CN105255484A - Preparation method of SrAlB2O7:Eu<3+> fluorescent probe for detection of OPs (organophosphorus pesticides) - Google Patents

Preparation method of SrAlB2O7:Eu<3+> fluorescent probe for detection of OPs (organophosphorus pesticides) Download PDF

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CN105255484A
CN105255484A CN201510667655.9A CN201510667655A CN105255484A CN 105255484 A CN105255484 A CN 105255484A CN 201510667655 A CN201510667655 A CN 201510667655A CN 105255484 A CN105255484 A CN 105255484A
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fluorescent probe
sral
detection
organophosphorus pesticide
preparation
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CN105255484B (en
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高大明
郑传阳
江晓敏
陈蓓丽
陈红
张慧
朱德春
侯婷婷
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Hefei University
Hefei College
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Abstract

The invention provides a preparation method of a SrAlB2O7:Eu<3+> fluorescent probe for detection of OPs (organophosphorus pesticides). The preparation method comprises two steps as follow: firstly, Eu<3+> and target analyte, OP molecules, interact to form organic ligand, then strontium nitrate, aluminum nitrate, boric acid and a pore-forming agent are added to a beaker accommodating deionized water, the mixture is stirred, and sol is formed; calcination is performed after gel is obtained, and Eu<3+> marked OP molecular printing SrAl2B2O7:Eu<3+> fluorescent probe is obtained. OP molecule selectivity recognition sites are available after template molecules are removed, the OP molecules further interact with Eu<3+> on the recognition sites after entering the recognition sites of the fluorescent probe, the OP molecules and the recognition sites form organic ligand, the organic ligand absorbs energy and transfers the energy to Eu<3+>, the fluorescence intensity of the fluorescent probe is changed, and selective recognition and detection of pesticide molecules are realized.

Description

A kind of SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe
Technical field
The present invention relates to material science, particularly to the SrAl of detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe.
Background technology
In recent years, paying close attention to widely and interest having caused society research mechanism in the detection of agricultural chemicals and the research of relevant fluorescent probe, and achieving some fruitful achievements.The test in laboratory of specific pesticide is widely used by the method for spectral method, chromatography and inhibiting AChE etc.These traditional analytical technologies can meet the basic demand in analysis, as selectivity, reliability, accuracy and repeatability, but these detection methods are expensive, consuming time with loaded down with trivial details heaviness, because sample must be depart from Test Field to be sent to laboratory for analysis in detecting, the detection of real-time on-site can not be accomplished.In sum, be necessary to seek a kind of method that can detect organophosphorus pesticide fast and easily.Therefore, in order to solve the problem of Pesticides Testing, need fluorescent probe can provide a kind of highly selective, highly sensitive, quick response, low cost and in situ detection for target analytes organophosphorus pesticide molecule urgently.
At present, China's sterilant accounts for agricultural chemicals ultimate production and accounts for about 75%, and wherein organophosphorus insecticides (Organophosphoruspesticides is called for short OPs) output accounts for 70%.Along with the forbidding of riskiest pesticide, the contour drugs kind of the former widely used acephatemet low toxicity kind in tick, chlorpyrifos_methyl etc. that dies like a rat gradually replaces.Chlorpyrifos 94 has another name called Le Siben or chlorine pyrrole phosphorus, have tag, stomach toxicity and fumigation action, can prevent and treat ground and the subterranean pest-insect of various crop preferably, be one of desirable kind replacing high-toxic organic phosphorus sterilant.If but Chlorpyrifos 94 residual quantity in plant materials is too much, also harm can be produced to human body.The toxicity of Chlorpyrifos 94 depends on exposure dose and target susceptibility.When the concentration of its meta-bolites can acetylcholine esterase inhibition, stop the degraded of vagusstoff, neurotransmitter is accumulated at nerve synapse, lasting receptor for stimulating can be caused and change relevant signal path to tissue biological horizontal functional changing.Acute toxicity involves respiratory system, cardiovascular and gi tract more, and blood, liver, kidney, skin irritation and immune system response are less or be not observed.And high dosage OPs initiation chronic poisoning is mainly the cognitive function obstructions such as psychoneural change, dysautonomia and memory, language, visual attention.Along with the complete prohibition of the malicious persistent pesticide of height in agriculture production, efficiently poisoning broad spectrum pesticide Chlorpyrifos 94 is widely used.
Chlorpyrifos 94 can be transferred to human body by the inrichment of food chain, has potential carcinogenesis to human body, is the important indicator that environment and Pesticide Residues detect always.Research finds, because chlopyrifos pesticides use range is wide, consumption radix is large, although its residual exceeding standard rate is not high, is in fact one of agricultural chemicals that in the detection of agricultural products such as current vegetables, recall rate is the highest.Adopt liquid-liquid extraction-vapor-phase chromatography to the detection of poisoning freshwater mussel with poison in existing country and industry standard, complex steps, organic reagent consumption cause environmental pollution greatly, easily more.In addition, food and environmental matrices complicated components, trace is designated as point easily masked, also for testing adds huge obstacle.
