CN103965504A - Preparation method of rear earth doped core-shell type fluorescent imprinting polymer - Google Patents
Preparation method of rear earth doped core-shell type fluorescent imprinting polymer Download PDFInfo
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- CN103965504A CN103965504A CN201410200236.XA CN201410200236A CN103965504A CN 103965504 A CN103965504 A CN 103965504A CN 201410200236 A CN201410200236 A CN 201410200236A CN 103965504 A CN103965504 A CN 103965504A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920001109 fluorescent polymer Polymers 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 claims description 37
- 239000005910 lambda-Cyhalothrin Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 11
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 239000011159 matrix material Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 11
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 3
- 239000002096 quantum dot Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910009372 YVO4 Inorganic materials 0.000 abstract 1
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 17
- 238000001514 detection method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000013047 polymeric layer Substances 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000005874 Bifenthrin Substances 0.000 description 2
- 241000723353 Chrysanthemum Species 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 2
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 1
- 229940125717 barbiturate Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 ethylene glycol bisthioglycolate (methacrylic acid) ester Chemical class 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005220 pharmaceutical analysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a preparation method of rear earth doped core-shell type fluorescent imprinting polymer. The preparation method comprises the following process steps of (1), preparing europium-doped yttrium vanadate nano particles; (2), preparing core-shell type molecular imprinting fluorescent polymer; and (3), preparing non-imprinted polymer (YVO4:Eu<3+>@NIPs) which is correspondingly applied as reference. The preparation method disclosed by the invention has advantages that rear earth europium doped yttrium vanadate nano particles are synthesized by utilizing a simple wet chemical method, and a molecular imprinting fluorescent sensor with a shell-core structure is prepared by utilizing a molecular imprinting technology. The fluorescent composite material obtained by the preparation method disclosed by the invention has good water-phase dispersion and optical stability, has a series of characteristics of small toxicity, high chemical stability, high and stable luminous intensity, great stokes displacement and the like in comparison with the sensor which is prepared by taking organic micromolecule dyes and quantum dots as fluorescent signals. And moreover, residual cyhalothrin in the aqueous liquor can be quickly identified and optically detected.
Description
Technical field
That the present invention relates to is a kind of preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer, belongs to environment functional material preparing technical field.
Background technology
Along with analyzing improving constantly of requiring, particularly pharmaceutical analysis, environmental analysis, food analysis and product detect the growing of demand, and sensor, as a kind of important detection means, more and more receives people's concern.Sensor is comprised of recognition component and chromacoder.Recognition component is the core of sensor, when it identifies target analytes from complex sample, the physics producing or Chemical response through transmodulator convert to one can be quantitative output signal (light, magnetic, electrical signal), by monitoring output signal, realize the real time measure to target compound to be measured.Therefore, performance perameter depends on recognition component to a great extent the selectivity of sensor, sensitivity, time of response etc.Organic have good molecular recognition function with biological sensitive materials, molecularly imprinted polymer material wherein can be for the target compound customization of " cutting the garment according to the figure ", the single-minded identification of realization to target molecule, can compare favourably with natural biological recognition system (enzyme-to-substrate), there is preparation simple, good stability (acid and alkali-resistance, high temperature, high pressure, organic solvent and severe rugged environment), life-span is long, easily preserve, the feature such as cheap, in Solid-Phase Extraction, chiral separation, simulation biological antibody, the aspect such as catalysis and organic synthesis is widely used, to solve environment, biology waits simple and direct that in complex system, specific target molecules highly selective is identified, reliable means.
Molecular imprinting fluorescent optical sensor is that the molecular imprinting with specific recognition capability is combined with highly sensitive fluoroscopic examination, meet anti-interference, the high selection of sensor material, highly sensitive requirement, become the study hotspot of current sensing, separation field.
According to investigations, the molecular imprinting fluorescent optical sensor major part of most of report is usingd organic molecule dyestuff and quantum dot as fluoroscopic examination signal, and these materials all have the limitation of itself, such as toxicity problem, this will limit their application in field of biological detection.And rare-earth vanadium-doped Barbiturates fluorescent material is just widely adopted for a long time and as a kind of effective method.Rare earth doped luminescent material has a series of features such as toxicity is low, chemical stability is high, luminous intensity is high and stable, stokes displacement is large, and there is unique Upconversion luminescence, be expected to develop into the novel light-emitting biomarker material with development prospect of a class.
