CN104211857A - Up-conversion fluorescent molecular imprinted polymer and preparation method thereof - Google Patents
Up-conversion fluorescent molecular imprinted polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides an up-conversion fluorescent molecular imprinted polymer and a preparation method thereof, and relates to the field of novel high polymer enrichment materials. Up-conversion fluorescent nano particles NaYF4:Yb<3+> and Er<3+> are used as novel carriers, the novel carriers are combined with a molecular imprinting technology. The invention particularly relates to an up-conversion fluorescent molecular imprinted polymer with good adsorbing and separating functions on carbamate pesticide metolcarb molecules and a preparation method of the up-conversion fluorescent molecular imprinted polymer. The synthesized up-conversion fluorescent molecular imprinted polymer is great in specific surface area, so that the mass transfer rate and the adsorbing capacity are improved greatly in comparison with those of the conventional materials. And moreover, the preparation method is low in cost, simple in synthesis process, and easy in reaction condition control. The prepared up-conversion fluorescent molecular imprinted polymer has the characteristics of high sensitivity and high selectivity on a target product, good reproducibility and good application prospect.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of up-conversion fluorescence molecularly imprinted polymer and preparation method thereof.
Background technology
Meta-tolyl-N-methylcarbamate (MTMC) is as the carbamate chemicals for agriculture of a quasi-representative, and output is large, and of a great variety, consumption is extensive.In organism and environment, be easily degraded to corresponding meta-bolites, these meta-bolitess have the activity identical or stronger with parent compound usually, and Intoxication is acetylcholine esterase inhibition, and toxicity symptom is similar to organophosphorus pesticide.Along with the continuous increase of its consumption in recent years, it is day by day serious to the harm of people and other biological body, is also day by day subject to people's attention its analyzing and testing.Along with adding of WTO, dining table problem, green food problem have enjoyed people to pay close attention to, and the detection residual about agriculture is also more aobvious important.European Union in explicit order regulation tap water single kind maximum residue limits for pesticide be 0.1 μ g/L.This has researched and proposed new challenge to this pesticide residue.At present domestic and international detection food in meta-tolyl-N-methylcarbamate (MTMC) content mostly adopt the method for immunization, liquid phase chromatography or liquid chromatography and mass spectrometry to carry out qualitative, quantitative detection.But when meta-tolyl-N-methylcarbamate (MTMC) trace is present in food, above-mentioned detection method is difficult to detect or apparatus expensive.Adopt the method for Solid-Phase Extraction quicker than traditional solvent extraction, more accurately, but need to use solid absorbent materials meta-tolyl-N-methylcarbamate (MTMC) being had to highly selective.In recent years, along with the development of nanotechnology, novel fluorescence nano material is arisen at the historic moment, and due to the character of its uniqueness, is widely used in the fields such as chemistry, medicine, biology.Wherein quantum dot (QDs) is that the widely used fluorescence that a class can replace conventional organic dyes partly leads nano material, but its toxicity is comparatively strong, and high-energy wavelength light excites, and easily causes damage to biological tissue, and background interference is larger.Compare with quantum dot with conventional organic dyes, it is high that upper conversion nano fluorescent nano particle (UCNPs) has quantum yield as a kind of novel fluorescent material, and emission peak is narrow, Stokes shift is large, and toxicity is low, and background interference is little, do not destroy the advantages such as biological tissue, be subject to extensive concern.
Summary of the invention
The problem that the invention will solve is to provide a kind of to meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer having highly selective and preparation method thereof.
For solving the problems of the technologies described above, the technical scheme that the invention adopts is: a kind of up-conversion fluorescence molecularly imprinted polymer, adopt upconversion fluorescence nano material as support, take meta-tolyl-N-methylcarbamate (MTMC) as template molecule, be function monomer with methacrylic acid, utilize the entrapping method in molecular imprinting to prepare.
Preferably, described upconversion fluorescence nano material is up-conversion fluorescence nanometer rod β – NaYF
4: Yb
3+, Er
3+.
