CN104610955B - A kind of Ratio-type detects the synthesis and application of fluorine ion and inferior sulfate radical fluorescent molecular probe simultaneously - Google Patents
A kind of Ratio-type detects the synthesis and application of fluorine ion and inferior sulfate radical fluorescent molecular probe simultaneously Download PDFInfo
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Abstract
The present invention relates to the preparation and application that a kind of Ratio-type detects fluorine ion and inferior sulfate radical fluorescence probe simultaneously, the Ratiometric fluorescent probe, as precursor structure, fluorine ion and inferior sulfate radical is measured based on ESIPT and ICT mechanism respectively using 2- (2- hydroxy phenyls) benzothiazole derivant.Maximum emission wavelength is in 498nm in 80% acetonitrile solution for the probe molecule, after fluorine ion is added, the fluorescence spectrum red shift 136nm of probe；After inferior sulfate radical is added, the fluorescence spectrum blue shift 127nm of probe.After fluorine ion or inferior sulfate radical is added, apparent red shift or blue shift occur respectively for the fluorescence spectrum of probe, show different fluorescence response signals, to realize that the difference to both ions detects.Fluorescence probe of the present invention is easy to operate, reaction condition is mild, be easy to purifying, synthesis yield is high, selectivity is good, high sensitivity, stable optical performance.Meanwhile it the design of the fluorescence probe and synthesizing the development of Multifunction fluorescent probe from now on and provides an important platform.
Description
Technical field
The present invention relates to chemical analysis detection technique fields, and in particular to a kind of Ratio-type detect simultaneously fluorine ion and
The preparation method of the difunctional fluorescent molecular probe of inferior sulfate radical and the fluorescent molecular probe are in detection fluorine ion and inferior sulfate radical
The application of aspect.
Background technology
Fluorine ion radius is small, electronegativity is strong, has special chemical property, thus causes the great interest of researchers.
In addition, fluorine plays pre- anti-caries and clinical treatment osteoporosis as one of trace element necessary to human life activity
To important function.But in human body excess intake fluorine, easily induce den tal fluorosis, fluorosis of bone, kidney stone and kidney disorder etc.
Disease.Sulphite is widely used in as a kind of important food additives in food industry, bleached since it has,
Antibacterial protects color, anti-corrosion and a variety of efficiencies such as anti-oxidant, is gradually added to the life of veterinary antibiotics, can based food, grape wine
During production and storage, to inhibit Enzymes In Food to promote the generation of brown stain and nonenzymatic browning reaction.However, the sulphite of high concentration
Health to human body is harmful, especially certain people to sulphite allergy, is held taking in a small amount of sulphite
It is also easy to produce the diseases such as asthma, skin allergy, upset,gastro-intestinal.In addition, contain a large amount of reproducibility sulphite in industrial wastewater, it can be tight
Ghost image rings the concentration of oxygen in water, to cause serious harm to ecological environment.Therefore, it establishes a kind of convenient and efficient, high
The method of selective enumeration method fluorine ion and inferior sulfate radical content causes the great interest of researchers.(Featherstone
J.D.B..Prevention and reversal of dental caries：role of low level fluoride
[J] .Community dentistry and oral epidemiology, 1999,27 (1)：31-40.Barbier O.,
Arreola-Mendoza L., Del Razo L.M..Molecular mechanisms of fluoride toxicity
[J] .Chemico-Biological Interactions, 2010,188 (2)：319-333.McFeeters R.F..Use
and removal of sulfite by conversion to sulfate in the preservation of salt-
free cucumbers[J].Journal of Food1998,61 (7)：885-890.Silva K.R.B.,
Raimundo I.M., Gimenez I.F., et al.Optical sensor for sulfur dioxide
Determination in wines [J] .Journal of agricultural and food chemistry, 2006,54
(23)：8697-8701.Kuratli M., Badertscher M., Rusterholz B., et al.Bisulfite
addition reaction as the basis for a hydrogensulfite bulk optode[J]
.Analytical Chemistry, 1993,65 (23)：3473-3479.)
