CN109406474A - A kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method and application detecting rhodamine B - Google Patents

A kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method and application detecting rhodamine B Download PDF

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CN109406474A
CN109406474A CN201811354429.5A CN201811354429A CN109406474A CN 109406474 A CN109406474 A CN 109406474A CN 201811354429 A CN201811354429 A CN 201811354429A CN 109406474 A CN109406474 A CN 109406474A
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李媛媛
李恺
吴东明
何娟
侯莉宇
张作粮
单方涧
李雅静
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Henan University of Technology
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    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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Abstract

The invention discloses a kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method and applications for detecting rhodamine B, this method is binding molecule engram technology and detection technique of fluorescence, use warfarin for template molecule, α-methacrylic acid is function monomer, ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, and acetonitrile is solvent, functionalization AIE molecule is added, AIE-MIPs is synthesized using precipitation polymerization method.AIE-MIPs of the present invention is not only easy to operate, less using organic reagent, and has stronger recognition capability to rhodamine B, and is 1 × 10 in concentration range‑5‑10×10‑5Linear relationship is good in mol/L.AIE-MIPs is used for dry, the Finda beverage to actual sample pawpaw and carries out recovery testu, the results showed that the rate of recovery range of rhodamine B is 96.2-103.5%, and relative standard deviation range is 1.5-4.7%.The AIE-MIPs that detection technique of fluorescence is combined with molecular imprinting technology, which is illustrated, in these tables of data can be applied to the detection of rhodamine B in actual sample.

Description

A kind of aggregation-induced emission-molecular engram fluorescent optical sensor system detecting rhodamine B Preparation Method and application
Technical field
The present invention relates to a kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation methods for detecting rhodamine B And application, belong to rhodamine B technical field of analysis and detection.
Background technique
Rhodamine B is a kind of orchil of synthesis, has been used for fluorescent marker and edible pigment.But it is to people Class and animal are all harmful, especially generate stimulation to skin, eyes and respiratory tract, belong to carcinogen.Therefore, forbid in food Middle addition rhodamine B is as food additives.But bright-colored since rhodamine B is cheap, many businessmans are in order to save into The bigger profit of this acquisition continues to use rhodamine B as food additives, this compromises the health of the mankind significantly.Detect Luo Dan The conventional method of bright B has thin-layered chromatography and high performance liquid chromatography etc., and not only cost is very expensive for these methods, but also deposits In cumbersome problem.And due to the complicated component of food, the content of rhodamine B is low in food, need to actual sample into Row sample pretreatment, sample-pretreating method not only complex steps can generate a large amount of organic liquid waste, and lack selective absorption Ability.Therefore, the rhodamine B established in a kind of simple and rapid method measurement actual sample is necessary.
Molecularly imprinted polymer (Molecular Imprinting Polymers, abbreviation MIPs) is a kind of using molecule The polymer that engram technology is process, this technology make cavity and selected " template " molecule in polymeric matrix have parent And power.The polymer not only has specific recognition capability, also has selective absorption.And MIPs also has the advantage that One, the method for preparing MIPs is comparatively simple and economical, and most of MIPs are synthesized by substance law and precipitation polymerization method；The Two, MIPs have good physics and chemical stability；Finally, MIPs can be used in severe chemical environment, do not lose Absorption property.
Fluorescent optical sensor, which is commonly divided into, is quenched type fluorescent optical sensor, enhanced fluorescent optical sensor and Ratio-type fluorescence sense Device three types.The difference of principle according to response, different types of sensor are also different to the response modes of different material. Up to the present, most of fluorescent materials are all detected using single response signal, and this signal becomes vulnerable to fluorescence intensity Change and the influence of the external factor such as environment and instrument efficiency.And ratio measure by comparing two fluorescence peaks ratio rather than The absolute intensity at one peak obtains more accurate as a result, having the advantages that eliminating environment influences.
