CN107828410A - A kind of preparation method of carbon quantum dot molecular imprinting composite material and the method using its analysis agricultural chemicals mesotrione residual - Google Patents

A kind of preparation method of carbon quantum dot molecular imprinting composite material and the method using its analysis agricultural chemicals mesotrione residual Download PDF

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CN107828410A
CN107828410A CN201711055068.XA CN201711055068A CN107828410A CN 107828410 A CN107828410 A CN 107828410A CN 201711055068 A CN201711055068 A CN 201711055068A CN 107828410 A CN107828410 A CN 107828410A
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CN107828410B (en
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陈立钢
孙雪
牛娜
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Northeast Forestry University
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Abstract

A kind of preparation method of carbon quantum dot molecular imprinting composite material and the method using its analysis agricultural chemicals mesotrione residual, it is related to a kind of preparation method of carbon quantum dot molecular imprinting composite material and the analysis method to agricultural chemicals mesotrione.Mesotrione analysis time is grown present invention aim to address existing method, the low and quantum dot molecular imprinting composite material synthetic method cost of selectivity is high, it is big for environment pollution the problem of.Preparation method：First, carbon quantum dot is prepared；2nd, modified carbon quantum dot；3rd, molecular engram, carbon quantum dot molecular imprinting composite material is obtained.Analysis method：First, dispersion liquid is prepared；2nd, control group fluorescence intensity is detected；3rd, quenching constant K is determinedsv；4th, testing sample is detected, calculates the concentration Q of mesotrione in testing sampleu.Present invention is mainly used for analysis environments water sample Pesticides mesotrione residual.

Description

The preparation method of carbon quantum dot-molecular imprinting composite material a kind of and utilize its analysis The method of agricultural chemicals mesotrione residual
Technical field
The present invention relates to a kind of preparation method of carbon quantum dot-molecular imprinting composite material and to agricultural chemicals mesotrione Analysis method.
Background technology
Carbon quantum dot is referred to using C as main component, and combines a kind of similar semiconductor amount of the elements such as H, O, N composition The material with fluorescent characteristic of son point, its particle size is from several nanometers to several tens of nanometers.With hypotoxicity, good life Thing compatibility and photostability.The primary raw material for preparing carbon quantum dot at this stage is graphene, CNT etc..Such raw material Mostly costly, and product needs just to can guarantee that carbon quantum dot is stable by means such as strong acid reflow treatment or surface modifications Optical property, limit large-scale production and the practical application of carbon quantum dot.Therefore, develop biomass presoma and prepare carbon amounts Son point has good application prospect.Such as in disclosed patent《A kind of side using cotton as raw material Hydrothermal Synthesiss carbon quantum dot Method》(application number：201410424098.3) and patent《A kind of preparation method of luminescence generated by light carbon quantum dot》(application number： 201310487328.6) method of cotton and milk for raw material Hydrothermal Synthesiss carbon quantum dot was all once used.
Molecular imprinting technology refers to that establishment has the polymer of specific binding site to a certain specific template molecule Process.Molecular imprinting technology, it is a kind of novel preparation technology of multi-crossed disciplines, the recognition mechanism of analogue antigen-antibody, synthesizes With fixing hole size and shape and having the polymer of the functional group necessarily to put in order, it can be to template molecule body Reveal special selectivity and good recognition capability.If can be incorporated into fluorescent material in molecularly imprinted polymer can make its tool There are fluorescent emission properties again while having high selectivity.Such as disclosed patent《One kind is based on core-shell quanta dots molecular engram Polymer and application thereof》(application number：201410520007.6).It is multiple that although quantum dot-molecular engram is successfully prepared in the invention Condensation material, but organic solvent and cadmium metal compound are largely used in preparation process, synthesis cost is high and big for environment pollution, limitation The practical application of quantum dot molecular imprinting composite material.
Mesotrione is the control Sexual behavior mode herbicide before the emergence for broad-leaved in corn and meadow weeds and after emergence. Due to its excellent Weeds distribution property, many growers control the weeds in rice field using mesotrione.Although nitre sulphur is careless Ketone plays an important role in the practice of agriculture, but has toxicity to nontarget organism body.Its growth to microalgae has negative effect, And the 26S Proteasome Structure and Function of aquatic ecosystem may be influenceed.The common analysis method to mesotrione, such as high performance liquid chromatography Need to expend substantial amounts of organic solvent and analysis time is longer (being more than 1h comprising pretreatment time), be not suitable for a large amount of samples of processing Product, cost are higher.
