CN104672476A - Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane - Google Patents
Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane Download PDFInfo
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Abstract
The invention belongs to the technical fields of material preparation, analysis and detection, and discloses a preparation method of a rare-earth fluorescent molecularly imprinted membrane and an application in detection of cyfluthrin. According to the technical scheme disclosed by the invention, the method comprises the following steps: preparing an Eu (III) rare-earth complex by a solution method; wrapping the rare-earth complex with a silicon-based surface; adopting a surface molecular imprinting technology; and with cyfluthrin as a template, methacrylic acid (MAA) as a functional monomer and EGDMA as a cross-linking agent and azobisisobutyronitrile (AIBN) as an initiator, preparing a rare-earth fluorescent molecularly imprinted probe. Trace cyfluthrin in a water sample is detected by a fluorescence analysis method; the related coefficient R2 is 0.99269; and the result proves that the rare-earth fluorescent molecularly imprinted probe obtained by the method has excellent recognition performance and extremely high sensitivity on cyfluthrin molecules.
Description
Technical field
The present invention relates to a kind of preparation method of rare-earth fluorescent blotting membrane, particularly relate to a kind of preparation method of cyfloxylate molecular fluorescence blotting membrane, and be applied to the cyfloxylate detecting underwater trace, belong to material preparation and determination methods technical field.
Background technology
Pyrethrin (Pyrethroid pesticides, PPs) is the broad spectrum insecticide of a class synthetic, has the features such as quick-acting, odorless, low toxicity, action of contace poison strong and residual effect time is long.Except having special efficacy to 140 various pests controls, some pyrethrin also has good prevention effect to subterranean pest-insect and mite pest.In recent years, after high toxicity organochlorine, organophosphorus pesticide are prohibited from using, PPs has had application space widely, and it has occupied the share of nearly 20% in international pesticide market.It is generally acknowledged, the mechanism of action of PPs is interference nerve conduction and makes insect loss of consciousness lethal, but PPs is also under a cloud has endocrine disrupting.At present, the research of the aspect such as monitoring analysis, migration, resistance that PPs in environment remains has been become to the focus of environmental recovery bonds scholar concern, the maximum constraint remained by PPs in environment as USEPA is 0.05 μ g/g.The analyzing and testing that PPs remains mainly uses chromatography, as liquid phase chromatography, vapor-phase chromatography and Liquid Chromatography/Mass Spectrometry.Chromatography has the high rate of recovery, good circulation ratio and lower detection limit, but needs loaded down with trivial details sample pretreatment process.The method of conventional sample pre-treatments has solvent extraction technology, supercritical extraction technique, microwave-assisted extraction technique, membrane separation technique and solid phase extraction techniques etc.Although these methods respectively have particular advantages, also respectively there is its limitation.As a large amount of in solvent extraction technology with an organic solvent, easily produce secondary pollution; Although supercritical extraction has and easily realizes that solvent is separated with target compound, free of contamination advantage, complicated operation, cost are high; There is the blockage problem of film in membrane separation technique; The sorbent material selectivity that solid phase extraction techniques is commonly used is poor.Fluorometry based on organic fluorescence film receives the extensive welcome of researcher, and numerous fluorescence analysis method of foundation has been widely used in and has measured inorganics, organism and biomacromolecule.Fluorometry based on organic fluorescence film has lower Monitoring lower-cut and certain selectivity, and can use popular instrument.With inorganic analysis reagents ratio comparatively, organic reagent is applied to that the alternative kind of fluorometric analysis is more, and general sensitivity is better, very responsive to environmental change, and Application Areas is more extensive.
Molecular imprinting (MIT) is as the Molecular Recognization of enzyme-to-substrate, antibody and antigen etc. in simulating nature circle, take target molecule as template molecule preparation has the polymer imprinted polymer (Molecularly Imprinted Polymers, MIPs) of specific selectivity recognition function a kind of technology to this molecule.