Since MIPs is polymer, belong to solid, thus find it is a kind of solid state issue intense fluorescence molecule be It is very important.Aggregation-induced emission (Aggregation-induced Emission, abbreviation AIE) molecule issues strong in solid-state Strong fluorescence, it is very useful for being introduced into MIPs.But there is presently no the reports for combining AIE with MIPs.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide one kind using AIE molecule as fluorophor, is with MIPs Recognition group, binding molecule engram technology and detection technique of fluorescence, using precipitation polymerization method, the aggregation of synthesis detection rhodamine B Induced luminescence-molecular engram fluorescent optical sensor (AIE-MIPs) preparation method and application, gained AIE-MIPs have rhodamine B There are stronger recognition capability and excellent selectivity.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method detecting rhodamine B, by functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate is combined with molecularly imprinted polymer, using precipitation polymerization Legal system obtains aggregation-induced emission-molecular engram fluorescent optical sensor AIE-MIPs.
Specifically, aggregation-induced emission-molecular engram fluorescent optical sensor of detection rhodamine B is the preparation method comprises the following steps: accurate It weighs warfarin 0.8-1.2mmol to be placed in there-necked flask, addition 0.1-0.3g azodiisobutyronitrile, 150-200mL acetonitrile, then 5-15mmol α-methacrylic acid is added, 60-100mmol ethylene glycol dimethacrylate adds 0.01-0.05mmol function AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate can be changed, ultrasonic vibration 15-30min dissolves it all, Under conditions of 70-90 DEG C, mechanic whirl-nett reaction 8-12h is filtered, and is dried, elution.
Preferably, aggregation-induced emission-molecular engram fluorescent optical sensor of rhodamine B is detected the preparation method comprises the following steps: accurate It weighs warfarin 1.0mmol to be placed in there-necked flask, 0.2g azodiisobutyronitrile is added, then 9mmol α-is added in 150mL acetonitrile Methacrylic acid, 60mmol ethylene glycol dimethacrylate add 0.01mmol functionalization AIE molecule 4- (1,2,2- tri- Phenyl vinyl) phenyl acrylate, ultrasonic vibration 15min, make its all dissolve, under conditions of 83 DEG C, mechanical stirring is anti- 8h is answered, is filtered, is dried, elution.
The method of elution are as follows: build soxhlet type apparatus, the mixed liquor of 200-300mL methanol and acetic acid is added, will synthesize Good AIE-MIPs is wrapped with filter paper to be put into Soxhlet extraction device, after 90-100 DEG C of temperature control, elution 2-3 days, uses 100- The pure methanol elution of 300mL, at regular intervals with the fluorescence spectrum of fluorescence detector measurement eluent, the fluorescence of warfarin molecule Launch wavelength is 385nm, then illustrates that elution is clean without peak at this wavelength, is finally dried for standby.
The volume ratio of methanol and acetic acid is 4:1-6:1 in the mixed liquor of methanol and acetic acid.
Functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate the preparation method comprises the following steps:
(1) it weighs 1.5-2.5mmol triphen vinyl bromide to be put into round-bottomed flask, 2-3mmol 4- hydroxy benzenes boron is then added Acid, 20-30mmol potassium carbonate, 0.05-0.10mmol tetra- (triphenyl phosphorus) palladium, 10-20mL water and 20-30mL tetrahydrofuran are taken out Empty flask is simultaneously filled with nitrogen protection, reacts 12-24h under conditions of 75-95 DEG C；Products therefrom is filtered, filtrate is collected, with two Organic phase is collected after chloromethanes extraction；After the drying of 5g anhydrous sodium sulfate is added, by pillar layer separation, functionalization AIE points are obtained Sub- intermediate 4- (1,2,2- triphenyl vinyl) phenol；
(2) 3-5mmol functionalization AIE molecule intermediate is dissolved in 25mL methylene chloride, tri- second of 10-12mmol is added Amine, and 8-10mmol acryloyl chloride is added dropwise, 4-6h is stirred at room temperature, is filtered, and vacuum distillation removes solvent, obtains functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate crude product；By pillar layer separation, pure functionalization is obtained AIE molecule.
