CN104610955A - Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical - Google Patents
Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical Download PDFInfo
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- 0 *C(C#N)=C[C@@](C1)C=CC(c2nc(cccc3)c3[s]2)=C1O Chemical compound *C(C#N)=C[C@@](C1)C=CC(c2nc(cccc3)c3[s]2)=C1O 0.000 description 1
Abstract
The invention relates to a synthesis method and application of a ratiometric fluorescent molecular probe for simultaneously detecting a fluorine ion and a sulfite radical. The ratiometric fluorescent molecular probe adopts a 2-(2-hydroxyphenyl)benzothiazole derivative as a matrix structure, and detects the fluorine ion and the sulfite radical based on excited-state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT) mechanisms, respectively. The probe has a maximum emission wavelength of 498 nm in an acetonitrile solution with a concentration of 80%, when the fluorine ion is added, the fluorescence spectrum of the probe has a red shift of 136 nm; and when the sulfite radical is added, the fluorescence spectrum of the probe has a blue shift of 127 nm. The differentiated detection of the two ions can be realized by the fact that the fluorescence spectrum of the probe has an obvious red shift or blue shift after the fluorine ion or sulfite radical is added, respectively, showing different fluorescence response signals. The inventive fluorescent probe has the advantages of simple operation, mild reaction conditions, easy purification, high synthesis yield, good selectivity, high sensitivity and stable optical performances. At the same time, the design and synthesis of the fluorescent probe provide an important foundation for development of multi-functional fluorescent probes in the future.
Description
Technical field
What the present invention relates to is chemical analysis detection technique field, is specifically related to preparation method and the application of this fluorescent molecular probe in detection fluorion and inferior sulfate radical that a kind of Ratio-type detects fluorion and the difunctional fluorescent molecular probe of inferior sulfate radical simultaneously.
Background technology
Fluorion radius is little, electronegativity strong, has special chemical property, thus causes investigators' interest greatly.In addition, fluorine, as one of required trace element of human life activity, plays an important role to preventing dental caries and clinical treatment osteoporosis.But the fluorine of excess intake in human body, easily brings out the diseases such as dental fluorosis, skeletal fluorosis, urinary stone disease and kidney disorder.Sulphite is as a kind of important foodstuff additive, be widely used in foodstuffs industry, due to its have bleaching, antibacterial, protect look, the multiple efficiency such as anticorrosion and anti-oxidant, be added in veterinary antibiotics, can based food, production vinous and storage process gradually, with the generation suppressing Enzymes In Food to urge brown stain and nonenzymatic browning reaction.But the health of sulphite to human body of high density is harmful, and especially some is to the people of sulphite allergy, even if take in a small amount of sulphite also easily produce the diseases such as asthma, allergic, gastrointestinal upset.In addition, containing a large amount of reductibility sulphite in trade effluent, the concentration of oxygen in water can be had a strong impact on, thus serious harm is caused to ecotope.Therefore, set up a kind of method that convenient and swift, highly selective detects fluorion and inferior sulfate radical content, cause investigators' interest greatly.(Featherstone J.D.B..Prevention and reversal of dental caries：role of low level fluoride[J].Community dentistry and oralepidemiology，1999，27(1)：31-40.Barbier O.，Arreola-Mendoza L.，Del Razo L.M..Molecularmechanisms 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-freecucumbers[J].Journal of Food
1998，61(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 ofagricultural and food chemistry，2006，54(23)：8697-8701.Kuratli M.，Badertscher M.，RusterholzB.，et al.Bisulfite addition reaction as the basis for a hydrogensulfite bulk optode[J].AnalyticalChemistry，1993，65(23)：3473-3479.)
