CN106220583A - Benzothiazole triphenyl amine dyes with AIE effect and preparation method and application - Google Patents
Benzothiazole triphenyl amine dyes with AIE effect and preparation method and application Download PDFInfo
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Abstract
The invention discloses benzothiazole triphenyl amine dyes with AIE effect and preparation method and application.The preparation method of benzothiazole triphenyl amine dyes: by benzothiazole 2 acetonitrile and diphenylamino 4 dissolution of benzaldehyde in dehydrated alcohol, adds ammonium acetate, and stirring at normal temperature is reacted；Obtain crude product through filtering, pass through recrystallization, it is thus achieved that pure products benzothiazole triphenyl amine dyes.Benzothiazole triphenyl amine dyes aqueous solution of the present invention can high selectivity, high sensitivity, do not disturbed by other aniones, detection limit as little as ppm rank, testing cost is low and the method for the detection cyanide ion of simple operation, can overcome that the cost run at cyanide ion detection field is high, operation is complicated and detects the problems such as insensitive.
Description
Technical field:
The present invention relates to the detection of cyanide ion, particularly relate to a kind of benzothiazole-triphen amine with AIE effect
Compound and preparation method thereof, and the method for this dyestuff of a kind of application detection cyanide ion, this is that one can be water-soluble
Liquid rapidly and efficiently detects the dyestuff of cyanide ion.
Technical background:
In fields such as medicine, health product, food, environmental science and commercial production, all relate generally to the inspection to anion
Survey.Wherein cyanide is the important source material of synthetic resin, medicine, pesticide, insecticide, chemical fertilizer etc., is widely used in each neck
In territory.But cyanide is as extremely toxic substance, the cyanide ion of trace can be with the ferric iron in cells in vivo chromo-oxidase
In conjunction with, so that cell loses the effect of transports oxygen, cause body anoxia to cause poisoning even dead.World Health Organization (WHO)
Regulation, in normal water, the content of cyanide ion should be less than 1.9 μMs of (World Health Organization Guidelines
For Drinking Water Quality (World Health Organization, Geneva) .2011.).Therefore find
Can be quick, efficiently, the method detected cyanide ion easily has important answering in life sciences, environment measuring field
With.Up to the present, although the method that have already been proposed multiple detection cyanide ion, but many methods need expensive
Instrument and complicated operation, such as atomic absorption spectrophotometry, flame spectrometry and ion selective electrode etc., seriously constrain
Promoting the use of of these methods.Therefore, develop easy and simple to handle, selectivity good and cyanide ion detection method with low cost has
Very important meaning.In recent years, in ion detection field, fluorescence method is due to simple to operate, and instrument the reason such as is easy to get and becomes
The focus of research.
But fluoroscopic examination cyanide ion yet suffers from two subject matters: assemble fluorescent quenching effect (aggregation
Caused quenching, ACQ) and be difficult to detect in aqueous.The design synthesis series such as Bin Chen is containing 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 is to detect cyanide ion in organic solvent, and
It is unfavorable for actual application.This loyalty of Tang test team calendar year 2001 propose there is aggregation-induced emission effect (aggregation
Induced emission, AIE) fluorescence molecule for solve two above subject matter provide new approaches.So-called gathering lures
Lead luminescent effect and refer to not show fluorescence under pure organic solution state, but have the most glimmering under coherent condition or solid state
Light.The design such as Yang little Dong has synthesized the fluorescent probe with aggregation-induced emission effect of a kind of triphen amine, can be water-soluble
Liquid detects cyanide ion, avoids ACQ effect (Yang X, Chen X, Lu X, et al..Journal of simultaneously
Materials Chemistry C, 2016,4 (2): 383-390.).Chinese invention patent application 2015107999552
(2016.2.17) a kind of method applying triphen amine dyestuff detection cyanide ion is disclosed.The method comprises the steps of:
(1) triphen amine dyestuff is dissolved in hydrophilic organic solvent, prepares triphen amine dyestuff storing solution, take triphen amine
Obtain containing triphen amine aqueous dye solutions after dyestuff storing solution dilute with water；(2) dropping detected sample, is 365nm at wavelength
Light excites down, observes the whether cancellation of aqueous solution fluorescence, if solution fluorescence cancellation, then containing cyanide ion, Asia in explanation sample
Sulfate ion or ferric ion, further by proton nmr spectra supplementary globe, it is determined whether containing cyanide ion.But
The method exist great defect be cyanide ion, sulfite ion or ferric ion all can this dyestuff of cancellation, also
Cyanide ion need to be determined whether by spectrum analyses such as nuclear-magnetisms, testing cost can be increased.