Preferably, functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate the preparation method comprises the following steps:
(1) it weighs 2mmol triphen vinyl bromide to be put into round-bottomed flask, 2.4mmol 4- hydroxyl phenyl boric acid is then added, 20mmol potassium carbonate, 0.1mmol tetra- (triphenyl phosphorus) palladium, 15mL water and 25mL tetrahydrofuran evacuate flask and are filled with nitrogen guarantor Shield, reacts 12h under conditions of 85 DEG C；Products therefrom is filtered, filtrate is collected, collects organic phase after being extracted with dichloromethane； After the drying of 5g anhydrous sodium sulfate is added, by pillar layer separation, functionalization AIE molecule intermediate 4- (1,2,2- triphenyl is obtained Vinyl) phenol；
(2) 4mmol functionalization AIE molecule intermediate is dissolved in 25mL methylene chloride, 12mmol triethylamine is added, and 8mmol acryloyl chloride is added dropwise, stirs 4h at room temperature, filters, vacuum distillation removes solvent, obtains functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate crude product；By pillar layer separation, pure functionalization AIE molecule is obtained.
Eluant, eluent used in pillar layer separation is the petroleum ether-ethyl acetate of volume ratio 1:30-1:10.
A method of rhodamine B being detected using aggregation-induced emission-molecular engram fluorescent optical sensor, by AIE- obtained MIPs is added in testing sample solution, and room temperature on shaking table is placed on after mediation 1-5min and adsorbs 1-3h, is filtered, with 5-15mL dichloromethane Alkane elution, is drained, fluorescence detection.
The condition of fluorescence detection: excitation wavelength is set as 345nm, and record transmitting range is 370-680nm.
The invention has the advantages that:
1, functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate prepared by the present invention belongs to four Phenylethylene AIE molecule, it is good with fluorescence quantum yield height, structural stability, and synthesize simple, low in cost, easy modification Outstanding advantages of.Since AIE molecule issues strong fluorescence in solid-state, AIE molecule is introduced into MIPs, fluorescence can be passed through Spectrometer in situ detection rhodamine B.
2, binding molecule engram technology and detection technique of fluorescence of the present invention, use warfarin for template molecule, Alpha-Methyl third Olefin(e) acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, and acetonitrile is solvent, Functionalization AIE molecule is added, AIE-MIPs is synthesized using precipitation polymerization method.After AIE-MIPs and determinand are specifically bound, Change in fluorescence can be directly generated in situ, by the variation of on-line checking fluorescence intensity, realize the detection to determinand.It is another Aspect, since target analytes rhodamine B itself has color, it is difficult to which elution is clean completely, influences AIE-MIPs absorption front and back The judgement of color change, therefore the present invention selects structure similar and does not have coloured warfarin as alternate template, using precipitating Polymerization synthesizes AIE-MIPs.
3, AIE-MIPs of the present invention is not only easy to operate, less using organic reagent, and has specific adsorption ability, energy Enough specific adsorption target molecules from complex system, the interference of despumation improve detection sensitivity and accuracy.Detection AIE-MIPs adsorbs the fluorescence spectrum discovery after the rhodamine B solution of various concentration, and AIE-MIPs has rhodamine B stronger Recognition capability, and linear relationship is good.It is 1 × 10 with AIE-MIPs difference adsorption concentration-5The rhodamine B of mol/L, brilliant blue, Famille rose, amaranth, famille rose and the red solution of temptation, and its fluorescence spectrum is tested respectively, discovery AIE-MIPs is molten to rhodamine B Liquid has excellent selectivity.And the AIE-MIPs after adsorbing can not have to elution, directly progress on-line checking.