The advantages such as fluorescent probe has easy and simple to handle, highly sensitive, and selectivity is good, linearity range is wide, are therefore widely used in the mensuration of ion content.In recent years, the fluorescent probe of the large flow measurement fluorion of bibliographical information, inferior sulfate radical.But the overwhelming majority is unifunctional in these probes, namely a kind of fluorescent probe can only identify single object.Therefore, the development of Multifunction fluorescent probe causes the great interest of people.Multifunction fluorescent probe refers to that a kind of fluorescent probe can identify different object, produces different fluorescent signals, thus realizes the multifunctional usage of probe.But at present, possess bifunctional fluorescent probe and rarely have report.In addition, Ratiometric fluorescent probe is by making ratio to two different wave length place fluorescence intensities, and using its ratio as detection signal, effectively eliminate the interference being such as vulnerable to the uncertain factors such as detection substrate concentration, outside atmosphere and plant and instrument sensitivity detecting fluorescent probe existence based on Single wavelength.Therefore, build one and detect fluorion and the difunctional Ratiometric fluorescent probe of inferior sulfate radical is of great significance HUMAN HEALTH and food safety tool simultaneously.(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 sensitivefluorescence ratiometric probe for cyanide and its application for the detection of cyanide in naturalwater 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 forcyanide anions[J].RSC Advances，2013，3(32)：13457-13462.)
Summary of the invention
For above-mentioned situation, an object of the present invention provides a kind of and synthesizes simple, gentle, the lower-cost fluorescent probe synthetic method of reaction conditions; Two of object be to provide a kind of selectivity good, highly sensitive, the difunctional fluorescent probe of fluorion and inferior sulfate radical can be detected by Ratio-type
The Ratio-type that the present invention uses detects the difunctional fluorescent molecular probe of fluorion and inferior sulfate radical, and adopt benzothiazole derivant and TERT-BUTYL DIMETHYL CHLORO SILANE to synthesize in methylene dichloride, tert-butyldimethyl silyl ether and 2-cyanoacrylate nitrile are as recognition group.
The present invention's technical scheme taked of dealing with problems is, a kind of Ratio-type detects the difunctional fluorescent molecular probe of fluorion and inferior sulfate radical, has following general structure:
Wherein: R
1for t-Butyldimethylsilyl and tert-butyl diphenyl silica-based in one, R
2for-CN ,-COOCH
2cH
3in one.
As R in formula I
1for t-Butyldimethylsilyl, R
2during for cyano group, the synthetic route of representative compound of the present invention is as follows:
Concrete preparation method comprises the following steps:
(1) near amino thiophenols and 4-cresotinic acid are dissolved in toluene, maintain the temperature at about 35 DEG C, slowly drip phosphorus trichloride, temperature reaction.After reaction terminates, be cooled to room temperature, be spin-dried for solvent, after column chromatographic isolation and purification, obtain 2-(4-methyl-2-hydroxy phenyl) benzothiazole;
(2) 2-(4-methyl-2-hydroxy phenyl) benzothiazole is dissolved in methylene dichloride, add Acetyl Chloride 98Min. and triethylamine, after stirred at ambient temperature 2h, reaction mixture is poured in water, dichloromethane extraction, saturated common salt water washing, merges organic layer and uses anhydrous sodium sulfate drying, be spin-dried for solvent, after column chromatographic isolation and purification, obtain 2-(4-methyl-2-acetoxyl group phenyl) benzothiazole (compound 5);
(3) compound 5, N-bromo-succinimide and benzoyl peroxide are dissolved in tetracol phenixin, reflux 24h.After reaction terminates, reaction mixture is poured in frozen water, chloroform extraction, merges organic layer and use anhydrous sodium sulfate drying, concentrating under reduced pressure, obtains 2-(4-brooethyl-2-acetoxyl group phenyl) benzothiazole (compound 4) after column chromatographic isolation and purification;
(4) be dissolved in chloroform by compound 4 and hexamethylenetetramine, reflux 12h, be spin-dried for solvent, add 50% Glacial acetic acid, reflux, after reaction terminates, hydro-oxidation sodium solution adjusts pH, chloroform extraction, anhydrous sodium sulfate drying, concentrating under reduced pressure.The solid obtained after concentrated is dissolved in methylene dichloride, add potassium hydroxide, reflux 1h, after reaction terminates, add hydrochloric acid soln and adjust pH, dichloromethane extraction, anhydrous sodium sulfate drying, be spin-dried for solvent, after column chromatographic isolation and purification, obtain 2-(4-aldehyde radical-2 hydroxy phenyl) benzothiazole (compound 3);
(5), under nitrogen protection, compound 3 and propane dinitrile are dissolved in dehydrated alcohol, add piperidines; after stirred at ambient temperature 4h, separate out yellow solid, vacuum filtration; use dehydrated alcohol and methylene dichloride rinse respectively, after column chromatographic isolation and purification, obtain pure compound 2.