Fluorescence probe has the advantages that easy to operate, high sensitivity, selectivity is good, the range of linearity is wide, therefore is used extensively
In the measurement of ion concentration.In recent years, the fluorescence probe of a large amount of measurement fluorine ions of document report, inferior sulfate radical.But these
The overwhelming majority is unifunctional in probe, i.e., single object can only be identified in a kind of fluorescence probe.Therefore, multi-functional glimmering
The development of light probe causes the great interest of people.Multifunction fluorescent probe refers to that a kind of fluorescence probe can be to different objects
It is identified, generates different fluorescence signals, to realize the multifunctional usage of probe.However currently, have difunctional glimmering
Light probe is rarely reported.In addition, Ratiometric fluorescent probe is to fluorescence intensity at two different wave lengths by making ratio, and compared with it
Value as detection signal, effectively eliminate based on Single wavelength detection fluorescence probe existing for be such as vulnerable to detection substrate concentration,
The interference of the uncertain factors such as external environment and instrument and equipment sensitivity.Therefore, structure is a kind of detecting fluorine ion and sulfurous simultaneously
The difunctional Ratiometric fluorescent probe of acid group has a very important significance health and food security.(Zhou Y., Zhang
J.F., Yoon J..Fluorescence and Colorimetric Chemosensors for Fluoride-Ion
Detection [J] .Chemical reviews, 2014.Komatsu H., Miki T., Citterio D., et
Al.Single molecular multianalyte (Ca2+, Mg2+) fluorescent probe and applications
To bioimaging [J] .Journal of the American Chemical Society, 2005,127 (31)：10798-
10799.Long L., Zhou L., Wang L., et al.A highly selective and sensitive
fluorescence ratiometric probe for cyanide and its application for the
detection of cyanide in natural water and biological samples[J].Analytical
Methods, 2013,5 (23)：6605-6610.Pati P. B., Zade S.S..Dicyanovinyl terthiophene
as a reaction based colorimetric and ratiometric fluorescence probe for
Cyanide anions [J] .RSC Advances, 2013,3 (32)：13457-13462.)
Invention content
For the above situation, a kind of synthesis of an object of the present invention offer is simple, reaction condition is mild, lower-cost
Fluorescence probe synthetic method；The second purpose be to provide a kind of good selectivity, high sensitivity, being capable of Ratio-type detection fluorine ion and Asia
The difunctional fluorescence probe of sulfate radical
The difunctional fluorescent molecular probe of Ratio-type detection fluorine ion and inferior sulfate radical that the present invention uses, using benzo thiophene
Zole derivatives and tert-butyl chloro-silicane synthesize in methylene chloride, and tert-butyldimethyl silyl ether and 2- cyanoacrylate nitriles are made
For recognition group.
The present invention solves the problems, such as that the technical solution taken is, a kind of Ratio-type detection fluorine ion and inferior sulfate radical it is difunctional
Fluorescent molecular probe has following structure general formula：
Wherein：R1For one kind in t-Butyldimethylsilyl and tert-butyl diphenyl silicon substrate, R2For-CN ,-COOCH2CH3
In one kind.
As R in Formulas I1For t-Butyldimethylsilyl, R2For cyano when, the synthetic route of representative compound of the present invention is such as
Shown in lower：
Specific preparation method includes the following steps：
(1) near amino thiophenols and 4- cresotinic acids are dissolved in toluene, maintain the temperature at 35 DEG C or so, is slowly added dropwise
Phosphorus trichloride, temperature reaction.After reaction, it is cooled to room temperature, is spin-dried for solvent, 2- (4- first is obtained after column chromatographic isolation and purification
Base -2- hydroxy phenyls) benzothiazole；
(2) 2- (4- methyl -2- hydroxy phenyls) benzothiazole is dissolved in dichloromethane, chloroacetic chloride and triethylamine is added,
After stirring 2h at room temperature, reaction mixture is poured into water, dichloromethane extraction, saturated common salt water washing merges organic layer
It is used in combination anhydrous sodium sulfate to dry, is spin-dried for solvent, 2- (4- methyl -2- acetoxyl groups phenyl) benzo thiophene is obtained after column chromatographic isolation and purification
Azoles (compound 5)；
(3) by compound 5, N- bromo-succinimides and benzoyl peroxide are dissolved in carbon tetrachloride, are heated to reflux
24h.After reaction, reaction mixture is poured into ice water, chloroform extraction, merges organic layer and is done with anhydrous sodium sulfate
It is dry, it is concentrated under reduced pressure, 2- (4- bromomethyl -2- acetoxyl groups phenyl) benzothiazole (compound 4) is obtained after column chromatographic isolation and purification；
(4) compound 4 and hexamethylenetetramine are dissolved in chloroform, are heated to reflux 12h, be spin-dried for solvent, 50% ice is added
Acetic acid is heated to reflux, and after reaction, sodium hydroxide solution tune pH, chloroform extraction, anhydrous sodium sulfate drying is added to be concentrated under reduced pressure.