Summary of the invention
It is an object of the invention to provide a kind of benzothiazole-triphenyl amine dyes with AIE effect and preparation method thereof, should
Aqueous dye solutions can high selectivity, high sensitivity, do not disturbed by other aniones, detection limit as little as ppm rank, testing cost
The method of the detection cyanide ion of low and simple operation, can overcome that the cost run at cyanide ion detection field is high, operation
Complicated and detect the problems such as insensitive.
Another object of the present invention is the application providing benzothiazole-triphenyl amine dyes at detection cyanide ion.
The object of the invention is achieved through the following technical solutions:
A kind of benzothiazole-triphenyl amine dyes, its structural formula is shown in (I):
Benzothiazole of the present invention-triphenyl amine dyes uses method commonly used in the art synthesis, can be by benzothiazole-2-acetonitrile
Obtain with the reaction of diphenylamino-4-benzaldehyde.
Synthetic method of the present invention is represented by reacting formula (II):
The preparation method of benzothiazole-triphenyl amine dyes of the present invention: by benzothiazole-2-acetonitrile and diphenylamino-4-benzene
Formaldehyde is dissolved in dehydrated alcohol, adds ammonium acetate, and stirring at normal temperature is reacted；Obtain crude product through filtering, by recrystallization, obtain
Obtain pure products benzothiazole-triphenyl amine dyes.
Preferably, the mol ratio of described benzothiazole-2-acetonitrile and diphenylamino-4-benzaldehyde is 1:1-1.2；Often
10mmol benzothiazole-2-acetonitrile adds 0.5-l mL triethylamine；Every 10mmol benzothiazole-2-acetonitrile add 50-100mL without
Water-ethanol.
Preferably, described recrystallization carries out recrystallization by dichloromethane-dehydrated alcohol mixed solution.Further, press
Calculating according to percent by volume, in the solution of recrystallization, the content of dichloromethane is 5%-15%.
Preferably, the time of described stirring at normal temperature reaction is 20-30 hour.
Benzothiazole-triphenyl amine dyes of the present invention there is AIE effect, therefore, this dyestuff can be entirely applied to
In water solution system, fluorescence spectrum has a hyperfluorescence peak at 580nm, excites lower display Chinese red fluorescence at 365nm light.Solution
Middle addition cyanide ion can make its fluorescence generation cancellation.
The present invention protects described benzothiazole-triphenyl amine dyes in the application of detection cyanide ion.Detection method is by following
Step forms:
1) benzothiazole-triphenyl amine dyes is dissolved in hydrophilic organic solvent, is prepared as dyestuff storing solution；With steaming
Dyestuff storing solution is diluted to aqueous dye solutions by distilled water；By volume percentages, hydrophilic organic solvent content is 0.1-10%,
In this aqueous dye solutions, the concentration of benzothiazole-triphenyl amine dyes is 5-20 μM；
2) add detected sample, be the excitation light irradiation of 365nm at wavelength, observe the change in fluorescence situation of aqueous solution,
If fluorescence generation cancellation, containing cyanide ion in solution to be measured, further by nmr spectrum assistant analysis, it is confirmed whether
Containing cyanide ion.
Preferably, described hydrophilic organic solvent is second eyeball, THF, DMF or DMSO；Containing in aqueous dye solutions, by body
Long-pending percentages, hydrophilic organic solvent content is 0.1%；Benzothiazole-the triphenyl amine dyes of described aqueous dye solutions
Concentration is 5 μMs.
