CN103275697A - Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof - Google Patents
Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof Download PDFInfo
- Publication number
- CN103275697A CN103275697A CN2013102045731A CN201310204573A CN103275697A CN 103275697 A CN103275697 A CN 103275697A CN 2013102045731 A CN2013102045731 A CN 2013102045731A CN 201310204573 A CN201310204573 A CN 201310204573A CN 103275697 A CN103275697 A CN 103275697A
- Authority
- CN
- China
- Prior art keywords
- pyrene
- fluorescent probe
- amphiphilic
- methylene dichloride
- amphiphilic fluorescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CCC(CCNS(c1ccc(cc2)c3c1ccc1cccc2c31)(=O)=O)OC*(C)CCNS(c1ccc(cc2)c3c1ccc1c3c2ccc1)(=O)=O Chemical compound CCC(CCNS(c1ccc(cc2)c3c1ccc1cccc2c31)(=O)=O)OC*(C)CCNS(c1ccc(cc2)c3c1ccc1c3c2ccc1)(=O)=O 0.000 description 1
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a di-pyrene amphiphilic fluorescent probe. The structural formula of the fluorescent probe is shown in the specification, wherein n is 2, 3, 4 or 5. The fluorescent probe has good chemical stability as well as high response speed, high sensitivity and wide response range against metal ions, and can qualitatively and quantitatively detect heavy metals such as Cu<2+>, Co<2+>, Cd<2+>, Fe<3+>, Ni<2+>, Mg<2+>, Ca<2+>, Pb<2+>, Zn<2+> and the like immediately on line. The experimental result indicates that the detection limits of Cu<2+> and Co<2+> can respectively reach 100nmol/L and 69nmol/L.
Description
Technical field
The invention belongs to the fluorescence analysis field, be specifically related to a kind of two pyrene amphiphilic fluorescent probes and synthetic method thereof that can be used for detecting metal ion.
Background technology
Metal is because good mechanical property, electric property and physical and chemical performance makes it obtain using widely in productive life.Because the difference of character, metal has been used to different fields, and in industrial production and daily life, but a large amount of uses of metal ion, especially transition metal ion have brought great influence for human life and health.Wherein most metal ions has extremely strong toxicity, and is associated with numerous disease, as alzheimer's disease.In addition, metal ion is difficult for by biodegradable character removing of its having been brought great inconvenience.Therefore, heavy metal ion has become the main source of environmental pollution, especially in the use and seawater of tap water.American National Bureau for Environmental Protection (EPA) is announced a series of transition metal ions such as chromium, manganese, cobalt, copper, zinc, molybdenum, silver, mercury, cadmium, lead, iron and nickel etc. as " primarily controlling pollutent ".
In various detection methods, fluorescent sensor molecule is simple owing to its preparation, easy handling, highly sensitive, selectivity good and it is external to can be used for or advantages such as somatometry, real-time online detection have obtained application widely.Fluorescent sensor molecule is made up of three parts usually, the connecting arm that comprises fluorescence species, acceptor and both are coupled together (can omit sometimes).The fluorescence species are exported group as signal, change recognition process into optical signal, and as the change of the optical physics signal of fluorescence species and express.These change by comprising forming or the disturbance of the generation that disappears and causing of photoinduction process that transfer transport, charge transfer, energy shift and excimer or exciplex.As the mainly highly selective combination efficiently of responsible determinand of acceptor of conjugated group, and these cohesive process depend on the character (being pH, ionic strength in the aqueous solution) of ligand molecular, cationic characteristic (ionic radius, electric charge, ligancy and ion hardness) and solvent.Because the factor that cohesive process relies on is numerous, so obtain a highly sensitive, soluble fluorescence chemical sensor is very difficult in highly selective and the water, and needs point-device design and loaded down with trivial details synthetic and purge process usually.
Summary of the invention
A technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned technology, provide a kind of highly sensitive, can detect the many two pyrene amphiphilic fluorescent probes of species of metal ion.
Another technical problem to be solved by this invention is to provide the synthetic method of the simple two pyrene amphiphilic fluorescent probes of a kind of synthetic method.
To be solved by this invention also have a technical problem to be to provide a kind of new purposes for two pyrene amphiphilic fluorescent probes.
Solving the problems of the technologies described above the technical scheme that adopts is: the structural formula of this fluorescent probe is suc as formula shown in the I:
The formula I
The value of n is 2,3,4 or 5 in the formula, and preferred n is 3.