The solid obtained after concentration is dissolved in dichloromethane, potassium hydroxide is added, is heated to reflux 1h, after reaction, adds hydrochloric acid molten
Liquid tune pH, dichloromethane extraction, anhydrous sodium sulfate drying are spin-dried for solvent, 2- (- 2 hydroxyls of 4- aldehyde radicals are obtained after column chromatographic isolation and purification
Base phenyl) benzothiazole (compound 3)；
(5) under nitrogen protection, compound 3 and malononitrile are dissolved in absolute ethyl alcohol, piperidines is added, stirs 4h at room temperature
Afterwards, yellow solid is precipitated, vacuum filtration is used absolute ethyl alcohol and dichloromethane rinse, obtained after column chromatographic isolation and purification pure respectively
Compound 2.
(6) compound 2 and tert-butyl chloro-silicane are dissolved in dichloromethane, triethylamine is added, stirs at room temperature
Overnight, after reaction, reaction mixture is poured into saturated salt solution, dichloromethane extraction merges organic layer, anhydrous sulphur
Sour sodium drying, is spin-dried for solvent, column chromatographic isolation and purification obtains pure probe compound 1.
It is described in more detail in the embodiment of this specification synthesis and the detection method of the probe.The fluorescence of the present invention
Molecular probe application method is not particularly limited.Probe molecule can be usually dissolved in acetonitrile and aqueous solution (4: 1), room temperature
Under tested.After fluorine ion is added, the tert-butyldimethyl silyl ether in molecular probe can be selectively cut due to fluorine ion
(seeing below formula) makes the ESIPT processes of probe restore to release hydroxyl, and red shift occurs for the ultraviolet and fluorescence spectrum of system.Separately
On the one hand, after inferior sulfate radical is added, since β-position that inferior sulfate radical adds to 2- cyanoacrylates nitrile in compound 1 (is seen below
Formula), destroy the conjugated structure of compound 1 leads to the ultraviolet and fluorescence spectrum of reaction system to make ICT processes be suppressed
Blue shift occurs.
The specific features of the difunctional fluorescent molecular probe of Ratio-type detection fluorine ion and inferior sulfate radical of the present invention are as follows：
Probe molecule maximum absorption wavelength is in 386nm, and maximum emission wavelength is in 498nm；Probe is in 80% acetonitrile solution
Middle dissolubility is preferable, and with the addition of fluorine ion, absorption maximum of the probe molecule at 386nm is gradually reduced, while probe point
The new absorption peak that son occurs at 352nm and 391nm gradually increases, absorption spectrum blue shift 34nm；In fluorescence spectrum, probe
Fluorescence intensity of the molecule at 498nm is gradually reduced, while occurring a new emission peak at 634nm, and the emission peak
It is gradually increased with the increase of fluorinion concentration, about 291 times of Fluorescence Increasing, fluorescence spectrum red shift 136nm, in ultraviolet lamp
Under irradiation, the color of probe solution becomes Chinese red by blue-green.When sulfurous acid is added into 80% acetonitrile solution of probe
After root, absorption maximum of the probe molecule at 386nm gradually weakens, while the new absorption peak occurred at 325nm and 299nm
It gradually increases；In fluorescence spectrum, fluorescence intensity of the probe molecule at 498nm is gradually reduced, while occurring one at 371nm
New emission peak, and the emission peak gradually increases, about 9445 times of Fluorescence Increasing, fluorescence with the increase of inferior sulfate radical concentration
Blue spectral shift 127nm, under the irradiation of ultraviolet lamp, the color of probe solution becomes bluish violet by blue-green.Be added fluorine from
After son or inferior sulfate radical, apparent red shift or blue shift occur respectively for the fluorescence spectrum of probe solution, show that different fluorescence is rung
Induction signal, to realize that the difference to both ions detects.