(6) compound 2 and TERT-BUTYL DIMETHYL CHLORO SILANE are dissolved in methylene dichloride, add triethylamine, room temperature for overnight, after reaction terminates, is poured into reaction mixture in saturated aqueous common salt, dichloromethane extraction, merge organic layer, anhydrous sodium sulfate drying, is spin-dried for solvent, column chromatographic isolation and purification, obtains pure probe compound 1.
Synthesis and the detection method of this probe is illustrate in greater detail in the embodiment of this specification sheets.Fluorescent molecular probe using method of the present invention is not particularly limited.Usually probe molecule can be dissolved in acetonitrile and the aqueous solution (4: 1), test under room temperature.After adding fluorion, due to the tert-butyldimethyl silyl ether (see following formula) in fluorion energy selectivity cutting molecular probe, thus discharge hydroxyl, make the ESIPT course recovery of probe, the ultraviolet of system and fluorescence spectrum generation red shift.On the other hand, after adding inferior sulfate radical, because inferior sulfate radical adds to the β-position (see following formula) of 2-cyanoacrylate nitrile in compound 1, destroy the conjugated structure of compound 1, thus ICT process is suppressed, cause ultraviolet and the fluorescence spectrum generation blue shift of reaction system.
The specific features that Ratio-type of the present invention detects the difunctional fluorescent molecular probe of fluorion and inferior sulfate radical is as follows:
Probe molecule maximum absorption wavelength is at 386nm, and maximum emission wavelength is at 498nm; Probe solvability in 80% acetonitrile solution is better, and along with adding of fluorion, probe molecule declines gradually in the maximum absorption at 386nm place, and the new absorption peak that probe molecule occurs at 352nm and 391nm place simultaneously strengthens gradually, absorption spectrum blue shift 34nm; In fluorescence spectrum, probe molecule declines gradually in the fluorescence intensity at 498nm place, simultaneously at the emission peak that 634nm place appearance one is new, and this emission peak strengthens gradually along with the increase of fluorinion concentration, Fluorescence Increasing about 291 times, fluorescence spectrum red shift 136nm, under the irradiation of ultraviolet lamp, the color of probe solution becomes orange by blue-greenish colour.After add inferior sulfate radical in probe 80% acetonitrile solution, probe molecule weakens gradually in the maximum absorption at 386nm place, and the new absorption peak simultaneously occurred at 325nm and 299nm place strengthens gradually; In fluorescence spectrum, probe molecule declines gradually in the fluorescence intensity at 498nm place, simultaneously at the emission peak that 371nm place appearance one is new, and this emission peak strengthens gradually along with the increase of inferior sulfate radical concentration, Fluorescence Increasing about 9445 times, fluorescence spectrum blue shift 127nm, under the irradiation of ultraviolet lamp, the color of probe solution becomes bluish voilet by blue-greenish colour.After adding fluorion or inferior sulfate radical, there is obvious red shift or blue shift in the fluorescence spectrum of probe solution respectively, demonstrates different fluorescence response signals, thus realize detecting the difference of these two kinds of ions.