The synthetic method of the two pyrene amphiphilic fluorescent probes of following formula is as follows:
1, synthetic 1-pyrene sodium sulfonate
Under nitrogen atmosphere, condition of ice bath, pyrene, chlorsulfonic acid are added in the methylene dichloride, stirring at room reaction 2 hours is poured reaction solution in the ice into, is stirred to the methylene dichloride volatilization fully, use the diatomite suction filtration, add the NaOH solid in filtrate, the mol ratio of pyrene and chlorsulfonic acid, NaOH is 1: 1: 1.2, suction filtration, drying, obtain 1-pyrene sodium sulfonate, its reaction equation is as follows:
2, synthetic 1-pyrene SULPHURYL CHLORIDE
1-pyrene sodium sulfonate is added N, in the dinethylformamide, be stirred to dissolving fully, the ether solution of hydrogen chloride that adds 1mol/L, stirred 10 minutes, drip thionyl chloride, the mol ratio of 1-pyrene sodium sulfonate and hydrogenchloride, thionyl chloride is 1: 0.1: 10, drips the back ice bath and stirs 3 hours, and reaction solution is poured in the ice, stirred 1 hour, suction filtration, vacuum-drying is that 1: 1.5 mixed solution is eluent silicagel column separation and purification product with the volume ratio of methylene dichloride and sherwood oil, obtain 1-pyrene SULPHURYL CHLORIDE, its reaction equation is as follows:
3, synthetic two pyrene amphiphilic fluorescent probe
Under nitrogen atmosphere, be to add in solvent at 2～2.5: 1 in molar ratio with the two propylamine of 1-pyrene SULPHURYL CHLORIDE and polyoxyethylene glycol, stir, back flow reaction 12～24 hours, extract with distilled water, the organic phase rotary evaporation is desolventized, be that 20～50: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, volume ratio with methylene dichloride and ethanol is 1: 1～5 mixed solution recrystallizations, obtain the two pyrene amphiphilic fluorescent probes of yellow-green colour lenticular solid, its reaction equation is as follows:
Above-mentioned solvent is trichloromethane or methylene dichloride; The two propylamine of polyoxyethylene glycol are ethylene glycol bis (3-amine propyl group) ether, 4,7,10-three oxygen-1,13-tridecane diamines, 4,7,10,13-four oxygen-1,16-n-Hexadecane diamines or 4,7,10,13,16-, five oxygen-1,19-nonadecane diamines, wherein preferred 4,7,10-three oxygen-1,13-tridecane diamines.
In synthetic two pyrene amphiphilic fluorescent probe steps 3 of the present invention, optimum condition is: under nitrogen atmosphere, be to add in solvent at 2.2: 1 in molar ratio with the two propylamine of 1-pyrene SULPHURYL CHLORIDE and polyoxyethylene glycol, stir, back flow reaction 24 hours, extract with distilled water, the organic phase rotary evaporation is desolventized, be that 50: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, volume ratio with methylene dichloride and ethanol is 1: 2 mixed solution recrystallization, obtains the two pyrene amphiphilic fluorescent probes shown in the formula I.
The purposes of the two pyrene amphiphilic fluorescent probes of the present invention in detecting metal ion, its using method is as follows:
Two pyrene amphiphilic fluorescent probes are dissolved in the acetonitrile, are mixed with two pyrene amphiphilic fluorescent probe acetonitrile solutions of 0.25mmol/L, join in the lauryl sodium sulfate aqueous solution of 7mmol/L, be made into two pyrene amphiphilic fluorescent probe solution of 1.0 μ mol/L; Two pyrene amphiphilic fluorescent probe solution to 1.0 μ mol/L add the known metal ion, measure fluorescence intensity with luminoscope, the drawing standard curve, and according to the I under the different emission
0/ I value standard profile the figure of main component analytical model recognition methods metals plotted ion, add the metal ion testing sample then and measure its fluorescence intensity, compare with the standard profile figure of metal ion, qualitative to the metal ion in the testing sample, compare with the typical curve of drawing, metal ion is carried out quantitatively.
Above-mentioned metal ion is Cu
2+, Co
2+, Cd
2+, Fe
3+, Ni
2+, Mg
2+, Ca
2+, Pb
2+Or Zn
2+Deng.