Probe molecule sensitivity of the present invention is higher, stable optical performance, raw material is easy to get, synthetic yield is higher, right
Fluorine ion and inferior sulfate radical recognition capability are strong, fast response time, make the difunctional fluorescence probe in biochemistry, environmental science
Equal fields have practical application value.
Description of the drawings
The ultraviolet suction before and after 400 μM of fluorine ions is added in acetonitrile and aqueous solution (4: 1) in the fluorescence probe 1 of Fig. 1 present invention
The situation of change of spectrum is received, abscissa is wavelength, and ordinate is absorbance.
In acetonitrile and aqueous solution (4: 1), fluorescence emission spectrum increases the fluorescence probe 1 of Fig. 2 present invention with fluorinion concentration
The situation of change added, abscissa are wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Fig. 3 present invention is in acetonitrile and aqueous solution (4: 1), and ultra-violet absorption spectrum is with inferior sulfate radical concentration
Increased situation of change, abscissa are wavelength, and ordinate is absorbance.
The fluorescence probe 1 of Fig. 4 present invention is in acetonitrile and aqueous solution (4: 1), and fluorescence emission spectrum is with inferior sulfate radical concentration
Increased situation of change, abscissa are wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Fig. 5 present invention is in acetonitrile and aqueous solution (4: 1), fluorescence intensity ratio (I634/I498) and fluorine from
The linear relationship of sub- concentration, abscissa are the concentration of fluorine ion, and ordinate is fluorescence intensity ratio (I634/I498)。
The fluorescence probe 1 of Fig. 6 present invention is in acetonitrile and aqueous solution (4: 1), fluorescence intensity ratio (I371/I498) and sulfurous
The linear relationship of acid group concentration, abscissa are the concentration of inferior sulfate radical, and ordinate is fluorescence intensity ratio (I371/I498)。
The fluorescence probe 1 of Fig. 7 present invention is separately added into different testers in acetonitrile and aqueous solution (4: 1)：blank；
Br-；I-；NO2 -；NO3 -；CO3 2-；ClO4 -；Cl-；SO4 2-；H2PO4 -；SCN-；Cys；AcO-；GSH；Hcy；F-Probe solution fluorescence afterwards
The situation of change of spectrum, abscissa are wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Fig. 8 present invention is separately added into different testers in acetonitrile and aqueous solution (4: 1)：blank；
AcO-；Br-；Cl-；ClO-；ClO4-；CN-；CO3 2-；Cys；GSH；H2O2；S2O3 2-；H2PO4 -；Hcy；I-；NO2 -；N3 -；NO3 -；
SCN-；SO4 2-；SO3 2-The situation of change of probe solution fluorescence spectrum afterwards, abscissa are wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Fig. 9 present invention is in acetonitrile and aqueous solution (4: 1), in other competing ions and sulfhydryl compound
Br-；I-；NO2 -；NO3 -；CO3 2-；ClO4 -；Cl-；SO4 2-；H2PO4 -；SCN-；Cys；AcO-；GSH；Fluorine ion is added in the presence of Hcy
Fluorescence intensity change afterwards.Abscissa is wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Figure 10 present invention is in acetonitrile and aqueous solution (4: 1), in other competing ions and sulfhydryl compound
AcO-；Br-；Cl-；ClO-；ClO4 -；CN-；CO3 2-；Cys；GSH；H2O2；S2O3 2-；H2PO4 -；Hcy；I-；NO2 -；N3 -；NO3 -；
SCN-；SO4 2-In the presence of be added inferior sulfate radical after fluorescence intensity change.Abscissa is wavelength, and ordinate is fluorescence intensity.
The fluorescence probe 1 of Figure 11 present invention reacts front and back fluorescence intensity ratio with fluorine ion in the ranges of pH=2~12
(I634/I498) with the situation of change of pH value, abscissa pH, ordinate is fluorescence intensity ratio (I634/I498)。
The fluorescence probe 1 of Figure 12 present invention reacts front and back fluorescence intensity ratio with inferior sulfate radical in the ranges of pH=2~12
It is worth (I371/I498) with the situation of change of pH value, abscissa pH, ordinate is fluorescence intensity ratio (I371/I498)。
The fluorescence probe 1 of Figure 13 present invention is in acetonitrile and aqueous solution (4: 1), and after 40 equivalent fluorine ions are added, fluorescence is strong
Spend ratio (I634/I498) change with time situation, abscissa is the time, and ordinate is fluorescence intensity ratio (I634/I498)。
The fluorescence probe of Figure 14 present invention is in acetonitrile and aqueous solution (4: 1), and after 7 equivalent inferior sulfate radicals are added, probe exists
Fluorescence intensity at 371nm changes with time situation, and abscissa is the time, and ordinate is fluorescence intensity.