With covalent linkage or non-covalent interaction by template molecule (target molecule) and function monomer at novel detection technique Middle molecule imprinting techniques, template molecule is fixed in crosslinked polymer network, the removing of template molecule, leave the hole matched with the shape of template molecule and function, thus in synthetic materials, create molecular recognition site (artificial antibody) (Wulff, the G. with high-affinity and highly selective chem.Rev., 2002, 102, 1.; Wulff, G. angew.Chem.Int.Ed. 1995, 34, 1812.; Haupt, K.; Mosbach, K.. chem.Rev. 2000, 100, 2495.; Zimmerman, S.C.; Lemcoff, N.G. chem.Commun. 2004, 5.).First molecularly imprinted polymer (Molecularlyimprintedpolymers has successfully been prepared as far back as Wulff research group in 1972, MIPs) its research mainly concentrates on pre-assembled Macroscopic single crystal, its principle makes template molecule and function monomer form after mixture crosslinking polymerization (WulffG, SarhanA.Useofpolymerswithenzyme-analogousstructuresforth eresolutionofracemates. again by reversible covalent bonds angew.Chem.Int.Ed. 1972, 11, 34l.).Pre-assembled Macroscopic single crystal advantage is that specificity is good and selectivity is strong.But there is the weakness that it is fatal, preparation process is complicated, severe reaction conditions, larger restriction is had to template molecule, function monomer and template molecule range of choice is little, response speed is slow and template molecule is difficult to remove completely, and prepared polymkeric substance in preparation and recognition process to shortcomings such as the low-responses of template molecule, therefore develop slower.After 1980, self-assembling polymers starts synthesis, particularly at Mosbach in 1993 about the report that Non-covalent molecular imprinted polymer synthesizes makes molecular imprinting more be filled with vigor (NorrlowO, GladM, MosbachK.Acrylicpolymerpreparationcontainingrecognitions itesonobtainedbyimprintingwithsubstrates. chromatography, 1984, 299, 29.).In this method, template molecule is combined with function monomer by multiple non covalent bond effect (comprising hydrogen bond, metallic bond, electrostatic force, hydrophobic force and Van der Waals force etc.), preparation is simple, applied widely, prepared polymkeric substance has the recognition performance that can compare favourably with natural antibody, and molecular imprinting just becomes study hotspot both domestic and external.
Molecule marking material really will be applied to separation, the fast enrichment of trace pesticide residue compositional selecting in actual sample, and export with the optical signalling of sensitivity, molecule marking material should possess and have high-affinity to target molecule, fast binding kinetics, can the requirement such as Post functionalization and consistent material shape.But, the imprinted polymer obtained by traditional method at present faces the difficult point that many needs overcome in molecular recognition practical application, sum up and can be divided into the following aspects: (1) due to the cross-linking density of molecularly imprinted polymer high, be in cross-linked network inside template molecule cannot remove completely(Markowitz, M.A.; Kust, P.R.; Deng, G.; Schoen, P.E.; Gaber, B.P. langmuir 2000, 16.1759.; Rao, M.S.; Dave, B.C. j.Am.Chem.Soc. 1998, 120, 13270.); (2) quantity due to effective site is little, right the avidity of target molecule is little; (3) target molecule is difficult to the marking point diffusing into network internal, so to target molecule binding kinetics is slow; (4) molecularly imprinted polymer normally the material of irregular shape, with the poor compatibility of senser element.Therefore, the molecularly imprinted polymer that traditional method is synthesized usually shows the site accessibility of highly selective, low binding capacity and difference and slow binding kinetics feature, Given this synthesis highly selective, binding capacity is high, site easily close to and binding kinetics fireballing and there is the molecularly imprinted polymer material of regular morphologytarget (Hayden, the O. that people pursue always; Mann, K.J.; Krassnig, S.; Dickert, F.L. angew.Chem.Int.Ed. 2006, 45, 2626; Schmidt, R.H.; Mosbach, K.; Haupt, K. adv.Mater. 2004, 16, 719.).
The text of an annotated book of Jilin University its master's Diplomarbeit " molecular imprinting organophosphorus pesticide poison with poison honeybee detect in applied research " in be template molecule with Chlorpyrifos 94, take methacrylic acid as function monomer, take ethylene glycol dimethacrylate as linking agent, take Diisopropyl azodicarboxylate as initiator, adopt mass polymerization and precipitation polymerization method to prepare Chlorpyrifos 94 molecular imprinting microballoon respectively, achieve molecular imprinting solid phase extraction techniques and the application of sensor technology in chlopyrifos pesticides detects.This traditional molecular imprinting is only solve the selective problems to target analytes Chlorpyrifos 94 molecule, and does not solve target analytes Chlorpyrifos 94 molecule and enter signal responsive after recognition site and export problem.
At sensitive signal output facet, fluorescence molecule is the ideal material of the highly sensitive response to target analytes.In various signal pick-off, optically addressable sensor based on fluorescence "Off" or fluorescence "ON" mechanism be proved to be investigator in the environment of many challenges expect method that various small molecules target analytes is detected, because the high signal of this detection method exports and reliable detected result.It is extremely beneficial that the chemical sensor of fluorescence "ON" mechanism detects with fluorescent method organophosphorus pesticide Chlorpyrifos 94.Energy level transition can occur by excited state rare earth ion after rayed, result in photoluminescence, this Fluorescence Increasing depends on the size of part Conversion of energy.The people such as the Liang Xingjie of State Nanometer Science Center disclose patent of invention " a kind of fluorescent molecular probe and its preparation method and application (CN201410231022.9) ", fluorescent molecular probe in this patent of invention, there is hydrophilic polypeptides and can improve fluorescent molecular probe solvability in aqueous and stability, hydrophobic alkyl chain can embed cytolemma, limited luminophore is emitting fluorescence under confined condition only, can be used for the fluorescent molecular probe of cytolemma mark.What this technology solved is the responsive output problem of fluorescent signal, does not solve target analytes Selective recognition problem, and therefore, synthesis highly selective, it is that scientific worker constantly pursues a goal that high sensitive signal exports fluorescent probe.