The chemical stability of the two pyrene amphiphilic fluorescent probes of the present invention is good, response speed to metal ion is fast, highly sensitive, can be directly used in fluorescent instrument detects, as FLS920 type single photon counting time resolution fluorescence spectral instrument or other similar optical detecting instruments, can realize Cu
2+, Co
2+, Cd
2+, Fe
3+, Ni
2+, Mg
2+, Ca
2+, Pb
2+, Zn
2+Etc. the qualitative and detection by quantitative of heavy metal ion, experimental result shows that it is to Cu
2+And Co
2+Detection limit can reach 100nmol/L and 69nmol/L respectively.
Description of drawings
Fig. 1 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Cu
2+The fluorescence intensity change curve.
Fig. 2 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Cu
2+Cu
2+Concentration-I
0/ I value graph of relation.
Fig. 3 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Co
2+The fluorescence intensity change curve.
Fig. 4 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Co
2+Co
+Concentration-I
0/ I value graph of relation.
Fig. 5 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Mg
2+The fluorescence intensity change curve.
Fig. 6 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Mg
2+Mg
2+Concentration-I
0/ I value graph of relation.
Fig. 7 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Fe
3+The fluorescence intensity change curve.
Fig. 8 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Fe
3+Fe
3+Concentration-I
0/ I value graph of relation.
Fig. 9 is that 1 pair of pyrene amphiphilic of embodiment fluorescent probe detects Fe
3+, Co
2+, Cu
2+And Mg
2+The PCA distribution plan.
Embodiment
The present invention is described in more detail below in conjunction with accompanying drawing and example, but the invention is not restricted to these embodiment.
Two pyrene amphiphilic fluorescent probes that the composite structure formula is following
1, synthetic 1-pyrene sodium sulfonate
At nitrogen atmosphere, under the condition of ice bath, in the three-necked flask that fills the 65mL methylene dichloride, add the 10g pyrene, getting the 3.5mL chlorsulfonic acid is dissolved in the 10mL methylene dichloride and splashes in the three-necked flask, room temperature reaction 2 hours, reaction solution is poured in the 50mL ice, be stirred to ice-out, produce the tiny precipitation of a large amount of yellow-green colours, continue stirring and make the methylene dichloride volatilization fully, use the diatomite suction filtration, get pale brown look filtrate, in filtrate, add 2.35g NaOH solid, produce a large amount of yellow-green precipitates, pyrene and chlorsulfonic acid, the mol ratio of NaOH is 1: 1: 1.2, wait to precipitate complete back and use the B suction filtration, put into the vacuum drying oven drying at room temperature 12 hours, obtain 1-pyrene sodium sulfonate.
2, synthetic 1-pyrene SULPHURYL CHLORIDE
To filling 260mL N, add 12.24g1-pyrene sodium sulfonate in the double-neck flask of dinethylformamide, be stirred to dissolving fully, adding 4.0mL concentration is the ether solution of hydrogen chloride of 1mol/L, stirred 10 minutes, splash into the 33mL thionyl chloride subsequently, 1-pyrene sodium sulfonate and hydrogenchloride, the mol ratio of thionyl chloride is 1: 0.1: 10, produce a large amount of glassy yellow precipitations in the dropping process, drip the back and continue ice bath stirring 3 hours, reaction solution is poured in the 150mL ice, stirred 1 hour, use the B suction filtration, get faint yellow solid, putting into the vacuum drying oven drying at room temperature 12 hours, is that 1: 1.5 mixed solution is eluent silicagel column separation and purification product with the volume ratio of methylene dichloride and sherwood oil, obtains glassy yellow product 1-pyrene SULPHURYL CHLORIDE.
3, synthetic two pyrene amphiphilic fluorescent probe
Under nitrogen atmosphere, in the double-neck flask that fills the 100mL trichloromethane, add 0.3g1-pyrene SULPHURYL CHLORIDE, 0.1mL4,7,10-three oxygen-1,13-tridecane diamines, 1-pyrene SULPHURYL CHLORIDE and 4,7,10-, three oxygen-1, the mol ratio of 13-tridecane diamines is 2.2: 1,78 ℃ of stirring and refluxing 24 hours with 150mL distilled water extraction 3 times, are removed trichloromethane with the organic phase rotary evaporation, be that 50: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, volume ratio with methylene dichloride and ethanol is 1: 2 mixed solution recrystallization, obtains two pyrene amphiphilic fluorescent probes, and its yield is 90%.