Using rear-earth-doped vanadate nano particle as shell structure with fluoroscopic examination signal, and the coated one deck in its surface thin molecular imprinting polymeric layer, make the molecular imprinting fluorescence composite material of core-shell type.Utilize the Quenching of fluorescence effect of environmental pollutant to molecular imprinting fluorescent optical sensor, can reach the ability of quantitative and qualitative analysis testing environment pollutent.
Pyrethroid insecticides, as lambda-cyhalothrin etc., owing to having the features such as pesticidal residual quantity high, in vegetables and fruit is lower, is widely used in China.Therefore the research that, utilizes rear-earth-doped type molecular imprinting fluorescent optical sensor to reach fast, conveniently detect residual quantity necessitates.
Summary of the invention
That the present invention proposes is a kind of preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer, it is the Yttrium Orthovanadate nano particle that has synthesized rare-earth europium doping under gentle condition, then utilize the method for simple precipitation polymerization, take lambda-cyhalothrin as template, methacrylic acid and ethylene glycol dimethacrylate are polymeric precursor, at the coated thin trace polymeric layer of one deck of Yttrium Orthovanadate nano grain surface of rare-earth europium doping.Then with soxhlet extraction, remove after template molecule, system there is the molecular imprinting fluorescent optical sensor of core-shell type structure, use it for optical detection template molecule lambda-cyhalothrin.And utilizing scanning electronic microscope, transmission electron microscope, infared spectrum, X-ray diffractogram spectrum analysis etc. has proved and has successfully synthesized the molecular imprinting fluorescent optical sensor with core-shell type structure.Further research shows: finite concentration lambda-cyhalothrin has quenching effect to the fluorescence of this molecular imprinting fluorescent optical sensor, and in certain scope, meet Stern Volmer equation (linearity range is 2.0 μ M 90 μ M, and lowest detectable limit can reach 1.76 μ M).The molecular imprinting fluorescent optical sensor of synthesized is also successfully applied in environment the detection by quantitative of residual lambda-cyhalothrin in material object.Known accordingly, the rear-earth-doped type molecular imprinting fluorescent optical sensor of synthesized has the ability that quantitative and qualitative analysis detects residual pyrethrin pesticide in the aqueous solution.
The technical solution used in the present invention is: the preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer, comprises following processing step:
1) preparation of the Yttrium Orthovanadate nanoparticle of europium doping;
2) preparation of core-shell type molecular imprinting fluorescent polymer;
3) the corresponding non-imprinted polymer YVO as reference
4: Eu
3+the preparation of@NIPs.
Advantage of the present invention: utilize simple wet chemistry method to synthesize the Yttrium Orthovanadate nano particle of rare-earth europium doping, and utilize the molecular imprinting to have made to have the molecular imprinting fluorescent optical sensor of core-shell type structure.Utilize the fluorescence composite material that the present invention obtains to there is better aqueous phase dispersibility and optical stability, with using the sensor that organic molecule dyestuff makes as fluorescent signal with quantum dot and compare, there are a series of features such as toxicity is little, chemical stability is high, luminous intensity is high and stable, stokes displacement is large.And can also realize residual lambda-cyhalothrin in quick identification and the optical detection aqueous solution.
Accompanying drawing explanation
In Fig. 1, a is YVO
4: Eu
3+transmission plot.
In Fig. 1, b is substrate material YVO
4: Eu
3+yVO for 10mg
4: Eu
3+@MIPs transmission plot.
In Fig. 1, c is substrate material YVO
4: Eu
3+yVO for 80mg
4: Eu
3+@MIPs transmission plot.
In Fig. 1, d is substrate material YVO
4: Eu
3+yVO for 50mg
4: Eu
3+@MIPs transmission plot.
In Fig. 1, a is known, YVO
4: Eu
3+for the nano particle formation of regular fusiform structure, diameter is 30-50nm, and length is 80-120nm.B in Fig. 1, c, the structure that the known synthetic polymkeric substance of d is core-shell type, as substrate material YVO
4: Eu
3+consumption while being 10mg, the coated very thick one layer of polymeric in the surface of nano particle, and major part is all pure polymkeric substance; As substrate material YVO
4: Eu
3+consumption while being 80mg, known major part has all formed the aggregated particles of core-shell type structure, but embedding is too dark, is unfavorable for absorption.Work as YVO
4: Eu
3+consumption while being 50mg, can obtain thinner core-shell type polymer beads.