Present invention also offers a kind of method preparing up-conversion fluorescence molecularly imprinted polymer as above, comprise following preparation process:
1) up-conversion fluorescence nanometer rod β – NaYF is first added
4: Yb
3+, Er
3+, then add solvents tetrahydrofurane and toluene and meta-tolyl-N-methylcarbamate (MTMC) template molecule, fully stir and make it dissolve completely, then add methacrylic acid, fully stir 1-2h; Add linking agent ethylene glycol dimethacrylate and initiator Diisopropyl azodicarboxylate reaction 0.3-0.5h; After logical nitrogen 3-10min, 55-60 DEG C of water-bath thermopolymerization 18-22h;
2) by step 1) polymkeric substance prepared pulverizes, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 40-48h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid, 50-60 DEG C of vacuum-drying 8-12h, obtains meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
Preferably, step 1) in, after adding methacrylic acid, fully stir 1h; 0.5h is reacted, logical nitrogen 10min, 60 DEG C of water-bath thermopolymerization 20h after adding linking agent and initiator.
Preferably, step 2) in, by step 1) polymkeric substance prepared pulverizes, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 48h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid, 60 DEG C of vacuum-drying 10h, obtain meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
Preferably, described up-conversion fluorescence nanometer rod and the mass ratio of meta-tolyl-N-methylcarbamate (MTMC) template molecule are 1:0.5-1:0.8, are preferably 1:0.66.
Preferably, step 1) in, the volume ratio of described solvents tetrahydrofurane and toluene is 1:0.5-1:2, is preferably 1:1.
Preferably, step 1) in, the molar ratio of described meta-tolyl-N-methylcarbamate (MTMC), methacrylic acid, ethylene glycol dimethacrylate is 1:3:3-1:4:10, is preferably 1:4:4.
Preferably, step 2) in, the extracting solution methyl alcohol of described methyl alcohol and glacial acetic acid and the volume ratio of glacial acetic acid are 10:1-8:1, are preferably 9:1.
Molecularly imprinted polymer (MIP) combines with up-conversion by the present invention first, with conversion nano rod on hexagonal crystal for β-NaYF
4: Yb
3+, Er
3+supporting carrier is template molecule with meta-tolyl-N-methylcarbamate (MTMC), synthesizes a kind of novel core-shell type organic inorganic hybridization molecularly imprinted polymer (UCNPs@MIP).This material can be used as solid extracting agent, can overcome the pre-treatment formality of environmental sample system complexity, for the collection of sample, concentration and analysis provide great convenience.Especially play an important role in the trace analysis of field of food.Trace substance under mmole level, after this method pre-concentration process, is easily detected in chromatogram.
The advantage that the invention has and positively effect are:
(1) the present invention first using upconversion fluorescence nano material as molecular imprinting synthesis in support, the sorbing material synthesized has the advantage that mass transfer velocity is fast, specific surface area is large compared with traditional molecular imprinting.The single-minded identification meta-tolyl-N-methylcarbamate (MTMC) of this material energy, has very high selectivity to target compound; Prepared by this material chemical synthesis process, highly sensitive, has higher stability, longer work-ing life and stronger anti-adverse environment ability.
(2) the present invention is with low cost, and experimental implementation is simple, easy control of reaction conditions, and obtained meta-tolyl-N-methylcarbamate (MTMC) molecularly imprinted polymer is used for Solid-Phase Extraction and liquid chromatography coupling as sorbent material, is applicable to trace meta-tolyl-N-methylcarbamate (MTMC) in food and detects and sample purification.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of UCNPs;
Fig. 2 is the scanning electron microscope (SEM) photograph of UCNPs@MIP in embodiment one
Fig. 3 is the transmission electron microscope picture of UCNPs crystal
Fig. 4 is the transmission electron microscope picture of UCNPs@MIP in embodiment one
Fig. 5 be in embodiment one UCNPs@MIP at the fluorescence spectrum figure of meta-tolyl-N-methylcarbamate (MTMC) concentration of aqueous solution in 50-2000ngmL-1 scope;
Fig. 6 be UCNPs@NIP at meta-tolyl-N-methylcarbamate (MTMC) concentration of aqueous solution at 50-2000ng mL
-1the fluorescence spectrum figure of scope;
Fig. 7 is meta-tolyl-N-methylcarbamate (MTMC), Propoxur, SevinCarbaryl and isoprocarb be respectively to the quenching of fluorescence amount preparing UCNPs@MIP and UCNPs@NIP in embodiment one;
Embodiment
Embodiment one
