CN107192693A - Preparation and application of rhodamine-based heavy metal ion solid-phase fluorescence sensor - Google Patents
Preparation and application of rhodamine-based heavy metal ion solid-phase fluorescence sensor Download PDFInfo
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- CN107192693A CN107192693A CN201610152311.9A CN201610152311A CN107192693A CN 107192693 A CN107192693 A CN 107192693A CN 201610152311 A CN201610152311 A CN 201610152311A CN 107192693 A CN107192693 A CN 107192693A
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- 239000007790 solid phase Substances 0.000 title claims abstract description 65
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 21
- 150000002500 ions Chemical class 0.000 title claims abstract description 21
- 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 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 27
- 239000003068 molecular probe Substances 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims abstract description 5
- 229920002223 polystyrene Polymers 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000523 sample Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000006557 surface reaction Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000002189 fluorescence spectrum Methods 0.000 description 16
- 230000005284 excitation Effects 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 0 CCN(CC)c1ccc(C(c2c3cccc2)(c(c(O2)c4)ccc4N(CC)CC)N(*CC(c4ccc(C(*)C*)cc4)=O)C3=O)c2c1 Chemical compound CCN(CC)c1ccc(C(c2c3cccc2)(c(c(O2)c4)ccc4N(CC)CC)N(*CC(c4ccc(C(*)C*)cc4)=O)C3=O)c2c1 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to preparation and application of a rhodamine-based heavy metal ion solid-phase fluorescence sensor, and the structural formula is as follows. The carrier is chloracetyl-acylated polystyrene microspheres, different fluorescent molecular probes are selected, and a series of solid-phase fluorescent sensors with the function of identifying metal ions are prepared in one step by adopting a surface modification method. The solid-phase fluorescence sensor has the advantages of uniform particle size distribution, good suspension property in aqueous solution, large specific surface area, good adsorbability, strong surface reaction capability, simple preparation, convenient use and the like. The invention can rapidly detect heavy metal ions including Cu2+，Mg2+，Cd2+，Mn2+，Pb2+，Co2+，Hg2+Heavy metal ions of equal weight, among them to Hg2+The selective detection effect is optimal, the EDTA is utilized to complex the heavy metal ions, the reuse of the solid-phase fluorescence sensor is realized, and the detection method has the characteristics of high sensitivity, good selectivity, small sample consumption, environmental friendliness and the like.Wherein the content of the first and second substances,
Description
Technical field
The invention belongs to field of food safety, passed the present invention relates to one kind based on rhodamine base heavy metal ion solid phase fluorescent
The preparation and application of sensor, the solid phase fluorescent sensor are applied to heavy metal ion quick detection analysis technical field.
Technical background
Heavy metal is first universally present in the weight such as copper, mercury, cadmium, lead, chromium and metalloid arsenic in nature, is primarily referred to as
Element.Heavy metal can not be biodegradable, conversely but can be under the biological magnification of food chain, thousands of hundred times of ground enrichments, finally
Into human body.Strong interaction occurs for heavy metal energy and protein and enzyme etc. in human body, them is lost activity, also may be used
It can be accumulated in some organs of human body, slow poisoning be caused, so as to threaten the health of the mankind.Therefore, set up fast and efficiently
Heavy metal detection method all has great importance in terms of life science, environmental science, medical science and agricultural production.
The foundation of efficient detection method not only contributes to grasp heavy metal propagation and flyway and feature, and can be what it be caused
Environmental pollution is estimated and carried out the guarantee on effectively control offer theory and technology.
At present, the common assay method of metal ion mainly has：Atomic absorption method (AAS), AAS, efficient liquid phase
Chromatography (HPLC), emission spectrometry (AES), inductively coupled plasma mass spectrometry (ICPMS), chemoluminescence method, electrochemistry
Method, XRF etc..These methods respectively have advantage and disadvantage, for example：Atomic absorption method have sensitivity it is high, selectivity it is good, by sample
The interference of organic impurities etc. is small in product, the advantages of have a wide range of application, but instrument complexity is, it is necessary to high temperature atomic parts, height
Energy consumption and high cost etc..Expensive equipment needed for inductively coupled plasma mass spectrometry and high performance liquid chromatography, sample pretreatment
Process is complicated, operates comparatively laborious.Chemoluminescence method selectivity ratios are poor, are unsuitable for the measure of low concentration biological sample.
