CN102190670A - Fluorescence chemical sensor and preparation method and application thereof - Google Patents
Fluorescence chemical sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a fluorescence chemical sensor and a preparation method and application thereof. The structural formula of the fluorescence chemical sensor is shown as the formula (I), wherein R1 refers to sulfur or oxygen; and R2 refers to sulphonate, iodate, fluorphosphate or fluoborate. The preparation method for the fluorescence chemical sensor comprises the following steps of: (1) performing oxidation reaction on 4'-(N,N-dimethyl pyridyl amido)benzene under the action of an oxidant to obtain 4'-(N,N-dimethyl pyridyl amido)benzaldehyde; (2) reacting the 4'-(N,N-dimethyl pyridyl amido)benzaldehyde with a compound in a formula (III) to obtain a compound in a formula (II); and (3) reacting the compound in the formula (II) with copper ion-containing inorganic salt to obtain the fluorescence chemical sensor, wherein in the formulas (II) and (III), R1 refers to sulfur or oxygen; and R2 refers to sulphonate, iodate, fluorphosphate or fluoborate. The fluorescence chemical sensor can specifically, efficiently, timely and easily detect cyanide ions in aqueous solution.
Description
Technical field
The present invention relates to a kind of fluorescence chemical sensor and preparation method thereof and application, belong to the chemical sensor technical field.
Background technology
Cryanide ion salt is widely used in industry, comprises metallurgy, plating, dyestuff, medicine etc.But cryanide ion has very strong toxicity, and the maximum permissible concentration of cryanide ion is 0.05mg/L in country's " Design of Industrial Enterprises hygienic standard " regulation surface water.Therefore cryanide ion is carried out timely and effective detection seems particularly important.Many in recent years cryanide ion chemical detection molecular devices are particularly reported in succession to the fluorescence chemical sensor that cryanide ion detects, but the report of the fluorescent optical sensor highly sensitive at aqueous phase, that highly selective detects cryanide ion is also relatively more rare.
Thereby fluorescence chemical sensor is the system fluorescent signal change that utilizes sensor molecule and target molecule interaction to cause reaches a kind of analytical procedure of testing goal.This method has advantages such as highly sensitive, simple to operate and with low cost, and in numerous areas extensive application prospect, the Optochemical sensor of dissimilar detected objects is also among constantly designing and developing.Wherein based on the interactional cryanide ion fluorescence chemical sensor of host-guest, the interaction owing between the solvation reduction host-guest strong in the aqueous solution reduces its sensitivity, so such transmitter can not effectively detect cryanide ion in the aqueous solution greatly.Therefore press for design, the synthetic fluorescence chemical sensor that can in the aqueous solution, carry out efficient identification to cryanide ion.
The response type fluorescence chemical sensor provides opportunity for the detection of exploitation aqueous phase cryanide ion, and this method utilizes chemical reaction single-minded between transmitter and the tested molecule to cause that the change of transmitter luminescent properties discerns.Thereby this method influenced by solvent polarity less, can detect target molecule at aqueous phase, and have excellent selectivity and sensitivity.
Summary of the invention
The purpose of this invention is to provide a kind of fluorescence chemical sensor and preparation method thereof and application.
Fluorescence chemical sensor provided by the invention, its structural formula is suc as formula shown in (I):
Wherein, R
1Be sulphur or oxygen; R
2Be sulphonate salt, salt compounded of iodine, fluorophosphate or fluoroborate.
The present invention also provides the preparation method of above-mentioned fluorescence chemical sensor, comprises the steps:
(1) 4 '-(N, N-lutidine base amido) benzene carries out oxidizing reaction and obtains 4 '-(N, N-lutidine base amido) phenyl aldehyde under the effect of oxygenant;
Compound reacts compound shown in the formula of obtaining (II) shown in (2) 4 '-(N, N-lutidine base amido) phenyl aldehyde and the formula (III);
(3) compound and copper ions inorganic salt shown in the formula (II) react and promptly get described fluorescence chemical sensor;
In formula (II) and the formula (III), R
1Be sulphur or oxygen; R
2Be sulphonate salt, salt compounded of iodine, fluorophosphate or fluoroborate.
Among the above-mentioned preparation method, 4 '-(N, N-lutidine base amido) benzene can be reacted by chloromethyl pyridine hydrochloride and aniline and obtain; In this reaction, with alkali such as sodium hydroxide as catalyzer, wherein the molar weight of sodium hydroxide can be chloromethylpyridine 2-5 doubly, optimum quantity is 2.5 times.