Preferably, the concentration of described cyanide ion is bent according to the work measuring sample fluorescence titration cyanide ion to be tested
Line computation, 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 dyestuff acetonitrile solutions in 10mL volumetric flask；Measure the tetra-n-butyl of different volumes
The aqueous solution of ammonium cyanide, adds in above-mentioned volumetric flask, with distilled water diluting to 10mL, be configured to cyanogen root containing variable concentrations from
Substandard test solution.Under the test condition that excitation wavelength is 455nm, it is thus achieved that its fluorescence spectrum, obtaining wavelength is at 580nm
The working curve of fluorescence intensity-cyanide ion concentration.
The fluorescence spectrum of benzothiazole of the present invention-triphen amine dyestuff shows the strongest fluorescence at 580nm
Peak, fluorescence color is Chinese red；After adding a certain amount of cyanide ion, its fluorescence generation cancellation.Its principle is that cyanide ion can
With with the vinyl generation additive reaction on dyestuff, affect the super of system and grip effect altogether, cause fluorescent quenching.
Triphen amine dyestuff of the present invention has a single-minded selectivity to cyanide ion, and other aniones such as HSO4 –,
SO4 2–,HSO3 –,CH3COO–,Cl–,Br–,I–,F–,NO3 –And H2PO4 –All can not the fluorescence of this dyestuff of cancellation.Further, above-mentioned the moon from
The detection of cyanide ion will not be caused any interference by the existence of son.
Benzothiazole of the present invention-triphen amine dye structure and the application in detection cyanide ion thereof, the most still do not have
Document is reported.
Benzothiazole-triphenyl amine dyes of the present invention has good selectivity, has cyanide ion single-minded glimmering
Photoresponse, other aniones do not have any impact to the fluorescence of dyestuff.Cyanide ion is by affine additive reaction attack benzo
Vinyl in thiazole-triphen amine dye structure, destroys the conjugate planes of structure so that fluorescent quenching, and other aniones
There is not the nucleophilic addition to vinyl.Therefore the material of patent 2015107999552 it is compared to, this benzothiazole-three
Aniline dyes has good selectivity to cyanide ion, can settle the cyanide ion in detection sample solution at one go, reduce behaviour
The step made, lowers testing cost.
Relative to prior art, present invention have the advantage that
This benzothiazole-triphenyl amine dyes synthesis step is easy, and intramolecular conjugate planes are big, and its fluorescence emission wavelengths is
580nm, fluorescence color is Chinese red, has the strongest penetrance.This structure has AIE effect, can be in aqueous to cyanogen
Radical ion detects, and can be widely applied in real life production.Use benzothiazole-triphenyl amine dyes, it is provided that one
Plant high selectivity, high sensitivity, low detection limit, the cyanide ion detection method of low cost, effectively solve existing cyanide ion
Detection method, as atomic absorption spectrophotometry, flame spectrometry, colorimetry, electron probe microanalysis method and ion select
Electrode methods etc., the testing cost brought is high, operation complexity, and amount of samples is big and can not the problem such as continuous detecting.
Accompanying drawing explanation
Fig. 1 is the fluorescence spectrum figure of embodiment 1 dyestuff and variable concentrations anion.
Fig. 2 is that embodiment 7 adds the fluorescence spectrum figure of dyestuff after variable concentrations cyanide ion, and wherein dye strength is 5 μMs.
Fig. 3 is the fluorescence intensity that embodiment 7 adds after cyanide ion and other aniones at the 580nm of dyestuff, Qi Zhongran
Material concentration is 5 μMs, and cyanide ion concentration is 50 μMs, and other anion concentrations are 50 μMs.
At transmitted wave when Fig. 4 is that in embodiment 7, triphen amine aqueous dye solutions is separately added into dissimilar interference anion
Fluorescence intensity figure at a length of 580nm.
Detailed description of the invention
For being more fully understood that the present invention, the present invention is further illustrated with embodiment below in conjunction with the accompanying drawings, but this
Bright embodiment does not limit so.