The content of the invention
Mesotrione analysis time is grown present invention aim to address existing method, the low and quantum dot of selectivity-point Sub- trace method for synthesizing composite material cost is high, it is big for environment pollution the problem of, and it is multiple to provide a kind of carbon quantum dot-molecular engram The preparation method of condensation material and the method using its analysis agricultural chemicals mesotrione residual.
A kind of preparation method of carbon quantum dot-molecular imprinting composite material, is specifically realized by the following steps：
First, carbon quantum dot is prepared：Mangrove bark is put into polytetrafluoroethyllining lining first, high purity water is added and is well mixed, It is put into after capping in stainless steel cauldron, reactor is sealed, be then placed in air dry oven, is 180 DEG C~220 in temperature 3h~7h is reacted at DEG C, after being cooled to room temperature, obtains reaction product, using the micropore filtering film that aperture is 20 μm~40 μm to anti- Answer product to be filtered, obtain lurid filtrate, the lurid filtrate is carbon quantum dot solution；Described in step 1 The quality of mangrove bark and the volume ratio of high purity water are 1g:(10~20) mL；
2nd, modified carbon quantum dot：3- aminopropyl triethoxysilanes are added into carbon quantum dot solution, low whipping speed is 100rpm~300rpm and temperature are that 20h~30h is reacted at 50 DEG C~70 DEG C, solution after being reacted, solution after reaction are existed Rotating speed centrifuges 5min~10min under the conditions of being 5000rpm~7000rpm, isolated supernatant, supernatant is entered using ether Row extraction 2~4 times, obtains carbon modified quantum dot solution；3- aminopropyl triethoxysilanes and carbon quantum described in step 2 The volume ratio of point solution is 1:(22~28)；
3rd, molecular engram：Mesotrione is put into container, then adds absolute ethyl alcohol, is 35 DEG C~45 DEG C in temperature Be completely dissolved mesotrione under ultrasonic wave added, add carbon modified quantum dot solution, 3- aminopropyl triethoxysilanes, just Silester and the ammonia spirit that mass fraction is 20%~30%, are put into sealing container after magnetic stir bar, and be transferred to magnetic On power agitator, magnetic agitation reacts 20h~30h under normal temperature lucifuge, obtains initial reaction product, initial reaction solution is existed Rotating speed centrifuges 5min~10min, solid product after being separated, using methanol to separation under the conditions of being 5000rpm~7000rpm Solid product elutes 2~4 times afterwards, carries out vacuum drying 10h~15h at being then 50 DEG C~70 DEG C in temperature, obtains carbon quantum Point-molecular imprinting composite material；The quality of mesotrione described in step 3 and the volume ratio of absolute ethyl alcohol are 1g:(0.075 ~0.125) mL；The volume of carbon modified quantum dot solution described in step 3 and the mass ratio of mesotrione are 1mL:(3~5) mg；The volume ratio of carbon modified quantum dot solution and 3- aminopropyl triethoxysilanes described in step 3 is 1mL:(6~8) μ L；The volume ratio of carbon modified quantum dot solution and tetraethyl orthosilicate described in step 3 is 1:(0.02~0.04)；In step 3 The volume ratio for the ammonia spirit that described carbon modified quantum dot solution is 20%~30% with mass fraction is 1mL:(3~5) μ L.