Probe molecule sensitivity of the present invention is higher, stable optical performance, raw material are easy to get, synthetic yield is higher, fast response time strong to fluorion and inferior sulfate radical recognition capability, make this difunctional fluorescent probe in biological chemistry, and the fields such as environmental science have actual using value.
Accompanying drawing explanation
Fig. 1 fluorescent probe 1 of the present invention, in acetonitrile and the aqueous solution (4: 1), adds the changing conditions of the ultra-violet absorption spectrum before and after 400 μMs of fluorions, and X-coordinate is wavelength, and ordinate zou is absorbancy.
Fig. 2 fluorescent probe 1 of the present invention is in acetonitrile and the aqueous solution (4: 1), and the changing conditions that fluorescence emission spectrum increases with fluorinion concentration, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 3 fluorescent probe 1 of the present invention is in acetonitrile and the aqueous solution (4: 1), and the changing conditions that ultra-violet absorption spectrum increases with inferior sulfate radical concentration, X-coordinate is wavelength, and ordinate zou is absorbancy.
Fig. 4 fluorescent probe 1 of the present invention is in acetonitrile and the aqueous solution (4: 1), and the changing conditions that fluorescence emission spectrum increases with inferior sulfate radical concentration, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 5 fluorescent probe 1 of the present invention in acetonitrile and the aqueous solution (4: 1), fluorescence intensity ratio (I
634/ I
498) and the linear relationship of fluorinion concentration, X-coordinate is the concentration of fluorion, and ordinate zou is fluorescence intensity ratio (I
634/ I
498).
Fig. 6 fluorescent probe 1 of the present invention in acetonitrile and the aqueous solution (4: 1), fluorescence intensity ratio (I
371/ I
498) and the linear relationship of inferior sulfate radical concentration, X-coordinate is the concentration of inferior sulfate radical, and ordinate zou is fluorescence intensity ratio (I
371/ I
498).
Fig. 7 fluorescent probe 1 of the present invention, in acetonitrile and the aqueous solution (4: 1), adds different tester: blank respectively; Br
-; I
-; NO
2 -; NO
3 -; CO
3 2-; ClO
4 -; Cl
-; SO
4 2-; H
2pO
4 -; SCN
-; Cys; AcO
-; GSH; Hcy; F
-the changing conditions of rear probe solution fluorescence spectrum, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 8 fluorescent probe 1 of the present invention, in acetonitrile and the aqueous solution (4: 1), adds different tester: blank respectively; AcO
-; Br
-; Cl
-; ClO
-; ClO4
-; CN
-; CO
3 2-; Cys; GSH; H
2o
2; S
2o
3 2-; H
2pO
4 -; Hcy; I
-; NO
2 -; N
3 -; NO
3 -; SCN
-; SO
4 2-; SO
3 2-the changing conditions of rear probe solution fluorescence spectrum, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 9 fluorescent probe 1 of the present invention in acetonitrile and the aqueous solution (4: 1), at other competing ions and sulfhydryl compound Br
-; I
-; NO
2 -; NO
3 -; CO
3 2-; ClO
4 -; Cl
-; SO
4 2-; H
2pO
4 -; SCN
-; Cys; AcO
-; GSH; Hcy adds the fluorescence intensity change after fluorion under existing.X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Figure 10 fluorescent probe 1 of the present invention in acetonitrile and the aqueous solution (4: 1), at other competing ions and sulfhydryl compound AcO
-; Br
-; Cl
-; ClO
-; ClO
4 -; CN
-; CO
3 2-; Cys; GSH; H
2o
2; S
2o
3 2-; H
2pO
4 -; Hcy; I
-; NO
2 -; N
3 -; NO
3 -; SCN
-; SO
4 2-the fluorescence intensity change after inferior sulfate radical is added under existence.X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Figure 11 fluorescent probe 1 of the present invention, in the scope of pH=2 ~ 12, reacts the fluorescence intensity ratio (I of front and back with fluorion
634/ I
498) with the changing conditions of pH value, X-coordinate is pH, and ordinate zou is fluorescence intensity ratio (I
634/ I
498).