Embodiment 1
1. the preparation method of benzothiazole-triphenyl amine dyes
Weigh 1.7422g benzothiazole-2-acetonitrile (10mmol) and 2.731g diphenylamino-4-benzaldehyde (10mmol) in
In the flask of 100mL, add the anhydrous alcohol solution of 50mL, stirring at normal temperature reaction 24h under the catalysis of 0.5mL ammonium acetate.So
After through filtration obtain crude product, carry out recrystallization by dichloromethane (5mL)-dehydrated alcohol (50mL) mixed solution, it is thus achieved that
Pure products 3.125g, in orange red solid.Productivity 73%.
2. the sign 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℃
The compound of above-mentioned Analysis of test results confirmation preparation synthesis is to obtain structure shown in chemistry formula (I).
3. the AIE effect of benzothiazole-triphenylamine
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 μ L dyestuff acetonitrile solution 11 parts respectively, is separately added into not
Water and acetonitrile solution in proportion are diluted to 10mL, and wherein the content of distilled water is respectively 99.9%, and 90%, 80%, 70%,
60%, 50%, 40%, 30%, 20%, 10%, 0.1%.
(2) Fig. 1 is the fluorescence spectrum figure of dyestuff and variable concentrations anion.Aqueous dye solutions is observed under 365nm laser
Change in fluorescence, there is no fluorescence when distilled water solution content is few, only at distilled water content higher than when being 70%, solution is gradually
Present fluorescent red-orange and gradually strengthen, it can thus be appreciated that benzothiazole-triphenyl amine dyes has aggregation-induced emission effect
(AIE), can apply in aqueous assay.Fluorescence intensity difference not shadow due to water content 99.9% and 90.0% solution
Ring the application in aqueous of this dyestuff, so using water content in the application detecting cyanide ion is 90.0-99.9%
(i.e. organic solvent content is 0.01-10%).
Embodiment 2
Dyestuff is utilized to detect cyanide ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 μ L dyestuff acetonitrile solution 2 parts respectively, all adds distillation
Water is dilute to 10mL, obtains 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl ammonium cyanide aqueous solution of 5mM, and concentration is the sodium sulfite aqueous solution of 5mM；
(3) drip respectively in 2 parts of 10mL aqueous dye solutions tetra-n-butyl ammonium cyanide aqueous solution that step (2) prepared and
Sodium sulfite aqueous solution each 0.l mL, after mix homogeneously, excites the change in fluorescence of lower observation aqueous dye solutions at 365nm light.
Result shows, after adding tetra-n-butyl ammonium cyanide aqueous solution, and the fluorescent quenching of aqueous dye solutions, and add sulfurous acid
After the aqueous solution of sodium, the fluorescence of aqueous dye solutions keeps constant.Thus illustrate that cyanide ion is demonstrated specially by the dyestuff of the present invention
The selectivity of one and outstanding fluorescence identifying ability.The reality detecting cyanide ion in complex sample solution of this this dyestuff favourable
Border is applied, it is not necessary to other materials i.e. can realize the detection to cyanide ion.
Embodiment 3
Dyestuff is utilized to detect cyanide ion
(1) compound concentration is the dyestuff DMSO solution of 2mM, takes 50 μ L dyestuff DMSO solution 2 parts respectively, all adds distilled water
Dilute to 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl ammonium cyanide aqueous solution of 10mM, and concentration is the sodium iodide aqueous solution of 10mM；
(3) drip respectively in 2 parts of 10mL aqueous dye solutions tetra-n-butyl ammonium cyanide aqueous solution that step (2) prepared and
Sodium iodide aqueous solution each 0.l mL, after mix homogeneously, excites the change in fluorescence of lower observation aqueous dye solutions at 365nm light.
Result shows, after adding tetra-n-butyl ammonium cyanide aqueous solution, and the fluorescent quenching of aqueous dye solutions, and add sodium iodide
Aqueous solution after, the fluorescence of aqueous dye solutions keeps constant.This result shows, dyestuff demonstrates selectivity and glimmering to cyanide ion
Light identification ability.
