CN106519112B - A kind of highly-water-soluble rhodamine base poly ion liquid and preparation method thereof, application - Google Patents
A kind of highly-water-soluble rhodamine base poly ion liquid and preparation method thereof, application Download PDFInfo
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- CN106519112B CN106519112B CN201610937041.2A CN201610937041A CN106519112B CN 106519112 B CN106519112 B CN 106519112B CN 201610937041 A CN201610937041 A CN 201610937041A CN 106519112 B CN106519112 B CN 106519112B
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- rhodamine
- water
- ion liquid
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- poly ion
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000007788 liquid Substances 0.000 title claims abstract description 87
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 24
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000000007 visual effect Effects 0.000 claims abstract description 4
- 240000000203 Salix gracilistyla Species 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000523 sample Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 4
- 238000004737 colorimetric analysis Methods 0.000 claims description 4
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- -1 methacryloxypropyl Chemical group 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 41
- 230000004044 response Effects 0.000 abstract description 9
- 230000036541 health Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000008520 organization Effects 0.000 abstract description 5
- 150000001455 metallic ions Chemical class 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 abstract 1
- 230000009871 nonspecific binding Effects 0.000 abstract 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000002798 spectrophotometry method Methods 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000023077 detection of light stimulus Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- 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
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- Medicinal Chemistry (AREA)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to detection of heavy metal ion field, and in particular to a kind of highly-water-soluble rhodamine base poly ion liquid and preparation method thereof, and it is applied to the quick visual colorimetric detection of pure water phase copper ion.The rhodamine base poly ion liquid is formed by ionic liquid monomer and bigcatkin willow aldehydes rhodamine B hydrazides monomer copolymerization, with raw material it is cheap and easy to get, prepare that easy, rhodamine content is high, water-soluble excellent and without advantages such as nonspecific binding sites, the efficient colorimetric detection to copper trace can be realized in pure water environment, bore hole and ultraviolet-visible spectrophotometry detection limit are respectively 0.5 μM and 0.15 μM, far below 31 μM as defined in the World Health Organization (WHO).In addition, the rhodamine base poly ion liquid detects copper ion, the detection response time is short, and 5s can complete to develop the color, and have excellent selectivity, hardly be disturbed by other coexistent metallic ions.
Description
Technical field
The invention belongs to detection of heavy metal ion field, and in particular to a kind of highly-water-soluble rhodamine base poly ion liquid and
Its preparation method, and the application of quick visual colorimetric detection pure water phase copper ion.
Background technology
Copper is the indispensable trace element of health, but when copper ion excess intake, will cause liver, courage,
The dysfunction of the organs such as brain, cornea and heart.With modern industry (the especially row such as mining and metallurgy, mechanical processing, chemical industry, electronics
Industry) fast development, copper ion pollution problem is increasingly serious in water environment.The World Health Organization (WHO) clear stipulaties life drink
It should be less than 2mg/L (i.e. 31 μM) with content of copper ion in water.Therefore, the copper ion in water environment is used for quickly detecting with weight
Want meaning.
Colorimetric method have the advantages that it is quick, conveniently, it is easy to operate and can field assay, be widely used in heavy metal ion
Detection field.In the various probe molecules that colorimetric method uses, rhodamine derivative have it is cheap and easy to get, wave-length coverage is wide,
The characteristics such as good light stability and absorptivity are big and enjoy people to pay close attention to.But the hydrophobicity of rhodamine derivative is very strong,
It is generally necessary to which adding more than 50% organic solvent could effectively use, this not only pollutes environment, but also is not suitable for biological sample
The detection of product.
For rhodamine derivative strong-hydrophobicity problem, polymerizable rhodamine derivative and parent are mainly utilized at present
Aqueous monomers are copolymerized to obtain water-soluble polymer, are mutually detected so as to fulfill pure water.However, the various hydrophilic monomers reported at present
Limited by itself water-soluble ability, it is necessary to rhodamine base monomeric charge molar ratio at least above 50:1 could cause polymer
Completely soluble, this undoubtedly result in higher manufacturing cost, and be unfavorable for highly sensitive detection.In addition, partial hydrophilicity monomer
The adsorption site of metal ion is included in molecule, significant non-specific absorption will be caused, so as to influence colorimetric detection effect.
