连理工大学 | A kind of Styryl cyanine dye fluorescent probe and preparation method thereof for detecting environment viscosity |
| CN108034421A (en) * | 2017-12-28 | 2018-05-15 | 中南大学 | A kind of new A IE feux rouges fluorescent dyes |
| CN109694361A (en) * | 2019-02-26 | 2019-04-30 | 南方医科大学 | A kind of benzothiazole 2- acetonitrile and its application |
| CN111978313B (en) * | 2020-08-28 | 2022-01-18 | 深圳大学 | Multi-modal light diagnosis and treatment agent with aggregation-induced emission property and preparation and application thereof |
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| FR2989377A1 (en) * | 2012-04-12 | 2013-10-18 | Ecole Norm Superieure Lyon | New substituted 2-(3H-indol-2-yl)-3-phenyl-propanenitrile compounds, useful in biological imaging, preferably angiography and as biological transducer or sensor, preferably biochips such as DNA chip for detection of biomolecules |
| CN105334202A (en) * | 2015-11-18 | 2016-02-17 | 华南理工大学 | Method for detecting cyanide ions through triphenylamine dye |
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| FR2989377A1 (en) * | 2012-04-12 | 2013-10-18 | Ecole Norm Superieure Lyon | New substituted 2-(3H-indol-2-yl)-3-phenyl-propanenitrile compounds, useful in biological imaging, preferably angiography and as biological transducer or sensor, preferably biochips such as DNA chip for detection of biomolecules |
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