Prepare a method for up-conversion fluorescence molecularly imprinted polymer, comprise following preparation process:
(1) 0.250g up-conversion fluorescence nanometer rod β – NaYF is first added
4: Yb
3+, Er
3+, then add solvent 2.0mL tetrahydrofuran (THF) and 2.0mL toluene and 0.165g meta-tolyl-N-methylcarbamate (MTMC) template, fully stir and make it dissolve completely, then add 0.340mL (4.0mmol) methacrylic acid, fully stir 1h; Add linking agent ethylene glycol dimethacrylate 0.760mL (4.0mmol) and initiator Diisopropyl azodicarboxylate 0.02g and react 0.5h; Logical nitrogen 10min, 60 DEG C of water-bath thermopolymerization 20h;
(2) pulverized by step (1) polymkeric substance, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 48h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid.60 DEG C of vacuum-drying 10h, obtain meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
Embodiment two
Prepare a method for up-conversion fluorescence molecularly imprinted polymer, comprise following preparation process:
(1) 0.330g up-conversion fluorescence nanometer rod β – NaYF is first added
4: Yb
3+, Er
3+, then add solvent 1.0mL tetrahydrofuran (THF) and 2.0mL toluene and 0.165g meta-tolyl-N-methylcarbamate (MTMC) template, fully stir and make it dissolve completely, then add 0.255mL methacrylic acid, fully stir 2h; Add linking agent ethylene glycol dimethacrylate 0.570mL and initiator Diisopropyl azodicarboxylate 0.02g and react 0.3h; Logical nitrogen 5min, 55 DEG C of water-bath thermopolymerization 18h;
(2) pulverized by step (1) polymkeric substance, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 40h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid.50 DEG C of vacuum-drying 8h, obtain meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
Embodiment three
Prepare a method for up-conversion fluorescence molecularly imprinted polymer, comprise following preparation process:
(1) 0.206g up-conversion fluorescence nanometer rod β – NaYF is first added
4: Yb
3+, Er
3+, then add solvent 2.0mL tetrahydrofuran (THF) and 1.0mL toluene and 0.165g meta-tolyl-N-methylcarbamate (MTMC) template, fully stir and make it dissolve completely, then add 0.300mL methacrylic acid, fully stir 1.5h; Add linking agent ethylene glycol dimethacrylate 1.880mL and initiator Diisopropyl azodicarboxylate 0.02g and react 0.4h; Logical nitrogen 8min, 57 DEG C of water-bath thermopolymerization 22h;
(2) pulverized by step (1) polymkeric substance, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 42h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid.55 DEG C of vacuum-drying 9h, obtain meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
By up-conversion fluorescence nanometer rod β – NaYF
4: Yb
3+, Er
3+, i.e. the meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer of UCNPs and embodiment one preparation, namely UCNPs@MIP carries out scanning electron microscope analysis respectively.
As depicted in figs. 1 and 2, UCNPs and UCNPs@MIP all presents hexagonal prism shape under scanning electron microscope.Fig. 1 is the scanning electron microscope (SEM) photograph of UCNPs, the β-NaYF in figure
4: Yb
3+, Er
3+six prismatic surface are smooth, and profile is homogeneous, and being cross section is hexagonal columnar structure, and mean length is about 2 μm, and particle diameter is about 110nm.At present in the document reported, the NaYF of hexagonal crystal phase
4: Yb
3+, Er
3+(i.e. β-NaYF
4: Yb
3+, Er
3+) be the up-conversion that a kind of luminous efficiency is the highest, its luminous efficiency will far above the NaYF of cube crystalline phase
4: Yb
3+, Er
3+.Fig. 2 is the scanning electron microscope (SEM) photograph of UCNPs@MIP, and as we can see from the figure, after molecularly imprinted polymer embedding, overall configuration is constant, and be still hexagon, but size slightly increases, the part of increase is MIP film.
In order to can the growth of research material more clearly and polymerization situation, transmission electron microscope observing be carried out to UCNPs@MIP prepared by UCNPs crystal and embodiment one.Fig. 3 is the transmission electron microscope picture of naked UCNPs crystal, and as can be seen from the figure, the monodispersity of sample is fine, and particle diameter ratio is comparatively even, and be six prism structures, nanocrystalline mean length is about 2 μm, and particle diameter is about 100-200nm, consistent with scanning electron microscope result.Fig. 4 is the UCNPs@MIP after embedding molecular engram film, can find out clearly, we are successful has wrapped one deck MIP in UCNPs nanocrystal surface, and the monodispersity of the sample after embedding is still better, particle diameter ratio is comparatively even, and the thickness of film is also more homogeneous.