4, fluorescent optical sensor AIE-MIPs of the invention, when detecting rhodamine B, with the increase of rhodamine B concentration, function The fluorescence peak that AIE molecule can be changed gradually decreases, and the fluorescence peak of rhodamine B gradually rises, and changes in Ratio-type.AIE-MIPs is to sieve After the standard curve of red bright B detection shows AIE-MIPs absorption rhodamine B solution, its fluorescence spectrum of on-line checking, in concentration model Enclose is 1 × 10-5-10×10-5Linear relationship is good in mol/L.AIE-MIPs is used to the dry, Finda to actual sample pawpaw to drink Material carries out recovery testu, the results showed that the rate of recovery range of rhodamine B is 96.2-103.5%, relative standard deviation range For 1.5-4.7%.The AIE-MIPs that detection technique of fluorescence is combined with molecular imprinting technology, which is illustrated, in these tables of data to answer Detection for rhodamine B in actual sample.
Detailed description of the invention
Fig. 1 is exciting light spectrogram (line a) and transmitted wave spectrogram (the line b) of functionalization AIE molecule.
Exciting light spectrogram (line a) and launching light spectrogram (the line b) that Fig. 2 is AIE-MIPs.
Fluorogram (a) of Fig. 3 functionalization AIE molecule in water/ethyl alcohol and uv absorption spectra (b).In figure, arrow Indicate that the volume fraction of water increases direction.
Fig. 4 is fluorescence spectra of the functionalization AIE molecule in glycerine/ethyl alcohol.In figure, arrow indicates the body of glycerine Fraction increases direction.
Fig. 5 is that AIE-MIPs adsorbs fluorescence spectra (a) and line style relational graph (b) after various concentration rhodamine B.
Fig. 6 is the fluorescence intensity ratio figure that AIE-MIPs and AIE-NIPs changes with rhodamine B concentration.
Fig. 7 is the fluorescence intensity ratio figure that AIE-MIPs adsorbs different pigments.
Fig. 8 is the standard curve that AIE-MIPs detects rhodamine B.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
The preparation of embodiment 1, functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate
(1) it weighs 2mmol triphen vinyl bromide to be put into 100mL round-bottomed flask, 2.4mmol 4- hydroxy benzenes boron is then added Acid, 20mmol potassium carbonate provide alkaline environment, add 0.10mmol tetra- (triphenyl phosphorus) palladium, 15mL water and 25mL tetrahydrofuran (THF) it is used as solvent, evacuate flask and is filled with nitrogen protection, reacts 12h under conditions of 85 DEG C；Products therefrom is filtered, is received Collect filtrate, collects organic phase after being extracted with dichloromethane；After the drying of 5g anhydrous sodium sulfate is added, pass through pillar layer separation (elution Agent be volume ratio 1:30-1:10 petroleum ether-ethyl acetate, gradient elution), obtain functionalization AIE molecule intermediate 4- (1,2, 2- triphenyl vinyl) phenol；
(2) 4mmol functionalization AIE molecule intermediate is dissolved in 25mL methylene chloride, 12mmol triethylamine is added, and 8mmol acryloyl chloride is added dropwise, stirs 4h at room temperature, filters, vacuum distillation removes solvent, obtains functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate crude product；By pillar layer separation, (eluant, eluent is volume ratio 1:30-1:10's Petroleum ether-ethyl acetate, gradient elution), obtain pure functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenylpropen Acid esters.
Products therefrom is characterized using high resolution mass spectrum, the cation peak that molecular weight is 403.1695 is obtained, with mesh The molecular weight (403.1693) for marking molecule protonation is consistent, it was demonstrated that is 4- (1,2,2- triphenyl vinyl) phenyl acrylate. Further, by elemental analysis, the constituent content obtained in product is C 86.59%, H 5.55%, O 7.86%, with theory Value C86.54%, H 5.51%, O 7.95% matches.To functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl Acrylate carries out spectrum analysis, the result is shown in Figure 1.As shown in Figure 1, the maximum excitation wavelength of functionalization AIE molecule is 365nm, Best launch wavelength is 453nm.