Although moreover, these hydrophobicity probe molecules (such as Rhodamine Derivatives) are covalently supported on hydrophilic polymer table
Face, can achieve the purpose that pure water mutually detects.But since these hydrophilic polymer own solubilities are not high, cause probe
The load capacity of molecule is very limited, and the state of chain-chain winding is often presented in these polymer in the solution, final so that visiting
Pin molecule grafting rate is low and the speed of response is slower when detecting.
Therefore, high rhodamine content, good water solubility and the Polymer-supported type without non-specific adsorption site are developed
Probe, for efficiently realizing that pure water colorimetric detection copper ion has great actual application value.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of high water-soluble in view of the deficiency of the prior art
Property rhodamine base poly ion liquid, there is highly-water-soluble, high selectivity, high sensitivity, can bore hole identification and quick ratio
Color detects copper ion.
The present invention is to solve the problems, such as that used technical solution set forth above is：
A kind of highly-water-soluble rhodamine base poly ion liquid, its molecular structure as shown in following formula 1, m/ (n+m) in formula 1=
0.02~0.05, abbreviation notation is P (RhBHSA-co-META), and gel permeation chromatography measures its average molecular weight MnFor 2000~
20000.Ionic liquid is liquid, and poly ion liquid is usually solid, highly-water-soluble rhodamine base poly ion liquid in the present invention
For solid.
1 highly-water-soluble rhodamine base poly ion liquid structural formula of formula
The preparation method of highly-water-soluble rhodamine base poly ion liquid of the present invention is：Acryloyl salicylide rhodamine B
The copolyreaction of hydrazides monomer (RhBHSA) and ionic liquid monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (META), obtains
To highly-water-soluble rhodamine base poly ion liquid (P (RhBHSA-co-META)).
By such scheme, the condition of the copolyreaction is：Acryloyl salicylide rhodamine B hydrazides monomer (RhBHSA) with
Ionic liquid monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (META) is raw material, and azodiisobutyronitrile (AIBN), which is used as, to be drawn
Agent is sent out, as solvent, isothermal reaction under an inert atmosphere, obtains subject copolymers P for dioxane and alcohol mixed solution
(RhBHSA-co-META)。
By such scheme, the acryloyl salicylide rhodamine B hydrazides monomer (RhBHSA), ionic liquid monomer methyl-prop
Alkene acyloxyethyl trimethyl ammonium chloride (META), the mass ratio of azodiisobutyronitrile (AIBN) are (0.6~1.2)：(0.2~
0.8)：(0.05~0.2).
By such scheme, dioxane and ethanol volume ratio are (16~63) in the solvent：(4~7).Preferably, it is molten
Agent dosage and the ratio of RhBHSA are (20~70) mL：(0.6~1.2) g.
By such scheme, the isothermal reaction temperature is 50~75 DEG C, and the reaction time is 10~24h.
By such scheme, the preparation method of the acryloyl salicylide rhodamine B hydrazides monomer (RhBHSA) can be：With
Salicylide rhodamine B hydrazides (RhBHS), triethylamine and acryloyl chloride are raw material, and dichloromethane is mixed under ice-water bath as solvent
After uniformly, react under room temperature, obtain acryloyl salicylide rhodamine B hydrazides monomer (RhBHSA).Preferably, reaction is completed
Afterwards, further include and filter out precipitation, filtrate decompression is concentrated, the purification such as column chromatography for separation and drying steps.It is further preferred that institute
The ratio for stating RhBHS, triethylamine and acryloyl chloride is (2~3) g：(0.5~1) mL：(0.2~0.4mL).It is further preferred that
The room temperature reaction temperature is 15~30 DEG C, and the reaction time is 10~24h.It is further preferred that the solvent dosage and RhBHS
Ratio be (100~200) mL：(2~3) g.It is further preferred that the column chromatography eluent is dichloromethane and methanol
The volume ratio of mixed solution, dichloromethane and methanol is (30~50)：1.