A kind of method that agricultural chemicals mesotrione residual is analyzed using carbon quantum dot-molecular imprinting composite material, is specifically pressed What following steps were completed：
First, dispersion liquid is prepared：Carbon quantum dot-molecular imprinting composite material is distributed in high purity water, obtains dispersion liquid；Step The quality of carbon quantum dot-molecular imprinting composite material described in rapid one and the volume ratio of high purity water are 1mg:(0.8~1.5) mL；
2nd, control group fluorescence intensity is detected：By dispersion liquid and high purity water by volume 1:1 is well mixed, obtains control group Solution, control group solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, is obtained Fluorescence intensity F0；
3rd, quenching constant K is determinedsv：1., by dispersion liquid and concentration be Q1The mesotrione aqueous solution by volume 1:1 is mixed Close uniform, 15nmol/L≤Q1, it is Q to obtain concentration1Test group solution, it is in excitation wavelength using sepectrophotofluorometer 350nm, launch wavelength are that detectable concentration is Q under 453nm1Test group solution, obtain fluorescence intensity F1；2., according to mesotrione water In solution 1. mesotrione increasing concen-trations form repeat step three operates n-1 times, when n-th operates, in the mesotrione aqueous solution Mesotrione concentration is Qn, Qn≤ 3000nmol/L, using sepectrophotofluorometer excitation wavelength be 350nm, launch wavelength be It is F that detection, which obtains fluorescence intensity, under 453nmn；3., according to Stern-Volmer equations be F0/ F=1+Ksv[Q], F in formula0For The fluorescence intensity of control group solution, F be test group solution fluorescence intensity, F=F1~Fn, Q is the test group mesotrione aqueous solution The concentration of middle mesotrione, Q=Q1~Qn, KsvFor quenching constant Ksv, according to Q1~QnAnd F1~Fn, with F0/ F is y, Q x, Ksv For k, linear equation y=kx+1, quenching constant K is finally givensvValue；
4th, testing sample is detected：By dispersion liquid and testing sample by volume 1:1 is well mixed, obtains to be measured group of solution, To be measured group of solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, obtains fluorescence Intensity Fu, it is F according to Stern-Volmer equations0/Fu=1+Ksv[Qu], F in formula0For the fluorescence intensity of control group solution, Fu For the fluorescence intensity of to be measured group of solution, KsvFor quenching constant, the concentration Q of mesotrione in testing sample is calculatedu。
Advantage of the present invention：1st, the mangrove bark that the raw material that the present invention uses is discarded for biological material, material environment friendly, is realized Refuse reclamation, and application prospect is bigger；2nd, carbon quantum dot-molecular imprinting composite material synthetic method that the present invention is prepared Simply, condition is easily controllable, and solvent for use is high purity water, reduces the use of organic solvent, and environmental pollution is small；3rd, present invention inspection The survey time is short, and 10min can complete to detect, and have the good rate of recovery and reappearance, have higher selectivity to mesotrione, Selectivity factor ＞ 2.5, rate of recovery ＞ 90%, RSD ＜ 5%.
Present invention is mainly used for analysis environments water sample Pesticides mesotrione residual.
Brief description of the drawings
Fig. 1 is the Fourier transform infrared spectroscopy figure of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；
Fig. 2 is the x-ray photoelectron spectrogram of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；
Fig. 3 is the transmission electron microscope picture of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；
Fig. 4 is the X-ray diffraction spectrogram of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；
Fig. 5 is the pH value influence figure of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；
Fig. 6 is quenching shadow of the mesotrione aqueous solution to carbon quantum dot-molecular imprinting composite material in the step 3 of embodiment 2 Ring figure；
Fig. 7 is Stern-Volmer Linear equations in the step 3 of embodiment 2.