Application and Development molecular imprinting being combined the molecular imprinting polymeric membrane (Molecular Imprinted Membrane, MIM) produced with membrane separation technique is one of research of most magnetism.Molecular imprinted polymer membrane (MIM) has the advantage of molecular imprinting and membrane separation technique concurrently, and on the one hand, this technology is convenient to operate continuously, is easy to amplify, and energy consumption is low, and capacity usage ratio is high, is the typical case of " Green Chemistry "; On the other hand, which overcoming current commercial membranes material and cannot realize as ultrafiltration, micro-filtration and reverse osmosis membrane etc. the shortcoming that single material selects separation, providing feasible effective solution route for being separated from the mixture of similar by specific molecular.Consider that the molecular engram film of synthesis has the single-minded Selective recognition function of predetermined substance, the dedoping step for wintergreen oil provides kind of a novel method, and constantly plays irreplaceable effect in large industrial goods separation and purification field.
Molecular imprinting polymeric membrane is combined the fluorescence molecule blotting membrane produced with fluorescence analysis, has two aspect advantages of blotting membrane technology and fluorometry concurrently: the superior character utilizing the specific adsorption of molecularly imprinted polymer on the one hand, improve the sensitivity of film.On the other hand, super-sensitive fluoroscopic examination is combined with MIPs, fluorescent signal is utilized to make up the defect of MIPs shortage intracellular signaling, prepare molecular imprinting fluorescent optical sensor and meet the anti-interference of sensor material, high selection, highly sensitive demand, has become the study hotspot in the fields such as current sensor separation.
Summary of the invention
The present invention take rare earth compounding as luminescent material synthesis to have specific recognition ability microsphere film to cyfloxylate molecule, and for the cyfloxylate molecule trace detection in water sample.This fluorescence blotting membrane has higher adsorptivity and selectivity to cyfloxylate molecule.
Technical scheme of the present invention is:
Cyfloxylate molecule is had to a preparation method for the rare-earth fluorescent molecular engram film of specific recognition ability, carries out according to the following steps:
(1) Europium trichloride (EuCl is got
3), 1,10-phenanthroline (phen), thenoyltrifluoroacetone (TTA) be dissolved in ethanol, magnetic agitation evenly after, drip strong aqua, regulator solution pH, solution turned cloudy; Continue to stir, centrifugal, washing, obtains Eu (III) title complex;
(2) Eu (III) title complex ultrasonic dissolution step (1) obtained is in DMF solution, then pour the solution of dissolving into ethanolic soln, then form solution A to mixed solution and dripping tetraethyl orthosilicate (TEOS); The mixing solutions that ammoniacal liquor, ethanol, distilled water are formed is called solution B; Whole solution A is poured into rapidly in solution B, magnetic agitation; Reacted rear centrifugal, washing, obtains Eu (III)@SiO
2;
(3) fluorescent material that step (2) obtains is scattered in acetonitrile, add methacrylic acid (MAA), Ethylene glycol dimethacrylate (EGDMA), cyfloxylate, self-assembly, then add azo-bis-isobutyl cyanide (AIBN) polymerization, obtain trace fluorescent microsphere;
(4) trace fluorescent microsphere methyl alcohol step (3) obtained and acetic acid mixed solution make vat liquor, surname extraction is adopted to be removed by template molecule, until template molecule cannot be detected by ultraviolet-visible spectrophotometer, product is dried in vacuum drying oven, obtains wash-out trace fluorescent microsphere completely;
(5) trace fluorescent microsphere ultrasonic disperse step (4) obtained, in distilled water, adds agarose, is heated to 70 DEG C, topples over, and compacting film forming, obtains molecular imprinting fluorescent screen.
Wherein, in step (1), described EuCl
3, phen, TTA three mol ratio be 1:1.5:1 ~ 1:1:1.
Described in step (1), pH value of solution is 7; Described continuation churning time is 2 h.
Wherein, in step (2), in described solution A, the concentration of Eu (III) title complex is the volume ratio of 3 ~ 4 g/L, DMF and ethanol is 1:5; The volume fraction in solution A of TEOS is 3% ~ 5%; In solution B, the volume fraction of ammoniacal liquor is 4% ~ 5%, and the volume ratio of second alcohol and water is 14:5;
In step (2), described solution A and solution B mixed reaction times are 2 h.