In the luminescent material of practicality, the application of rare earth ion doped phosphor is the most widely.Phosphor generally includes the various metal oxides of rare earth ion and doped transition metal ions, metallic sulfide, composite oxides and inorganic salt etc.Rare earth luminescent material replaces that non-rare earth luminescent material is widely used in display, illumination, information storage amplify and the every field such as medical diagnosis just gradually in recent years, plays a part not replace in national economy and people's daily life.The research of rare earth luminescent material also becomes emphasis and the forward position of luminescent material research.Its advantage is that turnover ratio is high, and emission wavelength is from ultraviolet, as seen until the light of infrared various wavelength, and physicochemical property are stablized.The absorption of rare earth ion to light simultaneously occurs in the transition between the different energy levels of internal layer 4f electronics, and produce absorption spectrum spectral line very narrow, what therefore present is bright-colored pure.With the fluorescent particles with specific physical and chemical property of rare earth ion doped preparation, at photonic crystal, catalyzer, diagnostics and application potential pharmacologically and cause the broad interest of investigator.The synthesis fluorescent particles such as the rare earth ion doped metal oxide such as terbium, europium, dysprosium, metallic sulfide, composite oxides and inorganic salt are used at present.Because they can provide comparatively bright luminescent properties, higher sharpness, lower scattering of light, the physical property of fluorescent particles can be changed by the doping changing rare earth ion.
In recent years, the research of Chinese scholars to rare earth ion is more and more interested, especially Europium Metal, and Zhejiang University state key Chemical Engineering Laboratory Xu deposits into seminar and synthesized containing Eu 3+the thenoyltrifluoroacetone 5-acrylamido-1,10-phenanthroline inner complex of ion, sample sends strong ruddiness under normal temperature, UV-light, mainly Eu 3+ion 5d0 → 7the transition of F2, and by analyzing the UV spectrum of this inner complex, luminescent lifetime, quantum yield draw rare earth elements europium be suitable as desirable intracellular signaling material ( spectrochimicaActaPartA, 2011, 82, 159.).As far back as 1999, the people such as AmandaL.Jenkins to detect the organophosphorus pesticide molecule of non-hydrolytic in water for target, were just corsslinking molecular with vinyl benzoate, take vinyl benzoate as function monomer, under the environment of pH=9 ~ 10, and synthesis imprinted polymer.Eu 3+ion is introduced into polymkeric substance as intracellular signaling element.Experimental result shows Eu 3+adding of ion not only can make optical signalling more easily conduct, and makes the combination in agricultural chemicals and marking hole more stable, thus more can play the advantage of molecular imprinting selectivity, enriching and susceptibility.The Wang Xingzhe of Dalian University of Technology is a kind of novel naphthyl substituted ter cycloheptapyridine poly carboxylic acid europium ligand of design and synthesis in " Synthesis and application of novel europium coordination compound fluorescent probe ": 4 '-(1-naphthyl)-2,2 ', 6 ', 2 "-ter cycloheptapyridine-6,6 "-dimethylamine tetraacethyl and Eu 3+title complex (NTTA-Eu 3+).NTTA-Eu 3+have good water-soluble, fluorescence measurement shows that this title complex not only has higher molar absorptivity and fluorescence quantum yield (0.152), larger Stokes displacement (more than 280nm), the fluorescence lifetime (1.30ms) of overlength and very high temporal resolution detection sensitivity (2.60 × 10 -11molL -1) etc. advantage, and the pH scope of application is also wider, is suitable as very much a kind of fluorescent probe for time resolved fluorescence biochemical analysis field.Yao Fei " the rear-earth-doped TiO of Northwest University 2the preparation of nano material and to the detection of Chlorpyrifos 94 and degraded " in, by the detection of nanotechnology and agricultural chemicals and process being combined, with the rare earth ion doped titanium dioxide nano material of Liquid preparation methods, have studied rare earth Eu 3+titania-doped colloid is as the detection of fluorescent probe to agricultural chemicals chlopyrifos residue amount, and result shows that Chlorpyrifos 94 is to Eu 3+doped Ti O 2the fluorescence of nanometer colloid has cancellation effect, and meets Stern-Volmer cancellation equation, according to Chlorpyrifos 94 concentration and Eu 3+titania-doped fluorescence intensity is directly proportional, establish a kind of novel method of rapid detection agricultural chemicals, but this method also has shortcoming, the exact level of pesticide residue cannot be measured exactly, simultaneously, the factor of fluorescent quenching impact is too many, so detected not as Fluorescence Increasing detects target analytes by fluorescent quenching, to drain immunity strong.This article sol-gel processing prepares pure titinium dioxide simultaneously, metal Fe, metal Tb be mono-mixes titanium dioxide and metal Fe, metal Tb mix nano TiO 2 powder altogether, learn when the doping mol ratio of metal Fe and metal Tb is 1:1 by characterizing, absorbancy is maximum, fluorescence intensity is minimum, shows that now catalytic activity is maximum, by contrasting the photocatalysis of Chlorpyrifos 94, it is more effective than pure titinium dioxide that titanium dioxide mixed by known metal list, and the effect that metal Fe, metal Tb mix altogether is best.Based on this, this problem passes through the rare earth ion doped titanium dioxide nano material of Liquid preparation methods, is applied to the detection of agricultural chemicals and the degraded to agricultural chemicals respectively.