Embodiment 4
Dyestuff is utilized to detect cyanide ion
(1) compound concentration is the dyestuff THF solution of 2mM, takes 50 μ L dyestuff THF solution 2 parts respectively, all adds distilled water dilute
To 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl ammonium cyanide aqueous solution of 10mM, and concentration is the aqueous sodium persulfate solution of 10mM；
(3) drip respectively in 2 parts of 10mL aqueous dye solutions tetra-n-butyl ammonium cyanide aqueous solution that step (2) prepared and
Aqueous sodium persulfate solution each 0.l mL, after mix homogeneously, excites the change in fluorescence of lower observation aqueous dye solutions at 365nm light.
Result shows, after adding tetra-n-butyl ammonium cyanide aqueous solution, and the fluorescent quenching of aqueous dye solutions, and add hydrogen sulfate
After the aqueous solution of sodium, the fluorescence of aqueous dye solutions keeps constant.This result shows, dyestuff cyanide ion is demonstrated selectivity and
Fluorescence identifying ability.
Embodiment 5
Dyestuff is utilized to detect cyanide ion
(1) compound concentration is the dyestuff DMF solution of 3mM, takes 50 μ L dyestuff DMF solution 2 parts respectively, all adds distilled water dilute
To 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl ammonium cyanide aqueous solution of 15mM, and concentration is the aqueous solution of sodium bisulfite of 15mM；
(3) drip respectively in 2 parts of 10mL aqueous dye solutions tetra-n-butyl ammonium cyanide aqueous solution that step (2) prepared and
Aqueous solution of sodium bisulfite each 0.l mL, after mix homogeneously, excites the change in fluorescence of lower observation aqueous dye solutions at 365nm light.
Result shows, after adding tetra-n-butyl ammonium cyanide aqueous solution, and the fluorescent quenching of aqueous dye solutions, and add sulfurous acid
After the aqueous solution of hydrogen sodium, the fluorescence of aqueous dye solutions keeps constant.This result shows, dyestuff demonstrates selectivity to cyanide ion
With fluorescence identifying ability.
Embodiment 6
Dyestuff is utilized to detect cyanide ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 μ L dyestuff acetonitrile solution 2 parts respectively, all adds distilled water
Dilute to 10mL, obtain 2 parts of aqueous dye solutions；
(2) compound concentration is the tetra-n-butyl ammonium cyanide aqueous solution of 5mM, and concentration is the sodium fluoride aqueous solution of 5mM；
(3) in 2 parts of 10mL aqueous dye solutions, drip the tetra-n-butyl ammonium cyanide aqueous solution that step (2) is prepared respectively
0.lmL, then a dropping sodium fluoride aqueous solution 0.l mL, another part dropping distilled water 0.l mL, after mix homogeneously,
365nm light excites the change in fluorescence of lower observation aqueous dye solutions.
Result shows, after being simultaneously introduced tetra-n-butyl ammonium cyanide aqueous solution and sodium fluoride aqueous solution, and aqueous dye solutions glimmering
Optical quenching, this and be individually added into the quenching effects that positive tetrabutyl ammonium cyanide aqueous solution is same.This result shows, fluorion is to cyanogen root
The detection identification of ion does not interferes with, and dyestuff demonstrates selectivity and fluorescence identifying ability to cyanide ion.
Embodiment 7
Below by chemistry formula (I) dyestuff as a example by, illustrate benzothiazole-triphen amine dyestuff can be applicable to detection cyanogen root from
Son, as the fluorescent probe of detection cyanide ion.
1. the fluorescent detection dye selectivity to cyanide ion
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 μ L dyestuff acetonitrile solution 11 parts, all uses distilled water diluting
To 10mL, obtain 11 parts of aqueous dye solutions.
(2) compound concentration is the NaHSO of 5mM respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl ammonium cyanide, KI,
NaNO3,NaH2PO4,Na2SO4,NaHSO4Aqueous solution with NaF.