The nuclear magnetic data of prepared two pyrene amphiphilic fluorescent probes is:
1H NMR (400MHz, CDCl
3) δ: 8.95 (d, J=9.4Hz, 1H, Ar H), 8.66 (d, J=8.2Hz, 1H, Ar H), 8.22 – 8.01 (m, 7H, Ar H), 6.03 (t, J=5.4Hz, 1H, NH), 3.64 – 3.58 (m, 2H, CH
2), 3.51 (dd, J=5.5,3.4Hz, 2H, CH
2), 3.36 (t, J=5.5Hz, 2H, CH
2), 3.07 (dd, J=11.5,5.7Hz, 2H, CH
2), 1.56 – 1.54 (m, 2H, CH
2).
In synthetic two pyrene amphiphilic fluorescent probe steps 3 of embodiment 1, under nitrogen atmosphere, in the double-neck flask that fills the 100mL trichloromethane, add 0.27g1-pyrene SULPHURYL CHLORIDE, 0.1mL4,7,10-three oxygen-1,13-tridecane diamines, 1-pyrene SULPHURYL CHLORIDE and 4,7,10-three oxygen-1, the mol ratio of 13-tridecane diamines is 2: 1,78 ℃ of stirring and refluxing 18 hours, with 150mL distilled water extraction 3 times, the organic phase rotary evaporation is removed trichloromethane, is that 20: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, is 1: 5 mixed solution recrystallization with the volume ratio of methylene dichloride and ethanol, obtain two pyrene amphiphilic fluorescent probes, its yield is 85%.
In synthetic two pyrene amphiphilic fluorescent probe steps 3 of embodiment 1, under nitrogen atmosphere, in the double-neck flask that fills the 100mL trichloromethane, add 0.34g1-pyrene SULPHURYL CHLORIDE, 0.1mL4,7,10-three oxygen-1,13-tridecane diamines, 1-pyrene SULPHURYL CHLORIDE and 4,7,10-three oxygen-1, the mol ratio of 13-tridecane diamines is 2.5: 1,78 ℃ of stirring and refluxing 12 hours, with 150mL distilled water extraction 3 times, the organic phase rotary evaporation is removed trichloromethane, is that 30: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, is 1: 1 mixed solution recrystallization with the volume ratio of methylene dichloride and ethanol, obtain two pyrene amphiphilic fluorescent probes, its yield is 80%.
Two pyrene amphiphilic fluorescent probes that the composite structure formula is following
In the synthetic two pyrene amphiphilic fluorescent probe steps 3 of embodiment 1～3, used 4,7,10-three oxygen-1,13-tridecane diamines are with the replacement of equimolar ethylene glycol bis (3-amine propyl group) ether, and other steps in this step are identical with corresponding embodiment.Other steps are identical with embodiment 1, are prepared into two pyrene amphiphilic fluorescent probes.
Two pyrene amphiphilic fluorescent probes that the composite structure formula is following
In the synthetic two pyrene amphiphilic fluorescent probe steps 3 of embodiment 1～3, used 4,7,10-three oxygen-1,13-tridecane diamines are with equimolar 4,7,10,13-four oxygen-1, and the replacement of 16-n-Hexadecane diamines, other steps in this step are identical with corresponding embodiment.Other steps are identical with embodiment 1, are prepared into two pyrene amphiphilic fluorescent probes.
Two pyrene amphiphilic fluorescent probes that the composite structure formula is following
In the synthetic two pyrene amphiphilic fluorescent probe steps 3 of embodiment 1～3, used 4,7,10-three oxygen-1,13-tridecane diamines is with equimolar 4,7,10,13,16-five oxygen-1,19-nonadecane diamines is replaced, and other steps in this step are identical with corresponding embodiment.Other steps are identical with embodiment 1, are prepared into two pyrene amphiphilic fluorescent probes.
1 pair of pyrene amphiphilic of embodiment fluorescent probe is detecting Cu
2+In purposes, its using method is as follows:
Two pyrene amphiphilic fluorescent probes are dissolved in the acetonitrile, be mixed with two pyrene amphiphilic fluorescent probe acetonitrile solutions of 0.25mmol/L, get the lauryl sodium sulfate aqueous solution of 2.5mL7mmol/L in cuvette, the two pyrene amphiphilic fluorescent probe acetonitrile solutions that add 10 μ L0.25mmol/L, be made into two pyrene amphiphilic fluorescent probe solution of 1.0 μ mol/L, be 350nm with FLS920 type single photon counting time resolution fluorescence spectral instrument at the maximum excitation wavelength, emission wavelength is that the fluorescence intensity I is measured at the 505nm place
0, the excitation-emission slit is 3nm, and adding 1,2,2,2,3,5,5,10 μ L concentration then successively is the copper nitrate aqueous solution of 2.5mmol/L, after mixing, measures the fluorescence intensity of solution I, and fluorescence intensity is with Cu
2+The fluorescence spectrum figure of change in concentration sees Fig. 1, and draws I
0/ I value is with Cu
2+The linear diagram of change in concentration the results are shown in Figure 2.