In the present invention, we report and have invented a kind of SrAl for detection of organic phosphorus pesticide based on rare earth chelating principle of luminosity 2b 2o 7: Eu 3+the preparation method of fluorescent probe, realizes the Selective recognition to trace organophosphorus pesticide molecule and detection.SrAl 2b 2o 7: Eu 3+especially be suitable as fluorescent probe, because Eu 3+compare Eu 2+have better stability, many experiments finds synthesis SrAl 2b 2o 7: Eu 2+though good blueness can be presented, Eu 3+need to be reduced into Eu 2+, need higher energy, and Eu after synthesis 2+easily be oxidized to Eu 3+, and SrAl 2b 2o 7: Eu 3+energy needed for synthesis is low, and it is enough stable, in 600nm ~ 620nm wavelength region, show a very strong visible absorbance peak, this discovery excites us to explore based on rare earth chelating principle of luminosity chemical sensor to organophosphorus pesticide target molecule highly selective, high-sensitive detection.When the fluorescent material that selection one is suitable, the energy of the organic ligand be excited after forming title complex with organic ligand can be transferred to when metal ion returns ground state releases energy, and fluorescence intensity strengthens.Therefore, SrAl 2b 2o 7: Eu 3+photoluminescence will effectively be strengthened.This SrAl 2b 2o 7: Eu 3+nanomolar concentration level organophosphorus pesticide molecule can be detected in the liquid phase by rare earth chelating principle of luminosity.This recognition site is entered, with Eu to organophosphorus molecular selectivity 3+form organic ligand, energy is from organophosphorus pesticide molecular transfer to Eu 3+, make SrAl 2b 2o 7: Eu 3+fluorescent probe fluorescence intensity strengthens, with SrAl 2b 2o 7: Eu 3+fluorescence is show the detection to organophosphorus pesticide molecule highly selective, highly sensitive and trace as the Selective recognition site in probe, matrix.
Summary of the invention
For the weak point that currently available technology exists, the present invention utilizes SrAl first 2b 2o 7for matrix, with rare earth ion Eu 3+for dopant ion, synthesize a kind of SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe, and first by SrAl 2b 2o 7: Eu 3+for to the identification of trace organophosphorus pesticide molecule (Chlorpyrifos 94 molecule and Malathion molecule) and detection.First described method is Eu 3+form organic ligand with the interaction of molecules of target analytes organophosphorus pesticide, and then strontium nitrate, aluminum nitrate, boric acid and pore-creating agent are placed in and fill deionized water beaker, after gel, calcining obtains Eu 3+the organophosphorus pesticide molecular imprinting SrAl of mark 2b 2o 7: Eu 3+fluorescent probe, eliminates the SrAl after template molecule 2b 2o 7: Eu 3+fluorescent probe, it has the recognition site to organophosphorus pesticide molecular selectivity, after organophosphorus pesticide molecule enters the recognition site of fluorescent probe, by further with the Eu on recognition site 3+interact, make itself and Eu 3+coordination forms organic ligand, after organic ligand absorbs energy, by energy trasfer to Eu 3+, utilize the fluorescence intensity of fluorescent probe to change, realize detecting the identification of pesticide molecule highly selective and high sensitivity.
Technical scheme of the present invention is: a kind of SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe, comprises Eu 3+form organic ligand with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, after colloidal sol, gel, calcining obtains Eu 3+the organophosphorus pesticide molecular imprinting SrAl of mark 2b 2o 7: Eu 3+fluorescent probe, is characterized in that: described SrAl 2b 2o 7: Eu 3+in fluorescent probe after wash-out template molecule, it has the recognition site to target analytes organophosphorus pesticide molecular selectivity, target analytes organophosphorus pesticide molecule enters SrAl 2b 2o 7: Eu 3+after the recognition site of fluorescent probe, by further with the Eu on recognition site 3+interact, make target analytes organophosphorus pesticide molecule and Eu 3+coordination forms organic ligand, after this organic ligand absorbs energy, by energy trasfer to Eu 3+, utilize SrAl 2b 2o 7: Eu 3+the fluorescence intensity of fluorescent probe changes, and achieve the molecular selectivity identification of agricultural chemicals target analytes organophosphorus pesticide and detection, preparation process of the present invention comprises following two steps:
1.1 the first steps are Eu 3+organic ligand is formed: first, with ten thousand/electronic balance weighing 0.3509g ~ 0.3529gEu with agricultural chemicals target analytes organophosphorus pesticide molecule 2o 3be placed in 100mL beaker, then pipette with scale adjustable 1mL microsyringe and add 1mL ~ 3mL nitric acid in above-mentioned beaker, after ultrasonic disperse reaction 5min ~ 10min, form transparent solution, and then take 0.700g ~ 1.500g organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add the dilution of 20mL deionized water, after ultrasonic disperse 5min ~ 10min, leave standstill 20min ~ 30min, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand;
1.2 second steps are the SrAl for organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe: weigh 1.6920g ~ 1.6940g strontium nitrate respectively, 7.5016g ~ 7.5036g aluminum nitrate, 1.2355g ~ 1.2375g boric acid and 3.25g ~ 3.45g pore-creating agent four kinds of reactants are placed in 250mL beaker, add 80mL ~ 100mL deionized water again, ultrasonic 5min ~ 10min makes above-mentioned four kinds of reactants dissolve completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in 80 DEG C ~ 100 DEG C water baths, under 700rpm ~ 800rpm, be stirred to solution become viscous gum, gained colloid is dried 12h at 150 DEG C, xerogel after oven dry is warming up to 800 DEG C ~ 950 DEG C at temperature programmed control stove, and continue calcining 2h ~ 4h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe.
