CN113072711A - Magnetic and photon-based dual-response virus molecularly imprinted sensor and construction method thereof - Google Patents
Magnetic and photon-based dual-response virus molecularly imprinted sensor and construction method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic and photon-based dual-response type virus molecular imprinting sensor and a construction method thereof. The magnetic and photon-based dual-response virus molecularly imprinted sensor has good combination behavior for template viruses, and is fast in combination kinetics, high in adsorption capacity and good in selectivity.
Description
Technical Field
The invention relates to the field of analytical chemistry, and mainly relates to a magnetic and photon-based dual-response type virus molecular imprinting sensor and a construction method thereof.
Background
Molecularly Imprinted Polymers (MIPs), a type of "artificial antibody," have great potential in various fields, particularly in the fields of health and life sciences, over the past several decades. By utilizing the molecular imprinting technology, a new artificial simulation binding site is constructed, the artificial simulation binding site has complementarity with the chemical structure and the space structure of a template molecule, and the molecular imprinting polymer has good selectivity, excellent stability and low preparation cost. To date, small molecular imprinting techniques have met with great success, however, the preparation of Molecularly Imprinted Polymers (MIPs) for biological macromolecules (e.g., proteins, viruses, etc.) remains a significant challenge due to factors such as size, structural complexity, and conformational flexibility. To address these problems, several Western blotting techniques have been implemented, including epitope blotting [ Zhang X, Zhang N, Du C, et al, Chemical Engineering Journal, 2017, 317: 988-.
Stimulus-responsive Molecularly Imprinted Polymers (MIPs) have received much attention because they are sensitive to external stimuli and have good recognition ability for target molecules. However, at present, no technical report about the virus imprinted polymer with magnetic and photon double stimulation responses exists.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a magnetic and photon based dual response type virus molecular imprinting sensor, and aims to provide a new molecular imprinting sensor for specific recognition and detection of virus molecules.
The technical scheme of the invention is as follows:
a magnetic and photon-based dual-response type virus molecular imprinting sensor takes magnetic particles as an inner core, silicon dioxide is coated on the surfaces of the magnetic particles, a metal organic framework is grafted on the silicon dioxide, a photoresponse polymer is connected on the metal organic framework, and the photoresponse polymer is connected with a target virus template.
The magnetic and photon-based dual-response type virus molecularly imprinted sensor is characterized in that the photoresponse type functional monomer is connected with the metal organic framework through a double bond, and the photoresponse type functional monomer is combined with an amino group of a target virus template through a covalent bond formed by a carboxyl group.
The magnetic and photon-based dual-response type virus molecularly imprinted sensor is characterized in that the photoresponse type functional monomer is 4- (4' -acryloyloxyphenylazo) benzoic acid
The magnetic and photon-based dual-response virus molecularly imprinted sensor is characterized in that the magnetic particles are ferroferric oxide particles; the particle size of the ferroferric oxide particles is 100-200 nm;
the metal organic framework is UiO-66-NH2。
A method for constructing a magnetic and photon-based dual-response virus molecularly imprinted sensor, comprising the following steps:
coating SiO on the surface of the magnetic particles2After the lamination, carrying out carboxylation treatment;
growing a metal organic framework on the surface of the magnetic particles subjected to carboxylation treatment;
double bonds are modified on the metal organic framework of the magnetic particles;
connecting a photoresponse functional monomer and a target virus template on the magnetic particles modified with double bonds.
The construction method of the magnetic and photon-based dual-response virus molecularly imprinted sensor comprises the step of coating SiO on the surface of magnetic particles2The layer process specifically comprises the following steps:
adding the magnetic particles into the mixed solution, and performing dispersion treatment;
adding a catalyst and a silane reagent, and stirring and reacting for 2-10 hours at 40-50 ℃;
collecting magnetic particles by magnetic force, washing the magnetic particles for a plurality of times by deionized water and ethanol in sequence, and drying the magnetic particles for later use;
the mixed solution is a mixed solution of isopropanol and ultrapure water or a mixed solution of ethanol and ultrapure water, and the mass ratio of the isopropanol or the ethanol to the water is 100: 2-8; adding 100mL of mixed solution into every 400-600 mg of magnetic particles;
the silane reagent is tetraethyl orthosilicate, and 1-5 mL of silane reagent is added into every 500mg of magnetic particles;
the catalyst is NH3·H2And O, adding 1-5 mL of silane reagent into every 5mL of catalyst.
The construction method of the magnetic and photon-based dual-response virus molecularly imprinted sensor, wherein the carboxylation treatment process specifically comprises the following steps:
mixing a carboxylation reagent, a carboxyl grafting intermediate and a solvent, performing dispersion treatment, and stirring and mixing for 1-5 hours in a water bath at 25-35 ℃;
adding coating SiO2Magnetic particles of the layer are subjected to dispersion treatment;
adding a catalyst solution, and reacting for 10-14 hours at 25-35 ℃;
washing with deionized water and ethanol for several times, and drying;
wherein the carboxylation reagent is succinic anhydride, and 50-200 mg of coated SiO is added to every 5 mmol of carboxylation reagent2Magnetic particles of the layer;
the intermediate of the grafted carboxyl is 3-Aminopropyltriethoxysilane (APTES), gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane or N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and 0.5-2 mL of the intermediate of the grafted carboxyl is added into every 5 mmol of carboxylation reagent;
the solvent is ethanol, and each 100mg of the solvent is coated with SiO2Adding 40-60 mL of solvent into the magnetic particles of the layer;
the catalyst solution is an acetic acid solution, the volume ratio of the catalyst to water in the catalyst solution is 20: 2-5, and 15-25 mL of the catalyst solution is added to every 1 mL of the intermediate of the grafted carboxyl.