In Fig. 2, a has represented YVO
4: Eu
3+xRD figure spectrum.
In Fig. 2, b has represented YVO
4: Eu
3+the XRD figure spectrum of@NIPs.
In Fig. 2, c has represented YVO
4: Eu
3+the XRD figure spectrum of@MIPs.
Three kinds of materials have the identical peak position that goes out, 2
θ=24.81
?, 2 θ=33.43
?with 2 θ=49.85
?peak correspond respectively to YVO
4crystal formation in (200), (112) and (312), just the intensity at peak is different, may be because YVO
4: Eu
3+nano grain surface has been coated the cause of one layer of polymeric layer.
Fig. 3 is YVO
4: Eu
3+(a), YVO
4: Eu
3+@NIPs(b), YVO
4: Eu
3+@MIPs(c) infared spectrum.YVO
4: Eu
3+@NIPs(b), YVO
4: Eu
3+1730,1253 and 1157cm of middle appearance@MIPs(c) occurring in collection of illustrative plates
-1correspond respectively to the stretching vibration peak of the C=O of methacrylic acid (MAA), unsymmetrically and the symmetrical stretching vibration peak of the middle C O of ethylene glycol bisthioglycolate (methacrylic acid) ester (EGDMA).1635cm
-1the peak occurring is corresponding to the C=C stretching vibration peak in MAA.Illustrate that imprinted polymer causes lower polymerization at 2,2'-azo two butyronitrile (AIBN) and forms.For pure YVO
4: Eu
3+at 826cm
-1and 454cm
-1occurred that V-O (comes from VO
4 3-) and the absorption peak of Y (Eu)-O.Peak 826cm
-1at YVO
4: Eu
3+@NIPs(b), YVO
4: Eu
3+@MIPs(c) in, all occur, YVO has been described
4: Eu
3+successfully be coated in polymkeric substance.
Fig. 4 is YVO
4: Eu
3+(a), YVO
4: Eu
3+@NIPs(b), YVO
4: Eu
3+@MIPs(c) thermogravimetric analysis collection of illustrative plates.The weightlessness of first stage is because moisture contained in material causes, YVO
4: Eu
3+@NIPs and YVO
4: Eu
3+the rate of weight loss of@MIPs is respectively 5.84% and 2.95%; Between 100 ℃ and 800 ℃, be mainly the weightlessness due to polymkeric substance, be respectively 86.88% and 87.15%, the difference slightly of the rate of weight loss of trace and non-trace may be to cause due to the polymerization degree in polymerization process and template molecule.There is YVO
4: Eu
3+weight-loss curve known, YVO
4: Eu
3+better heat stability, so remaining quality may be exactly YVO in trace and non-trace
4: Eu
3+residuals.
Fig. 5 is YVO
4: Eu
3+(a), YVO
4: Eu
3+@NIPs(b), YVO
4: Eu
3+exciting and launching collection of illustrative plates@MIPs(c).When excitation wavelength is during at 302nm, YVO
4: Eu
3+, YVO
4: Eu
3+@NIPs, YVO
4: Eu
3+the characteristic emission peak of@MIPs is all at 617nm, and just the intensity of emission peak changes to some extent, may be because YVO
4: Eu
3+surface coated polymer layer cause.
Fig. 6 is that the interior pH of different time is to YVO
4: Eu
3+and YVO
4: Eu
3+@MIPs optical property affect schematic diagram.For pure YVO
4: Eu
3+, pH is very large on the impact of its optical stability, and As time goes on, fluorescence intensity weakens gradually, and the optical property only keeing relative stability when (pH=7.0) under neutrallty condition; And for YVO
4: Eu
3+@MIPs, pH is on its almost not impact, and outer field polymkeric substance has stoped its impact of acid base pair.
Fig. 7 is that pH is to YVO
4: Eu
3+@MIPs quencher template molecule spreads the schematic diagram that affects of cyfloxylate.In scope at pH at 2.0-6.0, quencher rate reduces along with the increase of pH, and along with the increase of pH, quencher rate reduces gradually then, and when pH=6.0, quencher rate reaches maximum value.