As a further improvement of existing technologies, said fluorescent probe is SrAl 2b 2o 7: Eu 3+.Said organophosphorus pesticide is Chlorpyrifos 94 and Malathion.Said SrAl 2b 2o 7: Eu 3+innerly in fluorescent probe form the void structure with recognition site and organophosphorus pesticide molecular structure, size and the complementation of function base.Said SrAl 2b 2o 7: Eu 3+eu in recognition site in fluorescent probe 3+organophosphorus pesticide interaction of molecules in recognition site can form organism part and there occurs from organism to Eu 3+energy trasfer.Said SrAl 2b 2o 7: Eu 3+fluorescent probe is strengthen principle based on rare earth chelating fluorescent to trace organophosphorus pesticide molecular detection.Said SrAl 2b 2o 7: Eu 3+in fluorescent probe synthesis, pore-creating agent used is cetyl trimethylammonium bromide (CetyltrimethylAmmoniumBromide, CTAB).Said SrAl 2b 2o 7: Eu 3+fluorescent probe synthesis Program temperature control furnace heat-up rate is 1 DEG C/min.
beneficial effect relative to prior art:
In recent years, be that fluorescently-labeled molecular imprinting has attracted the interest of large quantities of investigator with metal ion in rare earth luminescent material.2007, the patent of invention that SouthardGlenE. discloses " Processablemolecularlyimprintedpolymers(US20070197746) ", this patent of invention provided a kind of method for the preparation of molecularly imprinted polymer, is exactly mainly utilize Eu 3+ion prepares imprinted polymer as part center, thus improves the accuracy detecting target analytes.The Lu Qing of Nanjing Medical University is in its master's Diplomarbeit " preparation of molecularly imprinted polymer on nano-silica gel surfaces and the application in chlorpyrifos pesticide residue detects thereof ", first finishing is carried out to nanometer silica gel bead, and under the effect of ethylene glycol dimethacrylate linking agent, by methacrylic acid-Chlorpyrifos 94 mixture graft polymerization to Silica Surface, synthesize the molecularly imprinted polymer on nano-silica gel surfaces important organophosphorus insecticide-Chlorpyrifos 94 to highly selective and high separating efficiency.In experimentation, by changing the condition of silica gel chemically modified, effectively controlling the double bond space of silica gel bead surface, then adding the thickness of imprint layer and the density in effective marking site.Adsorption experiment proves that this imprint surface polymkeric substance shows high Selective recognition and high avidity to template molecule Chlorpyrifos 94.When imprint surface material is used for single dispersing Solid-Phase Extraction, the average recovery of food samples can reach 76.1 ~ 93.5%.Above-mentioned adsorption experiment and dispersive solid-phase extraction result are use that the molecular imprinting of nano silica gel surface solves the high-affinity of pesticide residue compositions, highly selective separation problem provides a potential possibility.And it is relatively less about the report of the rare-earth fluorescent probe of aluminium borate doping.Rare-earth activated aluminium borate luminescent material is that a kind of synthesis temperature is low, the new and effective luminescent material of Heat stability is good.Owing to there is a large amount of boron oxygen and alumina group in aluminium borate luminescent material crystalline network, Qi VUV district is had and absorbs very by force, and this material has the ability of good vacuum-resistant ultraviolet radiation and anti-ion bombardment, meets the performance requriements of PDP fluorescent material.Jilin University appoints Zhou Yun in " synthesis of rear-earth-doped fluorescent powder of aluminium borate and the research of luminescent properties ", explores synthesizing efficient aluminium borate luminescent material SrAl 2b 2o 7, YAl 3(BO 3) 4top condition, have studied rare earth ion character, concentration, and the factor such as the temperature of synthesis, time, atmosphere and matrix composition is on the impact of luminescent properties, has synthesized doping with rare-earth ions Eu 3+, Tb 3+and Li +, Ba 2+, Ca 2+, Gd 3+srAl 2b 2o 7system and doping with rare-earth ions Eu 3+, Tb 3+yAl 3(BO 3) 4system.Prove by experiment: at SrAl 2b 2o 7in system, work as Eu 3+, Tb 3+doping content when being respectively 4% and 11%, red and green luminous intensity is the strongest, appropriate Ba 2+, Ca 2+, Li +, Gd 3+mix and can improve luminous intensity.At YAl 3(BO 3) 4in system, work as Eu 3+, Tb 3+the luminous intensity red and green when being respectively 3% and 11% of doping content the strongest.
The preparation method of the fluorescent probe in the present invention is as follows: first, Eu 3+organic ligand is formed with agricultural chemicals target analytes organophosphorus pesticide molecule.With ten thousand/electronic balance weighing 0.3509g ~ 0.3529gEu 2o 3be placed in 100mL beaker, then pipette with scale adjustable 1mL microsyringe and add 1mL ~ 3mL nitric acid in above-mentioned beaker, after ultrasonic disperse reaction 5min ~ 10min, form transparent solution, and then take 0.700g ~ 1.500g organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add the dilution of 20mL deionized water, after ultrasonic disperse 5min ~ 10min, leave standstill 20min ~ 30min, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand;
Then, be SrAl for organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe.Weigh 1.6920g ~ 1.6940g strontium nitrate respectively, 7.5016g ~ 7.5036g aluminum nitrate, 1.2355g ~ 1.2375g boric acid and 3.25g ~ 3.45g pore-creating agent four kinds of reactants are placed in 250mL beaker, add 80mL ~ 100mL deionized water again, ultrasonic 5min ~ 10min makes above-mentioned four kinds of reactants dissolve completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in 80 DEG C ~ 100 DEG C water baths, under 700rpm ~ 800rpm, be stirred to solution become viscous gum, gained colloid is dried 12h at 150 DEG C, xerogel after oven dry is warming up to 800 DEG C ~ 950 DEG C at temperature programmed control stove, and continue calcining 2h ~ 4h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe.
In sum, a kind of SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe has the following advantages:
One: prepared SrAl 2b 2o 7: Eu 3+fluorescent probe has identification and the output of high sensitive signal of highly selective to organophosphorus pesticide molecule.