The construction method of the magnetic and photon-based dual-response virus molecularly imprinted sensor, wherein the process of growing the metal-organic framework on the surface of the magnetic particle subjected to carboxylation treatment specifically comprises the following steps:
adding zirconium chloride, 2-amino terephthalic acid and acetic acid into a solvent, and performing dispersion treatment;
adding magnetic particles subjected to carboxylation treatment, and performing dispersion treatment;
stirring and reacting for 2-8 hours at 100-150 ℃;
collecting the product with a magnet, washing with deionized water and ethanol for several times, and drying for later use;
wherein the molar ratio of zirconium chloride to 2-amino terephthalic acid is 2: 1-2, and 3-7 mmol of ZrCl is added to 100mg of carboxylated magnetic particles4；
The solvent is N, N-Dimethylformamide (DMF); adding 20-50 mL of solvent into every 100mg of magnetic particles subjected to carboxylation treatment;
the catalyst is acetic acid, and 500-1000 mu L of the catalyst is added into each 30mL of the solvent.
The construction method of the magnetic and photon-based dual-response type virus molecularly imprinted sensor, wherein the process of modifying double bonds on the metal organic framework of the magnetic particles comprises the following steps:
adding magnetic particles with metal organic frameworks growing on the surfaces into a solvent, and performing dispersion treatment;
under the mechanical stirring, dropwise adding a compound with grafted double bonds, and continuously stirring and reacting for 60-80 hours at the temperature of 25-35 ℃;
washing with dichloromethane and ethanol for multiple times in sequence, and performing centrifugal separation to obtain magnetic particles grafted with double bonds;
wherein the solvent is anhydrous dichloromethane, and 10-30 mL of the solvent is added to every 50mg of the magnetic particles with the metal organic frameworks growing on the surfaces;
the compound of the grafted double bond is methacrylic anhydride, and 3-8 mmol of the compound of the grafted double bond is added to every 50mg of magnetic particles with metal organic frameworks growing on the surfaces.
The construction method of the magnetic and photon-based dual-response type virus molecularly imprinted sensor, wherein the process of connecting the photoresponse functional monomer and the target virus template on the magnetic particle modified with the double bond, comprises the following steps:
adding a photoresponse functional monomer and a target virus template into a buffer solution, dispersing for 10-20 minutes under a dark condition, and standing for 10-16 hours at room temperature in the dark;
adding magnetic particles modified with double bonds, and performing dispersion treatment for 15-45 minutes;
adding a cross-linking agent and an initiator, and stirring and reacting for 20-30 hours at the temperature of 50-70 ℃ in a dark place;
collecting the precipitate by magnetic force, and washing the precipitate by using 2% SDS-HAc solution and deionized water in sequence;
wherein the photoresponse functional monomer is AOPBA; adding 0.3-1 mmol of photoresponse functional monomer to each 50 mu L of target virus template;
the crosslinking agent is N, N' -methylene bisacrylamide, and the molar ratio of the crosslinking agent to the photoresponse functional monomer is 3: 1-3;
the initiator is ammonium persulfate, and the molar ratio of the initiator to the cross-linking agent is 1: 1-3;
the buffer solution is Tris-HCl buffer solution, phosphate buffer solution or Britton-Robinson buffer solution; adding 20-100 mu L of target virus template into every 200 mg of double-bond modified magnetic particles, and adding 50-100 mL of buffer solution.
Has the advantages that: according to the magnetic and photon-based dual-response virus molecularly imprinted sensor, the photoresponse functional monomer is added, so that the molecularly imprinted sensor has photoresponse performance on a target object; the magnetic nano particles are used as a substrate, and the magnetic nano particles are used for elution and purification, so that the preparation process of the molecular imprinting sensor is simpler and quicker; by grafting a layer of metal organic framework material on the surface of the magnetic nanoparticles, more binding sites can be provided, and the adsorption performance is strong. The magnetic and photon-based dual-response virus molecularly imprinted sensor has good combination behavior for template viruses, and is fast in combination kinetics, high in adsorption capacity and good in selectivity.
Drawings
FIG. 1 is a flow chart for preparing the magnetic and photon-based dual-response virus molecularly imprinted sensor.
FIG. 2 shows Fe in example 23O4Particles (a) and Fe3O4@SiO2-COOH particles (b), Fe3O4@SiO2@UiO-66-NH2Particles (c) and Fe3O4@SiO2@UiO-66-NH2-infrared spectrogram of C = C particles (d), mmips (e) and mnips (f).
FIG. 3 shows Fe in example 23O4 (A)、Fe3O4@SiO2@UiO-66-NH2(B) MMIPs (C) and MNIPs (D) scanning electron micrographs of the particles.
Fig. 4 is a graph of the resonance optical response of MMIPs and MNIPs particles to the template EV71 in example 2.
FIG. 5 is a graph showing the response of the virus molecularly imprinted resonance light sensors (MMIPs and MNIPs) in example 3 to different concentrations of EV 71.
FIG. 6 is a diagram showing the detection of different viruses by the light-responsive virus molecularly imprinted resonance light sensor in example 3.
FIG. 7 shows the use of the viral molecular imprinting resonance light sensor in example 3 for labeling recovery of EV 71.
Detailed Description
The invention provides a magnetic and photon-based dual-response virus molecularly imprinted sensor and a construction method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The invention provides a magnetic and photon-based dual-response virus molecular imprinting sensor, which takes magnetic particles as an inner core, and silicon dioxide (SiO) is coated on the surfaces of the magnetic particles2) The metal organic framework is grafted on the silicon dioxide, the metal organic framework is connected with the photoresponse polymer, and the photoresponse polymer is connected with the target virus template.
Further, a more preferable embodiment is provided in the present invention, the magnetic particles are preferably ferroferric oxide particles, and the ferroferric oxide particles have better magnetic responsiveness and stability, and are convenient and easy to obtain. The ferroferric oxide particles are preferably ferroferric oxide particles with the particle size of 100-200 nm.