By such scheme, the preparation method of the salicylide rhodamine B hydrazides (RhBHS) can be：With rhodamine B hydrazides
(RhBH) and 2,4- 4-dihydroxy benzaldehyde are raw material, and absolute ethyl alcohol is as solvent, under inert atmosphere after heating reflux reaction, cooling
To room temperature, filter and purify, vacuum drying obtains RhBHS.Preferably, the mass ratio of RhBH and 2,4- 4-dihydroxy benzaldehyde is (2
~3)：(1~2).Preferably, reaction temperature is 78~85 DEG C, and the reaction time is 6~12h.Preferably, solvent absolute ethyl alcohol with
The ratio of RhBH is (80~150) mL：(2~3) g.
By such scheme, the preparation method of the rhodamine B hydrazides (RhBH) can be：With rhodamine B (RhB) and hydration
Hydrazine is raw material, and absolute ethyl alcohol is as solvent, heating reflux reaction, is cooled to room temperature, rotary evaporation, then plus water and adjust pH to
8~9, filter and purify, vacuum drying obtains rhodamine B hydrazides (RhBH).Preferably, the mass ratio of the RhB and hydrazine hydrate
For (3~5) g：(7.5~12.5) mL.Preferably, the reaction temperature is 70~85 DEG C, and the reaction time is 1~3h.Preferably,
The ratio of the solvent and RhB is (80~150) mL：(3~5) g.
Rhodamine base poly ion liquid P (RhBHSA-co-META) of the present invention can be used as copper ion probe application.
Further, the rhodamine base poly ion liquid P (RhBHSA-co-META) can be used as copper ion probe to be used in pure water
Sensitive Detection copper ion in environment, has the characteristics that highly-water-soluble, high selectivity, high sensitivity.During concrete application, it can both lead to
Cross quick optical colorimetry and quantitatively or semi-quantitatively detect copper ion concentration, i.e., bore hole identification and quick colorimetric detection copper from
Son；Copper ion concentration can also be detected using UV-visible spectrophotometry, to obtain more accurate result.
Compared with prior art, the beneficial effects of the invention are as follows：
1. the rhodamine base poly ion liquid of the present invention has high sensitivity to copper ion detection, bore hole and ultraviolet-can
It is respectively 0.5 μM and 0.15 μM to see light spectrophotometry detection limit, far below 31 μM as defined in the World Health Organization (WHO).
2. the rhodamine base poly ion liquid of the present invention can make rhodamine base monomer on the premise of highly-water-soluble is ensured
With the molar ratio as low as 1 of ionic liquid monomer：1, there is superelevation hydrophily and rhodamine probe load capacity effectively improves, in water
Have the characteristics that the response time is short to copper ion detection in phase, detection response speed is very fast, can complete to develop the color within 5s, shows
Splendid application potential to copper ion detection is shown.
3. the rhodamine base poly ion liquid of the present invention has high selectivity and anti-interference, in Ag+、Al3+、Ba2+、Ca2 +、Cd2+、Co2+、Cr2+、Cu2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+The selection to copper ion can be realized in plasma
Property detection, other coexistent metallic ions without detection disturb.
4. raw material needed for the rhodamine base poly ion liquid synthesis of the present invention is cheap and easy to get, synthesis technique simple and fast, if
Standby simple, cost is low, is adapted to large-scale production, and detection efficiency is high, detection process is environmentally protective, has a extensive future.
Brief description of the drawings
Figure 1A is the basic synthetic route of rhodamine base poly ion liquid P (RhBHSA-co-META) of the present invention；Figure
1B is the specific synthetic route of rhodamine base poly ion liquid P (RhBHSA-co-META) described in the embodiment of the present invention 1.
Fig. 2 is Rhodamine Derivatives RhBHSA involved in the embodiment of the present invention 1, ionic liquid monomer META and rhodamine
The FT-IR spectrograms of base poly ion liquid P (RhBHSA-co-META).
Fig. 3 is Rhodamine Derivatives RhBHSA involved in the embodiment of the present invention 1, ionic liquid monomer META and rhodamine
The UV-vis spectrograms of base poly ion liquid P (RhBHSA-co-META).
