CN102190670B - Fluorescent chemical sensor and preparation method and application thereof - Google Patents
Fluorescent chemical sensor and preparation method and application thereof Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 abstract description 4
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 70
- 239000000243 solution Substances 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000010949 copper Substances 0.000 description 22
- 238000002211 ultraviolet spectrum Methods 0.000 description 22
- 238000002189 fluorescence spectrum Methods 0.000 description 21
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 17
- 125000003368 amide group Chemical group 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 15
- -1 ion salt Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 230000002452 interceptive effect Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XCYMLHQBXSDWOH-UHFFFAOYSA-N 2,3-dimethyl-2h-1,3-benzothiazole Chemical class C1=CC=C2N(C)C(C)SC2=C1 XCYMLHQBXSDWOH-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical compound Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a fluorescent chemical sensor and a preparation method and application thereof. TheThe structural formula of the fluorescence chemical sensor is shown as a formula , wherein R1Is sulfur or oxygen; r2Is sulfonate, iodide, fluorophosphate or fluoroborate. The preparation method of the chemical sensor provided by the invention comprises the following steps: (1)4 '- (N, N-dimethylpyridylamino) benzene is oxidized under the action of an oxidant to obtain 4' - (N, N-dimethylpyridylamino) benzaldehyde; (2) 4' - (N, N-dimethyl pyridyl amido) benzaldehyde reacts with the compound shown in the formula (III) to obtain a compound shown in the formula (II); (3) reacting the compound shown in the formula (II) with copper ion-containing inorganic salt to obtain the fluorescent chemical sensor; in the formulae (II) and (III), R1Is sulfur or oxygen; r2Is sulfonate, iodide, fluorophosphate or fluoroborate. The fluorescence chemical sensor provided by the invention can be used for specifically, efficiently, timely and simply detecting cyanide ions in an 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 field.
Background technology
Cryanide ion salt is widely used in industry, comprises metallurgy, plating, dyestuff, medicine etc.But cryanide ion has very strong toxicity, in country's " Design of Industrial Enterprises hygienic standard " regulation surface water, the maximum permissible concentration of cryanide ion is 0.05mg/L.Therefore cryanide ion is carried out to timely and effective detection seems particularly important.Many cryanide ion chemical detection molecular devices in recent years, the fluorescence chemical sensor particularly cryanide ion detected is reported in succession, but the report of the fluorescent optical sensor highly sensitive in water, that highly selective detects cryanide ion is also 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.The advantages such as it is highly sensitive, simple to operate and with low cost that the method has, in numerous areas extensive application prospect, the Optochemical sensor of dissimilar detected object is also among constantly designing and developing.Wherein, based on the interactional cryanide ion fluorescence chemical sensor of host-guest, because solvation strong in the aqueous solution reduces the interaction between host-guest, its sensitivity is reduced greatly, therefore such sensor can not effectively detect cryanide ion in the aqueous solution.Therefore can in the aqueous solution, to cryanide ion, carry out the fluorescence chemical sensor of efficient identification in the urgent need to designing, synthesizing.
The response type fluorescence chemical sensor provides opportunity for the detection of cryanide ion in the exploitation water, and the method utilizes chemical reaction single-minded between sensor and tested molecule to cause that the change of sensor luminescent properties is identified.Thereby the method affected by solvent polarity less, can in water, to target molecule, be detected, and be there is 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
1for sulphur or oxygen; R
2for 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;
(2) 4 '-(N, N-lutidine base amido) phenyl aldehydes are reacted compound shown in the formula of obtaining (II) with compound shown in formula (III);
(3) compound shown in formula (II) is reacted with the copper ions inorganic salt and is obtained described fluorescence chemical sensor;
In formula (II) and formula (III), R
1for sulphur or oxygen; R
2for sulphonate salt, salt compounded of iodine, fluorophosphate or fluoroborate.
In above-mentioned preparation method, 4 '-(N, N-lutidine base amido) benzene can be reacted and be obtained by chloromethyl pyridine hydrochloride and aniline; In this reaction, using alkali as sodium hydroxide as catalyzer, doubly, optimum quantity is 2.5 times to the 2-5 that wherein molar weight of sodium hydroxide can be chloromethylpyridine.
In above-mentioned preparation method, the oxygenant of the described oxidizing reaction of step (1) can be phosphorus oxychloride.
In 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.
In above-mentioned preparation method, the molfraction ratio of compound and 4 ' shown in formula (III) described in step (2)-(N, N-lutidine base amido) phenyl aldehyde can be 1: (2-6), and as 1: 3.
In above-mentioned preparation method, the catalyzer of the described 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 described formula (III) is 1%-3%, as 1% or 3%.
In 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; Shown in described formula (II), the mol ratio of compound and copper ions inorganic salt can be 1: 1.
The present invention also provides the application of above-mentioned fluorescence chemical sensor in detecting cryanide ion; In 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 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 to specific recognition.In addition, because fluorescence chemical sensor provided by the invention has good water-solublely as molecule inner salt, so greatly improved its application prospect in practice.In addition, described fluorescence chemical sensor has instant significantly colour-change to the detection of cryanide ion, is with the naked eye only the observable detected result.Therefore described fluorescence chemical sensor can carry out single-minded, efficient, timely, simple detection to cryanide ion in the aqueous solution.
The accompanying drawing explanation
Fig. 1 is that compound shown in formula (V) (concentration is 8 μ mol/l) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to the UV spectrum of cupric ion (concentration is 100mmol/l) response.
Fig. 2 is that compound shown in formula (V) (concentration is 8 μ mol/l) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to the fluorescence spectrum of cupric ion (concentration is 100mmol/l) response.
Fig. 3 is that fluorescence chemical sensor shown in formula (IV) (concentration is 8 μ mol/l) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to the UV spectrum of cryanide ion (concentration is 0.15mol/l) response.
Fig. 4 is that fluorescence chemical sensor shown in formula (IV) (concentration is 8 μ mol/l) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to the fluorescence spectrum of cryanide ion (concentration is 0.15mol/l) response.
Fig. 5 is that fluorescence chemical sensor shown in formula (IV) (concentration is 8 μ mol/l, and shown in formula (V), the mol ratio of compound and copper is 1: 1) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to cryanide ion (concentration is 0.15mol/l) UV spectrum optionally, wherein, the 1 blank UV spectrum that is fluorescence chemical sensor shown in formula (IV); The UV spectrum of the 2 cupric ion responses that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass; After the 3 cupric ion balances that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass, to the UV spectrum of the various negatively charged ion responses that add 75 times of cupric ion equivalents; 4 cupric ions that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass, then add the various negatively charged ion of 75 times of cupric ion equivalents, add the UV spectrum of cryanide ion response after balance.
Fig. 6 is that fluorescence chemical sensor shown in formula (IV) (concentration is 8 μ mol/l, and shown in formula (V), the mol ratio of compound and copper is 1: 1) is at HEPES (H
2o, 20mmol/l, pH=7.20) in buffered soln to cryanide ion (concentration is 0.15mol/l) fluorescence spectrum optionally.Wherein, the 1 blank fluorescence spectrum that is fluorescence chemical sensor shown in formula (IV); The fluorescence spectrum of the 2 cupric ion responses that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass; After the 3 cupric ion balances that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass, to the fluorescence spectrum of the various negatively charged ion responses that add 75 times of cupric ion equivalents; After the 4 cupric ion balances that are fluorescence chemical sensor shown in formula (IV) and 1: 1 molar mass, then, after adding the various anion balance of 75 times of cupric ion equivalents, add the fluorescence spectrum of cryanide ion response after balance.
Fig. 7 is the selectivity test of fluorescence chemical sensor shown in formula (IV) to 11 kinds of negatively charged ion and cryanide ion.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, fluorescence chemical sensor (structural formula is suc as formula shown in (IV))
(1) take 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 and obtain faint yellow 4 '-(N, N-lutidine base amido) benzene sterling.Slowly drip the 1ml phosphorus oxychloride to dry DMF sealed reaction bottle in ice bath, stir 30 minutes under 0 ℃, then add 4 ' of the above-mentioned preparation of 500mg-(N, N-lutidine base amido) benzene, be heated to 45 ℃ and stir 72 hours.System naturally cools to room temperature after completion of the reaction, adds distilled water to stir 30 minutes, and salt of wormwood is regulated pH value to 10, stir 30 minutes, methylene dichloride and water extract respectively 2 times, finally utilize column chromatography for separation to obtain described 4 '-(N, N-lutidine base amido) phenyl aldehyde;
(2) take 300mg 2-methylbenzothiazole and 300mg 1, the 3-sultone is added in reaction flask, trichloromethane is as solvent, being heated to 80 ℃ stirs 48 hours, have precipitation to generate, after reaction stops, naturally cooling to room temperature, filtration washing obtains flaxen 2-methyl-N-n-propyl sulfonate benzothiazole, and (its structural formula is suc as formula shown in (III), wherein, R
1for S, R
2for the n-propyl sulfonic group);
(3) take 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, add 3% hexahydropyridine of the quality percentage composition that accounts for 2-methyl-N-n-propyl sulfonate benzothiazole as catalyzer, be heated to 80 ℃ of stirring reactions 10 hours, there is precipitation to generate, reaction stops rear system and naturally cools to room temperature, the suction filtration precipitation, precipitation is used the ether washing, obtain compound shown in 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 56mg formula (V) is reacted in water with the 18.8mg cupric nitrate and is obtained the fluorescence chemical sensor shown in formula (IV).
The UV spectrum test of compound shown in formula (V) to cupric ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively the Cu (NO of compound solution shown in the formula (V) of 8 μ mol/l and 100mmol/l
3)
2solution.Get compound solution shown in the above-mentioned formula of 2ml (V) in cuvette, in cuvette, drip gradually above-mentioned Cu (NO
3)
2solution, to balance, detects UV spectrum, as shown in Figure 1.As can be known from Fig. 1, UV spectrum absorbs and reduces along with the increase of cupric ion at the 498nm place, but add, with the cupric ion of compound same molar shown in formula (V), changes afterwards no longer obvious; UV spectrum new absorption peak occurs in the absorption at 386nm place along with the increase of cupric ion, but after adding 1 times of cupric ion, changes no longer obvious.
The fluorescence spectrum test of compound shown in formula (V) to cupric ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively the Cu (NO of compound solution shown in the formula (V) of 8 μ mol/l and 100mmol/l
3)
2solution.Get compound solution shown in the above-mentioned formula of 2ml (V) in cuvette, and drip gradually above-mentioned Cu (NO in cuvette
3)
2solution, to balance, detects fluorescence spectrum, as shown in Figure 2.As can be known from Fig. 2, along with the amount of cupric ion increases fluorescence, reduce gradually, after the cupric ion added with compound same molar shown in formula (V), its fluorescence is by cancellation fully.
The UV spectrum test of fluorescence chemical sensor shown in formula (IV) to cryanide ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively the Cu (NO of compound solution shown in the formula (V) of 8 μ mol/l and 100mmol/l
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 drip above-mentioned Cu (NO in cuvette
3)
2solution, detect UV spectrum; Continue upwards to state the above-mentioned cryanide ion solution of dropping in system after the titration balance and, to balance, detect 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, but add, with the cryanide ion of 2 times of molar weight Cu ions, changes afterwards no longer obvious; Absorption at the 386nm place reduces along with the increase of cryanide ion, but add, with the cryanide ion of 2 times of molar weights of Cu ion, changes afterwards no longer obvious.
The fluorescence spectrum test of fluorescence chemical sensor shown in formula (IV) to cryanide ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively the Cu (NO of compound solution shown in the formula (V) of 8 μ mol/l and 100mmol/l
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 drip Cu (NO in cuvette
3)
2solution, detect fluorescence spectrum, after the titration balance, continues upwards to state in system to drip above-mentioned cryanide ion solution to balance, detects fluorescence spectrum, as shown in Figure 4.As shown in Figure 4, along with the amount of cryanide ion increases fluorescence, strengthen gradually, after the cryanide ion added with 2 times of molar weights of Cu ion, its fluorescence strengthens no longer obvious.
The UV spectrum test of fluorescence chemical sensor shown in formula (IV) to interfering ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively compound solution shown in the formula (V) of 8 μ mol/l, the Cu (NO of 100mmol/l
3)
2solution, the cryanide ion solution of 0.5mol/l, and 0.15mol/l contains respectively F
-, 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 fluorescence chemical sensor solution shown in the above-mentioned formula of 2ml (IV) in cuvette, in cuvette, drip Cu (NO
3)
2solution, detect UV spectrum.Drip respectively 100 times in the backward above-mentioned system of titration balance to the above-mentioned interfering ion solution of cupric ion molar equivalent, detect UV spectrum.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 disposable interfering ion that adds 75 times of amounts, comprise F
-, Cl
-, I
-, Ac
-, SO
4 2-, S
2o
8 2-, PO
4 -, S
2-, OH
-, CO
3 2-, BO
3 -deng, on the almost not impact of its UV spectrum; Add cryanide ion after balance, UV spectrum strengthens along with the increase of cryanide ion at 498nm place absorption peak again, but add, with the cryanide ion of 2 times of molar weight Cu ions, changes afterwards no longer obvious; Absorption at the 386nm place reduces along with the increase of cryanide ion, but add, with the cryanide ion of 2 times of molar weights of Cu ion, changes afterwards no longer obvious.
The fluorescence spectrum test of fluorescence chemical sensor shown in formula (IV) to interfering ion: use HEPES (H
2o, 20mmol/l, pH=7.20) buffered soln prepares respectively compound solution shown in the formula (V) of 8 μ mol/l, the Cu (NO of 100mmol/l
3)
2solution, the cryanide ion solution of 0.5mol/l, and 0.15mol/l contains respectively F
-, 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-, the various interfering ion solution such as I-.Get compound solution shown in the above-mentioned formula of 2ml (V) in cuvette, in cuvette, drip above-mentioned Cu (NO
3)
2solution, detect fluorescence spectrum.Drip respectively 100 times in the backward above-mentioned system of titration balance to the above-mentioned interfering ion solution of cupric ion molar equivalent, detect fluorescence spectrum.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 disposable interfering ion that adds 75 times of amounts, comprise F
-, Cl
-, I
-, Ac
-, SO
4 2-, S
2o
8 2-, PO
4 -, S
2-, OH
-, CO
3 2-, BO
3 -deng, on the almost not impact of its fluorescence spectrum, add again cryanide ion after balance, along with increasing fluorescence, the amount of cryanide ion strengthens gradually, and after the cryanide ion added with 2 times of molar weights of Cu ion, its fluorescence strengthens no longer obvious.
Fluorescence chemical sensor shown in formula (IV) is to optionally fluorescence spectrum test of cryanide ion: use HEPES (H2O, 20mmol/l, pH=7.20) buffered soln prepares respectively the Cu (NO of compound solution shown in the formula (V) of 8 μ mol/l and 100mmol/l
3)
2solution, and 0.15mol/l contains respectively F
-, 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-, the various solions such as I-.Get compound solution shown in the above-mentioned formula of 2ml (V) in cuvette, in cuvette, drip Cu (NO
3)
2solution, detect fluorescence spectrum after the titration balance, then to the disposable above-mentioned various interfering ion solution that add 100 times of cupric ion molar equivalents in cuvette, detect fluorescence spectrum, after balance, continue to drip cryanide ion solution to balance in cuvette, 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, only have 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))
Identical with in embodiment 1 of the preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde, wherein, the temperature of oxidizing reaction is 90 ℃, the time of oxidizing reaction is 24 hours.
(2) take 300mg 2-methylbenzothiazole and the 300mg methyl iodide is added in reaction flask, trichloromethane is as solvent, being heated to 80 ℃ stirs 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
1for S, R
2for methyl);
(3) take 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, add 1% hexahydropyridine of the quality percentage composition that accounts for 2-methyl-N-n-propyl sulfonate benzothiazole as catalyzer, be heated to 90 ℃ of stirring reactions 6 hours, there is precipitation to generate, reaction stops rear system and naturally cools to room temperature, the suction filtration precipitation, precipitation is used the ether washing, obtain compound shown in formula (VII).
(4) compound shown in 56mg formula (VII) is reacted in water with the 18.8mg cupric nitrate and is obtained the fluorescence chemical sensor shown in formula (VI).
The preparation of embodiment 3, fluorescence chemical sensor (structural formula is suc as formula shown in (VIII))
Identical with in embodiment 1 of the preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde, wherein, the temperature of oxidizing reaction is 65 ℃, the time of oxidizing reaction is 48 hours.
(2) identical with in embodiment 2 of 2-methyl-N-methylbenzothiazole salt compounded of iodine method.
(3) trans 2-[4 '-(N, N-lutidine base amido) vinylbenzene]-identical as in embodiment 2 of the preparation method of N-ylmethyl benzothiazole salt compounded of iodine.
(4) take 20 times of corresponding sodium tetrafluoroborates of equivalent of product reflux in water and ethanolic soln in (3) and within 24 hours, obtain the compound shown in formula (IX).
(5) compound shown in 54mg formula (VI) is reacted in water with the 18.8mg cupric nitrate and is obtained the fluorescence chemical sensor shown in formula (VIII).
The preparation of embodiment 4, fluorescence chemical sensor (structural formula is suc as formula shown in (X))
Identical with in embodiment 1 of the preparation method of (1) 4 '-(N, N-lutidine base amido) phenyl aldehyde.
(2) identical with in embodiment 2 of 2-methyl-N-methylbenzothiazole salt compounded of iodine method.
(3) trans 2-[4 '-(N, N-lutidine base amido) vinylbenzene]-identical as in embodiment 2 of the preparation method of N-ylmethyl benzothiazole salt compounded of iodine.
(4) take 20 times of corresponding Potassium Hexafluorophosphates of equivalent of product reflux in water and ethanolic soln in (3) and within 24 hours, obtain the compound shown in formula (XI).
(5) compound shown in 60mg formula (XI) is reacted in water with the 18.8mg cupric nitrate and is obtained the fluorescence chemical sensor shown in formula (X).
Claims (3)
1. the compound shown in following structural formula:
2. compound claimed in claim 1 application in detecting cryanide ion as fluorescence chemical sensor.
3. application according to claim 2 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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| 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 |
| 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 |
| CN103308672B (en) * | 2013-05-10 | 2014-10-22 | 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 nanosphere sensor and preparation method and application thereof |
| 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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