Embodiment
Embodiment one：Present embodiment is a kind of preparation method of carbon quantum dot-molecular imprinting composite material, tool Body is completed according to the following steps：
First, carbon quantum dot is prepared：Mangrove bark is put into polytetrafluoroethyllining lining first, high purity water is added and is well mixed, It is put into after capping in stainless steel cauldron, reactor is sealed, be then placed in air dry oven, is 180 DEG C~220 in temperature 3h~7h is reacted at DEG C, after being cooled to room temperature, obtains reaction product, using the micropore filtering film that aperture is 20 μm~40 μm to anti- Answer product to be filtered, obtain lurid filtrate, the lurid filtrate is carbon quantum dot solution；Described in step 1 The quality of mangrove bark and the volume ratio of high purity water are 1g:(10~20) mL；
2nd, modified carbon quantum dot：3- aminopropyl triethoxysilanes are added into carbon quantum dot solution, low whipping speed is 100rpm~300rpm and temperature are that 20h~30h is reacted at 50 DEG C~70 DEG C, solution after being reacted, solution after reaction are existed Rotating speed centrifuges 5min~10min under the conditions of being 5000rpm~7000rpm, isolated supernatant, supernatant is entered using ether Row extraction 2~4 times, obtains carbon modified quantum dot solution；3- aminopropyl triethoxysilanes and carbon quantum described in step 2 The volume ratio of point solution is 1:(22~28)；
3rd, molecular engram：Mesotrione is put into container, then adds absolute ethyl alcohol, is 35 DEG C~45 DEG C in temperature Be completely dissolved mesotrione under ultrasonic wave added, add carbon modified quantum dot solution, 3- aminopropyl triethoxysilanes, just Silester and the ammonia spirit that mass fraction is 20%~30%, are put into sealing container after magnetic stir bar, and be transferred to magnetic On power agitator, magnetic agitation reacts 20h~30h under normal temperature lucifuge, obtains initial reaction product, initial reaction solution is existed Rotating speed centrifuges 5min~10min, solid product after being separated, using methanol to separation under the conditions of being 5000rpm~7000rpm Solid product elutes 2~4 times afterwards, carries out vacuum drying 10h~15h at being then 50 DEG C~70 DEG C in temperature, obtains carbon quantum Point-molecular imprinting composite material；The quality of mesotrione described in step 3 and the volume ratio of absolute ethyl alcohol are 1g:(0.075 ~0.125) mL；The volume of carbon modified quantum dot solution described in step 3 and the mass ratio of mesotrione are 1mL:(3~5) mg；The volume ratio of carbon modified quantum dot solution and 3- aminopropyl triethoxysilanes described in step 3 is 1mL:(6~8) μ L；The volume ratio of carbon modified quantum dot solution and tetraethyl orthosilicate described in step 3 is 1:(0.02~0.04)；In step 3 The volume ratio for the ammonia spirit that described carbon modified quantum dot solution is 20%~30% with mass fraction is 1mL:(3~5) μ L.
Embodiment two：The difference of present embodiment and embodiment one is：It is in temperature in step 1 3h is reacted at 200 DEG C.Other are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Institute in step 1 The quality for the mangrove bark stated and the volume ratio of high purity water are 1g:15mL.Other are identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：In step 2 Mixing speed is 200rpm and temperature is to react 24h at 60 DEG C.Other are identical with embodiment one to three.
Embodiment five：Present embodiment is with one of embodiment one to four difference：In step 2 Rotating speed centrifuges 8min, isolated supernatant under the conditions of being 6000rpm.Other are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：In step 3 Magnetic agitation reacts 20h~30h under normal temperature lucifuge, and the rotating speed of magnetic agitation is 200rpm~300rpm, obtains initial reaction production Thing.Other are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Will in step 3 Initial reaction solution centrifuges 8min under the conditions of rotating speed is 6000rpm, solid product after being separated.Other and specific embodiment party Formula one to six is identical.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：It is sharp in step 3 With methanol to after separation solid product elute 3 times, then temperature be 60 DEG C at carry out vacuum drying 12h, obtain carbon quantum dot- Molecular imprinting composite material.Other are identical with embodiment one to seven.
Embodiment nine：Present embodiment is that one kind utilizes carbon quantum dot-molecular imprinting composite material analysis agricultural chemicals The method of mesotrione residual, is specifically realized by the following steps：
First, dispersion liquid is prepared：Carbon quantum dot-molecular imprinting composite material is distributed in high purity water, obtains dispersion liquid；Step The quality of carbon quantum dot-molecular imprinting composite material described in rapid one and the volume ratio of high purity water are 1mg:(0.8~1.5) mL；