Fig. 4 is that the colour developing that different metal ions are added in P (RhBHSA-co-META) aqueous solution prepared by embodiment 3 is shone
Piece (A) and UV-vis spectrograms (B).
Fig. 5 for embodiment 4 in the presence of disturbance metal ion, prepared P (RhBHSA-co-META) add Cu2+
The block diagram of the front and rear photon absorbing intensity at 561nm.
Fig. 6 is to add various concentrations Cu in P (RhBHSA-co-META) aqueous solution prepared by embodiment 52+Colour developing afterwards
Photo (A) and UV-vis spectrograms (B).
Fig. 7 be embodiment 5 prepared by P (RhBHSA-co-META) aqueous solution at 561nm photon absorbing intensity with Cu2+Concentration
Change curve and linear relationship.
Ps (RhBHSA-co-META) of the Fig. 8 prepared by embodiment 6 is at various ph values to Cu2+Detection absorbance
Line chart.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Embodiment 1
A kind of highly-water-soluble rhodamine base poly ion liquid, its molecular structure as shown in following formula 1, m/ (n+m) in formula 1=
0.02~0.05, abbreviation notation is P (RhBHSA-co-META).
1 highly-water-soluble rhodamine base poly ion liquid structural formula of formula
The synthetic method of above-mentioned rhodamine base poly ion liquid P (RhBHSA-co-META), key step are as follows：
1) synthesis of RhBH：4.8g rhodamine Bs (RhB) and 12mL hydrazine hydrates are dissolved in 130mL absolute ethyl alcohols, are heated to 80 DEG C
Reflux, reaction 2.5h postcoolings to room temperature, rotary evaporation, then adds water and adjusts pH to 8.5 or so, filter and distill water washing
Purification, vacuum drying obtain RhBH, yield：90.1%；
2) synthesis of RhBHS：2.3g rhodamine Bs hydrazides (RhBH) and 1.6g 2,4- 4-dihydroxy benzaldehydes be dissolved in 120mL without
Water-ethanol, 80 DEG C of reflux are heated under condition of nitrogen gas, react 10h, are cooled to room temperature, are filtered and absolute ethyl alcohol washing purification, very
Sky is dried to obtain RhBHS, yield：81.1%；
3) synthesis of RhBHSA：2.3g RhBHS and 0.5mL triethylamines are dissolved in 100mL dichloromethane, will be molten under ice-water bath
The 50mL dichloromethane for having 0.3mL acryloyl chlorides is added dropwise, and reacts 12h at 25 DEG C of room temperature after mixing, filters out precipitation, will
Filtrate decompression concentrates, column chromatography (methylene chloride/methanol, v/v=50:1) separating-purifying, is dried in vacuo RhBHSA, yield：
69.8%；
The nuclear magnetic resonance data of RhBHSA：1H NMR(400MHz,CDCl3)δ(ppm):11.09(s,1H),9.19(s,
1H), 8.06-7.93 (m, 1H), 7.62-7.44 (m, 2H), 7.22-7.16 (m, 1H), 7.10 (d, J=8.4Hz, 1H), 6.65
(d, J=2.1Hz, 1H), 6.58 (dd, J=16.1,9.8Hz, 2H), 6.51 (s, 1H), 6.48 (d, J=2.7Hz, 3H),
6.37-6.19 (m, 3H), 5.98 (d, J=10.5Hz, 1H), 3.33 (q, J=7.0Hz, 9H), 1.16 (t, J=7.0Hz,
13H)；
13C NMR(101MHz,CDCl3)δ(ppm):164.31,164.14,159.91,153.63,152.76,151.88,
150.86,149.23,133.60,132.79,132.20,130.06,128.69,128.17,127.87,124.27,123.41,
116.85,112.53,110.33,108.27,105.36,98.04,66.55,44.45,12.72.
4) synthesis of P (RhBHSA-co-META)：0.9g RhBHSA, 0.3g META and 0.1g AIBN, which are dissolved in 50mL, to be mixed
Close solution (dioxane/ethanol, v/v=6:1) it is used as solvent, 65 DEG C of reaction 18h of constant temperature under condition of nitrogen gas are filtered and anhydrous second
Ether washing purification, vacuum drying obtain subject copolymers P (RhBHSA-co-META).