As seen from Figure 1, along with Cu in the system
2+The increase of concentration, fluorescence intensity of solution changes clearly, illustrates that prepared fluorescent probe is to Cu
2+Detection sensitivity very high.After tested, this fluorescent probe is to Cu
2+Detect and be limited to 100nmol/L.As seen from Figure 2, at Cu
2+When concentration is 0～30 μ mol/L, I
0/ I value and Cu
2+Concentration is linear, and linear equation is:
y=1.18+0.23[Cu
2+]
Y is I in the formula
0/ I value, correlation coefficient r are 0.9994, by relation conefficient as seen, and I
0/ I value and Cu
2+The linear relationship of concentration is fine, can be to Cu
2+Carry out quantitative analysis.
1 pair of pyrene amphiphilic of embodiment fluorescent probe is detecting Co
2+In purposes, its using method is identical with embodiment 7.Experimental result is seen Fig. 3 and Fig. 4.As seen from Figure 3, along with Co in the system
2+The increase of concentration, fluorescence intensity of solution changes clearly, illustrates that prepared fluorescent probe is to Co
2+Detection sensitivity very high.After tested, this fluorescent probe is to Co
2+Detect and be limited to 69nmol/L.As seen from Figure 4, at Co
2+When concentration is 0～40 μ mol/L, I
0/ I value and Co
2+Concentration is linear, and linear equation is:
y=0.88+0.15[Co
2+]
Y is I in the formula
0/ I value, correlation coefficient r are 0.9995, by relation conefficient as seen, and I
0/ I value and Co
2+The linear relationship of concentration is fine, can be to Co
2+Carry out quantitative analysis.
1 pair of pyrene amphiphilic of embodiment fluorescent probe is detecting Mg
2+In purposes, its using method is identical with embodiment 7.Experimental result is seen Fig. 5 and Fig. 6.As seen from Figure 5, along with Mg in the system
2+The increase of concentration, fluorescence intensity of solution changes clearly, illustrates that prepared fluorescent probe is to Mg
2+Detection sensitivity very high.As seen from Figure 6, at Mg
2+When concentration is 0～30 μ mol/L, I
0/ I value and Mg
2+Concentration is linear, and linear equation is:
y=0.99+0.10[Mg
2+]
Y is I in the formula
0/ I value, correlation coefficient r are 0.9989, by relation conefficient as seen, and I
0/ I value and Mg
2+The linear relationship of concentration is fine, can be to Mg
2+Carry out quantitative analysis.
1 pair of pyrene amphiphilic of embodiment fluorescent probe is detecting Fe
3+In purposes, its using method is identical with embodiment 7.Experimental result is seen Fig. 7 and Fig. 8.As seen from Figure 7, along with Fe in the system
3+The increase of concentration, fluorescence intensity of solution changes clearly, illustrates that prepared fluorescent probe is to Fe
3+Detection sensitivity very high.As seen from Figure 8, at Fe
3+When concentration is 0～70 μ mol/L, I
0/ I value and Fe
3+Concentration is the cube relation, and equation is:
y=1.02-5.81E-4[Fe
3+]+7.72E-4[Fe
3+]
2+1.49E-5[Fe
3+]
3
Y is I in the formula
0/ I value, correlation coefficient r are 0.9995, by relation conefficient as seen, and I
0/ I value and Fe
3+The cube match of concentration is on good terms, can be to Fe
3+Carry out quantitative analysis.