Fig. 8 is definite schematic diagram of fluorescence imprinted material concentration used during for fluoroscopic examination solution lambda-cyhalothrin.The concentration affects of selected fluorescence imprinted material linearity range and the sensitivity detecting, and the two character of finally holding concurrently is usingd the concentration of 1.0mg/mL as fluoroscopic examination.
Fig. 9 is the selection schematic diagram of detection time.Within the initial time, As time goes on, fluorescence intensity reduces gradually, and in 55min left and right, fluorescence intensity remains unchanged.So be 55mim the detection time of selecting.
Figure 10 is YVO
4: Eu
3+the response curve of@MIPs to template molecule lambda-cyhalothrin.Along with the increase of concentration, fluorescence intensity weakens gradually, and meets certain linear relationship, according to Stern-Volmer equation (F
0/ F=1+K
sV[c]), take [c] as X-coordinate, relative intensity of fluorescence is ordinate zou, obtains two linear relationships.Linearity range is respectively 2.0-10.0 μ M and 10.0-90.0 μ M, and relation conefficient is respectively 0.986 and 0.993.The lowest detectable limit of this method can reach 1.76 μ M.This method that hence one can see that can detect for quantitative and qualitative analysis the ability of lambda-cyhalothrin in the aqueous solution.
Figure 11 is YVO
4: Eu
3+@MIPs and YVO
4: Eu
3+the selectivity of@NIPs detects research schematic diagram.The material that the logical lambda-cyhalothrin of selection has same structure is as detected object, research shows, the quenching of fluorescence amount of fluorescence imprinted polymer is all greater than the non-trace of fluorescence, and the quencher amount of template molecule is all greater than to other pyrethrin, illustrate that the recognition site in trace process has specific recognition capability to template molecule.
Figure 12 is YVO
4: Eu
3+the repeating utilization factor schematic diagram of@MIPs.The polymerization of the prepared fluorescence trace of the present invention has good repeating utilization factor, at least can reuse 6 times, and not affect its photoluminescent property.
Embodiment
Below in conjunction with specific embodiment and test example, the present invention will be further described.
Embodiment 1
Preparation (the YVO of the Yttrium Orthovanadate nanoparticle of europium doping
4: Eu
3+): a) first by 0.95mmol yttrium oxide (Y
2o
3) and 0.05mmol europium sesquioxide (Eu
2o
3) be dissolved in excessive rare nitric acid, heating evaporation is removed unnecessary nitric acid, makes the nitrate of yttrium and europium, and is scattered in the water of 40mL; B) then by 2.0mmol ammonium meta-vanadate (NH
4vO
3) join ultrasonic 10min in the water of 40mL, then with the NaOH solution of 2M, to regulate pH value be 13 to NH
4vO
3be dissolved to clear solution completely.Then the prepared solution of step a) is dropwise added to NH
4vO
3clear solution in, strong stirring 2h at 80 ℃, the white precipitate making is used respectively ethanol and water washing, and at 60 ℃, dries stand-by.Gained nanoparticle as shown in Figure 1a.
Preparation (the YVO of core-shell type molecular imprinting fluorescent polymer
4: Eu
3+@MIPs): take 10mgYVO
4: Eu
3+be scattered in the mixing solutions of first alcohol and water of 50mL (4/1, v/v), then add respectively 0.1mmol template molecule lambda-cyhalothrin (LC), 0.4mmol function monomer methacrylic acid (MAA) and 0.5mmol linking agent ethylene glycol dimethacrylate (EGDMA), ultrasonic being uniformly dispersed, logical nitrogen 30min gets rid of the air in three-necked flask, add 10mg initiator Diisopropyl azodicarboxylate (AIBN), be warming up to 50 ℃ of heating 6.0h, then at 60 ℃, continue reaction 18h again and complete to polymerization.Product water and washing with alcohol 3 times.Then use methyl alcohol and acetic acid mixed solution (95/5, v/v) for extracting solution soxhlet extraction is to removing template molecule LC, vacuum-drying at 50 ℃.Resulting polymers as shown in Figure 1 b.