Experiment confirms：To Rhodamine Derivatives the monomer RhBHSA and Luo Dan prepared by ionic liquid monomer META, the present invention
Bright base poly ion liquid P (RhBHSA-co-META) carries out infrared and ultraviolet characterization, as a result as shown in Figures 2 and 3, fully demonstrate,proves
(RhBHSA-co-META is by RhBHSA and META polymerization gained to bright P.
The rhodamine base poly ion liquid P (RhBHSA-co-META) that gel permeation chromatography is measured prepared by the present embodiment is flat
Average molecular weight MnFor 5000~15000.
Embodiment 2
Rhodamine B derivative functional group concentration's determines in rhodamine base poly ion liquid P (RhBHSA-co-META)
By Rhodamine Derivatives monomer RhBHSA and Cu synthesized by embodiment 12+It is dissolved in mixed solvent (acetonitrile/water, v/v=
3:1) in, 20 μM of RhBHSA and 20mM Cu are made into2+Standard mother liquor (note, wherein Cu2+It is significantly excessive compared to RhBHSA).
The volumetric flask of 8 100mL is taken, is diluted to the standard that RhBHSA contents are 10,8,6,5,4,3,2,1 μM respectively
Solution, and spectrophotometry test is carried out, make standard curve：A=0.10694c-0.00118 (R2=
0.99993)。
By rhodamine base poly ion liquid P (RhBHSA-co-META) and Cu synthesized by embodiment 12+It is dissolved in deionized water
In, it is made into the rhodamine base poly ion liquid and 100mM Cu of 100mg/L2+Aqueous solution, carries out spectrophotometry survey
Examination.
Combined standard curve calculates, and determines that rhodamine B derives in rhodamine base poly ion liquid P (RhBHSA-co-META)
Molar ratio shared by thing functional group is 3%, far above rhodamine B derivative official in the rhodamine based polyalcohol of other document reports
Can molar ratio shared by group.
Embodiment 3
Selectivity of the rhodamine base poly ion liquid P (RhBHSA-co-META) to copper ion colorimetric detection
Rhodamine base poly ion liquid P (RhBHSA-co-META) synthesized by embodiment 1 is dissolved in deionized water, is made into
The rhodamine base poly ion liquid storing solution of 90mg/L, rhodamine B derivative functional group concentration is measured as 12.5 by embodiment 2
μM。
The sample bottle of 16 5mL is taken, is separately added into 2mL rhodamine base poly ion liquid storing solutions, then be separately added into 0.5mL
500μM Ag+、Al3+、Ba2+、Ca2+、Cd2+、Co2+、Cr2+、Cu2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+And H2O, finally
Rhodamine base poly ion liquid (rhodamine B derivative functional group concentration be 10 μM) and 100 μM of the solution containing 72mg/L it is above-mentioned it
One metal ion.Spectrophotometry test is carried out respectively to solution therein, to verify rhodamine base polyion liquid
Body P (RhBHSA-co-META) is to copper ion selective enumeration method effect.
The results are shown in Figure 4, shows rhodamine base poly ion liquid P (RhBHSA-co-META) aqueous solution only to copper ion
There is obvious response, only add Cu2+Sample bottle be changed into pink colour from colourless, and have obvious UV absorption at 561nm
Peak, and during with other Ar ion mixings, the color and ultraviolet absorption peak of solution have no significant change.It can be seen from the above that the present invention is closed
Into rhodamine base poly ion liquid P (RhBHSA-co-META) selectivity of height is shown to copper ion.
Embodiment 4
Interference of the rhodamine base poly ion liquid P (RhBHSA-co-META) to copper ion colorimetric detection
Rhodamine base poly ion liquid P (RhBHSA-co-META) synthesized by embodiment 1 is dissolved in deionized water, is made into
Rhodamine base poly ion liquid storing solution, rhodamine B derivative functional group concentration are 12.5 μM.