(3) take 10mL aqueous dye solutions 11 parts, drip NaHSO respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl cyaniding
Ammonium, KI, NaNO3,NaH2PO4,Na2SO4,NaHSO4With the aqueous solution of NaF, after mix homogeneously, excite lower observation at 365nm light
The change in fluorescence of aqueous dye solutions.
It was found that the fluorescence color that aqueous dye solutions is originally is Chinese red, after adding tetra-n-butyl ammonium cyanide aqueous solution,
The fluorescent quenching of three aqueous dye solutions；And add NaHSO3,CH3COONa,KBr,NaCl,KI,NaNO3,NaH2PO4,Na2SO4,
NaHSO4With the aqueous solution of NaF, the fluorescence color of aqueous dye solutions is held essentially constant.Therefore cyanide ion is shown by this dyestuff
Go out selectivity and fluorescence identifying ability.
Detect the fluorescence spectrum figure of above-mentioned solution as shown in Figure 2.It was found that addition cyanide ion, the fluorescence light of solution
In spectrum, the fluorescence peak at 580nm disappears；And adding other aniones, the fluorescence intensity change of solution is less.Therefore, this dyestuff pair
Cyanide ion demonstrates 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) 50 μ L dyestuff acetonitrile solutions are taken in 10mL volumetric flask；Measure the water of the tetra-n-butyl ammonium cyanide of different volumes
Solution, adds in above-mentioned volumetric flask, with distilled water diluting to 10mL, is configured to the cyanide ion standard testing containing variable concentrations
Solution.Under the test condition that excitation wavelength is 455nm, it is thus achieved that its fluorescence spectrum, obtaining wavelength is that the fluorescence at 580nm is strong
The working curve of degree-cyanide ion concentration.Test result is shown in accompanying drawing 3；It is calculated triphen amine with nonlinear least square method
Dyestuff is 5.88*10 with the binding constant of cyanide ion7M-1。
3. cyanide ion Concentration Testing
Use the working curve of above-mentioned preparation, add with sample to be tested (prepared by our unit's laboratory) and replace deposit molten
Liquid, measures fluorescence intensity at 580nm, calculates cyanide ion content from working curve, below 5 μMs.
4. interfering ion coexists and detects cyanide ion experiment
(1) compound concentration is the dyestuff acetonitrile solution of 1mM, takes 50 μ L dyestuff acetonitrile solution 11 parts, all uses distilled water diluting
To 10mL, obtain 11 parts of aqueous dye solutions.
(2) compound concentration is the NaHSO of 5mM respectively3,CH3COONa, KBr, NaCl, positive tetrabutyl ammonium cyanide, KI,
NaNO3,NaH2PO4,Na2SO4,NaHSO4Aqueous solution with NaF.
(3) take 10mL triphen amine aqueous dye solutions 11 parts, be separately added into the tetra-n-butyl ammonium cyanide aqueous solution of 0.l mL,
Drip the NaHSO of 0.l mL the most respectively3,CH3COONa,KBr,NaCl,KI,NaNO3,NaH2PO4,Na2SO4,NaHSO4And NaF
Aqueous solution, after mix homogeneously, under the test condition that excitation wavelength is 455nm, it is thus achieved that its fluorescence spectrum, obtain every part of solution
Fluorescence intensity at a length of 580nm of transmitted wave.Test result such as Fig. 4.
By Fig. 4 it is apparent that the impact of the detection of cyanide ion is negligible by other anion.
Benzothiazole-the triphenyl amine dyes in the present invention with AIE effect very efficiently can detect cyanogen root in aqueous
Ion, its detection limit is low, up to ppm rank, has high selectivity and susceptiveness, is not disturbed by other aniones, behaviour
Making simple, testing cost is low.
Cyanide ion, by the vinyl in affine additive reaction attack benzothiazole-triphen amine dye structure, destroys
The conjugate planes of structure so that fluorescent quenching, and there is not the nucleophilic addition to vinyl in other aniones.Show the present invention
Dyestuff cyanide ion is demonstrated single-minded selectivity and outstanding fluorescence identifying ability, can be applicable to the water-soluble of complex sample
Liquid detects cyanide ion, simple to operate, low cost.