The preparation of embodiment 2, aggregation-induced emission-molecular engram fluorescent optical sensor (AIE-MIPs)
It accurately weighs warfarin 1.0mmol to be placed in 250mL there-necked flask, be added 0.2g azodiisobutyronitrile (AIBN), Then 9mmol α-methacrylic acid (α-MAA) is added in 150mL acetonitrile, 60mmol ethylene glycol dimethacrylate (EDMA), Add 0.01mmol functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate (the 1/ of template mole 100), ultrasonic vibration 15min dissolves it all, and under conditions of 83 DEG C, mechanic whirl-nett reaction 8h is filtered, and dries, elution, Obtain AIE-MIPs.
Wherein, the method for elution are as follows: build soxhlet type apparatus, the mixed of 200mL methanol and acetic acid (volume ratio 4:1) is added Liquid is closed, synthetic AIE-MIPs is wrapped with filter paper and is put into Soxhlet extraction device, after 90 DEG C of temperature control, elution 3 days, is used The pure methanol elution of 150mL, at regular intervals with the fluorescence spectrum of fluorescence detector measurement eluent, the fluorescence of warfarin molecule Launch wavelength is 385nm, then illustrates that elution is clean without peak at this wavelength, is finally dried for standby.
Fig. 2 is the fluorescence excitation and emission spectra figure of AIE-MIPs, as shown in Figure 2, the maximum excitation wavelength of AIE-MIPs It is 345nm, best launch wavelength is 450nm.
The test of embodiment 3, functionalization AIE molecule performance
Influence of 3.1 solvents to functionalization AIE molecular fluorescence intensity
Respectively with water/ethyl alcohol mixed solvent (volume fraction of water is respectively 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%) compound concentration be 1 × 10-5Mol/L functionalization AIE molecular solution, spare, inspection Fluorescence spectrum is surveyed, as a result sees Fig. 3 (a).By Fig. 3 (a) it is found that fluorescent emission obviously increases when the volume fraction of water reaches 70% By force.Fluorescence intensity ratio fluorescence intensity in straight alcohol of the functionalization AIE molecule in pure water is 45 times high.Under normal circumstances, water It is the poor solvent of most of organic matters, functionalization AIE molecule is assembled in water, therefore generates strong fluorescence, i.e. AIE It shines.Therefore, with the increase of the volume fraction of in the mixed solvent water, functionalization AIE molecule is gradually assembled, and functionalization AIE points The fluorescence of son gradually increases.
It is the aggregation because of functionalization AIE molecule to further verify the fluorescence in water/ethyl alcohol, has detected UV absorption Spectrum, as shown in Fig. 3 (b).In alcohol solvent, functionalization AIE molecule has good dissolubility, and occurs at 312nm One absorption peak.However, aggregation can be generated in the solution since the solubility of functionalization AIE molecule in water is lower, To which light scattering phenomenon occur.The fine structure of corresponding ultra-violet absorption spectrum disappears and in the visual field 260-500nm of spectrum It being capable of ultraviolet trailing phenomenon visible in detail, it was demonstrated that functionalization AIE molecule is in coherent condition in water.
Influence of 3.2 solvent viscosities to luminescent properties
Respectively with glycerine/ethyl alcohol mixed solvent (volume fraction of glycerine be 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%) compound concentration be 1 × 10-5Mol/L functionalization AIE molecular solution, it is standby With as a result detection fluorescence spectrum is shown in Fig. 4.As shown in Figure 4, the luminescent properties of functionalization AIE molecule are influenced by solvent viscosity. In glycerine/alcohol solvent of different proportion, as the volume fraction of glycerine increases, the fluorescence of functionalization AIE molecule is strong Degree gradually increases.This is because solvent viscosity increases, the Internal Rotations of Molecules of functionalization AIE molecule is limited, so that functionalization AIE Molecule issues very strong fluorescence.