2nd, control group fluorescence intensity is detected：By dispersion liquid and high purity water by volume 1:1 is well mixed, obtains control group Solution, control group solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, is obtained Fluorescence intensity F0；
3rd, quenching constant K is determinedsv：1., by dispersion liquid and concentration be Q1The mesotrione aqueous solution by volume 1:1 is mixed Close uniform, 15nmol/L≤Q1, it is Q to obtain concentration1Test group solution, it is in excitation wavelength using sepectrophotofluorometer 350nm, launch wavelength are that detectable concentration is Q under 453nm1Test group solution, obtain fluorescence intensity F1；2., according to mesotrione water In solution 1. mesotrione increasing concen-trations form repeat step three operates n-1 times, when n-th operates, in the mesotrione aqueous solution Mesotrione concentration is Qn, Qn≤ 3000nmol/L, using sepectrophotofluorometer excitation wavelength be 350nm, launch wavelength be It is F that detection, which obtains fluorescence intensity, under 453nmn；3., according to Stern-Volmer equations be F0/ F=1+Ksv[Q], F in formula0For The fluorescence intensity of control group solution, F be test group solution fluorescence intensity, F=F1~Fn, Q is the test group mesotrione aqueous solution The concentration of middle mesotrione, Q=Q1~Qn, KsvFor quenching constant Ksv, according to Q1~QnAnd F1~Fn, with F0/ F is y, Q x, Ksv For k, linear equation y=kx+1, quenching constant K is finally givensvValue；
4th, testing sample is detected：By dispersion liquid and testing sample by volume 1:1 is well mixed, obtains to be measured group of solution, To be measured group of solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, obtains fluorescence Intensity Fu, it is F according to Stern-Volmer equations0/Fu=1+Ksv[Qu], F in formula0For the fluorescence intensity of control group solution, Fu For the fluorescence intensity of to be measured group of solution, KsvFor quenching constant, the concentration Q of mesotrione in testing sample is calculatedu。
Embodiment ten：The difference of present embodiment and embodiment nine is：Carbon described in step 1 The quality of quantum dot-molecular imprinting composite material and the volume ratio of high purity water are 1mg:1mL.Other and the phase of embodiment nine Together.
Using following verification experimental verifications effect of the present invention
Embodiment 1：A kind of preparation method of carbon quantum dot-molecular imprinting composite material, is specifically realized by the following steps 's：
First, carbon quantum dot is prepared：2.0g mangrove barks are put into polytetrafluoroethyllining lining first, 30mL high purity waters is added and mixes Close uniformly, be put into after capping in stainless steel cauldron, reactor is sealed, be then placed in air dry oven, be 200 in temperature 3h is reacted at DEG C, after being cooled to room temperature, obtains reaction product, reaction product is carried out using the micropore filtering film that aperture is 22 μm Filtering, obtains lurid filtrate, the lurid filtrate is carbon quantum dot solution；
2nd, modified carbon quantum dot：50mL carbon quantum dots solution is added in there-necked flask, then adds 2mL 3- aminopropyls three Ethoxysilane, low whipping speed is 200rpm and temperature is to react 24h at 60 DEG C, solution after being reacted, will be molten after reaction Liquid centrifuges 8min under the conditions of rotating speed is 6000rpm, isolated supernatant, extraction 3 times is carried out to supernatant using ether, is obtained To carbon modified quantum dot solution；
3rd, molecular engram：200mg mesotriones are put into there-necked flask, 20mL absolute ethyl alcohols is then added, is in temperature Mesotrione is completely dissolved under 40 DEG C and ultrasonic wave added, adds 50mL carbon modifieds quantum dot solution, 350 μ L 3- aminopropyls Triethoxysilane, 1.5mL tetraethyl orthosilicates and 200 μ L mass fractions are 25% ammonia spirit, after being put into magnetic stir bar There-necked flask is sealed, and is transferred on magnetic stirring apparatus, magnetic agitation reacts 24h under normal temperature lucifuge, and the rotating speed of magnetic agitation is 250rpm, initial reaction product is obtained, initial reaction solution is centrifuged into 8min under the conditions of rotating speed is 6000rpm, separated Solid product afterwards, solid product after separation is eluted 3 times using methanol, vacuum drying 12h is carried out at being then 60 DEG C in temperature, Obtain carbon quantum dot-molecular imprinting composite material；
Carbon quantum dot-the molecular imprinting composite material prepared using Fourier's IR Characterization embodiment 1, as shown in figure 1, figure 1 is the Fourier transform infrared spectroscopy figure of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；Exist as shown in Figure 1 1124cm-1And 1050cm-1The strong broad peak of left and right is Si-O-Si and Si-O-C asymmetric stretching vibration peak, in 448cm-1With 784cm-1Place shows the vibration peak of Si-O keys；In 1652cm-1The peak of left and right is C=O characteristic absorption peak；In 2936cm-1It is left Right peak is C-H vibration absorption peak.3440cm-1The peak of left and right is N-H vibration absorption peaks.
Fig. 2 is the x-ray photoelectron spectrogram of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；Penetrated by X The surface-element analysis of Photoelectron spectrogram measure resulting materials.Carbon quantum dot-molecular imprinting composite material prepared by embodiment 1 Gamut x-ray photoelectron spectrum analysis clearly demonstrate 289.9ev, 406.1ev, 538.8ev, 108.4ev and 160.4ev five peaks, are attributed to C1s, N1s, O1s, Si2p and Si2s respectively.Illustrate the element composition and nitre sulphur of material Humulone is all eluted.
Fig. 3 is the transmission electron microscope picture of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；Transmission electron microscope can be with For observing pattern, 3 it can know that carbon quantum dot-molecular imprinting composite material is chondritic by figure, diameter is about 30~50nm, Regular shape and good dispersion.
Fig. 4 is the X-ray diffraction spectrogram of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；X-ray diffraction Spectrogram can reflect the Atomic Arrangement rule of crystals, and as can be seen from Figure 42 θ have one very in the range of 15 ° -40 ° Wide diffraction maximum, corresponding carbon quantum dot-molecular imprinting composite material diffraction crystal face.Carbon quantum dot-molecular imprinting composite material 002 crystal face is very wide, and a kind of state of longrange disorder is presented in this explanation product.This result and carbon in the transmission electron microscope picture in Fig. 3 The shape characteristic of quantum dot-molecular imprinting composite material is consistent.
Fig. 5 is the pH value influence figure of carbon quantum dot-molecular imprinting composite material prepared by embodiment 1；As shown in Figure 5, pH Be worth for 3~12 when carbon quantum dot-molecular imprinting composite material fluorescence intensity slightly fluctuate, it is but overall relatively stable, show carbon amounts Sub- point-molecular imprinting composite material has very strong stability.
Embodiment 2：A kind of method that agricultural chemicals mesotrione residual is analyzed using carbon quantum dot-molecular imprinting composite material, It is specifically realized by the following steps：
First, dispersion liquid is prepared：Carbon quantum dot-molecular imprinting composite material is distributed in high purity water, obtains dispersion liquid；Step The quality of carbon quantum dot-molecular imprinting composite material described in rapid one and the volume ratio of high purity water are 1mg:1mL；
2nd, control group fluorescence intensity is detected：1.5mL dispersion liquids are well mixed with 1.5mL high purity waters, it is molten to obtain control group Liquid, control group solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, is obtained glimmering Luminous intensity F0, F0=3197；
3rd, quenching constant K is determinedsv：1., by 1.5mL dispersion liquids and 1.5mL concentration be Q1The mesotrione aqueous solution mixing Uniformly, Q1=15nmol/L, it is Q to obtain concentration1Test group solution, using sepectrophotofluorometer excitation wavelength be 350nm, Launch wavelength is that detectable concentration is Q under 453nm1Test group solution, obtain fluorescence intensity F1；2., using concentration be successively Q2~Q11 The mesotrione aqueous solution replace concentration be Q1Mesotrione aqueous solution repeat step three 1. operate 10 times；Q2= 313.5nmol/L, fluorescence intensity F2；Q3=612nmol/L, fluorescence intensity F3；Q4=910.5nmol/L, fluorescence intensity are F4；Q5=1209nmol/L, fluorescence intensity F5；Q6=1507.5nmol/L, fluorescence intensity F6；Q7=1806nmol/L, it is glimmering Luminous intensity is F7；Q8=2104.5nmol/L, fluorescence intensity F8；Q9=2403nmol/L, fluorescence intensity F9；Q10= 2701.5nmol/L fluorescence intensity F10；Q11=3000nmol/L, fluorescence intensity F11；3., according to Stern-Volmer side Journey is F0/ F=1+Ksv[Q], F in formula0For the fluorescence intensity of control group solution, F is the fluorescence intensity of test group solution, F=F1 ~F11, Q be the test group mesotrione aqueous solution in mesotrione concentration, Q=Q1~Q11, KsvFor quenching constant Ksv, according to Q1 ~Q11And F1~F11, with F0/ F is y, Q x, KsvFor k, linear equation y=kx+1, y=is obtained by the Fitting Calculation 7.363×10-4x+1(R2=0.99) quenching constant K, is finally givensv=7.363 × 10-4；
4th, testing sample is detected：1.5mL dispersion liquids are well mixed with 1.5mL testing samples, obtain to be measured group of solution, To be measured group of solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, obtains fluorescence Intensity Fu, it is F according to Stern-Volmer equations0/Fu=1+Ksv[Qu], F in formula0For the fluorescence intensity of control group solution, Fu For the fluorescence intensity of to be measured group of solution, KsvFor quenching constant, the concentration Q of mesotrione in testing sample is calculatedu=22nmol/ L；The testing sample is the mesotrione aqueous solution that concentration is 22nmol/L.
Fig. 6 is quenching shadow of the mesotrione aqueous solution to carbon quantum dot-molecular imprinting composite material in the step 3 of embodiment 2 Ring figure；The mesotrione aqueous solution of the concentration between 15nmol/L~3000nmol/L is used to utilize in the present embodiment step 3 Stern-Volmer equations are analyzed experimental data (as shown in Figure 7), and Fig. 7 is Stern- in the step 3 of embodiment 2 Volmer Linear equations；There is good linear relationship, linear equation y between concentration 15nmol/L~3000nmol/L =7.363 × 10-4x+1(R2=0.99).

Claims (10)

  1. A kind of a kind of 1. preparation method of carbon quantum dot-molecular imprinting composite material, it is characterised in that carbon quantum dot-molecular engram The preparation method of composite is completed according to the following steps：
    First, carbon quantum dot is prepared：Mangrove bark is put into polytetrafluoroethyllining lining first, high purity water is added and is well mixed, be capped After be put into stainless steel cauldron, reactor is sealed, is then placed in air dry oven, temperature be 180 DEG C~220 DEG C at 3h~7h is reacted, after being cooled to room temperature, obtains reaction product, reaction is produced using the micropore filtering film that aperture is 20 μm~40 μm Thing is filtered, and obtains lurid filtrate, and the lurid filtrate is carbon quantum dot solution；Mango described in step 1 The quality of skin and the volume ratio of high purity water are 1g:(10~20) mL；
    2nd, modified carbon quantum dot：3- aminopropyl triethoxysilanes are added into carbon quantum dot solution, low whipping speed is 100rpm~300rpm and temperature are that 20h~30h is reacted at 50 DEG C~70 DEG C, solution after being reacted, solution after reaction are existed Rotating speed centrifuges 5min~10min under the conditions of being 5000rpm~7000rpm, isolated supernatant, supernatant is entered using ether Row extraction 2~4 times, obtains carbon modified quantum dot solution；3- aminopropyl triethoxysilanes and carbon quantum described in step 2 The volume ratio of point solution is 1:(22~28)；
    3rd, molecular engram：Mesotrione is put into container, then adds absolute ethyl alcohol, it is for 35 DEG C~45 DEG C and super in temperature Mesotrione is completely dissolved under sound auxiliary, adds carbon modified quantum dot solution, 3- aminopropyl triethoxysilanes, positive silicic acid Ethyl ester and the ammonia spirit that mass fraction is 20%~30%, are put into sealing container after magnetic stir bar, and be transferred to magnetic force and stir Mix on device, magnetic agitation reacts 20h~30h under normal temperature lucifuge, initial reaction product is obtained, by initial reaction solution in rotating speed To centrifuge 5min~10min, solid product after being separated, using methanol to solid after separation under the conditions of 5000rpm~7000rpm Body product elution 2~4 times, then temperature be 50 DEG C~70 DEG C at carry out vacuum drying 10h~15h, obtain carbon quantum dot-point Sub- trace composite；The quality of mesotrione described in step 3 and the volume ratio of absolute ethyl alcohol are 1g:(0.075~ 0.125)mL；The volume of carbon modified quantum dot solution described in step 3 and the mass ratio of mesotrione are 1mL:(3~5) mg；The volume ratio of carbon modified quantum dot solution and 3- aminopropyl triethoxysilanes described in step 3 is 1mL:(6~8) μ L；The volume ratio of carbon modified quantum dot solution and tetraethyl orthosilicate described in step 3 is 1:(0.02~0.04)；In step 3 The volume ratio for the ammonia spirit that described carbon modified quantum dot solution is 20%~30% with mass fraction is 1mL:(3~5) μ L.
  2. A kind of 2. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step 3h is reacted at being 200 DEG C in temperature in rapid one.