The sample bottle of 16 5mL is taken, 2mL rhodamine base poly ion liquid storing solutions is separately added into, is then separately added into
0.25mL 1000μM Ag+、Al3+、Ba2+、Ca2+、Cd2+、Co2+、Cr2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+And H2O,
1000 μM of Cu are separately added into again2+, final solution concentration is rhodamine base poly ion liquid (the rhodamine B derivative official of 72mg/L
Concentration can be rolled into a ball as 10 μM), 100 μM of different ions concentration and 100 μM of Cu2+.Ultraviolet-visible is carried out respectively to the solution in sample bottle
Spectrophotometric is tested, and is disturbed with verifying that rhodamine base poly ion liquid P (RhBHSA-co-META) aqueous solutions detect copper ion
Property.
The results are shown in Figure 5, the results showed that：Other coexistent metallic ions do not have to change substantially rhodamine base of the present invention gather from
Sub- liquid P (RhBHSA-co-META) aqueous solutions embody rhodamine base polyion liquid of the present invention to the detection result of copper ion
Body has good antijamming capability to detection copper ion.
Embodiment 5
Rhodamine base poly ion liquid P (RhBHSA-co-META) is to copper ion colorimetric detection
Rhodamine base poly ion liquid P (RhBHSA-co-META) synthesized by embodiment 1 is dissolved in deionized water, is made into
Rhodamine base poly ion liquid storing solution, rhodamine B derivative functional group concentration are 12.5 μM.
The sample bottle of 31 5mL is taken, is separately added into 2mL rhodamine base poly ion liquid storing solutions, then be separately added into difference
The Cu of concentration2+(1~1000 μM), final solution concentration are rhodamine base poly ion liquid (the rhodamine B derivative official of 72mg/L
Concentration can be rolled into a ball as 10 μM) and 0.2~200 μM of Cu2+。
After being added in rhodamine base poly ion liquid P (RhBHSA-co-META) aqueous solution to copper ion, within 5s i.e.
It can complete to develop the color, illustrate that rhodamine base poly ion liquid of the present invention has the characteristics that the response time is short to copper ion detection,
Quick detection copper ion can be applied in pure water environment.
Spectrophotometry test is carried out successively to the solution in sample bottle.Rhodamine base poly ion liquid P
(RhBHSA-co-META) aqueous solution detects copper ion in detection colour developing photo and uv-visible absorption spectra is as shown in Figure 6.It is aobvious
Color photographic result shows that the detectable minimum copper ion concentration of bore hole colorimetric detection is 5 × 10-7mol/L；Ultraviolet-ray visible absorbing light
Spectrum display：With Cu2+Increase, absorbance gradually increases at 561nm, until [Cu2+Absorbance is substantially saturated during]=100 μM.
Rhodamine base poly ion liquid P (RhBHSA-co-META) aqueous solutions are to copper ion detection response trend and detect the range of linearity such as
Shown in Fig. 7, the results showed that：In [Cu2+In the range of]=1~5 μM, a good linear relationship straight line (R can be made2=
0.99805), detection is limited to 1.5 × 10-7mol/L。
Therefore, the detection that the detectable least concentration of bore hole colorimetric detection and uv-visible absorption spectrum figure quantitatively detect
Limit illustrates that rhodamine base poly ion liquid P (RhBHSA-co-META) can far below 31 μM as defined in the World Health Organization (WHO)
It is short with the efficient detection applied to pure water Environmental Trace copper ion, response time.
Embodiment 6
Influences of the rhodamine base poly ion liquid P (RhBHSA-co-META) to copper ion colorimetric detection working environment
Rhodamine base poly ion liquid P (RhBHSA-co-META) synthesized by embodiment 1 is dissolved in deionized water, is made into
The rhodamine base poly ion liquid mother liquor of 180mg/L, rhodamine B derivative functional group concentration is measured as 25 μM by embodiment 2.