Embodiment 4, AIE-MIPs Static Adsorption curve measurement
Various concentration gradient (0,1 × 10 is prepared with distilled water-6、5×10-6、1×10-5、5×10-5、1×10-4、5×10-4Mol/L rhodamine B solution), accurately weigh 6 parts of AIE-MIPs and 6 part of AIE-NIPs (the same AIE-MIPs of preparation method, uniquely Difference is to be added without warfarin) 60mg is individually placed in 10mL centrifuge tube, each rhodamine B that the above-mentioned various concentration of 5mL is added Solution, after mediation 1min under be placed on room temperature on shaking table and adsorb 1h, filter, with 5mL eluent methylene chloride, drain, obtain adsorbing not With AIE-MIPs the and AIE-NIPs solid of concentration rhodamine B, for fluorescence spectrum detection (Fig. 5,6).
By Fig. 5 (a) it is found that after the rhodamine B solution of AIE-MIPs absorption various concentration, fluorescence peak at 450nm by It gradually reduces, fluorescence peak gradually rises at 582nm, changes in Ratio-type.By Fig. 5 (b) it is found that being 1 × 10 in rhodamine B concentration-6- 1×10-4In the range of mol/L, the 582nm and fluorescence intensity ratio (I at 450nm wavelength582/I450) and rhodamine B solution With good linear relationship, linear equation y=0.00606+0.02475x, wherein R2=0.9992.
It will be appreciated from fig. 6 that when the rhodamine B of absorption various concentration, I corresponding to AIE-MIPs582/I450Always compare AIE- I corresponding to NIPs582/I450Greatly.This illustrates that the adsorption capacity of the adsorption capacity ratio AIE-NIPs of AIE-MIPs is strong.
The adsorption selectivity test of embodiment 5, AIE-MIPs
1 × 10 is prepared respectively-5The temptation of mol/L is red, carmine, amaranth, magenta, brilliant blue, rhodamine B solution, accurately It weighs 6 parts of AIE-MIPs 60mg to be respectively put into 10mL centrifuge tube, each different material solution that the above-mentioned same concentrations of 5mL are added, It is placed on room temperature on shaking table after mediation 1min and adsorbs 1h, filters, with 5mL eluent methylene chloride, drains, obtains absorption different material AIE-MIPs solid.AIE-MIPs after absorption is used for fluorescence spectrum detection (Fig. 7).As shown in Figure 7, AIE-MIPs adsorbs sieve Corresponding I after red bright B solution582/I450Much larger than other pigments.This illustrates that AIE-MIPs has choosing very well to rhodamine B The absorption of selecting property and detectability.
Embodiment 6, actual sample analysis
The drafting of 6.1 standard curves
Prepare various concentration gradient (1 × 10-5、2×10-5、3×10-5、4×10-5、5×10-5、6×10-5、7×10-5、8 ×10-5、9×10-5、10×10-5Mol/L rhodamine B solution) accurately weighs 10 parts of AIE-MIPs 60mg and is respectively put into In 10mL centrifuge tube, the solution of the above-mentioned various concentration of 5mL is respectively added, room temperature on shaking table is placed on after mediation 1min and adsorbs 1h, is filtered, It with 5mL eluent methylene chloride, drains, obtains the AIE-MIPs solid of absorption rhodamine B, every a solid is subjected to fluorescence spectrum Detection.Above-mentioned experiment does three groups in parallel, as a result sees Fig. 8.
As shown in Figure 8,1 × 10-5-10×10-5Within the scope of mol/L, AIE-MIPs has rhodamine B solution good Linearity test ability, linear equation are as follows: y=0.44247+0.24773x, R2=0.99698.