The nuclear magnetic resonance spectroscopy of Figure 15 benzothiazole compounds 5.
The nuclear magnetic resonance spectroscopy of Figure 16 benzothiazole compounds 4.
The nuclear magnetic resonance spectroscopy of Figure 17 benzothiazole compounds 3.
2 nuclear magnetic resonance spectroscopy of Figure 18 benzothiazole compounds.
The nuclear magnetic resonance spectroscopy of Figure 19 probe compounds 1.
Specific implementation mode
Embodiment 1：The preparation of 2- (4- methyl -2- hydroxy phenyls)-benzothiazole
Method according to the literature synthesizes 2- (4- methyl -2- hydroxy phenyls)-benzothiazole.Weigh 8.2g
(66mmol) near amino thiophenols and 10.0g (66mmol) 4- cresotinic acids are dissolved in 70ml toluene, are added under nitrogen protection
Heat is to 50-55 DEG C, stir about 2.5h.Then, 35 DEG C or so are cooled to, the tri-chlorination of 6.2ml is slowly added dropwise into above-mentioned system
Phosphorus, after phosphorus trichloride drips, mixed solution is white thick, is continuously heating to 85 DEG C, and after stirring 5h, system becomes clear
Clear solution.It waits for after reaction, being spin-dried for solvent, (dichloromethane: petroleum ether=1: 10), 6.4g2- (4- is obtained through column chromatography for separation
Methyl -2- hydroxy phenyls)-benzothiazole, yield 40.3%.
Embodiment 2：The preparation of 2- (4- methyl -2- acetoxyl groups phenyl) benzothiazole (compound 5)
5.0g (20.7mmol) 2- (4- methyl -2- hydroxy phenyls)-benzothiazole is weighed to be dissolved in 60ml dichloromethane, add
Enter 2.5g (24.9mmol) triethylamine, after stirring 5min, 1.95g (24.9mmol) chloroacetic chloride is added into system, is stirred at room temperature
2h, TLC contact plate monitor, it is found that raw material point disappears substantially.40ml water quenchings are added to go out reaction, dichloromethane extracts, saturated salt solution
Washing, anhydrous sodium sulfate drying, column chromatographic isolation and purification (ethyl acetate: petroleum ether=1: 16) obtains 4.7g chemical combination after being spin-dried for solvent
Object 5, yield 80%.1H NMR (400MHz, CDCl3) δ 8.23 (d, J=8.1Hz, 1H), 8.11 (d, J=8.1Hz, 1H),
7.94 (d, J=7.5Hz, 1H), 7.53 (t, J=7.7Hz, 1H), 7.46-7.39 (m, 1H), 7.24 (d, J=8.1,1H),
7.09 (s, 1H), 2.51 (s, 3H), 2.46 (s, 3H).
Embodiment 3：The preparation of 2- (4- bromomethyl -2- acetoxyl groups phenyl) benzothiazole (compound 4)
Weigh 3.5g (12.4mmol) compound 5,0.06g (0.025mmol) benzoyl peroxide, 2.4g (13.5mmol)
N- bromo-succinimides are dissolved in 50ml drying carbon tetrachloride solutions, and return stirring is for 24 hours.After reaction, mixture is fallen
Enter into ice water, chloroform extraction, anhydrous sodium sulfate drying is spin-dried for solvent, column chromatographic isolation and purification (ethyl acetate: petroleum ether=1
: 14) obtain 2.3g compounds 4, yield 51.3%.1H NMR (400MHz, CDCl3) δ 8.35 (d, J=8.1Hz, 1H), 8.12
(d, J=7.9Hz, 1H), 7.96 (d, J=7.4Hz, 1H), 7.58-7.52 (m, 1H), 7.48-7.42 (m, 2H), 7.33 (s,
1H), 4.54 (s, 2H), 2.52 (s, 3H).