Figure 12 fluorescent probe 1 of the present invention, in the scope of pH=2 ~ 12, reacts the fluorescence intensity ratio (I of front and back with inferior sulfate radical
371/ I
498) with the changing conditions of pH value, X-coordinate is pH, and ordinate zou is fluorescence intensity ratio (I
371/ I
498).
Figure 13 fluorescent probe 1 of the present invention in acetonitrile and the aqueous solution (4: 1), after adding 40 equivalent fluorions, fluorescence intensity ratio (I
634/ I
498) situation over time, X-coordinate is the time, and ordinate zou is fluorescence intensity ratio (I
634/ I
498).
Figure 14 fluorescent probe of the present invention is in acetonitrile and the aqueous solution (4: 1), and after adding 7 equivalent inferior sulfate radicals, the fluorescence intensity of probe at 371nm place situation over time, X-coordinate is the time, and ordinate zou is fluorescence intensity.
The proton nmr spectra of Figure 15 benzothiazole compound 5.
The proton nmr spectra of Figure 16 benzothiazole compound 4.
The proton nmr spectra of Figure 17 benzothiazole compound 3.
Figure 18 benzothiazole compound 2 proton nmr spectra.
The proton nmr spectra of Figure 19 probe compound 1.
Embodiment
The preparation of embodiment 1:2-(4-methyl-2-hydroxy phenyl)-benzothiazole
According to the method for bibliographical information, synthesis 2-(4-methyl-2-hydroxy phenyl)-benzothiazole.Take 8.2g (66mmol) near amino thiophenols and 10.0g (66mmol) 4-cresotinic acid is dissolved in 70ml toluene, under nitrogen protection, be heated to 50-55 DEG C, stir about 2.5h.Then, be cooled to about 35 DEG C, in above-mentioned system, slowly drip the phosphorus trichloride of 6.2ml, after phosphorus trichloride drips, mixing solutions is thick white shape, continues to be warming up to 85 DEG C, and after stirring 5h, system becomes settled solution.After question response terminates, be spin-dried for solvent, through column chromatography for separation, (methylene dichloride: sherwood oil=1: 10), obtain 6.4g2-(4-methyl-2-hydroxy phenyl)-benzothiazole, productive rate is 40.3%.
The preparation of embodiment 2:2-(4-methyl-2-acetoxyl group phenyl) benzothiazole (compound 5)
Taking 5.0g (20.7mmol) 2-(4-methyl-2-hydroxy phenyl)-benzothiazole is dissolved in 60ml methylene dichloride, add 2.5g (24.9mmol) triethylamine, after stirring 5min, 1.95g (24.9mmol) Acetyl Chloride 98Min. is added in system, stirring at room temperature 2h, TLC point plate is monitored, and finds that raw material point disappears substantially.Add 40ml shrend to go out reaction, dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, be spin-dried for column chromatographic isolation and purification after solvent (ethyl acetate: sherwood oil=1: 16) 4.7g compound 5, productive rate is 80%.
1H NMR(400MHz，CDCl
3)δ8.23(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)。
The preparation of embodiment 3:2-(4-brooethyl-2-acetoxyl group phenyl) benzothiazole (compound 4)
Take 3.5g (12.4mmol) compound 5,0.06g (0.025mmol) benzoyl peroxide, 2.4g (13.5mmol) N-bromo-succinimide is dissolved in the dry carbon tetrachloride solution of 50ml, return stirring 24h.After reaction terminates, mixture is poured in frozen water, chloroform extraction, anhydrous sodium sulfate drying, is spin-dried for solvent, column chromatographic isolation and purification (ethyl acetate: sherwood oil=1: 14) obtain 2.3g compound 4, productive rate is 51.3%.
1H NMR(400MHz，CDCl
3)δ8.35(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)。
The preparation of embodiment 4:2-(4-aldehyde radical-2 hydroxy phenyl) benzothiazole (compound 3)
Take 1.5g (4.1mmol) compound 4 and 1.3g (9.1mmol) urotropin is dissolved in 40ml chloroform, return stirring 8h, is spin-dried for chloroform, adds the acetic acid solution of 20ml50%, return stirring 2h.After reaction terminates, the cancellation that adds water is reacted, and add appropriate sodium hydroxide solution regulation system pH to neutral, chloroform extraction, merges organic layer, anhydrous sodium sulfate drying, concentrating under reduced pressure.Then, the solid of concentrated gained is dissolved in 20ml methylene dichloride, adds 0.3g potassium hydroxide, return stirring 1h.Question response mixture is cooled to room temperature, add dilute hydrochloric acid solution regulation system pH to neutral, dichloromethane extraction, merge organic layer, anhydrous sodium sulfate drying, merge organic layer, be spin-dried for solvent, column chromatographic isolation and purification (ethyl acetate: sherwood oil=1: 16) obtain 317mg compound 3 (productive rate is 30%).
1H NMR(400MHz，CDCl
3)δ10.04(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; 300mg (1.17mmol) compound 3 and 156mg (2.34mmol) propane dinitrile is added in the round-bottomed flask of 50mL; use 30mL anhydrous alcohol solution; then in system, add 1-2 and drip piperidines; in stirred at ambient temperature 4h; TLC point plate is monitored, until raw material point disappears substantially.After reaction terminates, vacuum filtration, with dehydrated alcohol and each rinse 2-3 time of methylene dichloride, column chromatographic isolation and purification (ethyl acetate: sherwood oil=14: 1) obtain 180mg compound 2, productive rate is 50%.
1H NMR(400MHz，DMSO)δ12.08(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
To in the round-bottomed flask of 25mL, add 100mg (0.33mmol) compound 2, dissolve with 25mL methylene dichloride, then in system, add 75mg (0.5mmol) TERT-BUTYL DIMETHYL CHLORO SILANE and 66mg (0.66mmol) triethylamine, room temperature for overnight, TLC point plate is monitored, until raw material point disappears substantially.After reaction terminates, above-mentioned reaction system is poured in 25mL saturated aqueous common salt, dichloromethane extraction, merge organic layer, add anhydrous sodium sulfate drying, be spin-dried for solvent, column chromatographic isolation and purification (methylene dichloride: sherwood oil=4: 1) obtain 96mg probe compound 1, productive rate is 73%.
1HNMR(500MHz，CDCl
3)δ8.68(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: probe compound 1 is detecting the application of the application in fluorion and inferior sulfate radical
Probe 1 is dissolved in acetonitrile solution, adds corresponding tester solution, be mixed with 10 × 10
-6(acetonitrile: HEPES damping fluid=4: solution 1), after mixing sufficient reacting, surveys its ultra-violet absorption spectrum and fluorescence spectrum change to M.Fig. 1-Figure 17 shows, this difunctional fluorescent probe 1 pair of fluorion and inferior sulfate radical all have very high selectivity.Along with the increase of fluorinion concentration, its UV spectrum and fluorescence spectrum generation considerable change, fluorescence intensity strengthens about 291 times, and probe is not subject to the impact of other negatively charged ion and sulfhydryl compound, as Br
-; I
-; NO
2 -; NO
3 -; CO
3 2-; ClO
4 -; Cl
-; SO
4 2-; H
2pO
4 -; SCN
-; Cys; AcO
-; GSH; Hcy.Even if under interfering ion existent condition, this double function probe also has good response to fluorion; On the other hand, along with the increase of inferior sulfate radical concentration, the UV spectrum of probe and fluorescence spectrum generation considerable change, fluorescence intensity strengthens about 9445 times, and probe is not subject to the impact of other negatively charged ion and sulfhydryl compound, as AcO
-; Br
-; Cl
-; ClO
-; ClO
4 -; CN
-; CO
3 2-; Cys; GSH; H
2o
2; S
2o
3 2-; H
2pO
4 -; Hcy; I
-; NO
2 -; N
3 -; NO
3 -; SCN
-; SO
4 2-.Even if under interfering ion existent condition, this double function probe 1 also has good response to inferior sulfate radical.