The metal organic framework is UiO-66-NH2The target virus template and the photoresponse functional monomer are connected to UiO-66-NH through double bonds2(ii) a Because of UiO-66-NH2The surface of the polymer can be directly modified by double bonds, so that the molecularly imprinted polymer can be connected with UiO-66-NH2The above. The photoresponse functional monomer is preferably 4- (4' -acryloyloxyphenylazo) benzoic acid (AOPBA), and is combined with the virus template through a covalent bond. This AOPBA was synthesized as a reference ([ East AJ. Anisotropical porous polyester derived from 4-hydroxy-4' -carboxy azobenz)ene and process for preparation [P]. US4285852, 1981-08-25.][ Chenghao, arm spread Xinlin, Wang Xiao Gong, etc. Synthesis and performance research of novel side chain azo polyelectrolyte. The polymer scientific report 2002 (1) is 96-101.]) AOPBA contains carboxyl groups that can interact with groups such as amino groups on the surface of the virus.
The target virus template can be any virus template, and the magnetic and photon-based dual-response virus molecular imprinting sensor is suitable for detecting different viruses. In the embodiment of the present invention, enterovirus 71 (EV 71) is exemplified.
In the examples of the present invention, in the magnetic Fe3O4The MOF layer grown on the surface of the target virus template is used as a carrier material, so that more imprinting sites are provided for the target virus template, and the adsorption rate is improved due to high porosity; moreover, the prepared MIPs not only have good adsorption performance on a target object, but also have good magnetic responsiveness on a separation matrix of a system; can realize faster separation under the action of the magnet, and simplify the elution and detection processes.
The photoresponse polymer can realize photoisomerization through irradiation of light with different wavelengths, and the photoresponse is introduced into the magnetic molecularly imprinted polymer to realize the double-stimulus response polymer. On one hand, under the irradiation of ultraviolet light and visible light, the isomerization property of photons changes the geometric structure of the imprinting cavity, so that the absorption and release of template molecules are caused, the detection process can be simplified, the target object can be determined without adding an eluent, the damage of the eluent to the morphology of the imprinting particles can be avoided, in addition, the magnetic response and the light response double-stimulation response are combined by utilizing the high matching property of the imprinting sites and the target object and the isomerization effect of the functional monomer under different illumination, and the specific recognition of the target virus is improved; magnetic properties, on the other hand, allow for rapid separation of particles using an external magnet. In the preparation process, the photoresponse functional monomer containing the azobenzene chromophore is applied. The invention explores the virus imprinted polymer with magnetic and photon double-stimulus response, and prepares the double-response virus MIPs with photon and magnetism by using the functional monomer containing azobenzene.
In the embodiment of the invention, the MIPs are prepared by combining photon and magnetic response performance, 4- (4' -acryloyloxyphenylazo) benzoic acid containing azobenzene is used as a light response type functional monomer, and the light response type functional monomer is mixed with-NH of a target virus template2Covalent bond combination is formed, N, N' -methylene bisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, and photon and magnetic double-stimulus response type molecular imprinting polymer MMIPs are obtained. The result shows that the sensor constructed by the invention has the advantages of good selectivity, high sensitivity, excellent light response performance and the like on a target object, has important significance for specific identification and detection of viruses, obtains expected effect in application, and has potential application value in practical application.
Further, the invention also provides a construction method of the magnetic and photon-based dual-response virus molecularly imprinted sensor, which comprises the following steps:
coating SiO on the surface of the magnetic particles2After the lamination, carrying out carboxylation treatment;
growing a metal organic framework on the surface of the magnetic particles subjected to carboxylation treatment;
double bonds are modified on the metal organic framework of the magnetic particles;
connecting a photoresponse functional monomer and a target virus template on the magnetic particles modified with double bonds.
In the embodiment of the invention, the surface of the magnetic particle is coated with SiO2The layer process specifically comprises the following steps:
adding the magnetic particles into the mixed solution, and performing ultrasonic dispersion treatment for 10-30 minutes;
adding a catalyst and a silane reagent, and stirring and reacting for 2-10 hours at 40-50 ℃;
magnetic force is used for collecting magnetic particles, the magnetic particles are washed for a plurality of times by deionized water and ethanol in sequence, and the magnetic particles are dried for standby.
In the embodiment of the invention, the magnetic particles are preferably ferroferric oxide microspheres; the magnetic particles are used as magnetic inner cores, so that each synthesized nano particle has magnetic responsiveness, and the separation and collection of the particles are simplified;
the mixed solution is used for dispersing reactants and can be mixed solution of isopropanol and ultrapure water, or mixed solution of ethanol and ultrapure water and the like, and the mass ratio of the isopropanol or the ethanol to the water can be 100: 2-8; adding 100mL of mixed solution into every 400-600 mg of magnetic particles;
the silane reagent is used for generating a silicon dioxide layer on the surface of the magnetic particle, so that the magnetic particle is convenient to modify, for example, modifying carboxyl on the surface of the magnetic particle by using the silane reagent; the silane reagent may be tetraethyl orthosilicate (TEOS); adding 1-5 mL of silane reagent into every 500mg of magnetic particles;
the catalyst is used for catalyzing reaction and can be NH3·H2O; adding 1-5 mL of silane reagent into every 5mL of catalyst.
In the embodiment of the present invention, the carboxylation process specifically includes the following steps:
mixing a carboxylation reagent, a carboxyl grafting intermediate and a solvent, performing ultrasonic dispersion treatment for 10-30 min, and stirring and mixing for 1-5 hours at 25-35 ℃ in a water bath;
adding coating SiO2Carrying out ultrasonic dispersion treatment on the magnetic particles of the layer for 10-30 min;
adding a catalyst solution, and reacting for 10-14 hours at 25-35 ℃;
washing with deionized water and ethanol for several times, and drying.