Washing described in step (1) and step (2) is by washing with alcohol three times.
Wherein, in step (3), in the final whole mixing solutions of gained, Eu (III)@SiO
2concentration be concentration 10 ~ 20 mmol/L of 3 ~ 4 g/L, MAA, the percent by volume of EGDMA is 4.7 ~ 5.4%, and the concentration of cyfloxylate is the concentration of 3 ~ 5 mmol/ L, AIBN is 3 ~ 6.5 mmol/L.
In step (3), described self-assembly is under nitrogen protection condition, self-assembly 6 h at 40 DEG C; Described be polymerized to 60 DEG C at be polymerized 24 h.
In step (4), in described vat liquor, the volume ratio of methyl alcohol and acetic acid is 9:1; Described bake out temperature is 60 DEG C.
The preparation method of corresponding non-trace fluorescence silicon ball is same as described above, but does not add template molecule cyfloxylate.
Described in step (5), the concentration of agarose is 18 ~ 20 g/L, and the concentration of molecular engram microsphere is 0.75 ~ 0.8 g/L
Above-mentioned molecular imprinting fluorescent screen is applied to the cyfloxylate content of water sample in testing environment, and concrete grammar carries out according to following step.
(1) trace fluorescent screen and and the non-trace fluorescent screen of equivalent is accurately taken.
(2) get cyfloxylate distilled water to be configured to a series of 0 ~ 100 μm of ol/L and to be configured to hybrid standard liquid, getting the solution that 10 mL prepare joins in wide-necked bottle, respectively add trace fluorescent screen and non-blotting membrane again, 25 DEG C of concussions after even ten minutes, take out film, after its drying, use its fluorescence intensity of fluorescent spectrophotometer assay.
(3) if initial fluorescence intensity is I
0, fluorescence intensity is afterwards I, then the amount of quenching of fluorescence is linear in certain scope with the concentration of cyfloxylate, can pass through I
0--I measures the concentration of cyfloxylate.
Beneficial effect of the present invention:
(1) printing process occurs in fluorescent material surface, avoids conventional template molecule dark and cannot the problem of wash-out because embedding;
(2) at fluorescent material Surface coating imprinted layer, selective adsorption cyfloxylate, the sensitivity of the probe improved greatly;
(3) the fluorescence trace probe utilizing the present invention to obtain has high sensitivity, superior to cyfloxylate recognition performance;
(4) use membrane technique, simplify operation step and play, decrease detection time.
Accompanying drawing explanation
Fig. 1: Eu (III)@SiO
2, trace fluorescence silicon ball scanning electron microscope (SEM) photograph;
Fig. 2: Eu (III) title complex, Eu (III)@SiO
2, trace fluorescent microsphere, non-trace fluorescent microsphere fluorescence spectrum figure;
Fig. 3: trace probe in detecting Trace Fluoride Cypermethrin figure.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
embodiment 1
(1) EuCl
30.5 mmol, phen 0.75 mmol, TTA 0.5 mmol, is dissolved in magnetic agitation in 100 mL ethanol and evenly drips strong aqua afterwards.Regulate pH=7, solution turned cloudy.Continue stirring 2 h, centrifugal, wash three times with ethanol.Obtain Eu (III) title complex.
(2) Eu (III) title complex 100 mg in step (1) is dissolved in 5 mL DMF.Formed in solution A with the mixing solutions of 25 ml ethanol, 1 mL TEOS.Then 1 mL ammoniacal liquor adds in the mixing solutions of 14 ml ethanol and 5 ml distilled water and forms solution B, then solution A is poured into rapidly in solution B, magnetic agitation 2 h.Centrifugal, wash three times, obtain Eu (III)@SiO
2.
(3) Eu (III) the@SiO will obtained in (2)
20.1g is scattered in 30mL acetonitrile, then adds 0.35 mmol methacrylic acid (MAA), 1.50 mL Ethylene glycol dimethacrylate (EGDMA), 0.10 mmol cyfloxylate.N
2under protection, self-assembly 6 h at 40 DEG C, is polymerized 24 h at then adding 33 mg azo-bis-isobutyl cyanide (AIBN) 60 DEG C.Obtain trace fluorescent probe.