1 pair of pyrene amphiphilic of embodiment fluorescent probe is detecting Fe
3+, Co
2+, Cu
2+, Mg
2+In purposes, its using method is as follows:
Two pyrene amphiphilic fluorescent probes are dissolved in the acetonitrile, be mixed with two pyrene amphiphilic fluorescent probe acetonitrile solutions of 0.25mmol/L, get the lauryl sodium sulfate aqueous solution of 2.5mL7mmol/L in cuvette, the two pyrene amphiphilic fluorescent probe acetonitrile solutions that add 10 μ L0.25mmol/L, be made into two pyrene amphiphilic fluorescent probe solution of 1.0 μ mol/L, be 350nm with FLS920 type single photon counting time resolution fluorescence spectral instrument at the maximum excitation wavelength, emission wavelength is 381,400,460, the fluorescence intensity I is measured at the 505nm place
0The excitation-emission slit is 3nm, adding 10,20,30,40 μ L concentration then respectively is cupric nitrate, Xiao Suangu, magnesium nitrate or the cupric nitrate of 2.5mmol/L, after mixing, measure solution 381,400,460, the fluorescence intensity I at 505nm place, adopt main component analytical model recognition methods (PCA) that five kinds of ions are distinguished, analytical results is seen Fig. 9, is Fe in the curve a among the figure
3+, be Co in the curve b
2+, be Cu in the curve c
2+, be Mg in the curve d
2+Fig. 9 as seen, prepared fluorescent probe can well be distinguished Fe
3+, Co
2+, Cu
2+, Mg
2+
Claims (7)
1. two pyrene amphiphilic fluorescent probe is characterized in that the structural formula of this fluorescent probe is suc as formula shown in the I:
The formula I
The value of n is 2,3,4 or 5 in the formula.
2. according to claim 1 pair of pyrene amphiphilic fluorescent probe, it is characterized in that: the value of described n is 3.
3. the synthetic method of claim 1 a pair pyrene amphiphilic fluorescent probe is characterized in that it is made up of following step:
(1) synthetic 1-pyrene sodium sulfonate
Under nitrogen atmosphere, condition of ice bath, pyrene, chlorsulfonic acid are added in the methylene dichloride, stirring at room reaction 2 hours, reaction solution is poured in the ice, be stirred to the methylene dichloride volatilization fully, use the diatomite suction filtration, in filtrate, add the NaOH solid, the mol ratio of pyrene and chlorsulfonic acid, NaOH is 1: 1: 1.2, and suction filtration, drying obtain 1-pyrene sodium sulfonate;
(2) synthetic 1-pyrene SULPHURYL CHLORIDE
1-pyrene sodium sulfonate is added N, in the dinethylformamide, be stirred to dissolving fully, add the ether solution of hydrogen chloride of 1mol/L, stirred 10 minutes, drip thionyl chloride, the mol ratio of 1-pyrene sodium sulfonate and hydrogenchloride, thionyl chloride is 1: 0.1: 10, drip the back ice bath and stirred 3 hours, reaction solution is poured in the ice, stirred 1 hour, suction filtration, vacuum-drying is that 1: 1.5 mixed solution is eluent silicagel column separation and purification product with the volume ratio of methylene dichloride and sherwood oil, obtains 1-pyrene SULPHURYL CHLORIDE;
(3) synthetic two pyrene amphiphilic fluorescent probe
Under nitrogen atmosphere, be to add in solvent at 2～2.5: 1 in molar ratio with the two propylamine of 1-pyrene SULPHURYL CHLORIDE and polyoxyethylene glycol, stir, back flow reaction 12～24 hours, with distilled water extraction, the organic phase rotary evaporation is desolventized, be that 20～50: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, volume ratio with methylene dichloride and ethanol is 1: 1～5 mixed solution recrystallizations, obtains the two pyrene amphiphilic fluorescent probes shown in the formula I;
The two propylamine of above-mentioned polyoxyethylene glycol are ethylene glycol bis (3-amine propyl group) ether, 4,7,10-three oxygen-1,13-tridecane diamines, 4,7,10,13-four oxygen-1,16-n-Hexadecane diamines, 4,7,10,13,16-five oxygen-1, any one in the 19-nonadecane diamines; Solvent is trichloromethane or methylene dichloride.
4. the synthetic method of according to claim 3 pair of pyrene amphiphilic fluorescent probe, it is characterized in that: in synthetic two pyrene amphiphilic fluorescent probe steps (3), under nitrogen atmosphere, be to add in solvent at 2.2: 1 in molar ratio with the two propylamine of 1-pyrene SULPHURYL CHLORIDE and polyoxyethylene glycol, stir, back flow reaction 24 hours, extract with distilled water, the organic phase rotary evaporation is desolventized, be that 50: 1 mixed solution is eluent column chromatography separated product with the volume ratio of methylene dichloride and methyl alcohol, volume ratio with methylene dichloride and ethanol is 1: 2 mixed solution recrystallization, obtains the two pyrene amphiphilic fluorescent probes shown in the formula I.
5. the synthetic method of according to claim 3 pair of pyrene amphiphilic fluorescent probe is characterized in that: the two propylamine of the described polyoxyethylene glycol of institute are 4,7,10-three oxygen-1,13-tridecane diamines.