  3. A kind of 3. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step The quality of mangrove bark described in rapid one and the volume ratio of high purity water are 1g:15mL.
  4. A kind of 4. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step Low whipping speed is 200rpm in rapid two and temperature is to react 24h at 60 DEG C.
  5. A kind of 5. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step In rapid two 8min, isolated supernatant are centrifuged under the conditions of rotating speed is 6000rpm.
  6. A kind of 6. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step Magnetic agitation reacts 20h~30h under normal temperature lucifuge in rapid three, and the rotating speed of magnetic agitation is 200rpm~300rpm, obtains just Walk reaction product.
  7. A kind of 7. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step Initial reaction solution is centrifuged into 8min under the conditions of rotating speed is 6000rpm in rapid three, solid product after being separated.
  8. A kind of 8. preparation method of carbon quantum dot-molecular imprinting composite material according to claim 1, it is characterised in that step Solid product after separation is eluted 3 times using methanol in rapid three, carry out vacuum drying 12h at being then 60 DEG C in temperature, obtain Carbon quantum dot-molecular imprinting composite material.
  9. 9. one kind as claimed in claim 1 utilizes carbon quantum dot-molecular imprinting composite material analysis agricultural chemicals mesotrione residual Method, it is characterised in that a kind of method that agricultural chemicals mesotrione residual is analyzed using carbon quantum dot-molecular imprinting composite material Complete according to the following steps：
    First, dispersion liquid is prepared：Carbon quantum dot-molecular imprinting composite material is distributed in high purity water, obtains dispersion liquid；Step 1 Described in the quality of carbon quantum dot-molecular imprinting composite material and the volume ratio of high purity water be 1mg:(0.8~1.5) mL；
    2nd, control group fluorescence intensity is detected：By dispersion liquid and high purity water by volume 1:1 is well mixed, obtains control group solution, Control group solution is detected in the case where excitation wavelength is 350nm, launch wavelength is 453nm using sepectrophotofluorometer, obtains fluorescence Intensity F0；
    3rd, quenching constant K is determinedsv：1., by dispersion liquid and concentration be Q1The mesotrione aqueous solution by volume 1:1 mixing is equal It is even, 15nmol/L≤Q1, it is Q to obtain concentration1Test group solution, it is 350nm, sends out in excitation wavelength using sepectrophotofluorometer Detectable concentration is Q under a length of 453nm of ejected wave1Test group solution, obtain fluorescence intensity F1；2., according to nitre in the mesotrione aqueous solution 1. sulphur humulone increasing concen-trations form repeat step three operates n-1 times, when n-th operates, mesotrione in the mesotrione aqueous solution Concentration is Qn, Qn≤ 3000nmol/L, using sepectrophotofluorometer in the case where excitation wavelength is 350nm, launch wavelength is 453nm It is F that detection, which obtains fluorescence intensity,n；3., according to Stern-Volmer equations be F0/ F=1+Ksv[Q], F in formula0It is molten for control group The fluorescence intensity of liquid, F be test group solution fluorescence intensity, F=F1~Fn, Q is nitre sulphur grass in the test group mesotrione aqueous solution The concentration of ketone, Q=Q1~Qn, KsvFor quenching constant Ksv, according to Q1~QnAnd F1~Fn, with F0/ F is y, Q x, KsvFor k, fitting Linear equation y=kx+1, finally give quenching constant KsvValue；
    4th, testing sample is detected：By dispersion liquid and testing sample by volume 1:1 is well mixed, obtains to be measured group of solution, utilizes Sepectrophotofluorometer detects to be measured group of solution in the case where excitation wavelength is 350nm, launch wavelength is 453nm, obtains fluorescence intensity Fu, it is F according to Stern-Volmer equations0/Fu=1+Ksv[Qu], F in formula0For the fluorescence intensity of control group solution, FuTo treat The fluorescence intensity of survey group solution, KsvFor quenching constant, the concentration Q of mesotrione in testing sample is calculatedu。
  10. It is 10. according to claim 9 a kind of residual using carbon quantum dot-molecular imprinting composite material analysis agricultural chemicals mesotrione The method stayed, it is characterised in that the quality of carbon quantum dot-molecular imprinting composite material and the body of high purity water described in step 1 Product ratio is 1mg:1mL.
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