(4) vat liquor made by trace fluorescence silicon ball methyl alcohol step (3) obtained and the mixed solution of acetic acid, surname extraction is adopted to be removed by template molecule, until template molecule cannot be detected by ultraviolet-visible spectrophotometer, product is dried in 60 DEG C of vacuum drying ovens.
The preparation method of corresponding non-trace fluorescent probe is same as described above, but does not add template molecule.
(5) Eu (III)@SiO
2, trace fluorescence silicon ball scanning electron microscope (SEM) photograph as shown in Figure 1, illustrate that trace is successfully coated on silicon ball surface.
embodiment 2
(1) EuCl
30.5 mmol, phen 0.5 mmol, TTA 0.5 mmol, is dissolved in magnetic agitation in 100mL ethanol and evenly drips strong aqua afterwards.Regulate pH=7, solution turned cloudy.Continue stirring 2 h, centrifugal, wash three times with ethanol.Obtain Eu (III) title complex.
(2) Eu (III) title complex 20 mg in step (1) is dissolved in 1 mL DMF.Formed in solution A with the mixing solutions of 5 ml ethanol, 0.19 mL TEOS.Then 0.2 mL ammoniacal liquor adds in the mixing solutions of 3.5ml ethanol and 1.3 ml distilled water and forms solution B, then solution A is poured into rapidly in solution B, magnetic agitation 2 h.Centrifugal, wash three times, obtain Eu (III)@SiO
2.
(3) fluorescent material 0.12 g obtained in (2) is scattered in 30mL acetonitrile, then 0.50 mmol methacrylic acid (MAA), 1.55 mL Ethylene glycol dimethacrylate (EGDMA) are added, 0.12 mmol cyfloxylate.N
2under protection, self-assembly 6 h at 40 DEG C, is polymerized 24 h at then adding 25 mg azo-bis-isobutyl cyanide (AIBN) 60 DEG C.Obtain trace fluorescent probe.
(4) trace fluorescence silicon ball methyl alcohol step (3) obtained and acetic acid mixture make vat liquor, surname extraction is adopted to be removed by template molecule, until cyfloxylate cannot be detected by ultraviolet-visible spectrophotometer, product is dried in 60 DEG C of vacuum drying ovens.
The preparation method of corresponding non-trace fluorescent probe is same as described above, but does not add template molecule cyfloxylate.
(5) get 0.015 g trace fluorescence silicon ball ultrasonic disperse in 20 mL water, 70 DEG C of heating, magnetic agitation, adding 0.4 g agarose, continues to stir, pour out, pressurization film forming.Prepare rare-earth fluorescent blotting membrane.
Eu (III) title complex, Eu (III)@SiO
2, trace fluorescent microsphere, non-trace fluorescent microsphere fluorescence spectrum as shown in Figure 2.Fig. 2 shows Eu (III) title complex has very strong emission peak at 614 nm, and the fluorescence intensity of trace fluorescent microsphere, non-trace fluorescent microsphere is because coated organic layer, and fluorescence intensity reduces.
embodiment 3
(1) EuCl
30.5 mmol, phen 0.5 mmol, TTA 0.5 mmol, is dissolved in magnetic agitation in 100 mL ethanol and evenly drips strong aqua afterwards.Regulate pH=7, solution turned cloudy.Continue stirring 2 h, centrifugal, wash three times with ethanol.Obtain Eu (III) title complex.
(2) Eu (III) title complex 50 mg in step (1) is dissolved in 2 mL DMF.Formed in solution A with the mixing solutions of 10ml ethanol, 0.5 mL TEOS.Then 0.4 mL ammoniacal liquor adds in the mixing solutions of 7 ml ethanol and 2.5 ml distilled water and forms solution B, then solution A is poured into rapidly in solution B, magnetic agitation 2 h.Centrifugal, wash three times, obtain Eu (III)@SiO
2.