In the embodiment of the invention, the carboxylation reagent enables the magnetic particles to be provided with carboxyl groups, so that the metal organic framework can grow on the magnetic particles; the carboxylating agent may be succinic anhydride; 50-200 mg of coated SiO is added to every 5 mmol of carboxylation reagent2Magnetic particles of the layer;
the intermediate of the grafting carboxyl is a silanization reagent with amino, and can be 3-aminopropyl triethoxysilane (APTES), gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl methyldimethoxysilane and the like; adding 0.5-2 mL of carboxyl grafted intermediate into every 5 mmol of carboxylation reagent;
the solution isThe agent is used for dispersing reactants and can be ethanol; coating SiO in an amount of 100mg per2Adding 40-60 mL of solvent into the magnetic particles of the layer;
the catalyst solution can be an acetic acid solution, and the volume ratio of the catalyst to water in the catalyst solution is 20: 2-5; adding 15-25 mL of catalyst solution into each 1 mL of the intermediate grafted with carboxyl.
In the scheme of the embodiment of the invention, the metal organic framework is UiO-66-NH2The process of growing the metal organic framework on the surface of the magnetic particle subjected to carboxylation treatment specifically comprises the following steps:
zirconium chloride (ZrCl)4) Adding 2-amino terephthalic acid and acetic acid into a solvent, and performing ultrasonic dispersion treatment for 10-30 min;
adding magnetic particles subjected to carboxylation treatment, and performing ultrasonic dispersion treatment for 10-30 minutes;
stirring and reacting for 2-8 hours at 100-150 ℃;
the product was collected with a magnet, washed several times with deionized water and ethanol in sequence, and dried for use.
In the embodiment of the invention, ZrCl4And 2-amino terephthalic acid to synthesize UiO-66-NH2ZrCl as a starting material4And 2-amino terephthalic acid in a molar ratio of 2: 1-2, wherein 3-7 mmol of ZrCl is added to 100mg of the carboxylated magnetic particles4；
The solvent is used as the dispersed particles of the reaction solution and can be N, N-Dimethylformamide (DMF); adding 20-50 mL of solvent into every 100mg of magnetic particles subjected to carboxylation treatment;
the catalyst can be acetic acid, and 500-1000 mu L of the catalyst is added into each 30mL of the solvent.
In an embodiment of the present invention, the process of modifying double bonds on a metal organic framework of a magnetic particle includes the following steps:
adding magnetic particles with metal organic frameworks growing on the surfaces into a solvent, and performing ultrasonic dispersion treatment for 10-30 minutes;
under the mechanical stirring, dropwise adding a compound with grafted double bonds, and continuously stirring and reacting for 60-80 hours at the temperature of 25-35 ℃;
washing with dichloromethane and ethanol for several times, and centrifuging to obtain the magnetic particles grafted with double bonds.
In the embodiment of the invention, the solvent can be anhydrous dichloromethane, and 10-30 mL of the solvent is added to every 50mg of the magnetic particles with the metal organic frameworks growing on the surfaces;
the compound of the grafted double bond can be methacrylic anhydride, and 3-8 mmol of the compound of the grafted double bond is added to every 50mg of magnetic particles with metal organic frameworks growing on the surfaces.
In an embodiment of the present invention, the process of connecting the photoresponse functional monomer and the target virus template to the double-bond modified magnetic particle includes the following steps:
adding a photoresponse functional monomer and a target virus template into a buffer solution, carrying out ultrasonic dispersion treatment for 10-20 minutes under a dark condition, and then placing for 10-16 hours at room temperature in the dark;
adding magnetic particles modified with double bonds, and performing ultrasonic dispersion treatment for 15-45 minutes;
adding a cross-linking agent and an initiator, and stirring and reacting for 20-30 hours at the temperature of 50-70 ℃ in a dark place;
the pellet was magnetically collected and washed with 2% SDS-HAc solution and deionized water in sequence until no absorbance peak of the template virus was detected by UV-Vis spectroscopy of the supernatant.
In the embodiment of the present invention, the photoresponse functional monomer may be AOPBA; adding 0.3-1 mmol of photoresponse functional monomer to each 50 mu L of target virus template;
the cross-linking agent may be N, N' -Methylenebisacrylamide (MBA); the molar ratio of the cross-linking agent to the photoresponse functional monomer is 3: 1-3;
the initiator may be Ammonium Persulfate (APS); the molar ratio of the initiator to the cross-linking agent is 1: 1-3;
the buffer solution can be Tris-HCl buffer solution, Phosphate Buffer Solution (PBS), phosphate buffer solution (PB) or Britton-Robinson buffer solution and the like; adding 20-100 mu L of 50U/mL target virus template into every 200 mg of double-bond modified magnetic particles, and adding 50-100 mL buffer solution.
The invention relates to magnetism based on amino functionalizationThe preparation process of the metal organic framework photoresponse type molecularly imprinted polymer is simply described as follows: first, magnetic particles are coated with SiO2After layering, carboxylating, then growing a metal organic framework on the surface of the metal organic framework, and modifying double bonds on the magnetic particles; the magnetic particles are used as a carrier, a target virus template, a photoresponse functional monomer and a cross-linking agent are used for preparing a target virus imprinted polymer, the target virus template and the photoresponse functional monomer are combined through covalent bonds, the molecularly imprinted polymer is fixed on the surface of a metal organic framework material under the action of the cross-linking agent, and template molecules are eluted after polymerization is completed.
The polymer particles have photoresponsive performance by adding 4- (4' -acryloyloxyphenylazo) benzoic acid (AOPBA) as a photoresponsive functional monomer: in the process of synthesizing the imprinted polymer, AOPBA is added as a photoresponse functional monomer, which has an azobenzene chromophore, and can control the release and adsorption of a target virus template on the surface of imprinted particles under the illumination of different wavelengths (365 nm and visible light), probably because the azobenzene chromophore of the photoresponse functional monomer AOPBA is subjected to trans-cis and cis-trans isomerization under the induction of light, the imprinted site is changed, and the purpose of photoresponse release and target object combination is achieved. Therefore, the detection process can be simplified, the determination is carried out without adding an eluant additionally, and the damage to the morphology of the imprinted particles is avoided.
The invention also provides a detection method of the magnetic and photon-based dual-response virus molecularly imprinted sensor, which comprises the following steps:
adding a substance to be detected, and oscillating for 30 minutes at constant temperature under a dark condition;
and adding the reaction solution into a cuvette, measuring the resonance light intensity of the cuvette by adopting a QM phosphorescence/luminescence spectrophotometer, wherein the excitation wavelength range is 220-700 nm, the emission wavelength range is 220-700 nm, and judging the concentration of the target virus according to the resonance light intensity.
The magnetic and photon-based dual-response virus molecularly imprinted sensor has the following advantages:
(1) 4- (4' -acryloyloxyphenylazo) benzoic acid is used as a functional monomer, so that the molecularly imprinted sensor has a light response performance on a target;
(2) the magnetic nano particles are used as a substrate, and the magnetic nano particles are used for elution and purification, so that the preparation process of the molecular imprinting sensor is simpler and quicker;
(3) a layer of metal organic framework material is grafted on the surface of the magnetic nano particle and is used as a carrier material for virus molecular imprinting, the surface of the metal organic framework material is easy to modify, the porosity is high, the specific surface area is large, more binding sites can be provided, and the adsorption performance is strong; the thermal stability is good, and the long-term storage and use are facilitated;
(4) the experimental result shows that the molecular imprinting sensor has high selectivity and sensitivity to the target object and satisfactory imprinting effect;
(5) the molecular imprinting sensor has the potential possibility of being applied to other molecular detection, particularly the detection of macromolecules, has low professional requirements on operators in the detection process, and has important practical application value.
The present invention is further illustrated by the following specific examples.
Example 1:
a novel construction method of a magnetic and photon-based dual-response type virus molecularly imprinted sensor is shown in figure 1, and comprises the following steps:
(1) Fe3O4@SiO2preparing nano particles: fe was prepared using a mixed solution of 100mL of isopropyl alcohol and 4 mL of ultrapure water (isopropyl alcohol: ultrapure water =100: 2-8) as a solvent3O4@SiO2Nanoparticles. First, 500mg of Fe3O4Adding the nano particles (about 100-200 nm) into the mixed solution, and placing the mixed solution into an ultrasonic oscillator for ultrasonic treatment and dispersion for 20 minutes. 5mL of NH were added with mechanical stirring3·H2O was added to the above mixed solution, followed by slowly adding 2 mL of tetraethyl orthosilicate (TEOS) while controlling the dropping rate (20 drops/min), and allowing the reaction solution to stand at 45 ℃ for 6 hours. After the reaction was completed, the particles were collected with a magnet, washed several times with deionized water and ethanol in order, anddried in a vacuum drying oven at 60 ℃ for later use.
(2) Fe3O4@SiO2Preparation of-COOH particles: 5 mmol succinic anhydride, 1 mL 3-Aminopropyltriethoxysilane (APTES) and 50mL ethanol were added to the flask, the mixture was sonicated in a sonicator for 20 minutes, and the flask was placed in a 30 ℃ water bath and mixed with mechanical stirring for 3 hours. Subsequently, 100mg of Fe was added3O4@SiO2The nanoparticles were sonicated for 20 minutes, then 20 mL of acetic acid and 3 mL of H2O were added to the mixture and the reaction was continued for 12 hours at 30 ℃. Finally, the product was washed sequentially with deionized water and ethanol. The product obtained is dried in vacuo at 60 ℃ for further use.
(3) Fe3O4@SiO2@UiO-66-NH2Synthesis of particles: adding 0.5 mmoL zirconium chloride (ZrCl)4) And 0.5 mmoL of 2-aminoterephthalic acid were added to 30mL of a N, N-Dimethylformamide (DMF) solution, and 600. mu.L of acetic acid was added thereto, and sonication was carried out for 20 minutes to disperse solid particles. Thereafter, 100mg of Fe was added3O4@SiO2-COOH nanoparticles and sonicated for 20 minutes so that several particles are dispersed more uniformly. Then, the resulting mixture was placed at a temperature of 130 ℃ and reacted for 4 hours with mechanical stirring. After the reaction, the product was collected under the action of a magnet and washed several times with deionized water and ethanol in sequence. Subsequently, the obtained nanoparticles were dried in a vacuum oven at 60 ℃ for use.
(4) Fe3O4@SiO2@UiO-66-NH2Preparation of-C = C particles: 15 mL of anhydrous dichloromethane was used as a reaction solvent, and the reaction solvent was charged into a 50mL flask to obtain 50mg of Fe synthesized above3O4@SiO2@UiO-66-NH2Adding into solvent, oscillating under ultrasound for 20 minutes, slowly dropping 5 mmol methacrylic anhydride under mechanical stirring, and reacting for 72 hours under continuous stirring at 30 ℃. After the reaction is finished, washing the reaction product for multiple times by using dichloromethane and ethanol in sequence, and after centrifugal separation, drying the obtained nano particles in a vacuum oven at 40 ℃ for later use.
(5) MMIPs /MNPreparation of IPs: 50 μ L of EV71 template virus and 0.5 mmol of AOPBA were added to 60 mL of Tris-HCl buffer (pH = 7.4, 10 mM), and after light-shielding treatment, sonication was performed for 20 minutes, and the mixed solution was stored in the dark at room temperature for 12 hours. Then, 200 mg of Fe3O4@SiO2@UiO-66-NH2-C = C nanoparticles were added to the above mixed solution and dispersed by ultrasonic waves for 30 min. Subsequently, 1 mmol of MBA (N, N' -methylenebisacrylamide) and 1 mmol of APS (ammonium persulfate) were added to the mixed solution, and then the reaction was mechanically stirred at 60 ℃ for 24 hours in the dark. And (3) collecting precipitates by magnetic force, and then washing the nanoparticles by using 2% SDS-HAc solution and deionized water in sequence until the absorption peak of the template virus cannot be detected by the supernatant through UV-Vis spectrum, thus obtaining the Magnetic Molecular Imprinting Sensors (MMIPs).
For reference, the synthesis of magnetic non-Imprinted Sensors (MNIPs) was performed under the same conditions as those of Magnetic Molecular Imprinted Sensors (MMIPs) except that the template virus was not added.
In this embodiment, a double-bond modified magnetic metal organic framework is used as a carrier material of a sensor, 4- (4' -acryloyloxyphenylazo) benzoic acid (AOPBA) is used as a photoresponse functional monomer, and-COOH of the photoresponse functional monomer and-NH of a target virus template are introduced2Covalent bond interaction force is formed, and the azobenzene chromophore of the photoresponse functional monomer AOPBA has good light regulation performance under illumination of different wavelengths, so that the novel double-response virus sensor with photons and magnetism is prepared.
(4) The detection method of the molecular imprinting resonance light sensor (MMIPs sensor) comprises the following steps: dispersing MMIPs particles in a Tris-HCl diluent, adding EV71 for mixing, and oscillating for 30 minutes at constant temperature in the dark; then adding the reaction solution into a cuvette, and measuring the resonance light intensity of the cuvette by adopting a QM phosphorescence/luminescence spectrophotometer; the detection conditions are as follows: the excitation wavelength range is 220-700 nm, and the emission wavelength range is 220-700 nm.
Example 2: performance, morphology and structure characterization of MMIPs resonance optical sensor and intermediate product
Using Fourier transform infraredThe structures and the appearances of all the materials prepared in example 1 were characterized by a spectrometer, an X-ray diffractometer and a scanning electron microscope. FIG. 2 is Fe3O4Particles (a) and Fe3O4@SiO2-COOH particles (b), Fe3O4@SiO2@UiO-66-NH2Particles (c) and Fe3O4@SiO2@UiO-66-NH2-infrared spectrogram of C = C particles (d), mmips (e) and mnips (f). About 582 cm-1The absorption peak at (A) is due to Fe3O4Characteristic peak of Fe-O; 1095 cm-1The absorption peak is the stretching vibration peak of Si-O-Si; 1635 cm-1The peak at (a) was due to vibrational absorption of the C = O bond in the amide, indicating that APTES successfully coated the particles and modified-COOH from succinic anhydride; continuously modifies UiO-66-NH2Then, at 1572 cm-1The absorption peak is the stretching vibration of C-O in the organic ligand 2-amino terephthalic acid; 1431 cm-1And 1387 cm-1Is the characteristic absorption peak of 2-amino terephthalic acid. For Fe3O4@SiO2-@UiO-66-NH2-C = C nanoparticles at 1662 cm-1The absorption peak at (a) is caused by the vibration of the grafted C = C bond; the two infrared spectra were not significantly changed compared to the MMIPs and MNIPs particles, which demonstrates that the successful synthesis of imprinted polymers, repeated washing of the template did not affect the structure of MMIPs, and the presence of the template site of its imprinted particles did not affect the overall structural composition of the polymer. The above results indicate the successful preparation of each particle.
FIG. 3 is Fe3O4 (A)、Fe3O4@SiO2@UiO-66-NH2(B) MMIPs (C) and MNIPs (D) scanning electron micrographs of the particles. From FIG. 3, the surface morphology of the individual particles, Fe, can be seen3O4The particles are regular octahedron shapes with the size of about 150-200 nm. Fe3O4@SiO2@UiO-66-NH2Particles and Fe3O4Compared with the nano particles, the particle size of the nano particles is obviously increased, and the nano particles are spherical with the particle size of about 330-400 nm. After the coating of the imprinted layer, the MMIPs particles are comparable to Fe3O4@SiO2@UiO-66-NH2The particles have a rougher surface, irregular shape and increased particle size of about 480 to 550 nm. While there is little difference in morphology between MMIPs and MNIPs, demonstrating that repeated elution processes have negligible structural impact on MIPs. These results all indicate the successful preparation and structural integrity of each particle.
Fig. 4 is a graph of the resonant optical response of MMIPs and MNIPs particles to the template EV 71. In order to verify the feasibility of the proposed strategy, the prepared MMIPs and MNIPs are respectively detected with the target object EV71 with the same concentration (5U/mL), as shown in FIG. 4, when EV71 is added, comparing the difference of the resonant light intensity of the MMIPs and MNIPs at 470nm before and after the target object is adsorbed, namely Δ IRLS, MMIPs and Δ IRLS, MNIPs, and finding that Δ IRLS and MMIPs are far greater than Δ IRLS and MNIPs shows that the target object adsorbed on the surface of MMIPs is much greater than that adsorbed on the surface of MNIPs, so that the particle size of MMPs is increased, the resonant light intensity signal of MMIPs to the target object is obviously enhanced, the particle size of MNIPs is not obviously changed, and the change of the resonant light intensity is extremely small. The scheme strategy of the invention is proved to have feasibility for adsorbing the target object and can be used for relevant research and detection.
Example 3: application of resonance optical molecular imprinting sensor
(1) The experimental conditions of this example were: the amount of MMIPs was 90ng/mL, pH 7.4, adsorption time 20 min, temperature 25 ℃. The specific implementation scheme is as follows: taking 5U/mL EV71 and MMIPs in 90ng/mL Tris-HCl buffer solution, adjusting the pH value of the whole system to 7.4, oscillating and adsorbing at 25 ℃ for 20 min, and measuring the resonant light intensity; then irradiating under 365 nm ultraviolet lamp for 20 min, measuring the resonant light intensity, and then irradiating under visible light for 20 min, and measuring the resonant light intensity.
(2) Detection and analysis of MMIPs resonance light sensor on different concentrations of EV71
Under optimized conditions, different concentrations of EV71 were assayed using prepared MMIPs and MNIPs. As shown in fig. 5A, the resonant light intensities of MMIPs respond accordingly after addition of different concentrations of EV71, whereas under the same conditions,the changes in resonant light intensity for MNIPs are not significant, as shown in fig. 5B, because MNIPs do not have imprinted sites corresponding to template viruses and do not specifically recognize template molecules and are therefore not sensitive to EV71 concentration responses. When the concentration of EV71 is 0.02U/mL-5U/mL, the linear relation between the Δ IRLS and CEV71 is shown in FIG. 5C, and the linear regression equation of MMIPs is Δ IRLS = 6.26 × 105CEV71 +5249 (R is R)2= 0.9977), Δ IRLS = I-I0, I0 and I are the resonant light signal intensity of the system at 470nm when no target is added and after the target is added, respectively, i.e., Δ IRLS represents the resonant light intensity variation value of MMIPs to EV71, and CEV71 is the concentration of target EV 71. The results of fig. 5D represent a linear relationship for MNIPs.
(3) Selective adsorption of MMIPs resonant photosensors on HAV
In this example, HAV, HBV, IPV and RCV were selected as targets at concentrations of 1.0 nM to examine the HAV adsorption and detection ability of MMIPS resonance photosensors. The experiment was performed as described above, repeated three times and averaged. The latter three competitors have similar properties to the template virus hepatitis A, but differ in particle size, etc. As shown in FIG. 6A, the concentration of each virus was controlled to be the same, and in the Tris-HCl buffer solution system, the MMIPs and MNIPs of the imprinted polymer particles showed the corresponding values of Δ IRLS and IF for these viruses under the conditions of 90ng/mL, pH 7.4, incubation temperature 25 ℃ and incubation time 20 minutes. The highest Δ IRLS and IF of EV71 are detected, which shows that the adsorption capacity of MMIPs resonance light sensor of the invention to EV71 is obviously better than that to other viruses. MMIPs show good selectivity to different targets under different illumination, and show good light response performance only when template virus EV71 is added (as shown in FIG. 6B), and the light response performance of MMIPs is weaker when other viruses are added.
(4) Mark adding and recycling of MMIPs resonance light sensor pair EV71
To evaluate the recognition ability of imprinted polymers in real samples, sera were diluted and subjected to spiking recovery experiments under optimal experimental conditions. Each sample was measured in triplicate and recovery was calculated using a linear regression equation. The results are shown in figure 7 with recoveries between 94.00% and 108.49%, indicating that this method can be used to determine EV71 doses in human diluted serum.
(5) Comparison with the properties of the sensor particles prepared in patent application 201910822190.8
The particles of MMIPs of the present invention have an aggregated particle image of about 480 to 550 nm in size, whereas the sensor particles prepared using 201910822190.8 have an aggregated particle image of about 500nm in size, and thus, the particles of MMIPs of the present invention are larger. MMIPs are larger in size, have a larger surface area, provide more imprinting sites on a particle, and have greater affinity and adsorption capacity for recognizing targets.
The comparison of IF is: the IF value of MMIPS particles of the invention is 5.1, the IF value of sensor particles prepared by 201910822190.8 is 3.2, IF = IRLS, MMIPs/. DELTA.IRLS, MNIPs,. DELTA.IRLS = Ii-I0, wherein I0 represents the resonance light intensity value at 470nm when only MMIPS/MNIPs particles are added into the solution, and Ii represents the resonance light intensity value at 470nm after MMIPS/MNIPs particles and viruses are added into the solution system. The value of the resonance light intensity at 470nm is chosen as the detection effect value because the difference between the two is the largest at 470 nm. The higher the IF value, the better the detection effect of the blotting particles on the target.
In conclusion, the Magnetic Molecularly Imprinted Polymers (MMIPs) have good binding behavior to the template viruses, fast binding kinetics, high adsorption capacity and good selectivity. The results show that MMIPs have good light regulation effect on the template virus under the alternate irradiation of 365 nm and visible light: and controlling the release of the target at 365 nm, and combining the target at visible light. The results show that the method is successfully used for specifically recognizing target viruses from actual biological samples. Therefore, the MIPs with optical and magnetic dual response capability are prepared by combining the release and combination of the optical control target object, the rapid magnetic separation and the specific identification, and have important practical application value and significance in biosensing and virus detection and prevention.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A magnetic and photon-based dual-response type virus molecular imprinting sensor is characterized in that magnetic particles are used as an inner core, silicon dioxide is coated on the surfaces of the magnetic particles, a metal organic framework is grafted on the silicon dioxide, a photoresponse polymer is connected to the metal organic framework, and the photoresponse polymer is connected with a target virus template.
2. The magnetic and photon based dual responsive viral molecularly imprinted sensor of claim 1, wherein the photo responsive functional monomer is linked to the metal organic framework by a double bond, and the photo responsive functional monomer forms a covalent bond with an amino group of the target viral template by a carboxyl group.
3. The magnetic and photon based dual response viral molecularly imprinted sensor of claim 2, wherein the photo-responsive functional monomer is 4- (4' -acryloxyphenylazo) benzoic acid.
4. The magnetic and photon based dual response viral molecularly imprinted sensor of claim 1, wherein the magnetic particles are ferroferric oxide particles; the particle size of the ferroferric oxide particles is 100-200 nm;
the metal organic framework is UiO-66-NH2。
5. A method for constructing a magnetic and photon based dual response type virus molecular imprinting sensor according to any one of claims 1 to 4, comprising the steps of:
coating SiO on the surface of the magnetic particles2After the lamination, carrying out carboxylation treatment;
growing a metal organic framework on the surface of the magnetic particles subjected to carboxylation treatment;
double bonds are modified on the metal organic framework of the magnetic particles;
connecting a photoresponse functional monomer and a target virus template on the magnetic particles modified with double bonds.
6. The method for constructing the magnetic and photon-based dual-response type virus molecularly imprinted sensor according to claim 5, wherein the magnetic particles are coated with SiO2The layer process specifically comprises the following steps:
adding the magnetic particles into the mixed solution, and performing dispersion treatment;
adding a catalyst and a silane reagent, and stirring and reacting for 2-10 hours at 40-50 ℃;
collecting magnetic particles by magnetic force, washing the magnetic particles for a plurality of times by deionized water and ethanol in sequence, and drying the magnetic particles for later use;
the mixed solution is a mixed solution of isopropanol and ultrapure water or a mixed solution of ethanol and ultrapure water, and the mass ratio of the isopropanol or the ethanol to the water is 100: 2-8; adding 100mL of mixed solution into every 400-600 mg of magnetic particles;
the silane reagent is tetraethyl orthosilicate, and 1-5 mL of silane reagent is added into every 500mg of magnetic particles;
the catalyst is NH3·H2And O, adding 1-5 mL of silane reagent into every 5mL of catalyst.
7. The method for constructing the magnetic and photon-based dual-response virus molecularly imprinted sensor according to claim 5, wherein the carboxylation process specifically comprises the following steps:
mixing a carboxylation reagent, a carboxyl grafting intermediate and a solvent, performing dispersion treatment, and stirring and mixing for 1-5 hours in a water bath at 25-35 ℃;
adding coating SiO2Magnetic particles of the layer are subjected to dispersion treatment;
adding a catalyst solution, and reacting for 10-14 hours at 25-35 ℃;
washing with deionized water and ethanol for several times, and drying;
wherein the carboxylation reagent is succinic anhydride, and 50-200 mg of coated SiO is added to every 5 mmol of carboxylation reagent2Magnetic particles of the layer;
the intermediate of the grafted carboxyl is 3-Aminopropyltriethoxysilane (APTES), gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane or N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and 0.5-2 mL of the intermediate of the grafted carboxyl is added into every 5 mmol of carboxylation reagent;
the solvent is ethanol, and each 100mg of the solvent is coated with SiO2Adding 40-60 mL of solvent into the magnetic particles of the layer;
the catalyst solution is an acetic acid solution, the volume ratio of the catalyst to water in the catalyst solution is 20: 2-5, and 15-25 mL of the catalyst solution is added to every 1 mL of the intermediate of the grafted carboxyl.
8. The method for constructing the magnetic and photon-based dual-response type virus molecularly imprinted sensor, according to claim 5, wherein the process of growing the metal-organic framework on the surface of the carboxylated magnetic particle specifically comprises the following steps:
adding zirconium chloride, 2-amino terephthalic acid and acetic acid into a solvent, and performing dispersion treatment;
adding magnetic particles subjected to carboxylation treatment, and performing dispersion treatment;
stirring and reacting for 2-8 hours at 100-150 ℃;
collecting the product with a magnet, washing with deionized water and ethanol for several times, and drying for later use;
wherein the molar ratio of zirconium chloride to 2-amino terephthalic acid is 2: 1-2, and 3-7 mmol of ZrCl is added to 100mg of carboxylated magnetic particles4；
The solvent is N, N-Dimethylformamide (DMF); adding 20-50 mL of solvent into every 100mg of magnetic particles subjected to carboxylation treatment;
the catalyst is acetic acid, and 500-1000 mu L of the catalyst is added into each 30mL of the solvent.
9. The method for constructing the magnetic and photon-based dual-response virus molecularly imprinted sensor, according to claim 5, wherein the process of modifying the double bond on the metal-organic framework of the magnetic particle comprises the following steps:
adding magnetic particles with metal organic frameworks growing on the surfaces into a solvent, and performing dispersion treatment;
under the mechanical stirring, dropwise adding a compound with grafted double bonds, and continuously stirring and reacting for 60-80 hours at the temperature of 25-35 ℃;
washing with dichloromethane and ethanol for multiple times in sequence, and performing centrifugal separation to obtain magnetic particles grafted with double bonds;
wherein the solvent is anhydrous dichloromethane, and 10-30 mL of the solvent is added to every 50mg of the magnetic particles with the metal organic frameworks growing on the surfaces;
the compound of the grafted double bond is methacrylic anhydride, and 3-8 mmol of the compound of the grafted double bond is added to every 50mg of magnetic particles with metal organic frameworks growing on the surfaces.
10. The method for constructing the magnetic and photon-based dual-response type virus molecularly imprinted sensor according to claim 5, wherein the process for connecting the photoresponsive functional monomer and the target virus template on the double-bond-modified magnetic particle comprises the following steps:
adding a photoresponse functional monomer and a target virus template into a buffer solution, dispersing for 10-20 minutes under a dark condition, and standing for 10-16 hours at room temperature in the dark;
adding magnetic particles modified with double bonds, and performing dispersion treatment for 15-45 minutes;
adding a cross-linking agent and an initiator, and stirring and reacting for 20-30 hours at the temperature of 50-70 ℃ in a dark place;
collecting the precipitate by magnetic force, and washing the precipitate by using 2% SDS-HAc solution and deionized water in sequence;
wherein the photoresponse functional monomer is AOPBA; adding 0.3-1 mmol of photoresponse functional monomer to each 50 mu L of target virus template;
the crosslinking agent is N, N' -methylene bisacrylamide, and the molar ratio of the crosslinking agent to the photoresponse functional monomer is 3: 1-3;
the initiator is ammonium persulfate, and the molar ratio of the initiator to the cross-linking agent is 1: 1-3;
the buffer solution is Tris-HCl buffer solution, phosphate buffer solution or Britton-Robinson buffer solution; adding 20-100 mu L of target virus template into every 200 mg of double-bond modified magnetic particles, and adding 50-100 mL of buffer solution.
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