Claims (10)
1. benzothiazole-triphenyl amine dyes, it is characterised in that the structural formula of this dyestuff is lower formula (I):
2. the preparation method of the benzothiazole-triphenyl amine dyes described in claim 1, it is characterised in that: by benzothiazole-2-second
Nitrile and diphenylamino-4-dissolution of benzaldehyde, in dehydrated alcohol, add ammonium acetate, and stirring at normal temperature is reacted；Obtain slightly through filtering
Product, passes through recrystallization, it is thus achieved that pure products benzothiazole-triphenyl amine dyes.
The preparation method of benzothiazole-triphenyl amine dyes the most according to claim 2, it is characterised in that: described benzo thiophene
The mol ratio of azoles-2-acetonitrile and diphenylamino-4-benzaldehyde is 1:1-1.2；Every 10mmol benzothiazole-2-acetonitrile adds 0.5-
LmL triethylamine；Every 10mmol benzothiazole-2-acetonitrile adds 50-100mL dehydrated alcohol.
The preparation method of benzothiazole-triphenyl amine dyes the most according to claim 2, it is characterised in that: described recrystallization
Recrystallization is carried out by dichloromethane-dehydrated alcohol mixed solution.
The preparation method of benzothiazole-triphenyl amine dyes the most according to claim 4, it is characterised in that: according to volume hundred
Proportion by subtraction is calculated, and in the solution of recrystallization, the content of dichloromethane is 5%-15%.
The preparation method of benzothiazole-triphenyl amine dyes the most according to claim 2, it is characterised in that: described room temperature stirs
The time mixing reaction is 20-30 hour.
7. benzothiazole-triphenyl amine dyes described in claim 1 is in the application of detection cyanide ion.
Benzothiazole-triphenyl amine dyes the most according to claim 7 is in the application of detection cyanide ion, it is characterised in that:
Detection method comprises the steps of:
1) benzothiazole-triphenyl amine dyes is dissolved in hydrophilic organic solvent, is prepared as dyestuff storing solution；Use distilled water
Dyestuff storing solution is diluted to aqueous dye solutions；By volume percentages, hydrophilic organic solvent content is 0.1-10%, this dye
In material aqueous solution, the concentration of benzothiazole-triphenyl amine dyes is 5-20 μM；
2) add detected sample, be the excitation light irradiation of 365nm at wavelength, observe the change in fluorescence situation of aqueous solution, if glimmering
Light generation cancellation, containing cyanide ion in solution to be measured, further by nmr spectrum assistant analysis, be confirmed whether containing
Cyanide ion.
Benzothiazole-triphenyl amine dyes the most according to claim 7 is in the application of detection cyanide ion, it is characterised in that:
Described hydrophilic organic solvent is second eyeball, THF, DMF or DMSO；Containing in aqueous dye solutions, by volume percentages, hydrophilic
Property organic solvent content is 0.1%；The concentration of the benzothiazole-triphenyl amine dyes of described aqueous dye solutions is 5 μMs.
Benzothiazole-triphenyl amine dyes the most according to claim 7 is in the application of detection cyanide ion, it is characterised in that:
The concentration of described cyanide ion calculates, at 580nm according to the working curve measuring sample fluorescence titration cyanide ion to be tested
Place's fluorescence intensity, calculates cyanide ion content from working curve；The working curve of sample fluorescence titration cyanide ion to be tested
Obtain 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 dyestuff acetonitrile solutions in 10mL volumetric flask；Measure the aqueous solution of the tetra-n-butyl ammonium cyanide of different volumes,
Add in above-mentioned volumetric flask, with distilled water diluting to 10mL, be configured to the cyanide ion standard test solution containing variable concentrations.
Under the test condition that excitation wavelength is 455nm, it is thus achieved that its fluorescence spectrum, obtaining wavelength is the fluorescence intensity at 580nm-cyanogen root
The working curve of ion concentration.
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| CN109694361A (en) * | 2019-02-26 | 2019-04-30 | 南方医科大学 | A kind of benzothiazole 2- acetonitrile and its application |
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