Among the above-mentioned preparation method, the oxygenant of the described oxidizing reaction of step (1) can be phosphorus oxychloride.
Among the above-mentioned preparation method, the temperature of the described oxidizing reaction of step (1) can be 45 ℃-90 ℃, specifically can be 45 ℃, 65 ℃ or 90 ℃; The time of the described oxidizing reaction of step (1) can be 24 hours-72 hours, specifically can be 24 hours, 48 hours or 72 hours.
Among the above-mentioned preparation method, the molfraction ratio of compound and 4 ' shown in the formula (III) described in the step (2)-(N, N-lutidine base amido) phenyl aldehyde can be 1: (2-6), and as 1: 3.
Among the above-mentioned preparation method, the described catalyst for reaction of step (2) can be hexahydropyridine, ammonium acetate, salt of wormwood, triethylamine, quadrol, sodium hydroxide or potassium hydroxide; The quality percentage composition that described catalyzer accounts for compound shown in the described formula (III) is 1%-3%, as 1% or 3%.
Among the above-mentioned preparation method, the solvent of the described reaction of step (2) can be dehydrated alcohol, anhydrous methanol or acetone; The temperature of described reaction can be 80 ℃-90 ℃, as 80 ℃ or 90 ℃; The time of described reaction can be 6 hours-24 hours, as 6 hours, 10 hours or 24 hours; The described copper ions inorganic salt of step (3) can be water-soluble inorganic salt, specifically can be cupric nitrate, cupric chloride, neutralized verdigris, copper sulfate or cupric perchlorate; The mol ratio of compound and copper ions inorganic salt can be 1: 1 shown in the described formula (II).
The present invention also provides the application of above-mentioned fluorescence chemical sensor in detecting cryanide ion; In the described application, in the buffered soln of HEPES (4-hydroxyethyl piperazine ethanesulfonic acid), with described fluorescence chemical sensor cryanide ion is detected, the pH of described buffered soln can be 7.20.
The advantage of fluorescence chemical sensor provided by the present invention is: because the complexation constant of cryanide ion and cupric ion is huge, can seize the cupric ion in the described fluorescence chemical sensor, the electron donation of described fluorescence chemical sensor is recovered, its fluorescence is remotivated, UV spectrum generation red shift, make described fluorescence chemical sensor not audient's polyanionic disturb cryanide ion carried out specificity identification.In addition, because that fluorescence chemical sensor provided by the invention has as molecule inner salt is good water-soluble, improved its application prospect in practice so greatly.In addition, described fluorescence chemical sensor has instant obvious color variation to the detection of cryanide ion, only with the naked eye can observe detected result.Therefore described fluorescence chemical sensor can carry out single-minded, efficient, timely, simple detection to cryanide ion in the aqueous solution.
Description of drawings
Fig. 1 is that compound (concentration is 8 μ mol/l) shown in the formula V is at HEPES (H
2O, 20mmol/l, pH=7.20) UV spectrum that in the buffered soln cupric ion (concentration is 100mmol/l) is responded.
Fig. 2 is that compound (concentration is 8 μ mol/l) shown in the formula V is at HEPES (H
2O, 20mmol/l, pH=7.20) fluorescence spectrum that in the buffered soln cupric ion (concentration is 100mmol/l) is responded.
Fig. 3 is that fluorescence chemical sensor shown in the formula (IV) (concentration is 8 μ mol/l) is at HEPES (H
2O, 20mmol/l, pH=7.20) UV spectrum that in the buffered soln cryanide ion (concentration is 0.15mol/l) is responded.
Fig. 4 is that fluorescence chemical sensor shown in the formula (IV) (concentration is 8 μ mol/l) is at HEPES (H
2O, 20mmol/l, pH=7.20) fluorescence spectrum that in the buffered soln cryanide ion (concentration is 0.15mol/l) is responded.