Claims (3)
1. the present invention relates to preparation method and the application of this fluorescent molecular probe in detection fluorion and inferior sulfate radical that a kind of Ratio-type detects fluorion and the difunctional fluorescent molecular probe of inferior sulfate radical simultaneously, it is characterized in that the chemical structural formula had in formula I:
Wherein: R
1for t-Butyldimethylsilyl and tert-butyl diphenyl silica-based in one, R
2for-CN ,-COOCH
2cH
3in one.
2. Ratio-type according to claim 1 detects fluorion and inferior sulfate radical fluorescent molecular probe simultaneously, it is characterized in that synthetic method is carried out as follows:
1) 2-(4-methyl-2-hydroxy phenyl) benzothiazole is dissolved in methylene dichloride, add Acetyl Chloride 98Min. and triethylamine, after stirring at room temperature has been reacted, reaction mixture is poured in water, with dichloromethane extraction, saturated common salt water washing, merges organic layer and uses anhydrous sodium sulfate drying, be spin-dried for solvent, after column chromatographic isolation and purification, obtain 2-(4-methyl-2-acetoxyl group phenyl) benzothiazole;
2) by 2-(4-methyl-2-acetoxyl group phenyl) benzothiazole, N-bromo-succinimide and benzoyl peroxide are dissolved in tetracol phenixin, reflux.After reaction terminates, be poured into by reaction mixture in frozen water, chloroform extraction, merge organic layer and use anhydrous sodium sulfate drying, decompression removing organic solvent, obtains 2-(4-brooethyl-2-acetoxyl group phenyl) benzothiazole after column chromatographic isolation and purification;
3) 2-(4-brooethyl-2-acetoxyl group phenyl) benzothiazole and hexamethylenetetramine are dissolved in chloroform, reflux, be spin-dried for solvent, add 50% Glacial acetic acid, reflux, after reaction terminates, hydro-oxidation sodium solution adjusts pH, chloroform extraction, anhydrous sodium sulfate drying, concentrating under reduced pressure.The concentrated solid obtained is dissolved in methylene dichloride, adds potassium hydroxide, back flow reaction, after reaction terminates, add hydrochloric acid soln and adjust pH, dichloromethane extraction, anhydrous sodium sulfate drying, is spin-dried for solvent, obtains 2-(4-aldehyde radical-2 hydroxy phenyl) benzothiazole after column chromatographic isolation and purification;
4) under nitrogen protection; 2-(4-aldehyde radical-2 hydroxy phenyl) benzothiazole is dissolved in dehydrated alcohol with the one in propane dinitrile, ethyl cyanoacetate respectively; add piperidines; stirring at room temperature; after reaction terminates; vacuum filtration, dehydrated alcohol rinse, obtains the pure compound with chemical structural formula in formula II after column chromatographic isolation and purification:
Wherein: R
2for-CN ,-COOCH
2cH
3in one
5) compound in formula II is dissolved in methylene dichloride with the one in TERT-BUTYL DIMETHYL CHLORO SILANE, tert-butyl diphenyl chlorosilane respectively, add triethylamine, room temperature for overnight, after reaction terminates, is poured into reaction mixture in saturated aqueous common salt, dichloromethane extraction, merge organic layer, anhydrous sodium sulfate drying, is spin-dried for solvent, column chromatographic isolation and purification, obtains the target product in formula I.
3. Ratio-type according to claim 1 detects the application of fluorion and the difunctional fluorescent molecular probe of inferior sulfate radical, it is characterized in that: selected fluorion and inferior sulfate radical are respectively Sodium Fluoride, Potassium monofluoride and the inorganic salt such as S-WAT, potassium sulfite.
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