Embodiment 2
Preparation (the YVO of core-shell type molecular imprinting fluorescent polymer
4: Eu
3+@MIPs): the YVO that takes the above-mentioned preparation of 80mg
4: Eu
3+be scattered in the mixing solutions of first alcohol and water of 50mL (4/1, v/v), then add respectively 0.1mmol template molecule lambda-cyhalothrin (LC), 0.4mmol function monomer methacrylic acid (MAA) and 2.0mmol linking agent ethylene glycol dimethacrylate (EGDMA), ultrasonic being uniformly dispersed, logical nitrogen 30min gets rid of the air in three-necked flask, add 10mg initiator Diisopropyl azodicarboxylate (AIBN), be warming up to 50 ℃ of heating 6.0h, then at 60 ℃, continue reaction 18h again and complete to polymerization.Product water and washing with alcohol 3 times.Then use methyl alcohol and acetic acid mixed solution (95/5, v/v) for extracting solution soxhlet extraction is to removing template molecule LC, vacuum-drying at 50 ℃.Resulting polymers is as shown in Fig. 1 c.
Embodiment 3
Preparation (the YVO of core-shell type molecular imprinting fluorescent polymer
4: Eu
3+@MIPs): the YVO that takes the above-mentioned preparation of 50mg
4: Eu
3+be scattered in the mixing solutions of first alcohol and water of 50mL (4/1, v/v), then add respectively 0.1mmol template molecule lambda-cyhalothrin (LC), 0.4mmol function monomer methacrylic acid (MAA) and 2.0mmol linking agent ethylene glycol dimethacrylate (EGDMA), ultrasonic being uniformly dispersed, logical nitrogen 30min gets rid of the air in three-necked flask, add 10mg initiator Diisopropyl azodicarboxylate (AIBN), be warming up to 50 ℃ of heating 6.0h, then at 60 ℃, continue reaction 18h again and complete to polymerization.Product water and washing with alcohol 3 times.Then use methyl alcohol and acetic acid mixed solution (95/5, v/v) for extracting solution soxhlet extraction is to removing template molecule LC, vacuum-drying at 50 ℃.Resulting polymers as shown in Figure 1 d.
Fig. 2-4 are respectively synthetic tie substance YVO
4: Eu
3+, YVO
4: Eu
3+@MIPs, YVO
4: Eu
3+the XRD of@NIPs, infrared and thermogravimetric analysis collection of illustrative plates.The fluorescence excitation that Fig. 6 is them and transmitting collection of illustrative plates.These have all illustrated and have successfully synthesized the fluorescence imprinted polymer with core-shell type structure.
Test example 1
The optimization of this method test condition.Determined respectively the pH of test, the determining of the concentration of fluorescence imprinted material and test duration.
1, first investigated pH to the impact of material fluorescence intensity (as shown in Figure 6).Then test the impact of different pH on quenching of fluorescence amount: configuration concentration is that the lambda-cyhalothrin of 50 μ M adds in colorimetric cylinder pipe, and regulates pH to be respectively 2.0,4.0,6.0,8.0,10,12, add appropriate prepared fluorescence imprinted material (YVO
4: Eu
3+@MIPs), mix after placing for some time and test the slight variation of fluorescence.Finally select pH=6.0 for test condition, as shown in Figure 7.
2, continue to investigate YVO
4: Eu
3+the concentration optimal selection of@MIPs.Configuration has the not YVO of homogeneity concentration
4: Eu
3+@MIPs, makes YVO
4: Eu
3+the concentration range of@MIPs in this system is 0.01mg/mL-3.0mg/mL, and test adds blank solution and adds after the solution of lambda-cyhalothrin of 50 μ M of concentration the fluorescence intensity of system and fluorescence intensity change.Final definite best YVO
4: Eu
3+@MIPs concentration is 1.0mg/mL, as shown in Figure 8.
3, determining of best test duration, the lambda-cyhalothrin that configuration contains 50 μ M the YVO that adds 0.1mg/mL
4: Eu
3+@MIPs, fluorescence intensity during test different time, as shown in Figure 9, the selection test duration is 55min.