Fig. 5 is that fluorescence chemical sensor shown in the formula (IV) (concentration is 8 μ mol/l, and the mol ratio of compound shown in the formula V and copper is 1: 1) is at HEPES (H
2O, 20mmol/l, pH=7.20) in the buffered soln to cryanide ion (concentration is 0.15mol/l) UV spectrum optionally, wherein, 1 is the blank UV spectrum of fluorescence chemical sensor shown in the formula (IV); 2 is the UV spectrum of the cupric ion response of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass; 3 be the cupric ion balance of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass after, to adding the UV spectrum of the normal various negatively charged ion responses of 75 times of cupric ions; 4 is the cupric ion of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass, adds 75 times of normal various negatively charged ion of cupric ion again, adds the UV spectrum of cryanide ion response after the balance.
Fig. 6 is that fluorescence chemical sensor shown in the formula (IV) (concentration is 8 μ mol/l, and the mol ratio of compound shown in the formula V and copper is 1: 1) is at HEPES (H
2O, 20mmol/l, pH=7.20) in the buffered soln to cryanide ion (concentration is 0.15mol/l) fluorescence spectrum optionally.Wherein, 1 is the blank fluorescence spectrum of fluorescence chemical sensor shown in the formula (IV); 2 is the fluorescence spectrum of the cupric ion response of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass; 3 be the cupric ion balance of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass after, to adding the fluorescence spectrum of the normal various negatively charged ion responses of 75 times of cupric ions; 4 be the cupric ion balance of fluorescence chemical sensor shown in the formula (IV) and 1: 1 molar mass after, add 75 times of normal various anion balance of cupric ion again after, add the fluorescence spectrum of cryanide ion response after the balance.
Fig. 7 is that fluorescence chemical sensor shown in the formula (IV) is to the selectivity test of 11 kinds of negatively charged ion and cryanide ion.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The preparation of embodiment 1, fluorescence chemical sensor (structural formula is suc as formula shown in (IV))
(1) takes by weighing 180mg chloromethyl pyridine hydrochloride and 700mg aniline to reaction flask, sodium hydroxide solution is as solvent, add the hexadecyl brometo de amonio as phase-transfer catalyst, be heated to 45 ℃ of stirring reactions 48 hours, dichloromethane extraction, utilize column chromatography (ethyl acetate/petroleum ether=3: 1) to separate faint yellow 4 '-(N, N-lutidine base amido) the pure product of benzene that obtain.In ice bath, slowly drip the 1ml phosphorus oxychloride, stirred 30 minutes down, add 4 ' of the above-mentioned preparation of 500mg-(N, N-lutidine base amido) benzene then, be heated to 45 ℃ and stirred 72 hours at 0 ℃ to dry DMF sealed reaction bottle.System naturally cooled to room temperature after reaction finished, and added distilled water and stirred 30 minutes, and salt of wormwood is regulated pH value to 10, stirred 30 minutes, methylene dichloride and water extract respectively 2 times, utilize column chromatography for separation to obtain described 4 '-(N, N-lutidine base amido) phenyl aldehyde at last;
(2) take by weighing 300mg 2-methylbenzothiazole and 300mg 1, the 3-sultone is added in the reaction flask, trichloromethane is as solvent, being heated to 80 ℃ stirred 48 hours, have precipitation to generate, naturally cool to room temperature after reaction stops, filtration washing obtains flaxen 2-methyl-N-n-propyl sulfonate benzothiazole, and (its structural formula is suc as formula shown in (III), wherein, R
1Be S, R
2Be the n-propyl sulfonic group);
(3) take by weighing 150mg 2-methyl-N-n-propyl sulfonate benzothiazole and 500mg 4 '-(N, N-lutidine base amido) phenyl aldehyde (wherein, 2-methyl-N-n-propyl sulfonate benzothiazole and 4 '-(N, N-lutidine base amido) mol ratio of phenyl aldehyde is 1: 3) with reaction flask in, dehydrated alcohol is as solvent, 3% the hexahydropyridine that adds the quality percentage composition account for 2-methyl-N-n-propyl sulfonate benzothiazole is as catalyzer, be heated to 80 ℃ of stirring reactions 10 hours, there is precipitation to generate, reaction stops the back system and naturally cools to room temperature, suction filtration precipitation, precipitation are used the ether washing, promptly obtain compound shown in the formula V:
1H NMR (400MHz, DMSO-d6): δ 2.13 (m, 2H), 2.60-2.63 (t, 2H), 4.92-4.96 (t, 2H), 5.02 (s, 4H), 6.85 (d, 2H, J=9.2Hz), 7.31 (dd, 1H, J=4.8Hz), 7.33 (dd, 1H, J=5.2Hz), 7.38 (d, 2H), 7.69 (t, 1H, J=14.2Hz), 7.78 (dd, 1H, J=5.2Hz), 7.84 (dd, 2H, J=18Hz), 7.88 (dd, 2H, J=9.2Hz), 8.04 (d, 2H, J=18Hz), 8.25 (d, 1H), 8.30 (d, 1H), 8.60 (d, 2H, J=4.8Hz); MS (Maldi): m/z 556.7.