It is two: prepared SrAl years old 2b 2o 7: Eu 3+fluorescent probe has Selective recognition site to organophosphorus pesticide molecule, after organophosphorus pesticide molecule enters recognition site, with the Eu being marked at recognition site place 3+define organic ligand, form binary complex, the energy of the organic ligand be excited may be transferred to metal ion Eu 3+and produce metal ion excited state Eu 3+* (namely Eu is produced 3+→ Eu 3+* transition), then by excited state metal ion Eu 3+* ground state ion Eu is returned 3+and produce Eu 3+* → Eu 3+luminous.Therefore, organophosphorus pesticide molecule enters recognition site and and Eu 3+after forming part, the fluorescence intensity of fluorescent probe strengthens, and realizes the detection to organophosphorus pesticide molecule.Visible, method provided by the present invention is general, and usage range is more extensive.
Its three: with SrAl 2b 2o 7fluorescent probe for matrix has very high stability.Aluminates system synthesis temperature higher (>1300 DEG C), energy consumption is comparatively large, and cost is high, and by Eu 3+the Eu that reduction is obtained 2+easily by the O in air 2oxidation, decreases its work-ing life equally.But the Heat stability is good of aluminate, the ability of vacuum-resistant ultraviolet light irradiation and anti-particle bombardment is better.
Another kind of is that luminescent material synthesis temperature low (<900 DEG C), the easily preparation of matrix, brightness are high with borate, but the ability of its vacuum-resistant ultraviolet light irradiation and anti-particle bombardment is poor makes its work-ing life shorter.And in orthoborate fluorescence rouge and powder, Eu 3+magnetic dipole transition stronger than electric dipole transition, launch orange-red light, colourity is poor.
Aluminium borate combines the advantage of borate and aluminate, and synthesis temperature falls between, Heat stability is good, and Eu 3+electric dipole transition stronger than magnetic dipole transition, launch red light, colourity is better, therefore likely becomes the fluorescent probe of a new generation.To the detection of target analytes organophosphorus pesticide molecule, there is good stability.
It is four: synthesized SrAl years old 2b 2o 7: Eu 3+fluorescent probe is compared with traditional rare-earth luminescent material, have the recognition site of metal ion mark, improve while target molecule Selective recognition, also possess high sensitive signal to export, utilize rare earth chelating principle of luminosity, achieve the high responsive detection of the identification of target analytes organophosphorus pesticide molecular selectivity.
Accompanying drawing explanation
Fig. 1 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+after fluorescent probe calcining ( a) and before calcining ( b) optical property figure under fluorescent light.
Fig. 2 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+after fluorescent probe calcining ( a) and before calcining ( b) optical property figure under ultraviolet lamp.
Fig. 3 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe ethanol solution normalization method uv-visible absorption spectra ( a) and fluorescence emission spectrogram ( b).
Fig. 4 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe ( a), Eu 2o 3standard card ( b) and SrAl 2b 2o 7standard card ( c) with XRD spectrum.
Fig. 5 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe is used for organophosphorus pesticide molecule highly selective, highly sensitive detection schematic diagram based on fluorescence chelating principle of luminosity.
Fig. 6 is SrAl of the present invention 2b 2o 7: Eu 3+the fluorescence intensity change figure that fluorescent probe is limit Chlorpyrifos 94 (A) and Malathion (B) two kinds of Pesticides Testing.
explain embodiment further with reference to the accompanying drawings
Fig. 1 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe calcines rear (left side) and (right side) optical property figure under fluorescent light before calcining.First, Eu 3+organic ligand is formed with agricultural chemicals target analytes organophosphorus pesticide molecule.Use electronic balance weighing Eu 2o 3be placed in beaker, then pipette nitric acid in above-mentioned beaker with microsyringe, after ultrasonic disperse reaction, form transparent solution, and then take organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add deionized water dilution, after ultrasonic disperse, leave standstill, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand; Finally, for the SrAl of organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe.Weigh strontium nitrate respectively, aluminum nitrate, boric acid and pore-creating agent four kinds of reactants are placed in beaker, then add deionized water, ultrasonic above-mentioned four kinds of reactants are dissolved completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in water bath, be stirred to solution and become viscous gum, by gained colloid in lower oven dry, xerogel after oven dry is warming up to 900 DEG C at temperature programmed control stove, and continue calcining 2h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe, before calcining, the fluorescent probe on (right side) (left side) is afterwards placed in the picture of cuvette under natural light.
Fig. 2 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe calcines rear (left side) and (right side) optical property figure under ultraviolet lamp before calcining.First, Eu 3+organic ligand is formed with agricultural chemicals target analytes organophosphorus pesticide molecule.Use electronic balance weighing Eu 2o 3be placed in beaker, then pipette nitric acid in above-mentioned beaker with microsyringe, after ultrasonic disperse reaction, form transparent solution, and then take organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add deionized water dilution, after ultrasonic disperse, leave standstill, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand; Finally, for the SrAl of organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe.Weigh strontium nitrate respectively, aluminum nitrate, boric acid and pore-creating agent four kinds of reactants are placed in beaker, then add deionized water, ultrasonic above-mentioned four kinds of reactants are dissolved completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in water bath, be stirred to solution and become viscous gum, by gained colloid in lower oven dry, xerogel after oven dry is warming up to 900 DEG C at temperature programmed control stove, and continue calcining 2h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe, before calcining the fluorescent probe on (right side) (left side) be afterwards placed in cuvette under 265nm ultraviolet lamp under picture.
Fig. 3 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe ethanol solution normalization method uv-visible absorption spectra ( a) and fluorescence emission spectrogram ( b).SrAl 2b 2o 7: Eu 3+fluorescent probe is 240nm place at the visible maximum absorption band of ethanol solution medium ultraviolet, and this fluorescence emission maximum spectrum is at 610nm place, and visible fluorescence probe emission is ruddiness.