The processing of 6.2 actual samples
The processing of pawpaw dry-eye disease: it accurately weighs 30.00g and grinds that uniform pawpaw is dry to be placed in 250mL conical flask, be added 90mL Tris buffer solution (pH=7.5), concussion mixes 10min on shaking table, and ultrasonic extraction 10min is transferred to centrifuge tube In, 10min is centrifuged at 4000rpm with extraction fluid and the dry precipitating of pawpaw, it is dry heavy that repetition above step extracts pawpaw repeatedly It forms sediment three times, merges supernatant, be settled to 300mL with Tris buffer solution, reuse Buchner funnel, bottle,suction adds 0.45 μm of filter membrane Filtering, filtrate is stored in spare in conical flask.
The processing of Finda beverage: accurately weighing 30.00g beverage, and heating boils 5min to remove CO in beverage on electric furnace2And Other volatile impurity are settled to 300mL with Tris buffer solution, add 0.45 μm of membrane filtration using Buchner funnel, bottle,suction, It is stored in spare in conical flask.
The application of 6.3AIE-MIPs rhodamine B in detection actual sample
60mg AIE-MIPs is accurately weighed in 10mL centrifuge tube, testing sample solution 5mL is added, is put after mediation 1min Room temperature adsorbs 1h on shaking table, filters, with 5mL eluent methylene chloride, drains, and collects filter cake, is measured and is sent out using Fluorescence Spectrometer Penetrate spectrogram.It is parallel to carry out three groups, and repetition above step carries out 3.0 × 10 using actual sample as matrix respectively-5、6.0× 10-5、9.0×10-5The mark-on of mol/L rhodamine B solution is tested, and the results are shown in Table 1.
The recovery of standard addition of 1 actual sample of table
As shown in Table 1, recovery of standard addition the range 101.7-103.5%, relative standard deviation (Relative of Finda beverage Standard Deviation, abbreviation RSD) range be 2.2-3.5%；The dry recovery of standard addition range 96.2- of pawpaw The range of 98.7%, RSD are 1.5-4.7%.Thus it can illustrate that the recovering effect of this method is good, can be used for rhodamine in food The analysis detection of B.
The foregoing is merely preferred embodiments of the present invention, and for those skilled in the art, the present invention can have Various modifications and variations.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on, should all It is included within protection scope of the present invention.

Claims (10)

1. a kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method for detecting rhodamine B, which is characterized in that Functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate is combined with molecularly imprinted polymer, is used Aggregation-induced emission-molecular engram fluorescent optical sensor AIE-MIPs is made in precipitation polymerization method.
2. preparation method according to claim 1, which is characterized in that method particularly includes: accurately weigh warfarin 0.8- 1.2mmol is placed in there-necked flask, and 0.1-0.3g azodiisobutyronitrile is added, then 5-15mmol α-is added in 150-200mL acetonitrile Methacrylic acid, 60-100mmol ethylene glycol dimethacrylate add 0.01-0.05mmol functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate, ultrasonic vibration 15-30min dissolve it all, in 70-90 DEG C of item Under part, mechanic whirl-nett reaction 8-12h is filtered, and is dried, elution.
3. preparation method according to claim 2, which is characterized in that it is preferred, method particularly includes: accurately weigh warfarin 1.0mmol is placed in there-necked flask, and 0.2g azodiisobutyronitrile is added, then 9mmol α-methacrylic acid is added in 150mL acetonitrile, 60mmol ethylene glycol dimethacrylate adds 0.01mmol functionalization AIE molecule 4- (1,2,2- triphenyl vinyl) Phenyl acrylate, ultrasonic vibration 15min dissolve it all, and under conditions of 83 DEG C, mechanic whirl-nett reaction 8h is filtered, and dry It is dry, elution.
4. preparation method according to claim 2, which is characterized in that the method for elution are as follows: build soxhlet type apparatus, add Synthetic AIE-MIPs is wrapped with filter paper and is put into Soxhlet extraction device by the mixed liquor for entering 200-300mL methanol and acetic acid In, after 90-100 DEG C of temperature control, elution 2-3 days, is eluted with the pure methanol of 100-300mL, surveyed at regular intervals with fluorescence detector Determine the fluorescence spectrum of eluent, the fluorescence emission wavelengths of warfarin molecule are 385nm, then illustrate that elution is dry without peak at this wavelength Only, it is finally dried for standby.