(4) compound shown in the 56mg formula V and 18.8mg cupric nitrate react in water and promptly get the fluorescence chemical sensor shown in the formula (IV).
Compound shown in the formula V is tested the UV spectrum of cupric ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared the Cu (NO of compound solution shown in the formula V of 8 μ mol/l and 100mmol/l respectively
3)
2Solution.Get compound solution shown in the above-mentioned formula V of 2ml in cuvette, in cuvette, drip above-mentioned Cu (NO gradually
3)
2Solution detects UV spectrum, as shown in Figure 1 to balance.As can be known from Fig. 1, UV spectrum absorbs at the 498nm place and reduces along with the increase of cupric ion, but changes no longer obvious shown in adding and the formula V after the cupric ion of compound same molar; UV spectrum new absorption peak occurs in the absorption at 386nm place along with the increase of cupric ion, but changes no longer obvious after adding 1 times of cupric ion.
Compound shown in the formula V is tested the fluorescence spectrum of cupric ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared the Cu (NO of compound solution shown in the formula V of 8 μ mol/l and 100mmol/l respectively
3)
2Solution.Get compound solution shown in the above-mentioned formula V of 2ml in cuvette, and in cuvette, drip above-mentioned Cu (NO gradually
3)
2Solution detects fluorescence spectrum, as shown in Figure 2 to balance.As can be known from Fig. 2, the amount increase fluorescence along with cupric ion reduces its fluorescence quilt cancellation fully behind the cupric ion of compound same molar shown in adding and the formula V gradually.
Fluorescence chemical sensor shown in the formula (IV) is tested the UV spectrum of cryanide ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared the Cu (NO of compound solution shown in the formula V of 8 μ mol/l and 100mmol/l respectively
3)
2Solution, and the cryanide ion solution of 0.5mol/l.Get fluorescence chemical sensor solution shown in the above-mentioned formula of 2ml (IV) in cuvette, and in cuvette, drip above-mentioned Cu (NO
3)
2Solution detects UV spectrum; Continuation is upwards stated and is dripped above-mentioned cryanide ion solution in the system to balance after the titration balance, detects UV spectrum, as shown in Figure 3.As can be known from Fig. 3, UV spectrum strengthens along with the increase of cryanide ion at 498nm place absorption peak, changes no longer obvious but add afterwards with 2 times of molar weight Cu ionic cryanide ions; Absorption at the 386nm place reduces along with the increase of cryanide ion, but adds with the cryanide ion variation afterwards of 2 times of molar weights of Cu ion no longer obvious.
Fluorescence chemical sensor shown in the formula (IV) is tested the fluorescence spectrum of cryanide ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared the Cu (NO of compound solution shown in the formula V of 8 μ mol/l and 100mmol/l respectively
3)
2Solution, and the cryanide ion solution of 0.5mol/l.Get fluorescence chemical sensor solution shown in the above-mentioned formula of 2ml (IV) in cuvette, and in cuvette, drip Cu (NO
3)
2Solution detects fluorescence spectrum, continues after the titration balance upwards to state to drip above-mentioned cryanide ion solution in the system to balance, detects fluorescence spectrum, as shown in Figure 4.As shown in Figure 4, strengthen gradually along with the amount of cryanide ion increases fluorescence, its fluorescence strengthens no longer obvious behind the cryanide ion that adds with 2 times of molar weights of Cu ion.