UCNPs@MIP prepared by mensuration embodiment one and non-imprinted polymer UCNPs@NIP is to the adsorptive power of template molecule meta-tolyl-N-methylcarbamate (MTMC).Their fluorescent emission bands of a spectrum are all positioned at 542.5nm.Can find from Fig. 5, along with the increase of the concentration of meta-tolyl-N-methylcarbamate (MTMC), the quenching of fluorescence amount of UCNPs@MIP also increases gradually.In general, the size of quenching of fluorescence amount depends on the adsorptive capacity of material to template molecule.Due to UCNPs outsourcing one deck MIP, in the molecular imprinting layer of outside, there is a large amount of specificity holes formed for template molecule.Comparison diagram 5 and Fig. 6, can obviously find out, under identical meta-tolyl-N-methylcarbamate (MTMC) adsorption liquid concentration, UCNPs@MIP quenching of fluorescence amount is higher than the quencher amount of UCNPs@NIP.Imprinting factor IF can be calculated according to typical curve
2, method of calculation are K
mIPand K
nIPratio, be the slope of Fig. 5 and Fig. 6 standard curve respectively.Under condition optimum separately, calculate IF
2(K
mIP/ K
nIP) numerical value be 1.74.Imprinting factor can illustrate that the quenching of fluorescence efficiency of imprinted polymer UCNPs@MIP is higher compared with non-imprinted polymer UCNPs@NIP, obviously larger to the adsorptive capacity of template molecule.
UCNPs@MIP embodiment one prepared and UCNPs@NIP carries out the adsorption kinetic data respectively.The adsorption kinetic data can characterize the rate of mass transfer of the UCNPs@MIP of synthesis.Experimental result shows, and when adsorption time is only 15min, can complete 50% of adsorption equilibrium, reaching adsorption equilibrium completely only needs 30min.This phenomenon illustrates, compared with conventional molecular imprinted material, the type material UCNPs@MIP of synthesis has rate of mass transfer faster.Its reason may be, the imprinted sites of novel molecular engram material is positioned at top layer, template molecule more easily enters, and this novel molecular engram material simultaneously also demonstrating this experiment synthesis has the fast feature of rate of mass transfer, effectively can overcome the defect that conventional molecular trace rate of mass transfer is slower.
The UCNPs@MIP of preparation in embodiment one and UCNPs@NIP is carried out selectivity and competitive assay respectively.Specificity is the most significant advantage of molecular engram material.In order to UCNPs@MIP synthesized in evaluation experimental is to the specificity of template molecule, we have chosen meta-tolyl-N-methylcarbamate (MTMC) and analog Propoxur, SevinCarbaryl and isoprocarb carry out selectivity and competitive assay.First configure respective 1.0mg L
-1the list mark aqueous solution, use UCNPs@MIP and UCNPs@NIP respectively it is adsorbed, result is as shown in Figure 7.Only have template molecule meta-tolyl-N-methylcarbamate (MTMC) to create obvious quencher effect to UCNPs@MIP, but not imprinted polymer UCNPs@NIP is very little for the adsorptive capacity of several carbamate chemicals for agriculture.In these three kinds of competitor, the quencher amount of isoprocarb to UCNPs@MIP is relatively large, SevinCarbaryl and the quencher amount of Propoxur to UCNPs@MIP relatively little, its reason may be that the difference of the structure of material causes.Compared with other several competitor, the structure of isoprocarb structure that is relative and meta-tolyl-N-methylcarbamate (MTMC) is similar, and the difference of their structural formulas is only the difference of R substituent side chain length.There is naphthalene nucleus in the structural formula of SevinCarbaryl, increase the sterically hindered of SevinCarbaryl; And the structure of the R substituent of Propoxur is comparatively complicated, make the quenching of fluorescence amount of these two kinds of materials to UCNPs@MIP less, namely UCNPs@MIP is relatively little to the adsorptive capacity of these two kinds of competitor.
Configuration concentration is 1.0mg L
-1four kinds of carbamate chemicals for agriculture mixing mark liquid, respectively it is adsorbed with UCNPs@MIP and UCNPs@NIP, result shows, in testing with selectivity, meta-tolyl-N-methylcarbamate (MTMC) is to compared with the quencher result of material, under race condition, there is not obvious change in the fluorescence intensity of UCNPs@MIP, demonstrates UCNPs@MIP further for the good recognition performance of template molecule.The existence of competitor does not produce obviously interference to its fluorescence intensity, and the change of fluorescence intensity is only caused by template molecule meta-tolyl-N-methylcarbamate (MTMC).