The sample bottle of 22 20mL is taken, is separately added into 5mL rhodamine base poly ion liquid mother liquors, two one group of samples, often
It is 2,3,4,5,6,7,8,9,10,11 and 12 that group adjusts pH respectively, and each bottle liquor capacity is settled to 10mL.Then, 1 in every group
500 μM of Cu that 2.5mL corresponds to pH are added in number bottle2+, the deionized water that 2.5mL corresponds to pH is added in No. 2 bottles, finally every group 1
Rhodamine base poly ion liquid and Cu in number bottle2+Concentration is respectively 72mg/L (rhodamine B derivative functional group concentration is 10 μM)
With 100 μM, contain only rhodamine base poly ion liquid solution in every group of No. 2 bottles, its concentration is 72mg/L (rhodamine B derivative officials
Concentration can be rolled into a ball as 10 μM).Spectrophotometry test is carried out to the solution in every group of sample bottle respectively.
The results are shown in Figure 8, it is not difficult to find that in the presence of no copper ion, rhodamine base poly ion liquid P (RhBHSA-
Co-META) aqueous solution absorbance between pH=5~12 has almost no change, as addition Cu2+Afterwards, solution absorbance is obvious
Increase, absorbance is in highest level between pH=5~9, illustrates rhodamine base poly ion liquid of the present invention to inspection
Surveying copper ion has wider pH accommodations, has the good potentiality applied to various environmental and biological materials.
Embodiment 7
A kind of highly-water-soluble rhodamine base poly ion liquid, its molecular structure is as shown in Equation 1, and m/ (n+m)=0.02~
0.03, abbreviation notation is P (RhBHSA-co-META), average molecular weight MnFor 2000~10000.
The synthetic method of above-mentioned rhodamine base poly ion liquid P (RhBHSA-co-META), step are as follows：
1) 2.8g RhBHS and 1.0mL triethylamines are dissolved in 50mL dichloromethane, will be dissolved with 0.2mL acryloyl chlorides under ice-water bath
50mL dichloromethane be added dropwise, react 24h at 30 DEG C of room temperature after mixing, filter out precipitation, filtrate decompression is concentrated, column
Chromatograph (methylene chloride/methanol, v/v=30:1) separating-purifying, is dried in vacuo RhBHSA；
2) 0.6g RhBHSA, 0.8g META and 0.2g AIBN are dissolved in 30mL mixed solutions (dioxane/ethanol, v/
V=5:1) it is used as solvent, 55 DEG C of reaction 18h of constant temperature under condition of nitrogen gas, are filtered and anhydrous ether washing purification, vacuum drying obtain
Subject copolymers P (RhBHSA-co-META).
Infrared and ultraviolet characterization confirms：It is polymerize to obtain rhodamine base poly ion liquid P by RhBHSA and META
(RhBHSA-co-META), gel permeation chromatography measures P (RhBHSA-co-META) average molecular weight MnFor 2000~10000.
Embodiment 8
A kind of highly-water-soluble rhodamine base poly ion liquid, its molecular structure is as shown in Equation 1, and m/ (n+m)=0.03~
0.05, abbreviation notation is P (RhBHSA-co-META), average molecular weight MnFor 10000~20000.
The synthetic method of above-mentioned rhodamine base poly ion liquid P (RhBHSA-co-META), step are as follows：
1) 2.5g RhBHS and 0.7mL triethylamines are dissolved in 150mL dichloromethane, will be dissolved with 0.4mL acryloyls under ice-water bath
The 50mL dichloromethane of chlorine is added dropwise, and reacts 16h at 15 DEG C of room temperature after mixing, filters out precipitation, filtrate decompression is concentrated,
Column chromatography (methylene chloride/methanol, v/v=40:1) separating-purifying, is dried in vacuo RhBHSA；
2) by 1.0g RhBHSA, 0.2g META and 0.05g AIBN be dissolved in 60mL mixed solutions (dioxane/ethanol,
V/v=10:1) it is used as solvent, 75 DEG C of reaction 24h of constant temperature under condition of nitrogen gas are filtered and anhydrous ether washing purification, vacuum drying
Obtain subject copolymers P (RhBHSA-co-META).
Infrared and ultraviolet characterization confirms：It is polymerize to obtain rhodamine base poly ion liquid P by RhBHSA and META
(RhBHSA-co-META), gel permeation chromatography measures P (RhBHSA-co-META) average molecular weight MnFor 10000~20000.