Fluorescence chemical sensor shown in the formula (IV) is tested the UV spectrum of interfering ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared compound solution shown in the formula V of 8 μ mol/l, the Cu (NO of 100mmol/l respectively
3)
2Solution, the cryanide ion solution of 0.5mol/l, and 0.15mol/l contains F respectively
-, Cr
2O
7 2-, PO
4 2-, BO
3 2-, Cl
-, Ac
-, S
2-, MnO
4-, S
2O
8 2-, OH
-, SO
4 2-, CO
3 2-, I
-Etc. various solions.Get that fluorescence chemical sensor solution drips Cu (NO shown in the above-mentioned formula of 2ml (IV) in cuvette in cuvette
3)
2Solution detects UV spectrum.In above-mentioned system, drip 100 times of above-mentioned interfering ion solution after the titration balance respectively, detect UV spectrum to the cupric ion molar equivalent.Drip cryanide ion solution to above-mentioned system again after the titration balance, the test UV spectrum, as shown in Figure 5.As shown in Figure 5, the interfering ion of 75 times of amounts of disposable adding comprises F
-, Cl
-, I
-, Ac
-, SO
4 2-, S
2O
8 2-, PO
4 -, S
2-, OH
-, CO
3 2-, BO
3 -Deng, to the almost not influence of its UV spectrum; Add cryanide ion after the balance again, UV spectrum strengthens along with the increase of cryanide ion at 498nm place absorption peak, changes no longer obvious but add afterwards with 2 times of molar weight Cu ionic cryanide ions; Absorption at the 386nm place reduces along with the increase of cryanide ion, but adds with the cryanide ion variation afterwards of 2 times of molar weights of Cu ion no longer obvious.
Fluorescence chemical sensor shown in the formula (IV) is tested the fluorescence spectrum of interfering ion: use HEPES (H
2O, 20mmol/l, pH=7.20) buffered soln is prepared compound solution shown in the formula V of 8 μ mol/l, the Cu (NO of 100mmol/l respectively
3)
2Solution, the cryanide ion solution of 0.5mol/l, and 0.15mol/l contains F respectively
-, Cr
2O
7 2-, PO
4 2-, BO
3 2-, Cl
-, Ac
-, S
2-, MnO
4-, S
2O
8 2-, OH
-, SO
4 2-, CO
3 2-, various interfering ion solution such as I-.Get compound solution shown in the above-mentioned formula V of 2ml in cuvette, in cuvette, drip above-mentioned Cu (NO
3)
2Solution detects fluorescence spectrum.In above-mentioned system, drip 100 times of above-mentioned interfering ion solution after the titration balance respectively, detect fluorescence spectrum to the cupric ion molar equivalent.Drip cryanide ion solution to above-mentioned system again after the titration balance, the test fluorescence spectrum, as shown in Figure 6.As shown in Figure 6, the interfering ion of 75 times of amounts of disposable adding comprises F
-, Cl
-, I
-, Ac
-, SO
4 2-, S
2O
8 2-, PO
4 -, S
2-, OH
-, CO
3 2-, BO
3 -Deng, to the almost not influence of its fluorescence spectrum, add cryanide ion after the balance again, along with increasing fluorescence, the amount of cryanide ion strengthens gradually, and its fluorescence strengthens no longer obvious behind the cryanide ion that adds with 2 times of molar weights of Cu ion.
Fluorescence chemical sensor shown in the formula (IV) is to optionally fluorescence spectrum test of cryanide ion: (pH=7.20) buffered soln is prepared the Cu (NO of compound solution shown in the formula V of 8 μ mol/l and 100mmol/l respectively for H2O, 20mmol/l to use HEPES
3)
2Solution, and 0.15mol/l contains F respectively
-, Cr
2O
7 2-, PO
4 2-, BO
3 2-, Cl
-, Ac
-, S
2-, MnO
4 -, S
2O
8 2-, OH
-, SO
4 2-, CO
3 2-, various solions such as I-.Get that compound solution drips Cu (NO shown in the above-mentioned formula V of 2ml in cuvette in cuvette
3)
2Solution detects fluorescence spectrum after the titration balance, the more above-mentioned various interfering ion solution of 100 times of cupric ion molar equivalents of disposable adding in cuvette, detect fluorescence spectrum, continue in cuvette, to drip cryanide ion solution after the balance to balance, the test fluorescence spectrum, as shown in Figure 7.As shown in Figure 7,11 kinds of negatively charged ion comprise F
-, Cl
-, I
-, Ac
-, SO
4 2-, S
2O
8 2-, PO
4 -, S
2-, OH
-, CO
3 2-, BO
3 -Deng, have only cryanide ion to make the fluorescence of system significantly strengthen.
The preparation of embodiment 2, fluorescence chemical sensor (structural formula is suc as formula shown in (VI))
The preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde identical with among the embodiment 1, wherein, the temperature of oxidizing reaction is 90 ℃, the time of oxidizing reaction is 24 hours.