6. the purposes of claim 1 pair pyrene amphiphilic fluorescent probe in detecting metal ion.
7. the according to claim 6 pair of pyrene amphiphilic fluorescent probe purposes in detecting metal ion, it is characterized in that: described metal ion is Cu
2+, Co
2+, Cd
2+, Fe
3+, Ni
2+, Mg
2+, Ca
2+, Pb
2+Or Zn
2+
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310204573.1A CN103275697B (en) | 2013-05-28 | 2013-05-28 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310204573.1A CN103275697B (en) | 2013-05-28 | 2013-05-28 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103275697A true CN103275697A (en) | 2013-09-04 |
| CN103275697B CN103275697B (en) | 2014-09-17 |
Family
ID=49058327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310204573.1A Expired - Fee Related CN103275697B (en) | 2013-05-28 | 2013-05-28 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103275697B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498024A (en) * | 2014-12-31 | 2015-04-08 | 湘潭大学 | Copper ion ratio type fluorescence probe based on pyrene as well as preparation method and application of copper iron ratio type fluorescence probe |
| CN104592983A (en) * | 2014-11-28 | 2015-05-06 | 渤海大学 | Fluorescent probes based on pyrene, and preparation method and application thereof |
| CN106349331A (en) * | 2016-08-23 | 2017-01-25 | 国家纳米科学中心 | Bispyrene-based pH (Potential of Hydrogen)-response self-assembly polypeptide nano material, and preparation method and application thereof |
| CN106632101A (en) * | 2016-11-22 | 2017-05-10 | 华南理工大学 | Ratio-type fluorescent probe for simultaneously detecting silver ions and trivalent chromic ions as well as preparation method and application of ratio-type fluorescent probe |
| CN106749518A (en) * | 2016-11-10 | 2017-05-31 | 国家纳米科学中心 | A kind of polypeptide nano material containing double pyrenyl groups and its preparation method and application |
| CN107098852A (en) * | 2017-06-20 | 2017-08-29 | 陕西师范大学 | The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432492A (en) * | 2011-10-27 | 2012-05-02 | 华南师范大学 | N,N'-dipyrene butyryl lysine and application thereof |
| CN102634334A (en) * | 2012-04-06 | 2012-08-15 | 陕西师范大学 | Pyrene-dicholesterol-containing fluorescent probe, as well as synthetic method and application thereof |
-
2013
- 2013-05-28 CN CN201310204573.1A patent/CN103275697B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432492A (en) * | 2011-10-27 | 2012-05-02 | 华南师范大学 | N,N'-dipyrene butyryl lysine and application thereof |
| CN102634334A (en) * | 2012-04-06 | 2012-08-15 | 陕西师范大学 | Pyrene-dicholesterol-containing fluorescent probe, as well as synthetic method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| KERU ZHAO ET AL.: "《A Butterfly-Shaped Pyrene Derivative of Cholesterol and Its Uses as a Fluorescent Probe》", 《THE JOURNAL OF PHYSICAL CHEMISTRY B》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592983A (en) * | 2014-11-28 | 2015-05-06 | 渤海大学 | Fluorescent probes based on pyrene, and preparation method and application thereof |
| CN104498024A (en) * | 2014-12-31 | 2015-04-08 | 湘潭大学 | Copper ion ratio type fluorescence probe based on pyrene as well as preparation method and application of copper iron ratio type fluorescence probe |
| CN104498024B (en) * | 2014-12-31 | 2016-09-07 | 湘潭大学 | A kind of copper ion Ratiometric fluorescent probe based on pyrene and its preparation method and application |
| CN106349331A (en) * | 2016-08-23 | 2017-01-25 | 国家纳米科学中心 | Bispyrene-based pH (Potential of Hydrogen)-response self-assembly polypeptide nano material, and preparation method and application thereof |
| CN106349331B (en) * | 2016-08-23 | 2020-05-15 | 国家纳米科学中心 | Bipyrene-based pH response self-assembly polypeptide nano material and preparation method and application thereof |
| CN106749518A (en) * | 2016-11-10 | 2017-05-31 | 国家纳米科学中心 | A kind of polypeptide nano material containing double pyrenyl groups and its preparation method and application |
| CN106749518B (en) * | 2016-11-10 | 2021-01-01 | 国家纳米科学中心 | Polypeptide nano material containing pyrene group and preparation method and application thereof |
| CN106632101A (en) * | 2016-11-22 | 2017-05-10 | 华南理工大学 | Ratio-type fluorescent probe for simultaneously detecting silver ions and trivalent chromic ions as well as preparation method and application of ratio-type fluorescent probe |