4, the drafting of fluorescence response curve: get the lambda-cyhalothrin solution that 5.0mL starting point concentration is respectively 0,1,2,4,6,8,10,20,30,40,50,60,70,80,90,100 μ M and join in colorimetric cylinder, the pH value of regulation system is 6.0, adds respectively 0.1mg/mLYVO
4: Eu
3+@MIPs, after the 55min that vibrates under room temperature mixes, utilizing fluorimetric detector to select 302nm is excitation wavelength, under test different concns, the emission wavelength of solution is in the fluorescence intensity at 617nm place.According to Stern-Volmer equation (F
0/ F=1+K
sV[c]) to take concentration [c] be X-coordinate, relative intensity of fluorescence (F
0/ F) for ordinate zou is drawn fluorescence response curve.As shown in figure 10, the fluorescence intensity of solution weakens along with the increase of the concentration of lambda-cyhalothrin, illustrates that LC has certain quenching effect to the fluorescence of this system.From scheming, according to Stern-Volmer equation, obtained the linearity curve that two rules have fine relation conefficient, illustrated that this method also has the ability of residual lambda-cyhalothrin in detection by quantitative water.
Test example 2
Selectivity research: select cyfloxylate (BC), fenvalerate (FE), bifenthrin (BI) etc. and lambda-cyhalothrin (LC) analog as a comparison.The concentration that is configured to respectively 4 kinds of chrysanthemum esters is all the solution of 50 μ M, gets the solution that 5.0mL configures and joins in colorimetric cylinder, and regulating pH value is 6.0, adds respectively 0.1mg/mLYVO
4: Eu
3+@MIPs(correspondence adds 0.1mg/mLYVO
4: Eu
3+@MIPs is as a comparison), after the 55min that vibrates under room temperature mixes, fluorescence intensity changes.As shown in figure 11, prepared YVO
4: Eu
3+@MIPs is all greater than YVO to the quencher amount of 4 kinds of different chrysanthemum esters
4: Eu
3+@MIPs, and template molecule LC is had to selection binding ability specially.
Test example 3
Recycling experimental study: the lambda-cyhalothrin solution of configuration 50 μ M joins in colorimetric cylinder, and the pH value of regulation system is 6.0, adds 0.1mg/mLYVO
4: Eu
3+@MIPs, after the 55min that vibrates under room temperature mixes, test fluorescence intensity change.Take up the ball solid particulate YVO
4: Eu
3+@MIPs, centrifugation, dries.Then use methyl alcohol and acetic acid mixed solution (95/5, v/v) for extracting solution soxhlet extraction is to removing template molecule LC, vacuum-drying at 50 ℃.Then repeat above-mentioned steps, as shown in figure 12, at least can reuse 6 times, and not affect YVO
4: Eu
3+the ability of the photoluminescent property of@MIPs and detection LC thereof.
Claims (6)
1. the preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer, is characterized in that the method comprises following processing step:
1) preparation of the Yttrium Orthovanadate nanoparticle of europium doping;
2) preparation of core-shell type molecular imprinting fluorescent polymer;
3) the corresponding non-imprinted polymer YVO as reference
4: Eu
3+the preparation of@NIPs.
2. the preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer according to claim 1, is characterized in that the Yttrium Orthovanadate nanoparticle YVO that described step 1) europium adulterates
4: Eu
3+preparation: comprise processing step,
A) by europium sesquioxide (Eu
2o
3) and yttrium oxide (Y
2o
3) ratio that is 5.0% according to mol ratio is dissolved in heating in excessive rare nitric acid that it is dissolved completely, and evaporation removes unnecessary nitric acid, makes the nitrate of yttrium and europium, is added to the water the nitrate solution that makes 0.025mol/L;
B) then by ammonium meta-vanadate (NH
4vO
3) with Y
2o
3and Eu
2o
32 times of ultrasonic 10-30min that are added to the water of integral molar quantity, then with the NaOH solution of 2M, to regulate pH value be 13 to making it to be dissolved into completely clear solution, is configured to the solution of 0.05mol/L;
C) the prepared solution of step a) is dropwise added to NH
4vO
3clear solution in, strong stirring 2.0-10.0h at 80-100 ℃, the white precipitate making is used respectively ethanol and water washing, and at 60 ℃, dries stand-by.