(2) take by weighing 300mg 2-methylbenzothiazole and the 300mg methyl iodide is added in the reaction flask, trichloromethane is as solvent, being heated to 80 ℃ stirred 48 hours, there is precipitation to generate, after stopping, reaction naturally cools to room temperature, filtration washing obtain flaxen 2-methyl-N-methylbenzothiazole salt compounded of iodine (its structural formula is suc as formula shown in (III), wherein, R
1Be S, R
2Be methyl);
(3) take by weighing 150mg 2-methyl-N-methylbenzothiazole salt compounded of iodine and 500mg 4 '-(N, N-lutidine base amido) phenyl aldehyde (wherein, 2-methyl-N-methylbenzothiazole salt compounded of iodine and 4 '-(N, N-lutidine base amido) mol ratio of phenyl aldehyde is 1: 3) with reaction flask in, anhydrous methanol is as solvent, 1% the hexahydropyridine that adds the quality percentage composition account for 2-methyl-N-n-propyl sulfonate benzothiazole is as catalyzer, be heated to 90 ℃ of stirring reactions 6 hours, there is precipitation to generate, reaction stops the back system and naturally cools to room temperature, suction filtration precipitation, precipitation are used the ether washing, promptly obtain compound shown in the formula (VII).
(4) compound and 18.8mg cupric nitrate shown in the 56mg formula (VII) react in water and promptly get the fluorescence chemical sensor shown in the formula (VI).
The preparation of embodiment 3, fluorescence chemical sensor (structural formula is suc as formula shown in (VIII))
The preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde identical with among the embodiment 1, wherein, the temperature of oxidizing reaction is 65 ℃, the time of oxidizing reaction is 48 hours.
(2) identical among 2-methyl-N-methylbenzothiazole salt compounded of iodine method and the embodiment 2.
(3) trans 2-[4 '-(N, N-lutidine base amido) vinylbenzene]-identical among the preparation method of N-ylmethyl benzothiazole salt compounded of iodine such as the embodiment 2.
(4) take by weighing (3) middle 20 times of corresponding sodium tetrafluoroborates of equivalent of product reflux in water and ethanolic soln and promptly obtained the compound shown in the formula (IX) in 24 hours.
(5) compound and 18.8mg cupric nitrate shown in the 54mg formula (VI) react in water and promptly get the fluorescence chemical sensor shown in the formula (VIII).
The preparation of embodiment 4, fluorescence chemical sensor (structural formula is suc as formula shown in (X))
The preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde identical with among the embodiment 1.
(2) identical among 2-methyl-N-methylbenzothiazole salt compounded of iodine method and the embodiment 2.
(3) trans 2-[4 '-(N, N-lutidine base amido) vinylbenzene]-identical among the preparation method of N-ylmethyl benzothiazole salt compounded of iodine such as the embodiment 2.
(4) take by weighing (3) middle 20 times of corresponding Potassium Hexafluorophosphates of equivalent of product reflux in water and ethanolic soln and promptly obtained the compound shown in the formula (XI) in 24 hours.
(5) compound and 18.8mg cupric nitrate shown in the 60mg formula (XI) react in water and promptly get the fluorescence chemical sensor shown in the formula (X).
Claims (10)
1. fluorescence chemical sensor, its structural formula is suc as formula shown in (I):
Wherein, R
1Be sulphur or oxygen; R
2Be sulphonate salt, salt compounded of iodine, fluorophosphate or fluoroborate.
2. the preparation method of the described chemical sensor of claim 1 comprises the steps:
(1) 4 '-(N, N-lutidine base amido) benzene carries out oxidizing reaction and obtains 4 '-(N, N-lutidine base amido) phenyl aldehyde under the effect of oxygenant;
Compound reacts compound shown in the formula of obtaining (II) shown in (2) 4 '-(N, N-lutidine base amido) phenyl aldehyde and the formula (III);
(3) compound and copper ions inorganic salt shown in the formula (II) react and promptly get described fluorescence chemical sensor;
In formula (II) and the formula (III), R
1Be sulphur or oxygen; R
2Be sulphonate salt, salt compounded of iodine, fluorophosphate or fluoroborate.