Not only preparation method is simple, cheap for solid phase fluorescent sensor, easy to use, can the different heavy metals of quick detection
Ion, and complexing of metal ion is got off using EDTA, the recycling of solid phase fluorescent sensor is realized, detection method has
The features such as sensitivity is high, selectivity is good, amount of samples is few and environment-friendly.
At present, most widely used fluorescent microsphere is that organic dyestuff is incorporated into the microballoon prepared in polystyrene.It is used as one
The fluorescence molecule of high quantum production rate is planted, rhodamine, which is usually selected as fluorescent parent, is used for the design of metal-ion fluorescent molecular probe
Synthesis.Rhodamine and its derivative have that molar extinction coefficient is big, fluorescence quantum yield is high, relatively long excitation wavelength (＞
500nm) and the advantages of launch wavelength, it is widely used for detecting metal ion as fluorescent molecular probe.Sieve of closed loop configuration
The molar absorption coefficient and fluorescence quantum yield of red bright lactams are very low, almost without fluorescence.When recognition group is in carbonyl
Under synergy and when certain heavy metal ion is had an effect, the lactam bond of fluorescence molecule can be caused to be broken, form open loop knot
Structure, causes fluorescence intensity to significantly increase, so as to realize the Selective recognition to the ion.
The content of the invention
It is an object of the present invention to provide a kind of preparation and application based on rhodamine base heavy metal ion solid phase fluorescent sensor.
To achieve the above object, the present invention is adopted the following technical scheme that：
Chloracetyl chloride microballoon, fluorescent molecular probe and sodium carbonate are added into reactor, tetrahydrofuran and absolute methanol is added
Solvent hybrid reaction, obtains solid phase fluorescent sensor.
Brief description of the drawings
Fig. 1：Solid phase fluorescent sensor adds the fluorescence spectra of various concentrations heavy metal ion
Fig. 2：Solid phase fluorescent sensor adds EDTA fluorescence spectra
Fig. 3：The solid phase fluorescent sensor of recycling adds the fluorescence spectra of various concentrations heavy metal ion
Fig. 4：The solid phase fluorescent sensor of recycling adds EDTA fluorescence spectra
Fig. 5：Solid phase fluorescent sensor to the Selective recognition of many kinds of metal ions (black represent solid phase fluorescent sensor+
Many kinds of metal ions, red represents solid phase fluorescent sensor+Hg2++ many kinds of metal ions)
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among example scope.
(1) method for preparing fluorescent molecular probe：Take rhodamine B, absolute ethyl alcohol and hydrazine hydrate or ethylenediamine or divinyl
Triamine hybrid reaction, is made fluorescent molecular probe.
(2) method for making each chloracetyl chloride microballoon：Polystyrene microsphere, acylting agent and catalyst are pressed certain mole
Than feeding intake, methylene chloride is added, nitrogen is passed through, chloracetyl chloride polystyrene microsphere is made in the lower normal-temperature reaction of stirring.
(3) method for preparing solid phase fluorescent sensor：By chloracetyl chloride microballoon, fluorescent molecular probe and sodium carbonate by certain
Mol ratio feeds intake, and adds tetrahydrofuran and absolute methanol solvent hybrid reaction, solid phase sensor is made.
Embodiment 1
(1) fluorescent molecular probe RB-1 synthesis
Rhodamine B is weighed, absolute ethyl alcohol and hydrazine hydrate (volume ratio is 4: 1-10: 1) are placed in flask, and 80 DEG C are stirred at reflux
Reaction.Reaction solution cool overnight, is extracted, filtering, revolving removes ethyl acetate, obtains fluorescent molecular probe with ethyl acetate and water
RB-1。
(2) solid phase fluorescent sensor RB-L1 synthesis
Chloracetyl chloride microballoon, fluorescent molecular probe RB-1 and sodium carbonate 1: 1-4: 0.5-1 are placed in flask in molar ratio,
The mixed solvent (volume ratio is 1: 1-1: 3) of tetrahydrofuran and absolute methanol is added, first is used in 60 DEG C of -70 DEG C of agitating and heatings reactions
Alcohol is washed for several times, suction filtration, and surname extraction 24h, solvent is methanol, and 70 DEG C -80 DEG C of bath temperature is dried under vacuum to constant weight, obtained
Solid phase sensor RB-L1.