In conclusion a kind of highly-water-soluble rhodamine base poly ion liquid provided by the present invention and preparation method thereof, this
It is to be reported first using research of the poly ion liquid as hydrophobicity probe molecule carrier both at home and abroad, significantly improves hydrophobicity spy
The load capacity of pin molecule and the quick combination for being very beneficial for measured ion and probe molecule to be checked in aqueous solution, and be applied to
The quick visual colorimetric detection of pure water phase copper ion.Pure water phase copper ion testing result is shown, bore hole and ultraviolet-visible light point
The detection of light photometry is limited to respectively 0.5 μM and 0.15 μM, not only far below 31 μM as defined in the World Health Organization (WHO), and
Better than the testing result of most copper ion colorimetric detections.Moreover, extremely short to the pure water phase copper ion detection response time, 5s is
It can complete to develop the color.In addition, there is excellent selectivity to copper ion detection, hardly done by any other coexistent metallic ion
Disturb.Therefore, the rhodamine base poly ion liquid that present invention gained rhodamine content is high and water solubility is extremely excellent, realizes to pure
Underwater trace copper ion is quick, high selectivity and high sensitivity detect.
The above is only the preferred embodiment of the present invention, it is noted that is come for those of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
- A kind of 1. highly-water-soluble rhodamine base poly ion liquid, it is characterised in that its average molecular weight MnFor 2000~20000, Molecular structure is as shown in Equation 1：M/ (n+m)=0.02~0.05 in formula 1.
- A kind of 2. preparation method of highly-water-soluble rhodamine base poly ion liquid, it is characterised in that acryloyl salicylide rhodamine B The copolyreaction of hydrazides monomer and ionic liquid monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, obtains highly-water-soluble Luo Dan Bright base poly ion liquid.
- A kind of 3. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 2, it is characterised in that The condition of the copolyreaction is：Acryloyl salicylide rhodamine B hydrazides monomer and ionic liquid monomer methacryloxypropyl second Base trimethyl ammonium chloride is raw material, azodiisobutyronitrile as initiator, dioxane and alcohol mixed solution as solvent, Isothermal reaction under inert atmosphere, obtains highly-water-soluble rhodamine base poly ion liquid.
- A kind of 4. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 3, it is characterised in that The acryloyl salicylide rhodamine B hydrazides monomer, ionic liquid monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, azo The mass ratio of bis-isobutyronitrile is (0.6~1.2)：(0.2~0.8)：(0.05~0.2).
- A kind of 5. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 3, it is characterised in that The isothermal reaction temperature is 50~75 DEG C, and the reaction time is 10~24h.
- A kind of 6. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 3, it is characterised in that The preparation method of the acryloyl salicylide rhodamine B hydrazides monomer is：With salicylide rhodamine B hydrazides, triethylamine and propylene Acyl chlorides is raw material, and dichloromethane, reacts, obtain acryloyl bigcatkin willow under ice-water bath after mixing as solvent under room temperature Aldehyde rhodamine B hydrazides monomer.
- A kind of 7. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 6, it is characterised in that The ratio of the salicylide rhodamine B hydrazides, triethylamine and acryloyl chloride is (2~3) g：(0.5~1) mL：(0.2~ 0.4mL)；The room temperature reaction temperature is 15~30 DEG C, and the reaction time is 10~24h.
- A kind of 8. preparation method of highly-water-soluble rhodamine base poly ion liquid according to claim 6, it is characterised in that After the completion of the reaction, further include and filter out precipitation, filtrate decompression is concentrated, column chromatography for separation and drying steps；Wherein, it is described Column chromatography eluent is the mixed solution of dichloromethane and methanol, and the volume ratio of dichloromethane and methanol is (30~50)：1.
- 9. rhodamine base poly ion liquid is as copper ion probe application described in claim 1.
- 10. rhodamine base poly ion liquid described in claim 1 is as copper ion probe, the quick visual colorimetric method in water phase is examined Survey the application of copper ion.
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| CN103709321A (en) * | 2013-12-14 | 2014-04-09 | 聊城大学 | Rhodamine B based hydrophilic polymer probe for hyperchromic detection of Cu<2+> as well as preparation method and application thereof |
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