3. the preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer according to claim 1, is characterized in that described step 2) core-shell type molecular imprinting fluorescent polymer YVO
4: Eu
3+the preparation of@MIPs: comprise processing step,
A) take 10-80mg YVO
4: Eu
3+be scattered in the mixing solutions of first alcohol and water of 50mL, the volume ratio of first alcohol and water is 4/1;
B) according to mol ratio 0.1mmol:0.4mmol:(0.5-2.0mmol) ratio add respectively template molecule lambda-cyhalothrin (LC), function monomer methacrylic acid (MAA) and linking agent ethylene glycol dimethacrylate (EGDMA), ultrasonic being uniformly dispersed, logical nitrogen 15-30min gets rid of the air in three-necked flask, add initiator Diisopropyl azodicarboxylate (AIBN), be warming up to 50 ℃ of heating 6h;
C) then at 60 ℃, continuing reaction 18h again completes to polymerization;
D) product water and washing with alcohol are 3 times, the methyl alcohol that is then 95:5 by volume ratio and the mixed solution of acetic acid be extracting solution soxhlet extraction to removing template molecule LC, vacuum-drying at 50 ℃.
4. the preparation method of rear-earth-doped core-shell type fluorescence imprinted polymer according to claim 1, is characterized in that described step 3) correspondence is as the non-imprinted polymer YVO of reference
4: Eu
3+the preparation of@NIPs, its processing step is as step 2), step 3), but do not add template molecule LC.
5. the preparation method of silicon base lanthanon adulterated fluorescent type matrix material according to claim 2, is characterized in that described Y
2o
3: Eu
2o
3mol ratio be 0.95mmol:0.05mmol, NH
4vO
3molar weight be Y
2o
3and Eu
2o
32 times of total amount, the concentration of NaOH is 2M.
6. the preparation method of a kind of silicon base lanthanon adulterated type fluorescence composite material according to claim 3, is characterized in that described YVO
4: Eu
3+: the quality of LC:MAA:EGDMA and mol ratio are (10-80mg): 0.1mmol:0.4mmol:(0.5-2.0mmol), in system, solution used is the mixing solutions of 50mL first alcohol and water, and volume ratio is 4/1, and the consumption of initiator A IBN is 10mg.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136758A (en) * | 2015-08-28 | 2015-12-09 | 合肥学院 | A preparation method of Eu3+ labeled molecularly imprinted sensor for the detection of pesticide residues |
| WO2019243617A1 (en) * | 2018-06-22 | 2019-12-26 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und - Prüfung (Bam) | Fluorescent particles with molecularly imprinted fluorescent polymer shells for cell staining applications in cytometry and microscopy |
| CN113933274A (en) * | 2021-10-12 | 2022-01-14 | 青岛农业大学 | Ratiometric fluorescent molecularly imprinted chitosan gel ball based on europium-doped carbon dots, and preparation method and application thereof |
| CN114062336A (en) * | 2021-11-23 | 2022-02-18 | 陕西师范大学 | A method for detection of pesticide herbicide based on nitrogen-doped carbon quantum dots fluorescence "on-off-on" mode |
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| CN103739846A (en) * | 2013-12-27 | 2014-04-23 | 江苏大学 | Preparation method for quantum dot fluorescent imprinted polymer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105136758A (en) * | 2015-08-28 | 2015-12-09 | 合肥学院 | A preparation method of Eu3+ labeled molecularly imprinted sensor for the detection of pesticide residues |
| WO2019243617A1 (en) * | 2018-06-22 | 2019-12-26 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und - Prüfung (Bam) | Fluorescent particles with molecularly imprinted fluorescent polymer shells for cell staining applications in cytometry and microscopy |
| US12173211B2 (en) | 2018-06-22 | 2024-12-24 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie | Fluorescent particles with molecularly imprinted fluorescent polymer shells for cell staining applications in cytometry and microscopy |
| CN113933274A (en) * | 2021-10-12 | 2022-01-14 | 青岛农业大学 | Ratiometric fluorescent molecularly imprinted chitosan gel ball based on europium-doped carbon dots, and preparation method and application thereof |
| CN113933274B (en) * | 2021-10-12 | 2022-07-01 | 青岛农业大学 | Ratiometric fluorescent molecularly imprinted chitosan gel ball based on europium-doped carbon dots, and preparation method and application thereof |
| CN114062336A (en) * | 2021-11-23 | 2022-02-18 | 陕西师范大学 | A method for detection of pesticide herbicide based on nitrogen-doped carbon quantum dots fluorescence "on-off-on" mode |
| CN114062336B (en) * | 2021-11-23 | 2023-06-30 | 陕西师范大学 | Method for detecting pesticide weed control intensity based on nitrogen-doped carbon quantum dot fluorescence on-off-on mode |
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