(3) apply
Appropriate solid phase fluorescent sensor is weighed, 1ml acetonitriles are first added into solid phase fluorescent sensor, 5- is added dropwise respectively every time
10 drop various concentrations metal ion solutions, it is ensured that liquor capacity is certain in each cuvette and concentration of metal ions increases.Colorimetric
Metal ion solution concentration gradient gradually increases in ware, at excitation wavelength 543nm, and various concentrations metal ion is scanned respectively
Under, solid phase fluorescent sensor emission fluorescence spectrum, experimental result is as shown in Figure 1.
Be separately added into the EDTA solution of 10-15 drop various concentrations again, it is ensured that in each cuvette liquor capacity it is certain and
The increase of EDTA concentration.EDTA solution concentrations gradient gradually increases in cuvette, at excitation wavelength 543nm, scans solid phase fluorescent
Sensor emission fluorescence spectra, experimental result is as shown in Figure 2.
The above-mentioned solid phase fluorescent sensor for being complexed metal ion is washed with acetonitrile for several times, the first step is repeated, in excitation wave
At long 543nm, scan respectively under various concentrations metal ion, solid phase fluorescent sensor emission fluorescence spectrum, experimental result such as Fig. 3
It is shown.
EDTA is added dropwise into the solid phase fluorescent sensor of above-mentioned recycling, the gold on solid phase fluorescent sensor is complexed again
Belong to ion, repeat second step, at excitation wavelength 543nm, scan solid phase fluorescent sensor emission fluorescence spectra, experimental result
As shown in Figure 4.
Embodiment 2
(1) fluorescent molecular probe RB-2 synthesis
Rhodamine B is taken, absolute ethyl alcohol and ethylenediamine (volume ratio is 4: 1-8: 1) are placed in flask, and 75 DEG C -80 DEG C are stirred back
Stream reaction.Reaction solution cool overnight, is extracted, filtering, revolving removes ethyl acetate, obtains fluorescent molecular probe with ethyl acetate and water
RB-2。
(2) solid phase fluorescent sensor RB-L2 synthesis
Chloracetyl chloride microballoon, fluorescent molecular probe RB-2 and sodium carbonate 1: 1-3: 0.5-1 are placed in flask in molar ratio,
The mixed solvent (volume ratio is 1: 1-1: 3) of tetrahydrofuran and absolute methanol is added, first is used in 60 DEG C of -70 DEG C of agitating and heatings reactions
Alcohol is washed for several times, suction filtration, and surname extraction 24h, solvent is methanol, and 70 DEG C -80 DEG C of bath temperature is dried under vacuum to constant weight, obtained
Solid phase sensor RB-L2.
(3) apply
Appropriate solid phase fluorescent sensor is weighed, 1ml acetonitriles are first added into solid phase fluorescent sensor, 5- is added dropwise respectively every time
The metal ion solution of 10 drop various concentrations, it is ensured that liquor capacity is certain in each cuvette and concentration of metal ions increases.Than
Metal ion solution concentration gradient gradually increases in color ware, at excitation wavelength 543nm, and various concentrations metal ion is scanned respectively
Under, solid phase fluorescent sensor emission fluorescence spectrum, experimental result be the same as Example 1.
Be separately added into the EDTA solution of 10-15 drop various concentrations again, it is ensured that in each cuvette liquor capacity it is certain and
The increase of EDTA concentration.EDTA solution concentrations gradient gradually increases in cuvette, at excitation wavelength 543nm, scans solid phase fluorescent
Sensor emission fluorescence spectra, experimental result be the same as Example 1.
The above-mentioned solid phase fluorescent sensor for being complexed metal ion is washed with acetonitrile for several times, the first step is repeated, in excitation wave
At long 543nm, scan respectively under various concentrations metal ion, solid phase fluorescent sensor emission fluorescence spectrum, experimental result is with real
Apply example 1.
EDTA is added dropwise into the solid phase fluorescent sensor of above-mentioned recycling, the gold on solid phase fluorescent sensor is complexed again
Belong to ion, repeat second step, at excitation wavelength 543nm, scan solid phase fluorescent sensor emission fluorescence spectra, experimental result
Be the same as Example 1.