| CN106632101B (en) * | 2016-11-22 | 2019-06-18 | 华南理工大学 | A kind of Ratiometric fluorescent probe and the preparation method and application thereof that can be used for silver ion and trivalent chromic ion detection simultaneously |
| CN107098852A (en) * | 2017-06-20 | 2017-08-29 | 陕西师范大学 | The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application |
| CN107098852B (en) * | 2017-06-20 | 2020-04-24 | 陕西师范大学 | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103275697B (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dong et al. | A new application of Salamo-type bisoximes: as a relay–sensor for Zn2+/Cu2+ and its novel complexes for successive sensing of H+/OH− | |
| CN103275697B (en) | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof | |
| Das et al. | Stimuli-responsive discriminative detection of Cu2+ and Hg2+ with concurrent sensing of S2-from aqueous medium and bio-fluids by CN fused azophenine functionalized “smart” hydrogel assay@ A potential biomarker sensor for Wilson’s disease | |
| Kolcu et al. | A Schiff base based on triphenylamine and thiophene moieties as a fluorescent sensor for Cr (III) ions: Synthesis, characterization and fluorescent applications | |
| Sun et al. | A simple, reversible, colorimetric and water-soluble fluorescent chemosensor for the naked-eye detection of Cu2+ in~ 100% aqueous media and application to real samples | |
| Xiong et al. | Two new quinoline-based regenerable fluorescent probes with AIE characteristics for selective recognition of Cu 2+ in aqueous solution and test strips | |
| Ghorai et al. | Solvent-dependent fluorescent-colorimetric probe for dual monitoring of Al 3+ and Cu 2+ in aqueous solution: an application to bio-imaging | |
| Peralta-Domínguez et al. | A Schiff base derivative from cinnamaldehyde for colorimetric detection of Ni2+ in water | |
| Song et al. | A fluorescence sensor for Zn2+ that also acts as a visible sensor for Co2+ and Cu2+ | |
| Farhi et al. | A quinoline-based fluorescent probe for selective detection and real-time monitoring of copper ions–a differential colorimetric approach | |
| Xu et al. | A colorimetric and fluorometric dual-modal chemosensor for cyanide in water | |
| Gao et al. | An ICT colorimetric chemosensor and a non-ICT fluorescent chemosensor for the detection copper ion | |
| Li et al. | A more flexible long-chain bis (salamo)-like fluorescent probe based on FRET and ICT effects for the identification of aluminum ion in the environment and plants | |
| Huo et al. | The synthesis, characterization of three isomers of rhodamine derivative and their application in copper (II) ion recognition | |
| Li et al. | Novel mercury sensor based on water soluble styrylindolium dye | |
| Sun et al. | A turn-off fluorescent probe for the detection of copper (II) ion based on a salicylaldehyde derivatives Schiff-base | |
| Bhatti et al. | New water soluble p-sulphonatocalix [4] arene chemosensor appended with rhodamine for selective detection of Hg2+ ion | |
| Zhang et al. | A fluorescent bis-NBD derivative of calix [4] arene: Switchable response to Ag+ and HCHO in solution phase | |
| Fang et al. | A highly sensitive fluorescent probe with different responses to Cu2+ and Zn2+ | |
| Sidqi et al. | Photochemical processing potential of a novel Schiff base as a fluorescent probe for selective monitoring of Al3+ ions and bioimaging in human cervical cancer HeLa cells | |
| Xing et al. | The contrastive study of two thiophene-derived symmetrical Schiff bases as fluorescence sensors for Ga3+ detection | |
| Chen et al. | A highly sensitive fluorogenic “turn-on” chemosensor for the recognition of Cd2+ based on a hybrid purine-quinoline Schiff base | |
| Kundu et al. | Triphenylamine based reactive coloro/fluorimetric chemosensors: structural isomerism and solvent dependent sensitivity and selectivity | |
| Li et al. | Fluorescence chemosensor properties of two coumarin-based compounds for environmentally and biologically important Al3+ ion | |
| Bu et al. | A phenanthro [9, 10-d] imidazole-based AIE active fluorescence probe for sequential detection of Ag+/AgNPs and SCN− in water and saliva samples and its application in living cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140917 Termination date: 20170528 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |