CN108299262B - A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof - Google Patents
A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof Download PDFInfo
- Publication number
- CN108299262B CN108299262B CN201810065151.3A CN201810065151A CN108299262B CN 108299262 B CN108299262 B CN 108299262B CN 201810065151 A CN201810065151 A CN 201810065151A CN 108299262 B CN108299262 B CN 108299262B
- Authority
- CN
- China
- Prior art keywords
- aniline
- benzylthio
- crocic acid
- chemical sensor
- identification
- 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.)
- Active
Links
- RBSLJAJQOVYTRQ-UHFFFAOYSA-N croconic acid Chemical compound OC1=C(O)C(=O)C(=O)C1=O RBSLJAJQOVYTRQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YOLYJTSQMGIQOP-UHFFFAOYSA-N 2-benzylsulfanylaniline Chemical compound NC1=CC=CC=C1SCC1=CC=CC=C1 YOLYJTSQMGIQOP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000975 dye Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 10
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 241000736199 Paeonia Species 0.000 claims description 6
- 235000006484 Paeonia officinalis Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000000862 absorption spectrum Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ATZBPOVXVPIOMR-UHFFFAOYSA-N dimethylmercury Chemical compound C[Hg]C ATZBPOVXVPIOMR-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LKMCJXXOBRCATQ-UHFFFAOYSA-N benzylsulfanylbenzene Chemical compound C=1C=CC=CC=1CSC1=CC=CC=C1 LKMCJXXOBRCATQ-UHFFFAOYSA-N 0.000 description 1
- -1 benzylthio aniline crocic acid cyanine compound Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000469 dry deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QFAXIZQBSCGJMA-UHFFFAOYSA-N mercury;hydrate Chemical compound O.[Hg] QFAXIZQBSCGJMA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008844 regulatory mechanism Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/29—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to a kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor, preparation method, comprising steps of 2- amido benzenethiol and benzyl chloride are synthesized 2- benzylthio aniline, 2- benzylthio aniline synthesizes 2- benzylthio aniline crocic acid cyanine dye compound with crocic acid.The beneficial effects of the present invention are: synthesis process is relatively simple, the 2- benzylthio aniline crocic acid cyanine dyes of easy control of reaction conditions, preparation has excellent optical property and optical stability.2- benzylthio aniline crocic acid cyanine dyes is in mercury ion identification process, and in addition to absorption spectrum changes, solution colour also changes, and has colorimetric identification function, is conducive to detect mercury ion.In addition, being had good selectivity to the identification of mercury ion and anti-interference.
Description
Technical field
Present invention relates particularly to a kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and its preparation side
Method belongs to chemical analysis test field.
Background technique
Mankind's activity causes water body mercury pollution, mainly from the industrial discharges such as chlor-alkali, plastics, battery, electronics waste water with
And waste and old medical instrument.It is estimated that the annual whole world is since mankind's activity is directly to about 1.6 ten thousand tons of the total amount of discharge into water mercury；
It arranges to the total mercury of atmosphere up to 100,000 tons or so；Being discharged into soil total mercury is about 100,000 tons, and arrange to atmosphere and soil also will be with
Dampening, which is recycled back to, is included into water body.
Since mercury is distributed in atmosphere, soil and water body under natural environment, thus the Transport And Transformation of mercury also land,
Occur between water, sky.The mercury of gaseous state and particulate form drifts with the wind in atmosphere, and a part is fallen to the ground by wet deposition or dry deposition
Or in water body.Mercury in soil is volatilizable into atmosphere, and the surface water can also be entered by precipitation shower and is infiltrated through in underground water.Ground
Mercury a part in the water of face enters atmosphere due to volatilization, most of then precipitate into bed mud.Mercury in bed mud, no matter which kind of is in
Form all can directly or indirectly be converted into methyl mercury or dimethylmercury under the action of microorganism.Dimethylmercury is in acid item
Part can be decomposed into methyl mercury.Methyl mercury is water-soluble, therefore returns in water from bed mud again.The methyl mercury of aquatile intake,
It can accumulate, and be constantly enriched with by food chain in vivo.Fish in mercury contaminated water body, internal methyl mercury concentration is than in water
It is up to ten thousand times high, jeopardize fish and by food chain harmful to human.Therefore, to the detection of natural environment and the intracorporal mercury ion of biology
It is necessary.In recent years, the chemical sensor of design and synthesis mercury ion is concerned, have become chemical science,
The research hotspot in the fields such as bioscience, environmental science.
Currently, the fluorescence chemical sensor based on Regulation Mechanism identification mercury ion of not sharing the same light has lot of documents report, but
Wherein most is by other metal ions such as Ag+And Cu2+Interference.Therefore, research has efficient selective and spirit to mercury ion
The new chemical sensor of sensitivity is still challenging.
Crocic acid cyanines are located at UV-visible region near infrared absorption wavelength as a kind of novel organic functions dyestuff
Domain, and the light of such dyestuff, thermal stability are good, therefore show in the fields such as optical recording and storage, liquid crystal display excellent
Application performance.Since the five-membered ring of crocic acid molecule is the aromatic conjugated system with push-pull electronic capability, there is electronics
There is very big separation of charge in the molecular structure of donor-receiver, intramolecular, so crocic acid mountain valley with clumps of trees and bamboo dyestuff, which has, identifies certain metals
The characteristic of ion.
Novel it can be used for Hg present invention relates particularly to a kind of2+The crocic acid cyanines chemical sensor of detection, the side of synthesis
Method is fairly simple, easy control of reaction conditions, and can obtain pure product by simple processing after reaction, this
It is outer to be used as Hg2+Detection chemical sensor, the advantages of this crocic acid cyanine dyes is that have very high sensitivity and selectivity.
Summary of the invention
The technical problem to be solved by the present invention is the present invention is in order to solve existing probe to Hg2+The chemical sensor of detection
Deficiency, providing one kind being capable of efficient identification Hg2+2- benzylthio aniline crocic acid cyanine dyes and preparation method thereof.
The present invention solves a technical solution used by its technical problem: a kind of Hg for identification2+2- benzene first sulphur
Base aniline crocic acid cyanine dyes, structure are as follows:
A kind of identification Hg of the present invention2+2- benzylthio aniline crocic acid cyanines chemical sensor preparation method,
Include the following steps:
(1) 2- amido benzenethiol and benzyl chloride are added in round-bottomed flask according to molar ratio 1:1, deionized water are added,
It is stirred overnight under normal temperature condition, solution slowly becomes clarifying from muddiness.To after reaction, stop stirring, with methylene chloride into
Row extraction three times, rotates out solvent with Rotary Evaporators.Using petroleum ether and ethyl acetate mixed solvent as eluant, eluent, using silica gel
Chromatographic column is separated, and isolated product, which hang with Rotary Evaporators, steams eluant, eluent, and the product outstanding steamed is put into
In evaporating dish, it is placed at 60 DEG C of baking oven and obtains 2- benzylthio aniline after drying.
(2) 2- benzylthio aniline and crocic acid that step (1) is prepared round bottom is added to according to molar ratio 2:1 to burn
In bottle, n-butanol and toluene Mixed Solvent is added, connects condenser pipe and Stark trap, nitrogen is passed through, at 110-140 DEG C
It is heated to reflux 6-9 hours, solution becomes peony from yellow, and the water generated in reaction is separated with water segregator.After reaction, to
Its cooled to room temperature removes solvent with Rotary Evaporators rotation under reduced pressure.Several times with ethanol washing, it is solid to obtain peony
Body.It will obtain solid to be put into evaporating dish, and be placed in drying at 60 DEG C of baking oven, obtain 2- benzylthio aniline crocic acid cyanine dyes.
Further, the volume ratio of petroleum ether and ethyl acetate is 10:1 in the step (1).
Further, the volume ratio of n-butanol and toluene is 1:1 in the step (2).
Based on the application of 2- benzylthio aniline crocic acid cyanines chemical sensor, chemical sensor be can be used to identify in solution
Mercury ion.
The beneficial effects of the present invention are: (1) 2- benzylthio aniline crocic acid cyanine dyes synthesis process of the invention is more
Simply, easy control of reaction conditions can obtain pure product by simply post-processing.In addition, the 2- benzene first sulphur of preparation
Base aniline crocic acid cyanine dyes has excellent optical property and optical stability.(2) 2- benzylthio aniline gram of the invention
Ketone acid cyanine dyes is in mercury ion identification process, and in addition to absorption spectrum changes, solution colour also changes, have than
Color identification function is conducive to detect mercury ion.(3) 2- benzylthio aniline crocic acid cyanine dyes of the invention to mercury from
The identification of son has good selectivity and anti-interference.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings and examples:
Fig. 1 be the 2- benzylthio aniline crocic acid cyanines that prepare of embodiment 1 existing for other metal ions under the conditions of it is right
The UV absorption figure of mercury ion identification；
Fig. 2 is ultraviolet after the 2- benzylthio aniline crocic acid mountain valley with clumps of trees and bamboo prepared by embodiment 1 is complexed with various concentration mercury ion
Abosrption spectrogram；
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment and the application examples content that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to embodiment and application examples below.
Embodiment 1
1.252g 2- amido benzenethiol (about 0.01mol) and 1.266g benzyl chloride (about 0.01mol) are added to round bottom to burn
In bottle, 150ml deionized water is added, is stirred overnight under normal temperature condition, solution slowly becomes clarifying from muddiness.To the end of reacting
Afterwards, stop stirring, extracted three times with methylene chloride, rotate out solvent with Rotary Evaporators.With 200ml petroleum ether and 20ml
Ethyl acetate mixed solvent be eluant, eluent, separated using silica gel chromatographic column, isolated product Rotary Evaporators into
Row is outstanding to steam eluant, eluent, and the outstanding product steamed is put into evaporating dish, is placed at 60 DEG C of baking oven and obtains 2- benzylthio after drying
Aniline.
The 2- benzylthio aniline of the crocic acid (about 0.000352mol) and 0.15g that weigh 0.05g is (about
It 0.000704mol) is added in round-bottomed flask, 20mL toluene and 20mL n-butanol is added, connect condenser pipe and stoke divides water
Device, 9 hours of stirring are heated to reflux at 110 DEG C, and solution becomes peony, the water generated in reaction water segregator point from yellow
Out.After reaction, stop heating, after solution is cooled to room temperature, remove solvent with Rotary Evaporators rotation under reduced pressure.Ethyl alcohol
Washing several times, obtains dark red solid.Solid is put into evaporating dish, is dried at 60 DEG C of baking oven to get 2- benzylthio benzene is arrived
Amine crocic acid cyanine dyes.
Embodiment 2
0.751g 2- amido benzenethiol (about 0.006mol) and 0.760g benzyl chloride (about 0.006mol) are added to round bottom
In flask, 100ml deionized water is added, is stirred overnight under normal temperature condition, solution slowly becomes clarifying from muddiness.To the end of reacting
Afterwards, stop stirring, extracted three times with methylene chloride, rotate out solvent with Rotary Evaporators.With petroleum ether and ethyl acetate
Mixed solvent is eluant, eluent, is separated using silica gel chromatographic column, and isolated product carries out outstanding steam with Rotary Evaporators
The outstanding product steamed is put into evaporating dish by eluant, eluent, is placed at 60 DEG C of baking oven and is obtained 2- benzylthio aniline after drying.
Weigh the crocic acid (about 0.000704mol) of 0.1g and the 2- benzylthio aniline (about 0.001408mol) of 0.3g
It is added in round-bottomed flask, 30mL toluene and 30mL n-butanol is added, connect condenser pipe and Stark trap, add at 140 DEG C
6 hours of hot return stirring, solution become peony from yellow, and the water generated in reaction is separated with water segregator.After reaction,
Stop heating, after solution is cooled to room temperature, removes solvent with Rotary Evaporators rotation under reduced pressure.Ethanol washing several times, obtains
Dark red solid.Solid is put into evaporating dish, dries at 60 DEG C of baking oven and is contaminated to get to 2- benzylthio aniline crocic acid cyanines
Material.
Application examples
In order to detect identification of the 2- benzylthio aniline crocic acid cyanines probe of the preparation of embodiment 1 to mercury ion, with DMSO
Make solvent, it is 5 × 10 that the 2- benzylthio aniline crocic acid cyanine dyes of synthesis, which is configured to concentration,-5Mol/L takes 10mL respectively
The solution prepared is in 16 test tubes, label 1-16.Sequentially add 1mL 1 × 10-2The Hg of mol/L2+、Zn2+、K+、Na+、Ba2+、
Mg2+、Ni2+、Ca2+、Ag+、Cu2+、Cr3+、 Fe3+、Co2+、Pb2+、Al3+、Cd2+Solution measures its UV absorption, such as Fig. 1 respectively
It is shown, 2- benzylthio aniline crocic acid cyanines-Hg2+Curve has occurred apparent displacement, and 2- benzylthio aniline crocic acid cyanines-
There is no displacements for other metal ion curves, this demonstrate that prepared 2- benzylthio aniline crocic acid cyanine dyes is to Hg2+Have
Unique recognition performance.
In order to further detect 2- benzylthio aniline crocic acid mountain valley with clumps of trees and bamboo probe to the recognition performance of mercury ion, with DMSO's
Mixed solution makees solvent, and it is 5 × 10 that the 2- benzylthio aniline crocic acid cyanine dyes of synthesis, which is configured to concentration,-5Mol/L's is molten
Liquid takes 50mL, and 1 × 10 is added dropwise into solution-2The mercury ion solution of mol/L, is successively surveyed using ultraviolet-visible light protractor
The variation of its fixed absorption spectrum, absorption spectrum are as shown in Figure 2.As seen from the figure, with the increase of mercury ion dripping quantity, 2-
The absorption spectrum of benzylthio aniline crocic acid cyanine compound changes, and the absorption peak at 460nm is gradually subjected to displacement
And it increases, and final mean annual increment movement is to 480nm.This further demonstrates 2- benzylthio aniline crocic acid mountain valley with clumps of trees and bamboo dyestuffs to Hg2+Have very well
Recognition effect.
It is enlightenment with the embodiment of the present invention, according to above-mentioned description, relevant staff can be without departing from this
In the range of item inventive technique thought, the change and modification of multiplicity are carried out.The technical scope of the present invention is not limited to
On content, it is necessary to the technical scope thereof is determined according to the scope of the claim.
Claims (5)
1. a kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor, it is characterized in that: 2- benzylthio aniline gram
The structural formula of ketone acid cyanines chemical sensor is as shown in figure I:
2. the preparation method of 2- benzylthio aniline crocic acid cyanines chemical sensor described in claim 1, it is characterized in that: including
Following steps:
(1) 2- amido benzenethiol and benzyl chloride are added in round-bottomed flask according to molar ratio 1:1, deionized water, room temperature is added
Under the conditions of be stirred overnight, solution slowly becomes clarifying from muddiness, to after reaction, stops stirring, is extracted with methylene chloride
It takes three times, rotates out solvent with Rotary Evaporators, using petroleum ether and ethyl acetate mixed solvent as eluant, eluent, using silica gel chromatograph
Column is separated, and isolated product, which hang with Rotary Evaporators, steams eluant, eluent, and the product outstanding steamed is put into evaporation
In ware, it is placed at 60 DEG C of baking oven and obtains 2- benzylthio aniline after drying；
(2) 2- benzylthio aniline and crocic acid that step (1) is prepared are added to round-bottomed flask according to molar ratio 2:1
In, n-butanol and toluene Mixed Solvent is added, connects condenser pipe and Stark trap, is passed through nitrogen, adds at 110-140 DEG C
Heat reflux 6-9 hours, solution becomes peony from yellow, and the water generated in reaction is separated with water segregator, after reaction, to it
Cooled to room temperature removes solvent with Rotary Evaporators rotation under reduced pressure, later several times with ethanol washing, it is solid to obtain peony
Body will obtain solid and be put into evaporating dish, is placed in drying at 60 DEG C of baking oven, obtains 2- benzylthio aniline crocic acid cyanine dyes.
3. the preparation method of 2- benzylthio aniline crocic acid cyanines chemical sensor according to claim 2, it is characterized in that:
The volume ratio of eluent petroleum ether and ethyl acetate is 10:1 in the step (1).
4. according to the preparation method of 2- benzylthio aniline crocic acid cyanines chemical sensor described in claims requirement 2,
It is characterized in that: the molar ratio of 2- benzylthio aniline and crocic acid is 2:1 in the step (2).
5. the application of 2- benzylthio aniline crocic acid cyanines chemical sensor described in claim 1, it is characterized in that: the change
Learn the Hg that sensor can for identification in solution2+。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065151.3A CN108299262B (en) | 2018-01-23 | 2018-01-23 | A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065151.3A CN108299262B (en) | 2018-01-23 | 2018-01-23 | A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108299262A CN108299262A (en) | 2018-07-20 |
| CN108299262B true CN108299262B (en) | 2019-10-11 |
Family
ID=62866042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810065151.3A Active CN108299262B (en) | 2018-01-23 | 2018-01-23 | A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299262B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112268936B (en) * | 2020-10-15 | 2022-07-19 | 苏州大学 | Croconium cyanine polymer sensor for low-concentration nitrogen dioxide and preparation method thereof |
| CN113588728B (en) * | 2021-07-05 | 2023-08-08 | 苏州大学 | Croconic acid cyanine polymer sensor capable of being used for trace detection of nitrogen dioxide in high humidity environment and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801465A (en) * | 2016-04-11 | 2016-07-27 | 常州大学 | Water-soluble indole croconium cyanine colorimetric probe, preparation method and application |
| CN106220584A (en) * | 2016-07-21 | 2016-12-14 | 常州大学 | Ketobenzocyanine colorimetric probe, preparation method and application |
-
2018
- 2018-01-23 CN CN201810065151.3A patent/CN108299262B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801465A (en) * | 2016-04-11 | 2016-07-27 | 常州大学 | Water-soluble indole croconium cyanine colorimetric probe, preparation method and application |
| CN106220584A (en) * | 2016-07-21 | 2016-12-14 | 常州大学 | Ketobenzocyanine colorimetric probe, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Infrared Absorbing Croconaine Dyes: Synthesis and Metal Ion Binding Properties;Rekha R. Avirah et al.;《J. Org. Chem.》;20071112;第73卷;第274-279页 * |
| Linear and Nonlinear Optical Properties of Mesoionic Oxyallyl Derivatives: Enhanced Non-Resonant Third Order Optical Nonlinearity in Croconate Dyes;Ch. Prabhakar et al.;《J. Phys. Chem. C》;20080805;第112卷(第34期);第13272–13280页 * |
| Visible absorbing croconium dyes with intramolecular hydrogen bonding: A combined experimental and computational study;Ch. Prabhakar et al.;《Journal of Molecular Structure》;20170604;第1146卷;第684-691页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108299262A (en) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108299262B (en) | A kind of identification Hg2+2- benzylthio aniline crocic acid cyanines chemical sensor and preparation method thereof | |
| CN103013495B (en) | Copper ion fluorescence probe and synthetic method thereof | |
| CN104710816B (en) | Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof | |
| CN105385439A (en) | Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof | |
| CN106883207A (en) | A kind of preparation method of trimeric indenyl bicoumarin fluorescent dye | |
| CN108192599B (en) | Preparation and application of pyrene 2- (2-methylthiopyridine) aniline Schiff base Zn2+ fluorescent probe | |
| CN109734738A (en) | A kind of fluorescence probe and the preparation method and application thereof that can quickly detect sulfurous acid hydrogen radical ion | |
| CN105801465A (en) | Water-soluble indole croconium cyanine colorimetric probe, preparation method and application | |
| CN113004313A (en) | Double-thiophene-double-coumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof | |
| CN114573544A (en) | Molecular switch with multiple stimulus responses and synthesis method thereof | |
| CN106496065B (en) | A kind of o-phenylenediamine Schiff base derivatives and the preparation method and application thereof | |
| CN113831339B (en) | Perylene bisimide derivative fluorescent probe, preparation method and application thereof | |
| CN113416203B (en) | Near-infrared-emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift and preparation method thereof | |
| CN111208125A (en) | Dual-mode sensor array and application thereof in distinguishing and identifying hydrazine and organic amine | |
| CN105566247B (en) | A kind of benzothiazole crocic acid cyanines colorimetric probe, preparation method and application | |
| CN108912037B (en) | A kind of identification Cu2+Sulfonic group indoles Isatine derivatives chemical sensor and preparation method thereof | |
| CN111233767B (en) | Anthracene-based dipyrazole compound and preparation method and application thereof | |
| CN102584808B (en) | Methods for preparing and applying fluorescent material containing thienyl benzothiazole unit | |
| CN104004028A (en) | Hg detection method2+Multi-channel molecular probe and its preparing process | |
| CN106220584A (en) | Ketobenzocyanine colorimetric probe, preparation method and application | |
| CN115322262B (en) | Be used for detecting Fe 3+ Dialdehyde cellulose coumarin fluorescent probe and preparation method and application thereof | |
| CN108997304B (en) | Alkyl chain thienyl Schiff base and synthetic method thereof | |
| LU501426B1 (en) | MOLECULAR SENSOR CAPABLE OF DETECTING Cu2+ AND Zn2+ IN WATER AND USE THEREOF | |
| CN103626405B (en) | Single fluorescent conjugated polymer film and preparation method thereof | |
| CN110981892A (en) | Covalent organic framework material with spiropyran molecular switch and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |