CN116970390B - Hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere, preparation method and application thereof - Google Patents
Hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere, preparation method and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 26
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 45
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention provides a hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere, a preparation method and application thereof. The preparation method of the microsphere provided by the invention comprises the following steps: and synthesizing a Sudan red I molecularly imprinted shell layer on the surface of the ZIF-8 by taking the metal organic framework ZIF-8 as a support carrier, eluting and removing template molecules under an acidic condition, decomposing the ZIF-8 carrier at the same time, enabling the obtained molecularly imprinted polymer to take on a hollow structure, mixing the molecular imprinted polymer as an encoding matrix with all-inorganic perovskite quantum dots, preparing the hollow fluorescent encoding microsphere, and rapidly detecting the Sudan red I. The invention not only simplifies the synthesis mode of the hollow molecularly imprinted polymer, but also greatly shortens the coding time in the fluorescent coding process and improves the fluorescent intensity of the coded microsphere due to the advantages of the hollow molecularly imprinted polymer in the rapid mass transfer and adsorption quantity, shortens the detection time to 10min in the detection process, and has great potential in the rapid detection aspect.
Description
Technical Field
The invention belongs to the technical field of optical sensing material preparation and food safety detection, and particularly relates to a hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere, a preparation method and application thereof.
Background
Through continuous research in recent years, the molecular imprinting technology has been developed into a mature method for preparing a specific adsorption material, and the molecular imprinting polymer (Molecular Imprinting Polymers, MIPs) obtained by the method can specifically identify target molecules and can realize accurate capture of the target molecules in a complex sample matrix, so that MIPs are widely applied to the field of fluorescence sensing to solve the problem of lack of specificity of fluorescent materials. However, in the preparation process of the traditional fluorescent molecularly imprinted polymer, compatibility of a fluorescent material and a molecularly imprinted polymer synthesis system needs to be considered, and the layer-by-layer coating not only makes the steps complicated, but also easily causes the performance of the fluorescent material to be weakened.
The optical coding microsphere can be obtained by embedding different fluorescent elements into a coding matrix, and has the advantages of simple operation, quick reading, low cost and the like. Aiming at the preparation problem of the traditional molecularly imprinted fluorescent sensing material, the combination of the molecularly imprinted polymer and the optical coding concept can well solve the problem that the molecularly imprinted polymer is taken as a coding matrix and the fluorescent material is taken as a coding element, so that the fluorescent material enters the matrix through the interaction between the molecularly imprinted polymer and the coding element, and the fluorescent property of the molecularly imprinted polymer is endowed.
However, the development of the optical coding microsphere is limited by the high crosslinking property of the solid molecularly imprinted polymer, the embedding depth of imprinting sites and long coding time, and when the optical coding microsphere is used for food detection, the detection time is long due to large mass transfer resistance and slow mass transfer rate.
In order to reduce mass transfer resistance and provide a way to more easily access target molecules, many strategies such as hollow molecularly imprinted polymers, surface molecularly imprinted, mesoporous molecularly imprinted polymers, etc. have been proposed so far, among molecularly imprinted polymers having good morphology, molecularly imprinted polymers (HMIPs) having a hollow structure have been receiving increasing attention due to their excellent properties (low density, large specific surface area, large adsorption capacity and fast mass transfer rate); the surface imprinting process is to polymerize the molecularly imprinted polymer on the surface of the molecularly imprinted polymer by taking the core layer particles as a supporting material, and imprinting sites only exist in a shell layer, which is very beneficial to elution and re-adsorption of a target object, but the introduced core layer particles do not have specific recognition sites, but occupy the mass of the molecularly imprinted polymer instead, and the binding capacity of the molecularly imprinted polymer per unit mass is reduced. Therefore, the support material of the inner layer is removed, the hollow molecularly imprinted polymer is prepared, namely, only the imprinted shell layer is reserved, the combination capacity of the polymer per unit mass is greatly improved, and meanwhile, the metal organic framework material ZIF-8 has the characteristics of good thermal stability, large specific surface area, unique pore channel structure, easiness in synthesis and the like, and is an ideal support material when disintegrated under an acidic condition.
All-inorganic perovskite quantum dot CsPbX 3 (x=cl, br, I) has attracted extensive attention as a novel fluorescent material because of its advantages of higher photoluminescence quantum yield (PLQY > 90%), narrower half-width, adjustable emission wavelength, and the like, and has shown great potential in many fields such as solar cells, photodetectors, and light emitting diodes. However, all-inorganic perovskite quantum dots can accelerate the decomposition rate in high temperature, high humidity, oxygen or strong light irradiation environments, and particularly show strong instability when exposed to water. Therefore, the fluorescent coding microsphere is prepared by combining the specific recognition of the hollow molecularly imprinted polymer and the excellent optical characteristics of the all-inorganic perovskite quantum dot, so that the specific recognition capability and the fluorescence intensity of the fluorescent coding microsphere are improved, and the stability of the perovskite quantum dot is also improved.
Sudan red i is a lipophilic azo dye commonly used as a colorant in motor oils, waxes, textiles, and greases. The food standards agency and the European Union have stipulated that Sudan red I, II, III and IV have been identified as potential carcinogens and mutagens and have been listed by the International agency for research on cancer (IARC) as class III carcinogens. At present, a chromatographic analysis method is mostly adopted for quantitative analysis of Sudan red, and although the accuracy is high and the sensitivity is strong, the equipment is large in size, special technicians are required for operation, the detection time is long, and especially the real-time detection requirement cannot be met for emergency. Therefore, on the basis of ensuring accuracy and sensitivity, a novel rapid detection method is developed, and the detection flow and time are shortened, so that the research is necessary.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere, a preparation method and application thereof.
The hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere provided by the invention is prepared by the following method: adding all inorganic perovskite quantum dots into an organic solvent, then adding a hollow molecularly imprinted polymer, dispersing uniformly, combining the quantum dots and the hollow molecularly imprinted polymer to finish coding, washing to obtain a supernatant without fluorescence, and drying to obtain the hollow molecularly imprinted perovskite quantum dot fluorescence coding microsphere.
According to the invention, the hollow molecularly imprinted polymer is adopted to replace the traditional molecularly imprinted polymer to be combined with the all-inorganic perovskite quantum dots, so that the problems of deep embedding of imprinted sites, influence on release rate of fluorescent materials and the like caused by high crosslinking degree of the traditional molecularly imprinted polymer are avoided, the mass transfer rate between the fluorescent materials and the Molecularly Imprinted Polymer (MIPs) is accelerated, and the coding time is shortened.
In addition, the hollow MIPs provided by the invention not only have larger specific surface area, but also have a stable framework structure, so that when the perovskite quantum dots are filled in the hollow positions inside the hollow MIPs, the interaction of the perovskite quantum dots and the hollow MIPs improves the stability of the perovskite quantum dots in the environment.
Furthermore, the preparation method of the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere provided by the invention comprises the following steps:
(1) Preparing a metal organic framework material;
(2) Preparing a hollow molecularly imprinted polymer;
(3) Preparing hollow molecular imprinting perovskite quantum dot fluorescent coding microspheres: adding all inorganic perovskite quantum dots into an organic solvent, adding the hollow molecularly imprinted polymer prepared in the step (2), uniformly dispersing, enabling the quantum dots and the hollow molecularly imprinted polymer to be combined to finish coding, washing to obtain a supernatant without fluorescence, and drying in a dark place at the temperature of 23-26 ℃ to obtain the hollow molecularly imprinted perovskite quantum dot fluorescence coding microsphere.
In the above steps, the all-inorganic perovskite quantum dot is CsPbBr 3 Quantum dot CsPbCl 1.5 Br 1.5 Quantum dot and CsPbI 2 Any one of the Br quantum dots.
The organic solvent is selected from any one of straight-chain saturated alkane with 5-8 carbon atoms.
Preferably, the organic solvent is n-hexane.
In the above steps, the metal organic framework material is ZIF-8.
In the step (1), the preparation method of the metal organic framework material comprises the following steps: respectively dissolving zinc nitrate and 2-methylimidazole in methanol, dissolving the zinc nitrate and the 2-methylimidazole by ultrasonic treatment, slowly adding the methanol solution of the 2-methylimidazole into the methanol solution of the zinc nitrate, stirring in a dark place, centrifuging the obtained suspension, washing with methanol, and drying in vacuum to constant temperature to obtain the metal organic framework material ZIF-8.
Preferably, in the step (1), the ratio of the amount of the zinc nitrate to the amount of the substance of 2-methylimidazole is 1:4.
preferably, in step (1), stirring is carried out at 1,000rpm for 24 hours in the absence of light.
In the step (2), the preparation method of the hollow molecularly imprinted polymer is as follows:
adding the metal organic framework material obtained in the step (1) into a pore-forming agent acetonitrile, dispersing, adding template molecules, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate, divinylbenzene and initiator azodiisobutyronitrile, uniformly mixing, introducing nitrogen for deoxidization, sealing and heating, and reacting to prepare a polymer; eluting the prepared polymer with a mixed solution of methanol and acetic acid, removing template molecules, dissolving out a metal organic framework material, washing with methanol to be neutral, and drying to obtain the hollow molecularly imprinted polymer.
In the invention, the polymer obtained by the reaction is eluted by adopting the organic solvent with stronger polarity, namely methanol, so that the polymer can be well cleaned, and the residual acetic acid in the polymer can be washed away.
Preferably, the template molecule in the step (2) is any one of Sudan red I, sudan red II, sudan red III and Sudan red IV.
Preferably, the template molecule in step (2) is sudan red I.
Preferably, the template molecule described in step (2): functional monomer: the mass ratio of the cross-linking agent is 1:4:20.
preferably, in the crosslinking agent described in the step (2), the ratio of ethylene glycol dimethacrylate to divinylbenzene is 1:1.
preferably, in the mixed solution of methanol and acetic acid in the step (2), the volume ratio of methanol to acetic acid is 8-9: 2 to 1.
Preferably, in the mixed solution of methanol and acetic acid in the step (2), the volume ratio of methanol to acetic acid is 8:2.
preferably, in the step (2), the raw materials are uniformly mixed in an ultrasonic vibration mode.
Preferably, in the step (2), the water bath heating is carried out for 20 to 30 hours at the temperature of 50 to 65 ℃.
Preferably, in the step (2), the polymer is eluted by using a mixed solution of methanol and acetic acid using a Soxhlet extraction apparatus.
Preferably, the drying in the step (2) is performed under the condition of 50-65 ℃ for 20-30 hours.
More specifically, in the step (2), the preparation method of the hollow molecularly imprinted polymer comprises the following steps: adding the metal organic framework material obtained in the step (1) into a pore-forming agent acetonitrile, performing ultrasonic treatment to disperse the metal organic framework material in the acetonitrile, and adding template molecules, functional monomer methacrylic acid, cross-linking agent glycol dimethacrylate, divinylbenzene and initiator azo diisobutyronitrile; ultrasonic mixing, introducing nitrogen to deoxidize, sealing, and placing in a water bath at 50-65 ℃ to stir for 20-30 h; and eluting the polymer by using a soxhlet extraction device and using a mixed solution of methanol and acetic acid to remove template molecules, dissolving out a metal organic framework material, washing to be neutral by using methanol, and drying for 20-30 hours at 50-65 ℃ to obtain the hollow molecularly imprinted polymer.
In the preparation process of the hollow molecularly imprinted polymer, the instability of the ZIF-8 metal organic framework material under an acidic condition is skillfully utilized, and the ZIF-8 core is removed simultaneously when a methanol-acetic acid mixed solution is adopted for template elution, so that the uniformity of the hollow molecularly imprinted polymer and the overall stability of the polymer are improved, the problems of poor polymer uniformity, poor stability and the like possibly caused by directly filling the hollow metal organic framework material and template molecules are avoided, and in addition, the dissolution mode adopted in the preparation process of the hollow molecularly imprinted polymer is mild, and the damage of a strong acid and strong alkali use or calcination processing mode to the molecularly imprinted layer in the traditional preparation process of the hollow molecularly imprinted polymer is avoided.
In the step (3), the mass ratio of the all-inorganic perovskite quantum dots to the hollow molecularly imprinted polymer is 1:10.
further, the preparation method of the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere provided by the invention comprises the following steps:
(1) Preparing a metal organic framework material: zinc nitrate and 2-methylimidazole were dissolved in methanol respectively, and the ratio of the amounts of the zinc nitrate and 2-methylimidazole was 1:4, dissolving the two by ultrasonic, slowly adding a methanol solution of 2-methylimidazole into a methanol solution of zinc nitrate, stirring for 24 hours in a dark place at a rotating speed of 1,000rpm, centrifuging the obtained suspension, washing with methanol, and drying in vacuum to a constant temperature to obtain a metal organic framework ZIF-8;
(2) Preparation of hollow molecularly imprinted polymer: adding the metal organic framework material obtained in the step (1) into a pore-forming agent acetonitrile, performing ultrasonic treatment to disperse the metal organic framework material in the acetonitrile, and adding a template molecule, a functional monomer methacrylic acid, a cross-linking agent glycol dimethacrylate, divinylbenzene and an initiator azodiisobutyronitrile, wherein the template molecule is as follows: functional monomer: the mass ratio of the cross-linking agent is 1:4:20, a step of; in the cross-linking agent, the ratio of the ethylene glycol dimethacrylate to the divinylbenzene is 1:1, uniformly mixing by ultrasonic, introducing nitrogen to remove oxygen, sealing, and then placing in a water bath at 50-65 ℃ to stir for 20-30 h to obtain a polymer; eluting the polymer by using a mixed solution of methanol and acetic acid by using a Soxhlet extraction device, wherein the volume ratio of the methanol to the acetic acid is 8-9: 2-1, removing template molecules, dissolving out metal organic frame materials, washing to neutrality by methanol, and drying at 50-65 ℃ for 20-30 h to obtain a hollow molecularly imprinted polymer corresponding to the template molecules;
(3) Preparing hollow molecular imprinting perovskite quantum dot fluorescent coding microspheres: adding all-inorganic perovskite quantum dots into an organic solvent, adding a hollow molecularly imprinted polymer, and uniformly dispersing, wherein the mass ratio of the all-inorganic perovskite quantum dots to the hollow molecularly imprinted polymer is 1: and 10, mixing the quantum dots and the hollow molecular imprinting polymer to finish encoding, washing the mixture to obtain a supernatant without fluorescence, and drying the supernatant in a dark place at 25 ℃ to obtain the hollow molecular imprinting perovskite quantum dot fluorescence encoding microsphere corresponding to the template molecule.
In addition, the application of the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere in detecting the content of sudan I in food is also the important protection scope of the invention.
Preferably, the food is any one of chili powder, chili oil, tomato sauce, egg and duck egg.
In the invention, the hollow molecularly imprinted polymer is taken as a coding matrix, and three CsPbX with different colors are taken 3 The quantum dot is used as a fluorescent signal and combined with a fluorescent coding technology to prepare CsPbX for specifically recognizing Sudan red I 3 The molecularly imprinted fluorescent coded microsphere has a strong identification function on Sudan red I and CsPbX at the same time 3 Is excellent in fluorescence properties.
In addition, when the Sudan red I is taken as a template molecule, the hollow molecularly imprinted polymer is obtained by dissolving a polymer formed by combining the Sudan red I and a metal organic framework material ZIF-8 through a methanol-acetic acid mixed solution, so that the problems of large instrument, professional staff and long detection time required in the current detection process of the Sudan red I are solved, particularly, a fluorescent rapid quantitative analysis method suitable for the Sudan red I is established by constructing a hollow molecularly imprinted perovskite quantum dot fluorescent coding system, a rapid detection method suitable for the Sudan red I in different matrixes is developed, the detection time is shortened to 10min in the actual detection process of the Sudan red I, and the detection efficiency is improved by 66.7 percent compared with that of a solid molecularly imprinted perovskite quantum dot fluorescent coding system.
Furthermore, the invention provides a preparation method of hollow molecular imprinting perovskite quantum dot fluorescent coding microspheres, which comprises the following steps:
(1) Dissolving 0.7344g of zinc nitrate and 0.8106g of 2-methylimidazole in 50mL of methanol respectively, dissolving the two by ultrasonic treatment, slowly adding a methanol solution of 2-methylimidazole into the methanol solution of zinc nitrate, stirring the mixture for 24 hours at room temperature in a dark place, centrifuging the obtained suspension at 8,000rpm for 5 minutes to obtain a precipitate, washing the precipitate with methanol for 3 times, and drying the precipitate in a vacuum drying oven at 40 ℃ for 8 hours to obtain a metal organic framework material ZIF-8;
(2) Adding 100mg of ZIF-8 into a 50mL round-bottom flask containing 20mL of acetonitrile, carrying out ultrasonic treatment for 10min to enable the ZIF-8 to be completely dispersed in the acetonitrile, adding 0.1mmol of template molecule Sudan red I, carrying out ultrasonic treatment to enable the template molecule Sudan red I to be dissolved, continuously adding 0.4mmol of functional monomer methacrylic acid, 1mmol of cross-linking agent ethylene glycol dimethacrylate, 1mmol of cross-linking agent divinylbenzene and 20mg of initiator azodiisobutyronitrile into the round-bottom flask, carrying out ultrasonic treatment for 5min, introducing nitrogen for 15min to remove oxygen, sealing under the protection of the nitrogen, and carrying out water bath polymerization reaction at 60 ℃ to obtain a polymer (MIPs@ZIF-8) with a core-shell structure; the polymer obtained is washed with acetonitrile, suction filtered, dried in an oven at 60 ℃ for 24 hours, and then treated with a volume ratio of 8:2 eluting the mixed solution of methanol and acetic acid in a Soxhlet extraction device, removing template molecule Sudan I, simultaneously destroying a supporting material ZIF-8, washing an adsorptive polymer with methanol to be neutral, and drying in an oven at 60 ℃ for 24 hours to obtain a Sudan I Hollow Molecularly Imprinted Polymer (HMIPs);
(3) Three all-inorganic perovskite quantum dot solutions with different colors are selected as fluorescent elements, HMIPs are used as a coding matrix for coding, and fluorescent coding microspheres are prepared.
1mL of n-hexane and 100. Mu.L of 10mg mL were added -1 CsPbX of (A) 3 Adding the quantum dot solution into a 2mL centrifuge tube, ultrasonically mixing, adding 10mg of HMIPs into the system, and ultrasonically processingDispersing uniformly, shaking in dark on an oscillator for 5min, centrifuging at 10,000rpm for 10min, removing supernatant, washing precipitate with n-hexane for 3 times until no fluorescence signal of perovskite quantum dot is detected in supernatant, and drying at 25deg.C in dark until constant weight to obtain three different colors of HMIPs-CsPbX 3 Microspheres: HMIPs-CsPbCl 1.5 Br 1.5 、HMIPs-CsPbBr 3 HMIPs-CsPbI 2 Br microsphere.
The invention has the beneficial effects that:
(1) According to the invention, the hollow molecularly imprinted polymer with high adsorption capacity, high mass transfer rate and low density is combined with the perovskite quantum dots with excellent fluorescence performance to prepare the hollow molecularly imprinted perovskite quantum dot fluorescence coding microsphere, so that the specific surface area of the traditional material is increased, the mass transfer rate between a coding matrix and the quantum dots is increased, the coding time is shortened, and the microsphere has the advantages of high selectivity, high adsorption rate, high fluorescence quantum yield and the like.
(2) The invention simplifies the preparation process of the hollow molecularly imprinted polymer, skillfully utilizes the instability of the ZIF-8 under the acidic condition, simultaneously removes the core of the ZIF-8 when the methanol-acetic acid mixed solution is adopted for template elution, avoids the damage of a molecular imprinting layer in the traditional processing mode of using strong acid and strong alkali or calcining in the preparation process of the hollow molecularly imprinted polymer, and simultaneously adopts the method of firstly carrying out surface imprinting on the ZIF-8 serving as a carrier and then removing the ZIF-8 and template molecules, thereby further improving the uniformity and the stability of the hollow molecularly imprinted polymer.
(3) The hollow molecular imprinting fluorescent coding sensing system constructed by the invention has the advantages of short detection time and simple pretreatment flow, and realizes rapid identification and quantitative analysis of Sudan red I in chilli powder, chilli oil, tomato sauce, eggs and duck eggs.
(4) Compared with the prior art, the preparation method takes ZIF-8 as a core for the first time, prepares the hollow molecularly imprinted polymer, combines the hollow molecularly imprinted polymer with perovskite quantum dots for the first time, is used for constructing the coding microsphere, and the established detection method has important practical significance in the field of rapid detection of food safety.
Drawings
FIG. 1 is a transmission electron microscope image of ZIF-8 prepared in example 1 of the present invention;
FIG. 2 shows (a) HMIPs, (b) HMIPs-CsPbCl 1.5 Br 1.5 、(c)HMIPs-CsPbBr 3 、(d)HMIPs-CsPbI 2 A transmission electron microscope image of the Br microspheres;
FIG. 3 is an XRD pattern of ZIF-8, MIPs@ZIF-8 and HMIPs materials prepared in example 1 of the present invention;
FIG. 4 is a nitrogen adsorption-desorption isotherm plot of HMIPs prepared in example 1 of the present invention and SMIs prepared in comparative example 1;
FIG. 5 shows the different encoding times for (a) HMIPs-CsPbBr prepared in example 1 3 Fluorescent encoded microspheres and (b) SMIPs-CsPbBr prepared in comparative example 1 3 Influence of fluorescence intensity of fluorescent coded microspheres;
FIG. 6 is (a) CsPbBr 3 Quantum dots and (b) HMIPs-CsPbBr 3 Fluorescence intensity of fluorescent coded microspheres in different solvents;
FIG. 7 is a hollow HMIPs-CsPbBr prepared in example 4 of the present invention 3 /HNIPs-CsPbBr 3 Fluorescence encoded microspheres and solid SMIPs-CsPbBr prepared in comparative example 3 3 Time response of fluorescent coded microspheres to sudan red i detection; wherein (a) is HMIPs-CsPbBr 3 /HNIPs-CsPbBr 3 Time response of fluorescent encoded microspheres; (b) For SMIPs-CsPbBr 3 Time response of fluorescent encoded microspheres;
fig. 8 is a flowchart of the whole preparation of hollow molecular imprinting perovskite quantum dot fluorescence encoding microsphere provided by the invention.
Detailed Description
The present invention will now be further described in connection with specific embodiments in order to enable those skilled in the art to better understand the invention.
Example 1
(1) Adding 0.7344g of zinc nitrate and 0.8106g of 2-methylimidazole into 50mL of methanol respectively, slowly adding a methanol solution of the 2-methylimidazole into a methanol solution of the zinc nitrate after ultrasonic dissolution, sealing, stirring for 24h at room temperature in a dark place, centrifuging at 8,000rpm for 5min, removing supernatant, washing precipitate with methanol for 3 times, and drying in a vacuum drying oven at 40 ℃ for 8h to obtain a metal organic framework material ZIF-8;
(2) Adding 100mg of ZIF-8 into a 50mL round-bottom flask containing 20mL of acetonitrile, carrying out ultrasonic treatment for 10min to enable the ZIF-8 to be completely dispersed in the acetonitrile, adding 0.1mmol of template molecule Sudan red I, carrying out ultrasonic treatment to enable the template molecule Sudan red I to be dissolved, continuously adding 0.4mmol of functional monomer methacrylic acid, 1mmol of cross-linking agent ethylene glycol dimethacrylate, 1mmol of cross-linking agent divinylbenzene and 20mg of initiator azodiisobutyronitrile into the round-bottom flask, carrying out ultrasonic treatment for 5min, introducing nitrogen for 15min to remove oxygen, sealing under the protection of the nitrogen, and placing into a water bath kettle at 60 ℃ to be stirred for 24h to obtain a imprinted polymer (MIPs@ZIF-8) with a core-shell structure; the polymer obtained was washed with acetonitrile and dried in an oven at 60 ℃ for 24h, using soxhlet extraction with methanol and acetic acid in a volume ratio of 8:2, eluting the polymer by using the mixed solution, removing template molecule Sudan I, dissolving ZIF-8, washing the polymer to be neutral by using methanol, drying the polymer in a baking oven at 60 ℃ for 24 hours, and carrying out proper grinding to obtain the Sudan I Hollow Molecularly Imprinted Polymer (HMIPs) in the invention;
(3) 1mL of n-hexane and 100. Mu.L of CsPbX 3 Adding the (X=Cl, br, I) quantum dot solution into a 2mL centrifuge tube, ultrasonically mixing, adding 10mg of hollow molecularly imprinted polymer, completely dispersing the polymer by ultrasonic, shaking for 5min in a dark place, centrifuging at 10,000rpm for 10min, retaining the precipitate, washing the precipitate with n-hexane for 3 times until the supernatant has no all inorganic perovskite quantum dots, removing the supernatant, and drying at 25 ℃ in a dark place until the weight is constant to obtain the HMIPs-CsPbX 3 (x=cl, br, I) fluorescent encoded microspheres.
In order to better understand the performance of the coded microsphere provided by the invention, the obtained ZIF-8 and Sudan red I Hollow Molecularly Imprinted Polymer (HMIPs) and hollow molecularly imprinted perovskite quantum dot fluorescent coded microsphere (HMIPs-CsPbX 3 ) Respectively performing Transmission Electron Microscope (TEM), X-ray diffraction experiment (XRD), and nitrogen adsorption-desorptionCharacterization of the situation, results are shown in FIGS. 1-4.
FIG. 1 is a transmission electron microscope image of ZIF-8 prepared in example 1.
As can be seen from FIG. 1, the prepared metal organic framework material ZIF-8 has a rhombic dodecahedron structure, and the average grain size of the ZIF-8 is 72+ -5 nm.
FIG. 2 shows the Sudan red I Hollow Molecularly Imprinted Polymer (HMIPs) and three different colors HMIPs-CsPbX described in this example 1 3 Is a microsphere transmission electron microscopy image.
As can be seen from fig. 2 (a), the obtained molecularly imprinted polymer has an obvious hollow structure, and the outer layer is a molecularly imprinted layer, which indicates that the strategy of disintegration of the ZIF-8 structure is feasible through acidic eluent, and the formation of the hollow structure is beneficial to accelerating the mass transfer rate in the later detection process and shortening the detection time.
As can be seen from fig. 2 (b) - (d), after encoding the matrix HMIPs, the presence of perovskite quantum dots is clearly found in the molecularly imprinted shell layer of the three different color fluorescent encoding microspheres, and the microspheres still maintain the original hollow structure, and almost only the imprinted shell layer exists in the loaded perovskite quantum dots, and these results indicate successful preparation of the hollow molecularly imprinted polymer and the hollow molecularly imprinted fluorescent encoding microspheres.
FIG. 3 is an XRD pattern for ZIF-8, MIPs@ZIF-8 and HMIPs as described in this example.
As can be seen from FIG. 3, the presence of the characteristic diffraction peak of ZIF-8 in the uneluted polymer material MIPs@ZIF-8, which indicates that the material contained ZIF-8 carrier, and the absence of the characteristic diffraction peak of ZIF-8 in the XRD pattern of HMIPs after elution, indicates that ZIF-8 has been completely removed after the polymer was eluted with a methanol/acetic acid mixed solution due to the instability of ZIF-8 under acidic conditions, further demonstrating the successful preparation of hollow molecularly imprinted polymers.
In FIG. 4, the specific surface area of HMIPs is 36.9m calculated according to Brunauer-Emmett-Teller (BET) theory 2 g -1 。
Example 2
Based on example 1, the preparation was carried out as HMIPs-CsPbBr 3 For example, the fluorescent coding microsphere is optimized for coding time.
100. Mu.L of CsPbBr 3 Adding quantum dots into 1mL solution containing 10mg HMIPs, respectively shaking for 1, 3, 5, 10, 15, 20, 25, and 30min, and testing fluorescence intensity (E x ＝365nm，E m =515 nm), the relationship between the fluorescence intensity and the oscillation encoding time was analyzed, and the experimental results are shown in table 1 and fig. 5 (a).
TABLE 1 fluorescence intensity of encoded microspheres at different shock encoding times
| Coding time (min) | Fluorescence intensity (a.u.) |
| 1 | 3381 |
| 3 | 4464 |
| 5 | 6383 |
| 10 | 6415 |
| 15 | 6441 |
| 20 | 6489 |
| 25 | 6501 |
| 30 | 6513 |
As can be seen from Table 1 and FIG. 5 (a), HMIPs-CsPbBr 3 The fluorescent coding microsphere has short coding time and higher coding efficiency, and when the coding time is 1min, the HMIPs-CsPbBr 3 The fluorescence intensity of the fluorescence coding microsphere reaches 53.0% of the maximum value, the maximum value is reached within 5min, the coding time is prolonged continuously, and the coding can be completed within 5min without obvious increase.
Example 3
Based on example 1, HMIPs-CsPbBr was used 3 The fluorescent coded microspheres are exemplified, and the stability of the obtained fluorescent coded microspheres in organic solvents with different polarities is evaluated.
1mg HMIPs-CsPbBr respectively 3 Fluorescent coding microsphere and CsPbBr 3 The quantum dots were added to the following solvents of different polarity: n-hexane, petroleum ether, cyclohexane, toluene, methylene chloride, sonicated for 10min, and then the encoded microspheres and CsPbBr were measured with a fluorescence spectrophotometer 3 Fluorescence intensity of quantum dots in different solutions (E x ＝365nm，E m =515 nm), the results are shown in table 2 below and fig. 6.
TABLE 2 CsPbBr in different solvents 3 Fluorescence emission wavelength and fluorescence intensity of quantum dots and fluorescence-encoded microspheres
Fig. 6 (a) shows: csPbBr 3 Quantum dots due to the ionic nature of the crystals, organic solvents of 6 different polarities were tested: the n-hexane, petroleum ether, cyclohexane, toluene and methylene dichloride all show instability, the fluorescence emission peak is blue-shifted, the fluorescence intensity is greatly reduced, and the fluorescence intensity is compared with that of pure CsPbBr 3 Compared with PQD, HMIPs-CsPbBr 3 The fluorescent coded microspheres (see FIG. 6 (b)) still exhibit a bright characteristic fluorescence emission peak, fluorescenceThe strength is slowly reduced along with the increase of the polarity of the solvent, so that the protection effect of the hollow molecularly imprinted polymer on the quantum dot is proved, the anti-interference capability of the quantum dot on the external environment is improved, the stability of the quantum dot is enhanced, and the n-hexane with smaller polarity is further selected as the solvent in the invention.
Example 4
With HMIPs-CsPbBr in example 1 3 For example, fluorescent coding microsphere is used for constructing HMIPs-CsPbBr 3 /HNIPs-CsPbBr 3 And (3) analyzing the relationship between different response times and the variation of fluorescence intensity under a certain Sudan red I concentration.
1mg of HMIPs-CsPbBr 3 /HNIPs-CsPbBr 3 The fluorescent-encoded microspheres were added to 1mL of n-hexane, to which was added a solution of Sudan red I (final concentration 200. Mu. g L) -1 ) Shaking for different times (1, 3, 5, 7, 10, 15, 20, 30 min), and measuring fluorescence intensity (E) x ＝365nm，E m =515 nm). To clarify the advantages of the hollow molecularly imprinted fluorescence sensing system in rapid detection, the results are shown in table 3 and fig. 7 (a).
TABLE 3 fluorescence change of differently encoded microspheres for Sudan I solutions at different response times
The results show that: for constructed HMIPs-CsPbBr 3 /HNIPs-CsPbBr 3 Fluorescence sensor system, when response time is 0-10min, fluorescence intensity variation (F 0 and/F) is obviously increased, and when the response time is continuously increased to 30min, the change amount of the fluorescence intensity is not obviously changed, so that 10min is finally selected as the detection time; it was also found that HNIPs-CsPbBr 3 The change of the fluorescence intensity of the fluorescent microsphere is smaller than that of HMIPs-CsPbBr 3 The main reason for this difference is found in HMIPs-CsPbBr 3 The microsphere has imprinting cavity matched with Sudan red I in chemical structure and shape, while HNIPs-CsPbBr 3 The microsphere is not added with a die in the synthesis processThe plate molecule sudan I lacks the specific imprinting site, and the adsorption of sudan I only depends on the nonspecific adsorption of sudan I by the functional groups exposed on the surface of the material.
Example 5
And constructing a rapid quantitative sensing system for sudan I by using fluorescent coding microspheres, and evaluating the applicability of the sensing system in actual samples.
Five samples of duck eggs, chilli powder, chilli oil and tomato sauce are selected as actual samples.
1g or 1mL of the sample is weighed and added into 10mL of normal hexane respectively, ultrasonic extraction is carried out for 5min, centrifugation is carried out for 10min at 10,000rpm, the steps are repeated for three times, all supernatant liquid is collected, normal hexane is distilled until the solution is nearly dry, and then redissolved in 1.0mL of normal hexane to be used as a liquid to be detected. Adding 1.0mg of HMIPs-CsPbBr to the liquid to be tested 3 And (3) fluorescent coding microspheres, shaking for 10min at room temperature in a dark place, and testing the fluorescence intensity of each group of sample solution by adopting a fluorescence spectrophotometer after full reaction.
To verify the accuracy of actual sample use, three concentration levels were labeled (0.5, 10 and 50 μ g L) for 5 samples -1 /μg kg -1 ) The recovery of each sample was determined at different concentrations. The recovery rate of the marked sample is 94.91-105.36% and the relative standard deviation is 2.04-6.28%, thus meeting the requirement of quantitative analysis. Proof that the prepared HMIPs-CsPbBr 3 The fluorescent coding microsphere has feasibility and practicability for analyzing the Sudan I in the labeled sample, has higher accuracy and repeatability, and can meet the detection of the Sudan I in the actual sample.
Comparative example 1
To embody the advantages of the hollow structure, solid Molecularly Imprinted Polymers (SMIPs) and corresponding fluorescent coding microspheres were prepared without adding carrier ZIF-8 based on example 1.
N was carried out on SMIPs prepared in this comparative example 2 The adsorption-desorption conditions are characterized, and the characterization results are shown in fig. 4.
As shown in FIG. 4, the specific surface area of the solid imprinted polymer (SMIPs) was 2.8m calculated according to Brunauer-Emmett-Teller (BET) theory 2 g -1 。
It is apparent that the specific surface area of HMIPs is significantly higher than SMIPs, the higher specific surface area also suggests that the HMIPs prepared in example 1 of the present invention have a greater adsorption capacity, more perovskite quantum dots are also driven into the polymer microsphere during the encoding process.
Comparative example 2
On the basis of example 2, solid Molecularly Imprinted Polymers (SMIPs) without ZIF-8 were encoded in the same manner, and respectively shaken for 1, 5, 10, 20, 30, and 40min, and fluorescence intensities in different solutions were measured by a fluorescence spectrophotometer (E x ＝365nm，E m =515 nm), and the relationship between the fluorescence intensity and the oscillation encoding time was analyzed, and the experimental results are shown in table 4 and fig. 5 (b).
TABLE 4 fluorescence intensity of encoded microspheres at different shock encoding times
| Coding time (min) | Fluorescence intensity (a.u.) |
| 1 | 2101 |
| 5 | 2556 |
| 10 | 2959 |
| 20 | 3842 |
| 30 | 3863 |
| 40 | 3901 |
As can be seen from FIG. 5 (b), SMIPs-CsPbBr 3 Fluorescent encoded microspheres required 20min to complete encoding, and HMIPs-CsPbBr of example 2 3 Compared with fluorescent coded microspheres, longer coding time is required, mainly because: the hollow structure is used as the coding matrix, and benefits from the advantages of the hollow structure adsorption material in the rapid mass transfer rate.
Comparative example 3
Based on example 4, solid SMIPs-CsPbBr at the same Sudan I concentration were determined 3 The relationship between the different response times (5, 15, 30, 60, 90, 120 min) of the fluorescent-encoded microspheres to sudan I was also determined by the amount of change in fluorescence intensity (F 0 The results of the evaluation of/F) are shown in Table 5 and FIG. 7 (b).
TABLE 5SMIPs-CsPbBr 3 Fluorescence change of Sudan red I solution under different response time
| Response time (min) | F 0 /F |
| 5 | 1.39 |
| 15 | 1.68 |
| 30 | 1.99 |
| 60 | 2.05 |
| 90 | 2.05 |
| 120 | 2.07 |
As can be seen from Table 5 and FIG. 7 (b), for solid SMIPs-CsPbBr 3 The detection time of the fluorescent microspheres is about 30 minutes.
Compared with the method for detecting the HMIPs-CsPbBr3 fluorescence sensing system constructed by adopting the HMIPs-CsPbBr3 fluorescence encoding microspheres in the embodiment 4 of the invention, the detection method provided in the embodiment 4 of the invention only needs 10 minutes for detecting sudan I, and compared with the detection time shortened by 66.7% by adopting the solid SMIPs-CsPbBr3 fluorescence microspheres in the embodiment 3, the detection efficiency of sudan I in foods is greatly improved by adopting the fluorescence encoding microspheres prepared by the invention.
Here, in order to facilitate a clearer understanding of the present invention, the overall flow of the method of the present invention is shown in a diagrammatic form, see fig. 8.
Claims (9)
1. The hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere is characterized by being prepared by the following method: adding all inorganic perovskite quantum dots into an organic solvent, then adding a hollow molecularly imprinted polymer, dispersing uniformly, combining the quantum dots and the hollow molecularly imprinted polymer to finish coding, washing to obtain a supernatant without fluorescence, and drying to obtain the hollow molecularly imprinted perovskite quantum dot fluorescence coding microsphere, wherein the hollow molecularly imprinted polymer is obtained by using the instability of a ZIF-8 metal organic framework material under an acidic condition and simultaneously removing a ZIF-8 core when a methanol-acetic acid mixed solution is adopted for template elution.
2. The method as claimed in claim 1The hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere is characterized in that the all-inorganic perovskite quantum dot is CsPbBr 3 Quantum dot CsPbCl 1.5 Br 1.5 Quantum dot and CsPbI 2 Any one of the Br quantum dots; the organic solvent is selected from any one of straight-chain saturated alkane with the carbon number of 5-8.
3. The method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 1, which is characterized by comprising the following steps:
(1) Preparing a metal organic framework material ZIF-8;
respectively dissolving zinc nitrate and 2-methylimidazole in methanol, dissolving the two by ultrasonic treatment, slowly adding the methanol solution of 2-methylimidazole into the methanol solution of zinc nitrate, stirring in a dark place, centrifuging the obtained suspension, washing with methanol, and vacuum drying to constant temperature to obtain a metal organic frame material ZIF-8; wherein the ratio of the amount of zinc nitrate to the amount of 2-methylimidazole is 1:4, a step of;
(2) Preparing a hollow molecularly imprinted polymer;
adding the metal organic framework material ZIF-8 obtained in the step (1) into a pore-forming agent acetonitrile, dispersing, adding template molecules, functional monomer methacrylic acid, cross-linking agent ethylene glycol dimethacrylate, divinylbenzene and initiator azo diisobutyronitrile, uniformly mixing, introducing nitrogen for deoxidization, sealing and heating for reaction to prepare a polymer; eluting the prepared polymer with a mixed solution of methanol and acetic acid, removing template molecules, dissolving out a metal organic framework material ZIF-8, washing with methanol to be neutral, and drying to obtain a hollow molecularly imprinted polymer;
wherein, the template molecule: functional monomer: substances as crosslinking agents the ratio of the amount of (2) is 1:4:20, a step of; in the cross-linking agent, the ratio of the ethylene glycol dimethacrylate to the divinylbenzene is 1:1, a step of; in the mixed solution of methanol and acetic acid, the volume ratio of the methanol to the acetic acid is 8-9: 2-1;
(3) Preparing hollow molecular imprinting perovskite quantum dot fluorescent coding microspheres: adding all inorganic perovskite quantum dots into an organic solvent, adding the hollow molecularly imprinted polymer prepared in the step (2), uniformly dispersing, enabling the quantum dots and the hollow molecularly imprinted polymer to be combined to finish coding, washing to obtain a supernatant without fluorescence, and drying in a dark place at the temperature of 23-26 ℃ to obtain the hollow molecularly imprinted perovskite quantum dot fluorescence coding microsphere; wherein, the mass ratio of the all-inorganic perovskite quantum dot to the hollow molecularly imprinted polymer is 1:10.
4. the method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 3, wherein in the step (2), the metal organic framework material ZIF-8 is dispersed in acetonitrile by adopting ultrasonic.
5. The method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 3, wherein in the step (2), ultrasonic mixing is adopted for the mixing; and (3) introducing nitrogen to remove oxygen, sealing and placing in a water bath at 50-65 ℃ to stir for 20-30 h.
6. The method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 3, wherein in the step (2), a mixed solution of methanol and acetic acid is used for eluting a polymer, and the polymer is subjected to a Soxhlet extraction device and then dried for 20-30 hours at 50-65 ℃.
7. The method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 3, wherein the template molecule in the step (2) is any one of sudan red I, sudan red II, sudan red III and sudan red IV.
8. The method for preparing the hollow molecular imprinting perovskite quantum dot fluorescent coding microsphere according to claim 7, wherein the template molecule in the step (2) is sudan red I.
9. The method of claim 8, wherein the hollow molecular imprinting perovskite quantum dot fluorescent encoding microsphere is used for detecting sudan I content in food.
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| CN114456800A (en) * | 2022-02-10 | 2022-05-10 | 齐鲁工业大学 | Preparation method and application of perovskite quantum dot-molecularly imprinted fluorescent coding microsphere for detecting Sudan red I |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114456800A (en) * | 2022-02-10 | 2022-05-10 | 齐鲁工业大学 | Preparation method and application of perovskite quantum dot-molecularly imprinted fluorescent coding microsphere for detecting Sudan red I |
Non-Patent Citations (2)
| Title |
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| Tongqing Liu.Preparation of metal-organic framework @molecularly imprinted polymers for extracting strobilurin fungicides from agricultural products.《Journal of Chromatography B》.2022,第1209卷全文. * |
| 孙赟.分子模拟辅助设计光响应分子印迹聚合物的制备及性能研究.《中国优秀硕士学位论文全文数据库》.2023,第2-3页第1.2.2.3小节. * |
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