5. the preparation method according to claim 4, which is characterized in that methanol and acetic acid in the mixed liquor of methanol and acetic acid Volume ratio is 4:1-6:1.
6. preparation method according to claim 1-5, which is characterized in that functionalization AIE molecule 4- (1,2,2- tri- Phenyl vinyl) phenyl acrylate the preparation method comprises the following steps:
(1) it weighs 1.5-2.5mmol triphen vinyl bromide to be put into round-bottomed flask, 2-3mmol 4- hydroxyl phenyl boric acid is then added, 20-30mmol potassium carbonate, 0.05-0.10mmol tetra- (triphenyl phosphorus) palladium, 10-20mL water and 20-30mL tetrahydrofuran are evacuated and are burnt Bottle is simultaneously filled with nitrogen protection, reacts 12-24h under conditions of 75-95 DEG C；Products therefrom is filtered, filtrate is collected, uses dichloromethane Organic phase is collected after alkane extraction；After the drying of 5g anhydrous sodium sulfate is added, by pillar layer separation, obtain in functionalization AIE molecule Mesosome 4- (1,2,2- triphenyl vinyl) phenol；
(2) 3-5mmol functionalization AIE molecule intermediate is dissolved in 25mL methylene chloride, 10-12mmol triethylamine is added, And 8-10mmol acryloyl chloride is added dropwise, 4-6h is stirred at room temperature, is filtered, and vacuum distillation removes solvent, obtains functionalization AIE Molecule 4- (1,2,2- triphenyl vinyl) phenyl acrylate crude product；By pillar layer separation, pure functionalization AIE points are obtained Son.
7. preparation method according to claim 6, which is characterized in that preferred, functionalization AIE molecule 4- (1,2,2- tri- Phenyl vinyl) phenyl acrylate the preparation method comprises the following steps:
(1) it weighs 2mmol triphen vinyl bromide to be put into round-bottomed flask, 2.4mmol 4- hydroxyl phenyl boric acid, 20mmol is then added Potassium carbonate, 0.1mmol tetra- (triphenyl phosphorus) palladium, 15mL water and 25mL tetrahydrofuran evacuate flask and are filled with nitrogen protection, 85 12h is reacted under conditions of DEG C；Products therefrom is filtered, filtrate is collected, collects organic phase after being extracted with dichloromethane；Be added 5g without After aqueous sodium persulfate is dry, by pillar layer separation, functionalization AIE molecule intermediate 4- (1,2,2- triphenyl vinyl) benzene is obtained Phenol；
(2) 4mmol functionalization AIE molecule intermediate is dissolved in 25mL methylene chloride, 12mmol triethylamine is added, and dropwise Be added 8mmol acryloyl chloride, stir 4h at room temperature, filter, vacuum distillation remove solvent, obtain functionalization AIE molecule 4- (1,2, 2- triphenyl vinyl) phenyl acrylate crude product；By pillar layer separation, pure functionalization AIE molecule is obtained.
8. preparation method according to claim 6, which is characterized in that eluant, eluent used in pillar layer separation is volume ratio 1: The petroleum ether-ethyl acetate of 30-1:10.
9. a kind of aggregation-induced emission using the preparation of claim 1 the method-molecular engram fluorescent optical sensor detects Luo Dan The method of bright B, which is characterized in that AIE-MIPs obtained is added in testing sample solution, is placed on shaking table after mediation 1-5min Upper room temperature adsorbs 1-3h, filters, with 5-15mL eluent methylene chloride, drains, fluorescence detection.
10. method according to claim 9, which is characterized in that the condition of fluorescence detection: excitation wavelength is set as 345nm, record Transmitting range is 370-680nm.
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