3. preparation method according to claim 2 is characterized in that: 4 '-(N, N-lutidine base amido) benzene is reacted by chloromethyl pyridine hydrochloride and aniline and obtains.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: the oxygenant of the described oxidizing reaction of step (1) is a phosphorus oxychloride.
5. according to arbitrary described preparation method among the claim 2-4, it is characterized in that: the temperature of the described oxidizing reaction of step (1) is 45 ℃-90 ℃; The time of the described oxidizing reaction of step (1) is 24 hours-72 hours.
6. according to arbitrary described preparation method among the claim 2-5, it is characterized in that: the molfraction ratio of compound and 4 ' shown in the formula (III) described in the step (2)-(N, N-lutidine base amido) phenyl aldehyde is 1: (2-6).
7. according to arbitrary described preparation method among the claim 2-6, it is characterized in that: the described catalyst for reaction of step (2) is hexahydropyridine, ammonium acetate, salt of wormwood, triethylamine, quadrol, sodium hydroxide or potassium hydroxide; The quality percentage composition that described catalyzer accounts for compound shown in the described formula (III) is 1%-3%.
8. according to arbitrary described preparation method among the claim 2-7, it is characterized in that: the solvent of the described reaction of step (2) is dehydrated alcohol, anhydrous methanol or acetone; The temperature of described reaction is 80 ℃-90 ℃; The time of described reaction is 6 hours-24 hours; The described copper ions inorganic salt of step (3) are cupric nitrate, cupric chloride, neutralized verdigris, copper sulfate or cupric perchlorate.
9. the application of the described fluorescence chemical sensor of claim 1 in detecting cryanide ion.
10. application according to claim 9 is characterized in that: in the buffered soln of 4-hydroxyethyl piperazine ethanesulfonic acid, with described fluorescence chemical sensor cryanide ion is detected.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863406A (en) * | 2012-07-16 | 2013-01-09 | 西北师范大学 | Receptor compound for detecting CN- by colorimetry-fluorescence two channels, synthesis thereof and application thereof |
| CN102879369A (en) * | 2012-09-27 | 2013-01-16 | 西北师范大学 | 2,2'-bibenzimidazole as acceptor molecule in CN- detection and identification |
| CN103134787A (en) * | 2013-02-25 | 2013-06-05 | 太原理工大学 | Application method of ratio-type cyanide ion fluorescent probe molecule |
| CN103308672A (en) * | 2013-05-10 | 2013-09-18 | 西北师范大学 | Application of 3-hydroxy-4-amino-1-naphthalene sulfonic acid serving as receptor compound of cyanide ions in detection of CN<-> |
| CN105115953A (en) * | 2015-09-07 | 2015-12-02 | 中国科学院理化技术研究所 | Ratio type nano ball sensor as well as preparation method and application thereof |
| 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 |
| CN111205242A (en) * | 2020-02-24 | 2020-05-29 | 山西大学 | Benzothiazole derivative and synthesis method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863406A (en) * | 2012-07-16 | 2013-01-09 | 西北师范大学 | Receptor compound for detecting CN- by colorimetry-fluorescence two channels, synthesis thereof and application thereof |
| CN102863406B (en) * | 2012-07-16 | 2014-04-16 | 西北师范大学 | Receptor compound for detecting CN- by colorimetry-fluorescence two channels, synthesis thereof and application thereof |
| CN102879369A (en) * | 2012-09-27 | 2013-01-16 | 西北师范大学 | 2,2'-bibenzimidazole as acceptor molecule in CN- detection and identification |
| CN102879369B (en) * | 2012-09-27 | 2014-08-06 | 西北师范大学 | Application of 2,2'-biphenyl imidazole serving as acceptor molecule in CN- detection and recognition |
| CN103134787A (en) * | 2013-02-25 | 2013-06-05 | 太原理工大学 | Application method of ratio-type cyanide ion fluorescent probe molecule |
| CN103308672A (en) * | 2013-05-10 | 2013-09-18 | 西北师范大学 | Application of 3-hydroxy-4-amino-1-naphthalene sulfonic acid serving as receptor compound of cyanide ions in detection of CN<-> |
| CN105115953A (en) * | 2015-09-07 | 2015-12-02 | 中国科学院理化技术研究所 | Ratio type nano ball sensor as well as preparation method and application thereof |
| 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 |
| CN111205242A (en) * | 2020-02-24 | 2020-05-29 | 山西大学 | Benzothiazole derivative and synthesis method and application thereof |
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