Fig. 4 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe ( a), Eu 2o 3standard card ( b) and SrAl 2b 2o 7standard card ( c) with XRD spectrum.That represent respectively in figure is the SrAl of 900 DEG C 2b 2o 7: Eu 3+fluorescent probe ( a), SrAl 2b 2o 7standard card ( c) and Eu 2o 3standard card ( b) XRD spectrum.Compare and can find out by composing with three XRD, SrAl 2b 2o 7: Eu 3+fluorescent probe and SrAl 2b 2o 7standard card many places overlap, illustrates prepare host matrix be exactly SrAl 2b 2o 7, be about 40.138 places at 2 θ, the peak of three overlaps substantially, can infer Eu simultaneously 3+successfully be doped to SrAl 2b 2o 7in matrix.
Fig. 5 is the SrAl prepared by the present invention 2b 2o 7: Eu 3+fluorescent probe is used for organophosphorus pesticide molecule highly selective, highly sensitive detection schematic diagram based on fluorescence chelating principle of luminosity.Target analytes organophosphorus pesticide molecule enters SrAl 2b 2o 7: Eu 3+fluorescent probe recognition site, and is marked at recognition site metal ion Eu 3+define binary organic ligand, the energy of the organic ligand be excited may be transferred to metal ion Eu 3+and produce metal ion excited state Eu 3+* (namely Eu is produced 3+→ Eu 3+* transition), then by excited state metal ion Eu 3+* ground state ion Eu is returned 3+and produce Eu 3+* → Eu 3+luminous.Therefore, when target analytes organophosphorus pesticide molecule enters recognition site and metal ion Eu 3+after forming organic ligand, SrAl after organic ligand is excited 2b 2o 7: Eu 3+the fluorescence intensity of fluorescent probe strengthens, and realizes the Selective recognition to organophosphorus pesticide molecule and the detection of high sensitivity.
Fig. 6 is SrAl of the present invention 2b 2o 7: Eu 3+the fluorescence intensity change figure that fluorescent probe is limit Chlorpyrifos 94 (A) and Malathion (B) two kinds of Pesticides Testing.SrAl 2b 2o 7: Eu 3+fluorescent probe, with the fluorescence emission spectrum change curve of different concns Chlorpyrifos 94, Malathion add-on, can find out the continuous increase along with two kinds of pesticide concentrations, SrAl 2b 2o 7: Eu 3+the fluorescence intensity of fluorescent probe obviously strengthens, and shows SrAl 2b 2o 7: Eu 3+in fluorescent probe target analytes organophosphorus pesticide molecule enter fluorescent probe recognition site and be marked at recognition site Eu 3+between form organic ligand, after being excited fluorescence intensity strengthen.This illustrates the SrAl of two kinds of agricultural chemicals to preparation 2b 2o 7: Eu 3+fluorescent probe has Fluorescence Enhancement, and detection sensitivity reaches 1 × 10 -9molL -1, successfully achieve the trace detection to organophosphorus pesticide Chlorpyrifos 94, Malathion.
embodiment:a kind of SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe, comprises Eu 3+form organic ligand with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, after colloidal sol, gel, calcining obtains Eu 3+the organophosphorus pesticide molecular imprinting SrAl of mark 2b 2o 7: Eu 3+fluorescent probe, is characterized in that: described SrAl 2b 2o 7: Eu 3+after eliminating template molecule in fluorescent probe, it has the recognition site to target analytes organophosphorus pesticide molecular selectivity, and target analytes organophosphorus pesticide molecule enters SrAl 2b 2o 7: Eu 3+after the recognition site of fluorescent probe, by further with the Eu on recognition site 3+interact, make target analytes organophosphorus pesticide molecule and Eu 3+coordination forms organic ligand, after this organic ligand absorbs energy, by energy trasfer to Eu 3+, utilize SrAl 2b 2o 7: Eu 3+the fluorescence intensity of fluorescent probe changes, and achieve the molecular selectivity identification of agricultural chemicals target analytes organophosphorus pesticide and detection, preparation process of the present invention comprises following two steps:
1.1 the first steps are Eu 3+organic ligand is formed: first, with ten thousand/electronic balance weighing 0.3509g ~ 0.3529gEu with agricultural chemicals target analytes organophosphorus pesticide molecule 2o 3be placed in 100mL beaker, then pipette with scale adjustable 1mL microsyringe and add 1mL ~ 3mL nitric acid in above-mentioned beaker, after ultrasonic disperse reaction 5min ~ 10min, form transparent solution, and then take 0.700g ~ 1.500g organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add the dilution of 20mL deionized water, after ultrasonic disperse 5min ~ 10min, leave standstill 20min ~ 30min, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand;
1.2 second steps are the SrAl for organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe: weigh 1.6920g ~ 1.6940g strontium nitrate respectively, 7.5016g ~ 7.5036g aluminum nitrate, 1.2355g ~ 1.2375g boric acid and 3.25g ~ 3.45g pore-creating agent four kinds of reactants are placed in 250mL beaker, add 80mL ~ 100mL deionized water again, ultrasonic 5min ~ 10min makes above-mentioned four kinds of reactants dissolve completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in 80 DEG C ~ 100 DEG C water baths, under 700rpm ~ 800rpm, be stirred to solution become viscous gum, gained colloid is dried 12h at 150 DEG C, xerogel after oven dry is warming up to 800 DEG C ~ 950 DEG C at temperature programmed control stove, and continue calcining 2h ~ 4h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe.
Embodiment: utilize metal ion Eu 3+form organic ligand with target analytes Chlorpyrifos 94, recycling sol-gel method-calcining is obtained to Chlorpyrifos 94 Selective recognition and the responsive SrAl detected 2b 2o 7: Eu 3+fluorescent probe.