(3) fluorescent material 0.12 g obtained in (2) is scattered in 30mL acetonitrile, then 0.60 mmol methacrylic acid (MAA), 1.70 mL Ethylene glycol dimethacrylate (EGDMA) are added, 0.15 mmol cyfloxylate.N
2under protection, self-assembly 6 h at 40 DEG C, is polymerized 24 h at then adding 16 mg azo-bis-isobutyl cyanide (AIBN) 60 DEG C.Obtain trace fluorescence silicon ball.
(4) vat liquor made by trace fluorescence silicon ball methyl alcohol step (3) obtained and the mixed solution of acetic acid, surname extraction is adopted to be removed by template molecule, until cyfloxylate cannot be detected by ultraviolet-visible spectrophotometer, product is dried in 60 DEG C of vacuum drying ovens.
(5) get 0.016 g trace fluorescence silicon ball ultrasonic disperse in 20 mL water, 70 DEG C of heating, magnetic agitation, adding 0.36 g agarose, continues to stir, pour out, pressurization film forming.Prepare rare-earth fluorescent blotting membrane.
(6) the rare-earth fluorescent blotting membrane of preparation is used for the cyfloxylate detecting trace
Get cyfloxylate to be configured to a series of 0 ~ 100 μm of ol/L water-ethanol (1:1) solution allocation and to become reference liquid.Get the solution that 10 mL prepare to join in wide-necked bottle, respectively add 1mg trace fluorescent screen, water-bath concussion at 25 DEG C, after being taken out by film, after its drying, uses its fluorescence intensity of fluorescent spectrophotometer assay.
If initial fluorescence intensity is I
0, the fluorescence intensity after adding is I, then the amount of change in fluorescence is linear in certain scope with cyfloxylate concentration.I can be passed through
0--I measures the concentration of cyfloxylate.
Test result as shown in Figure 3.Result shows, trace fluorescent screen when concentration range 0 to 100 μm of ol/L, the variable quantity of fluorescence and the concentration of cyfloxylate linear, relation conefficient is 0.998.May be used for the trace detection analysis to cyfloxylate.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for rare-earth fluorescent molecular engram film, is characterized in that, carries out according to the following steps:
(1) get Europium trichloride, 1,10-phenanthroline, thenoyltrifluoroacetone be dissolved in ethanol, magnetic agitation evenly after, drip strong aqua, regulator solution pH, solution turned cloudy; Continue to stir, centrifugal, washing, obtains Eu (III) title complex;
(2) Eu (III) title complex ultrasonic dissolution step (1) obtained, in DMF solution, then pours the solution of dissolving into ethanolic soln, then forms solution A to mixed solution and dripping tetraethyl orthosilicate; The mixing solutions that ammoniacal liquor, ethanol, distilled water are formed is called solution B; Whole solution A is poured into rapidly in solution B, magnetic agitation; Reacted rear centrifugal, washing, obtains Eu (III)@SiO
2;
(3) fluorescent material that step (2) obtains is scattered in acetonitrile, adds methacrylic acid, Ethylene glycol dimethacrylate, cyfloxylate, self-assembly, then add azo-bis-isobutyl cyanide polymerization, obtain trace fluorescent microsphere;
(4) vat liquor made by trace fluorescent microsphere methanol acetic acid mixed solution step (3) obtained, surname extraction is adopted to be removed by template molecule, until template molecule cannot be detected by ultraviolet-visible spectrophotometer, product is dried in vacuum drying oven, obtains wash-out trace fluorescent microsphere completely;
(5) trace fluorescent microsphere ultrasonic disperse step (4) obtained, in distilled water, adds agarose, is heated to 70 DEG C, topples over, and compacting film forming, obtains molecular imprinting fluorescent screen.
2. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, in step (1), the mol ratio of described Europium trichloride, 1,10-phenanthroline, thenoyltrifluoroacetone is 1:1.5:1 ~ 1:1:1.
3. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, in step (1), described pH value of solution is 7; Described continuation churning time is 2 h; Described washing is for using washing with alcohol three times.
4. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, in step (2), in described solution A, the concentration of Eu (III) title complex is the volume ratio of 3 ~ 4 g/L, DMF and ethanol is 1:5; The volume fraction in solution A of TEOS is 3% ~ 5%; In described solution B, the volume fraction of ammoniacal liquor is 4% ~ 5%, and the volume ratio of second alcohol and water is 14:5.
5. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, solution A described in step (2) and solution B mixing rear reaction times are 2 h; Described washing is for using washing with alcohol three times.
6. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, in step (3), in the final whole mixing solutions of gained, and Eu (III)@SiO
2concentration be concentration 10 ~ 20 mmol/L of 3 ~ 4 g/L, MAA, the percent by volume of EGDMA is 4.7 ~ 5.3%, and the concentration of cyfloxylate is the concentration of 3 ~ 5 mmol/ L, AIBN is 3 ~ 6.5 mmol/L.
7. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, self-assembly described in step (3) is under nitrogen protection condition, self-assembly 6 h at 40 DEG C; Described be polymerized to 60 DEG C at be polymerized 24 h.
8. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, in the vat liquor described in step (4), methanol acetic acid mixed solution liquor capacity compares 9:1; Described bake out temperature is 60 DEG C.
9. the preparation method of a kind of rare-earth fluorescent molecular engram film according to claim 1, is characterized in that, described in step (5), the concentration of agarose is 18 ~ 20 g/L, and the concentration of molecular engram microsphere is 0.75 ~ 0.8 g/L.
10. according to the preparation method of a kind of rare-earth fluorescent molecular engram film described in claim 1 ~ 9, it is characterized in that, prepared trace fluorescent screen is applied to the cyfloxylate in testing environment.
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| CN105136758A (en) * | 2015-08-28 | 2015-12-09 | 合肥学院 | Method for preparing Eu3+ labelled molecule imprinted sensor used for pesticide residue detection |
| CN106496641A (en) * | 2016-10-09 | 2017-03-15 | 江苏大学 | A kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane |
| CN105255484B (en) * | 2015-10-16 | 2017-05-31 | 合肥学院 | A kind of SrAl for detection of organic phosphorus pesticide2B2O7:Eu3+The preparation method of fluorescence probe |
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| CN105136758A (en) * | 2015-08-28 | 2015-12-09 | 合肥学院 | Method for preparing Eu3+ labelled molecule imprinted sensor used for pesticide residue detection |
| CN105136758B (en) * | 2015-08-28 | 2017-12-08 | 合肥学院 | A kind of Eu to the residual detection of agriculture3+Mark molecule marking transducer production method |
| CN105255484B (en) * | 2015-10-16 | 2017-05-31 | 合肥学院 | A kind of SrAl for detection of organic phosphorus pesticide2B2O7:Eu3+The preparation method of fluorescence probe |
| CN106496641A (en) * | 2016-10-09 | 2017-03-15 | 江苏大学 | A kind of preparation method and its usage of daiamid/rare-earth fluorescent blotting membrane |
| CN107064007A (en) * | 2017-06-27 | 2017-08-18 | 中国计量科学研究院 | Time-resolved fluorescence enzyme micro-plate reader testing standard plate and its preparation and application |
| CN107064007B (en) * | 2017-06-27 | 2024-04-02 | 中国计量科学研究院 | Time-resolved fluorogenic enzyme-labeled analyzer test standard plate and preparation and use methods thereof |
| CN108134101A (en) * | 2017-12-29 | 2018-06-08 | 西北师范大学 | A kind of preparation method of conducting polymer-rare earth compounding composite electrocatalyst |
| CN108134101B (en) * | 2017-12-29 | 2020-11-03 | 西北师范大学 | Preparation method of conductive polymer-rare earth complex composite electrocatalyst |
| CN110618117A (en) * | 2019-08-30 | 2019-12-27 | 江苏大学 | Preparation method and application of hollow hemispherical lanthanide fluorescent imprinted sensor |
| CN112480426A (en) * | 2020-12-09 | 2021-03-12 | 平顶山学院 | Metal organic framework material for detecting copper ions and pH, and preparation method and application thereof |
| CN112480426B (en) * | 2020-12-09 | 2021-12-03 | 平顶山学院 | Metal organic framework material for detecting copper ions and pH, and preparation method and application thereof |
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Application publication date: 20150603 |