Above the embodiment of the invention has been described in detail, but described content being only the preferred embodiment of the invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the invention scope change and improve, and all should still belong within this patent covering scope.
Claims (9)
1. a up-conversion fluorescence molecularly imprinted polymer, is characterized in that: adopt upconversion fluorescence nano material as support, being template molecule with meta-tolyl-N-methylcarbamate (MTMC), is function monomer with methacrylic acid, utilizes the entrapping method in molecular imprinting to prepare.
2. up-conversion fluorescence molecularly imprinted polymer according to claim 1, is characterized in that: described upconversion fluorescence nano material is up-conversion fluorescence nanometer rod β – NaYF
4: Yb
3+, Er
3+.
3. prepare a method for up-conversion fluorescence molecularly imprinted polymer as claimed in claim 2, it is characterized in that, comprise following preparation process:
1) up-conversion fluorescence nanometer rod β – NaYF is first added
4: Yb
3+, Er
3+, then add solvents tetrahydrofurane and toluene and meta-tolyl-N-methylcarbamate (MTMC) template molecule, fully stir and make it dissolve completely, then add methacrylic acid, fully stir 1-2h; Add linking agent ethylene glycol dimethacrylate and initiator Diisopropyl azodicarboxylate reaction 0.3-0.5h; After logical nitrogen 3-10min, 55-60 DEG C of water-bath thermopolymerization 18-22h;
2) by step 1) polymkeric substance prepared pulverizes, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 40-48h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid, 50-60 DEG C of vacuum-drying 8-12h, obtains meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
4. the preparation method of up-conversion fluorescence molecularly imprinted polymer according to claim 3, is characterized in that: step 1) in, after adding methacrylic acid, fully stir 1h; 0.5h is reacted, logical nitrogen 10min, 60 DEG C of water-bath thermopolymerization 20h after adding linking agent and initiator.
5. the preparation method of up-conversion fluorescence molecularly imprinted polymer according to claim 3, it is characterized in that: step 2) in, by step 1) polymkeric substance prepared pulverizes, be placed in soxhlet's extractor, add 270mL methyl alcohol and 30mL glacial acetic acid makes extraction solvent, continuous extraction 48h, to detecting without meta-tolyl-N-methylcarbamate (MTMC) in extraction liquid, 60 DEG C of vacuum-drying 10h, obtain meta-tolyl-N-methylcarbamate (MTMC) up-conversion fluorescence molecularly imprinted polymer.
6., according to the preparation method of the up-conversion fluorescence molecularly imprinted polymer described in claim 3 ~ 5, it is characterized in that: step 1) in, described up-conversion fluorescence nanometer rod and the mass ratio of meta-tolyl-N-methylcarbamate (MTMC) template molecule are 1:0.5-1:0.8, are preferably 1:0.66.
7., according to the preparation method of the up-conversion fluorescence molecularly imprinted polymer described in claim 3 ~ 5, it is characterized in that: step 1) in, the volume ratio of described solvents tetrahydrofurane and toluene is 1:0.5-1:2, is preferably 1:1.
8. according to the preparation method of the up-conversion fluorescence molecularly imprinted polymer described in claim 3 ~ 5, it is characterized in that: step 1) in, the molar ratio of described meta-tolyl-N-methylcarbamate (MTMC), methacrylic acid, ethylene glycol dimethacrylate is 1:3:3-1:4:10, is preferably 1:4:4.
9., according to the preparation method of the up-conversion fluorescence molecularly imprinted polymer described in claim 3 ~ 5, it is characterized in that: step 2) in, the extracting solution methyl alcohol of described methyl alcohol and glacial acetic acid and the volume ratio of glacial acetic acid are 10:1-8:1, are preferably 9:1.
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| CN105238402A (en) * | 2015-11-23 | 2016-01-13 | 天津科技大学 | Salmonella upconversion fluorescence sensing material and preparing method thereof |
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| CN111171806B (en) * | 2020-01-09 | 2023-03-21 | 南昌航空大学 | Preparation method and application of molecular imprinting ratio type fluorescent probe based on up-conversion nano material |
| CN114486825A (en) * | 2021-12-31 | 2022-05-13 | 江苏大学 | Rapid detection method of carbendazim based on up-conversion-molecular imprinting fluorescence sensor |
| CN114486825B (en) * | 2021-12-31 | 2023-01-17 | 江苏大学 | Rapid detection method of carbendazim based on up-conversion-molecular imprinting fluorescence sensor |
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