Embodiment 4：The preparation of 2- (- 2 hydroxy phenyl of 4- aldehyde radicals) benzothiazole (compound 3)
It weighs 1.5g (4.1mmol) compound 4 and 1.3g (9.1mmol) urotropine is dissolved in 40ml chloroforms,
Return stirring 8h, is spin-dried for chloroform, and the acetic acid solution of 20ml50%, return stirring 2h is added.After reaction, water quenching is added to go out instead
It answers, suitable sodium hydroxide solution regulation system pH is added to neutrality, chloroform extraction merges organic layer, and anhydrous sodium sulfate is dried,
It is concentrated under reduced pressure.Then, the solid of concentration gained is dissolved in 20ml dichloromethane, 0.3g potassium hydroxide, return stirring 1h is added.
It waiting for that reaction mixture is cooled to room temperature, adds dilute hydrochloric acid solution regulation system pH to neutrality, dichloromethane extraction merges organic layer,
Anhydrous sodium sulfate is dried, and organic layer is merged, and is spin-dried for solvent, and column chromatographic isolation and purification (ethyl acetate: petroleum ether=1: 16) obtains
317mg compounds 3 (yield 30%).1H NMR (400MHz, CDCl3) δ 10.04 (s, 1H), 8.07 (d, J=7.8Hz, 1H),
7.97 (d, J=8.0Hz, 1H), 7.87 (d, J=8.0Hz, 1H), 7.63-7.55 (m, 2H), 7.50 (t, J=7.5Hz, 2H).
Embodiment 5：The preparation of compound 2
Under nitrogen protection, in addition 300mg (1.17mmol) compound 3 and 156mg in the round-bottomed flask of 50mL
(2.34mmol) malononitrile is dissolved with 30mL absolute ethyl alcohols, and 1-2 drop piperidines is then added into system, stirs 4h at room temperature,
TLC contact plates monitor, until raw material point disappears substantially.After reaction, it is filtered by vacuum, with absolute ethyl alcohol and each rinse of dichloromethane
2-3 times, column chromatographic isolation and purification (ethyl acetate: petroleum ether=14: 1) obtains 180mg compounds 2, yield 50%.1H NMR
(400MHz, DMSO) δ 12.08 (s, 1H), 8.56 (s, 1H), 8.49 (d, J=8.3Hz, 1H), 8.20 (d, J=7.9Hz, 1H),
8.12 (d, J=8.0Hz, 1H), 7.71 (d, J=1.5Hz, 1H), 7.62-7.55 (m, 2H), 7.53-7.48 (m, 1H).
Embodiment 6：The preparation of probe compound 1
Into the round-bottomed flask of 25mL, 100mg (0.33mmol) compound 2 is added, is dissolved with 25mL dichloromethane, then
75mg (0.5mmol) tert-butyl chloro-silicanes and 66mg (0.66mmol) triethylamine are added into system, stirs at room temperature
Overnight, TLC contact plates monitoring, until raw material point disappears substantially.After reaction, above-mentioned reaction system is poured into 25mL saturated common salts
In water, dichloromethane extraction merges organic layer, adds anhydrous sodium sulfate to dry, be spin-dried for solvent, column chromatographic isolation and purification (dichloromethane
Alkane: 96mg probe compounds 1, yield 73% petroleum ether=4: 1) are obtained.1HNMR (500MHz, CDCl3) δ 8.68 (d, J=
8.2Hz, 1H), 8.18 (d, J=8.2Hz, 1H), 8.01 (d, J=8.0Hz, 1H), 7.79-7.73 (m, 2H), 7.60-7.56
(m, 1H), 7.47 (m, 2H), 1.07 (s, 9H), 0.52 (s, 6H).