The first step is Eu 3+organic ligand is formed: first, with ten thousand/electronic balance weighing 0.3519gEu with agricultural chemicals target analytes Chlorpyrifos 94 molecule 2o 3be placed in 100mL beaker, then pipette with scale adjustable 1mL microsyringe and add 2mL nitric acid in above-mentioned beaker, after ultrasonic disperse reaction 8min, form transparent solution, and then take 1.10g Chlorpyrifos 94 be positioned over above-mentioned reaction after in transparent solution, add the dilution of 20mL deionized water, after ultrasonic disperse 8min, leave standstill 25min, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand;
Second step is the SrAl for Chlorpyrifos 94 Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe: weigh 1.6930g strontium nitrate respectively, 7.5026g aluminum nitrate, 1.2365g boric acid and 3.35g pore-creating agent four kinds of reactants are placed in 250mL beaker, then add 90mL deionized water, ultrasonic 8min makes above-mentioned four kinds of reactants dissolve completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes Chlorpyrifos 94 molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then, the beaker containing this mixing solutions is placed in 90 DEG C of water baths, under 750rpm, be stirred to solution become viscous gum, gained colloid is dried 12h at 150 DEG C, and the xerogel after oven dry is warming up to 900 DEG C at temperature programmed control stove, and continues calcining 3h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes Chlorpyrifos 94 molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe.

Claims (8)

1. the SrAl for detection of organic phosphorus pesticide 2b 2o 7: Eu 3+the preparation method of fluorescent probe, comprises Eu 3+form organic ligand with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, after colloidal sol, gel, calcining obtains Eu 3+the organophosphorus pesticide molecular imprinting SrAl of mark 2b 2o 7: Eu 3+fluorescent probe, is characterized in that: described SrAl 2b 2o 7: Eu 3+after eliminating template molecule in fluorescent probe, it has the recognition site to target analytes organophosphorus pesticide molecular selectivity, and target analytes organophosphorus pesticide molecule enters SrAl 2b 2o 7: Eu 3+after the recognition site of fluorescent probe, by further with the Eu on recognition site 3+interact, make target analytes organophosphorus pesticide molecule and Eu 3+coordination forms organic ligand, after this organic ligand absorbs energy, by energy trasfer to Eu 3+, utilize SrAl 2b 2o 7: Eu 3+the fluorescence intensity of fluorescent probe changes, and achieve the molecular selectivity identification of agricultural chemicals target analytes organophosphorus pesticide and detection, preparation process of the present invention comprises following two steps:
1.1 the first steps are Eu 3+organic ligand is formed: first, with ten thousand/electronic balance weighing 0.3509g ~ 0.3529gEu with agricultural chemicals target analytes organophosphorus pesticide molecule 2o 3be placed in 100mL beaker, then pipette with scale adjustable 1mL microsyringe and add 1mL ~ 3mL nitric acid in above-mentioned beaker, after ultrasonic disperse reaction 5min ~ 10min, form transparent solution, and then take 0.700g ~ 1.500g organophosphorus pesticide be positioned over above-mentioned reaction after in transparent solution, add the dilution of 20mL deionized water, after ultrasonic disperse 5min ~ 10min, leave standstill 20min ~ 30min, Eu 3+with the interaction of molecules of agricultural chemicals target analytes organophosphorus pesticide, form organic ligand;
1.2 second steps are the SrAl for organophosphorus pesticide Molecular Detection 2b 2o 7: Eu 3+the preparation of fluorescent probe: weigh 1.6920g ~ 1.6940g strontium nitrate respectively, 7.5016g ~ 7.5036g aluminum nitrate, 1.2355g ~ 1.2375g boric acid and 3.25g ~ 3.45g pore-creating agent four kinds of reactants are placed in 250mL beaker, add 80mL ~ 100mL deionized water again, ultrasonic 5min ~ 10min makes above-mentioned four kinds of reactants dissolve completely, then by Eu obtained for the first step 3+the organic ligand solution formed with agricultural chemicals target analytes organophosphorus pesticide molecule joins in the mixing solutions of above-mentioned four kinds of reactants, then the beaker containing this mixing solutions is placed in 80 DEG C ~ 100 DEG C water baths, under 700rpm ~ 800rpm, be stirred to solution become viscous gum, gained colloid is dried 12h at 150 DEG C, xerogel after oven dry is warming up to 800 DEG C ~ 950 DEG C at temperature programmed control stove, and continue calcining 2h ~ 4h at such a temperature, take out porphyrize, finally obtain the SrAl to target analytes organophosphorus pesticide molecular recognition and detection 2b 2o 7: Eu 3+fluorescent probe.
2. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said fluorescent probe is SrAl 2b 2o 7: Eu 3+.
3. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said organophosphorus pesticide is Chlorpyrifos 94 and Malathion.
4. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said SrAl 2b 2o 7: Eu 3+innerly in fluorescent probe form the void structure with recognition site and organophosphorus pesticide molecular structure, size and the complementation of function base.
5. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said SrAl 2b 2o 7: Eu 3+eu in recognition site in fluorescent probe 3+organophosphorus pesticide interaction of molecules in recognition site can form organism part and there occurs from organism to Eu 3+energy trasfer.
6. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said SrAl 2b 2o 7: Eu 3+fluorescent probe is strengthen principle based on rare earth chelating fluorescent to trace organophosphorus pesticide molecular detection.
7. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said SrAl 2b 2o 7: Eu 3+in fluorescent probe synthesis, pore-creating agent used is cetyl trimethylammonium bromide (CetyltrimethylAmmoniumBromide, CTAB).
8. a kind of SrAl for detection of organic phosphorus pesticide according to claim 1 2b 2o 7: Eu 3+the preparation method of fluorescent probe, is characterized in that: said SrAl 2b 2o 7: Eu 3+fluorescent probe synthesis Program temperature control furnace heat-up rate is 1 DEG C/min.
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