Embodiment 3
(1) fluorescent molecular probe RB-3 synthesis
Rhodamine B is taken, absolute ethyl alcohol and diethylenetriamine (volume ratio is 4: 1-6: 1) are placed in flask, and 75 DEG C -80 DEG C are stirred
Mix back flow reaction.Reaction solution cool overnight, is extracted, filtering, revolving removes ethyl acetate, obtains fluorescence molecule with ethyl acetate and water
Probe RB-3.
(2) solid phase fluorescent sensor RB-L3 synthesis
Chloracetyl chloride microballoon, fluorescent molecular probe RB-3 and sodium carbonate 1: 1-5: 0.6-1 are placed in flask in molar ratio,
The mixed solvent (volume ratio is 1: 1-1: 4) of tetrahydrofuran and absolute methanol is added, first is used in 60 DEG C of -70 DEG C of agitating and heatings reactions
Alcohol is washed for several times, suction filtration, and surname extraction 24h, solvent is methanol, and 70 DEG C -80 DEG C of bath temperature is dried under vacuum to constant weight, obtained
Solid phase sensor RB-L3.
(3) apply
Appropriate solid phase fluorescent sensor is weighed, 1ml acetonitriles are first added into solid phase fluorescent sensor, 5- is added dropwise respectively every time
The metal ion solution of 10 drop various concentrations, it is ensured that liquor capacity is certain in each cuvette and concentration of metal ions increases.Than
Metal ion solution concentration gradient gradually increases in color ware, at excitation wavelength 543nm, and various concentrations metal ion is scanned respectively
Under, solid phase fluorescent sensor emission fluorescence spectrum, experimental result be the same as Example 1.
The EDTA solution of 10 drop various concentrations is separately added into again, it is ensured that liquor capacity is certain in each cuvette and EDTA is dense
Degree increase.EDTA solution concentrations gradient gradually increases in cuvette, at excitation wavelength 543nm, scans solid phase fluorescent sensor
Launch fluorescence spectra, experimental result be the same as Example 1.
The above-mentioned solid phase fluorescent sensor for being complexed metal ion is washed with acetonitrile for several times, the first step is repeated, in excitation wave
At long 543nm, scan respectively under various concentrations metal ion, solid phase fluorescent sensor emission fluorescence spectrum, experimental result is with real
Apply example 1.
EDTA is added dropwise into the solid phase fluorescent sensor of above-mentioned recycling, the gold on solid phase fluorescent sensor is complexed again
Belong to ion, repeat second step, at excitation wavelength 543nm, scan solid phase fluorescent sensor emission fluorescence spectra, experimental result
Be the same as Example 1.
It is finally noted that, the purpose for publicizing and implementing mode is that help further understands the present invention.But ability
The technical staff in domain is appreciated that：In the spirit and scope for not departing from the claims in the present invention, various substitutions and modifications are all
It is possible.Therefore, the present invention should not be limited to embodiment disclosure of that.The scope of protection of present invention is with claim
The scope that book is defined is defined.
Claims (4)
1. a kind of preparation and application based on rhodamine base heavy metal ion solid phase fluorescent sensor, it is characterised in that：It is used to carry
Body is the polystyrene microsphere of chloroacetylation, using the method for surface modification prepares it is a series of have recognize metal ion function
Solid phase fluorescent sensor.
2. a series of solid phase fluorescent sensors described in claim 1 contain following structure：
Wherein,
。
3. a series of preparation method of solid phase fluorescent sensors described in claim 2 has following characteristics：
(1) chloracetyl chloride microballoon, fluorescent molecular probe RB-1 and sodium carbonate are added into reactor, adds tetrahydrofuran and anhydrous
Methanol solvate hybrid reaction, obtains solid phase sensor RB-L1.
(2) chloracetyl chloride microballoon, fluorescent molecular probe RB-2 and sodium carbonate are added into reactor, adds tetrahydrofuran and anhydrous
Methanol solvate hybrid reaction, obtains solid phase sensor RB-L2.
(3) chloracetyl chloride microballoon, fluorescent molecular probe RB-3 and sodium carbonate are added into reactor, adds tetrahydrofuran and anhydrous
Methanol solvate hybrid reaction, obtains solid phase sensor RB-L3.
4. the solid phase fluorescent sensor described in claim 2 has following characteristics：
(1) lowest detection of solid phase fluorescent sensor detection heavy metal ion is limited to 0.5mM.
(2) reusable more than 5 times of the solid phase fluorescent sensor.
(3) heavy metal ion that the solid phase fluorescent sensor can be used in detection environment, food.
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