Embodiment 7：Application application of the probe compound 1 in detection fluorine ion and inferior sulfate radical
Probe 1 is dissolved in acetonitrile solution, corresponding tester solution is added, is configured to 10 × 10-6M (acetonitriles: HEPES
Buffer solution=4: 1) solution after being uniformly mixed reaction fully, surveys its ultra-violet absorption spectrum and fluorescence spectrum variation.Fig. 1-Figure 17
Show that the difunctional fluorescence probe 1 all has very high selectivity to fluorine ion and inferior sulfate radical.With the increasing of fluorinion concentration
Add, significant change occurs for ultraviolet spectra and fluorescence spectrum, and fluorescence intensity enhances about 291 times, and probe not by other it is cloudy from
The influence of son and sulfhydryl compound, such as Br-；I-；NO2 -；NO3 -；CO3 2-；ClO4 -；Cl-；SO4 2-；H2PO4 -；SCN-；Cys；AcO-；
GSH；Hcy.Even if there is response well to fluorine ion if the double function probe under the conditions of existing for interfering ion；It is another
Aspect, with the increase of inferior sulfate radical concentration, significant change, fluorescence intensity enhancing occur for the ultraviolet spectra and fluorescence spectrum of probe
About 9445 times, and probe is not influenced by other anion and sulfhydryl compound, such as AcO-；Br-；Cl-；ClO-；ClO4 -；
CN-；CO3 2-；Cys；GSH；H2O2；S2O3 2-；H2PO4 -；Hcy；I-；NO2 -；N3 -；NO3 -；SCN-；SO4 2-.Even if being deposited in interfering ion
Under the conditions, which also has response well to inferior sulfate radical.
Claims (2)
1. a kind of Ratio-type detects fluorine ion and the difunctional fluorescent molecular probe of inferior sulfate radical simultaneously, it is characterized in that in Formulas I
Chemical structural formula：
Wherein：R1For one kind in t-Butyldimethylsilyl and tert-butyl diphenyl silicon substrate, R2For-CN ,-COOCH2CH3
In one kind.
2. Ratio-type according to claim 1 detects fluorine ion and inferior sulfate radical fluorescent molecular probe simultaneously, feature exists
It is carried out as follows in synthetic method：
1) 2- (4- methyl -2- hydroxy phenyls) benzothiazole is dissolved in dichloromethane, chloroacetic chloride is added and triethylamine, room temperature are stirred
After the completion of mixing reaction, reaction mixture is poured into water, is extracted with dichloromethane, saturated common salt water washing merges organic layer
It is used in combination anhydrous sodium sulfate to dry, is spin-dried for solvent, 2- (4- methyl -2- acetoxyl groups phenyl) benzo thiophene is obtained after column chromatographic isolation and purification
Azoles；
2) by 2- (4- methyl -2- acetoxyl groups phenyl) benzothiazole, N- bromo-succinimides and benzoyl peroxide are dissolved in
It in carbon tetrachloride, is heated to reflux, after reaction, reaction mixture is poured into ice water, chloroform extraction merges organic layer simultaneously
It is dried with anhydrous sodium sulfate, organic solvent is removed under reduced pressure, 2- (4- bromomethyl -2- acetoxyl groups are obtained after column chromatographic isolation and purification
Phenyl) benzothiazole；
3) 2- (4- bromomethyl -2- acetoxyl groups phenyl) benzothiazoles and hexamethylenetetramine are dissolved in chloroform, are heated to reflux,
It is spin-dried for solvent, 50% glacial acetic acid is added, is heated to reflux, after reaction, adds sodium hydroxide solution tune pH, chloroform extraction anhydrous
Sodium sulphate is dried, and is concentrated under reduced pressure, the solid being concentrated to give is dissolved in dichloromethane, and potassium hydroxide, back flow reaction, reaction is added
After, add hydrochloric acid solution tune pH, dichloromethane extraction, anhydrous sodium sulfate drying to be spin-dried for solvent, after column chromatographic isolation and purification
To 2- (- 2 hydroxy phenyl of 4- aldehyde radicals) benzothiazole；
4) under nitrogen protection, by 2- (- 2 hydroxy phenyl of 4- aldehyde radicals) benzothiazole respectively in malononitrile, ethyl cyanoacetate
One kind is dissolved in absolute ethyl alcohol, and piperidines is added, is stirred at room temperature, after reaction, vacuum filtration, absolute ethyl alcohol rinse, column chromatography
The pure compound with chemical structural formula in Formula II is obtained after isolating and purifying：
Wherein：R2For-CN ,-COOCH2CH3In one kind
5) compound in Formula II is dissolved in one kind in tert-butyl chloro-silicane, tert-butyl diphenyl chlorosilane respectively
In dichloromethane, triethylamine is added, is stirred overnight at room temperature, after reaction, reaction mixture is poured into saturated salt solution
In, dichloromethane extraction merges organic layer, and anhydrous sodium sulfate drying is spin-dried for solvent, column chromatographic isolation and purification obtains in Formulas I
Target product.
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