CN112462049B - Preparation method of artificial antibody for detecting heavy metal ions - Google Patents
Preparation method of artificial antibody for detecting heavy metal ions Download PDFInfo
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- CN112462049B CN112462049B CN202011423135.0A CN202011423135A CN112462049B CN 112462049 B CN112462049 B CN 112462049B CN 202011423135 A CN202011423135 A CN 202011423135A CN 112462049 B CN112462049 B CN 112462049B
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Classifications
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Abstract
The preparation method of the artificial antibody for detecting heavy metal ions comprises the steps of coating the surfaces of nano SiO 2 spheres in the synthesized artificial antibody with acrylamide and ethylene glycol dimethacrylate polymer shells to form a core-shell structure, and is characterized in that: the invention combines a nano synthesis technology, a molecular imprinting technology and a material surface post-functionalization modification technology, solves the key science problem of no signal output of the traditional molecular imprinting material, and has the advantages of simple method, good selectivity, high sensitivity and broad spectrum on heavy metal ions.
Description
Technical Field
The invention relates to the field of material science, in particular to a preparation method of a fluorescent probe artificial antibody SiO 2 @MIPs for detecting heavy metal ions.
Background
In recent decades of rapid development of the economy in China, the emission of three industrial wastes and motor vehicle exhaust, sewage irrigation, the use of pesticides, herbicides, fertilizers and the like and the development of mining industry lead to the entry of a large amount of heavy metals into soil and water bodies. According to statistics, about 20% of the land in China is polluted by serious heavy metals, and the total area of the land is about 0.11 hundred million km 2; the total amount of heavy metal pollutants in rivers such as Yangtze river, zhujiang river, yellow river and the like is about 3.4 ten thousand tons. The overscaling phenomenon of lead, copper, mercury and cadmium in the seawater sampling sample in the coastal area of China is all caused, wherein the overscaling rate of copper is 25.9%, the overscaling rate of lead is 62.9%, and the overscaling rate is 49 times of the standard of the seawater of the first class. Foreign soil and water heavy metal pollution is not up to standard. It can be seen that heavy metal pollution has become a global environmental pollution problem.
Heavy metals in soil and water body enter the plant body through the root system of the plant, and are enriched in the plant body along with the transpiration of plant leaves. Heavy metals cannot be biodegraded, and the residual heavy metal is amplified step by step and enters the human body through accumulation of food chains. Heavy metals are easy to accumulate in organs such as brain, kidney, liver and the like, and combine with proteins, DNA and RNA, so that normal functions of a human body are gradually damaged. Therefore, rapid recognition and trace detection of heavy metal residues are challenging problems to be solved in China at present, and are important research fields of general concern in the international society, and advanced sensing materials and rapid, sensitive and reliable analysis and detection technologies are urgently needed to solve challenges of recognition and trace detection of heavy metal residues in water bodies.
Currently, the most common methods for heavy metal detection include laser induced breakdown spectroscopy, inductively coupled plasma mass spectrometry, atomic absorption spectrophotometry, atomic fluorescence spectrometry, ultraviolet-visible spectrometry, ion chromatography, and the like. These methods are highly sensitive, but require expensive equipment, and require complex and time-consuming sample pretreatment.
In recent years, a biomimetic sensitive material containing a characteristic structure is increasingly paid attention to by a chemical synthesis method, wherein a molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) prepared by a molecularly imprinted technology (Molecular Imprinting Technique, MIT) is a representative biomimetic functional material. The molecularly imprinted polymer has good specificity, sensitivity and stability, and the preparation method is simple and the cost is low. The molecular imprinting technology is to fix template molecules in a crosslinked polymer network through covalent bond or noncovalent interaction between the template molecules (target molecules) and functional monomers, remove the template molecules, leave holes matched with the shape and function of the template molecules, thereby creating molecular recognition sites with high affinity and high selectivity in synthetic materials (artificial antibodies ）（Wulff, G. Chem. Rev., 2002, 102, 1.;Wulff, G. Angew.Chem. Int. Ed. 1995, 34, 1812.;Haupt, K.; Mosbach, K.. Chem. Rev.2000, 100, 2495.;Zimmerman, S. C.; Lemcoff, N. G. Chem. Commun.2004, 5.）. realize enrichment of target substances in complex matrixes through simulation of the molecular recognition effect of antigen-antibody, and realize the aim of measuring the concentration of the target substances with high selectivity and high sensitivity) （Katz, A.; Davis, M. E. Nature,2000, 403, 286.;Bass, J. D.; Katz, A. Chem. Mater.2003, 15, 2757.;Zimmerman, S. C.; Wendland, M. S.; Rakow, N. A.; Suslick, K. S. Nature2002, 418, 399.;Mertz, E.; Zimmerman, S. C. J. Am. Chem. Soc.2003, 125, 3424.）.
The polymer material synthesized by the traditional molecular imprinting technology has the defects of small saturated combination amount, slow adsorption kinetics and the like, and contributes to some new imprinting technologies such as surface imprinting, film imprinting, single-molecule dendritic imprinting and the like to be focused by researchers. The invention discloses an invention patent (CN 110354826A) 'A lead-cadmium ion double-template magnetic molecularly imprinted polymer and a preparation method thereof', which are disclosed by the culprit academy of culprit Wei Shoulian and the like. The magnetic molecularly imprinted polymer can adsorb Pb 2+、Cd2+ heavy metal ions simultaneously with high adsorption capacity and high selectivity, has wider application range, and has wide application prospect in rapid magnetic separation, enrichment and analysis of Pb 2+、Cd2+ in biological samples, environmental samples, foods and agricultural products. The invention discloses an invention patent (CN 103769059) plant straw surface imprinting adsorption material and a preparation method thereof, and discloses a plant straw surface imprinting adsorption material and a preparation method thereof, which are disclosed in the salt city institute of technology Wang Jingjing and the like. Firstly, plant straws are subjected to NaOH solution pretreatment and silane coupling agent modification in sequence, then the modified straws, functional monomers, a crosslinking agent and an initiator are uniformly mixed in absolute ethyl alcohol, and the mixture reacts under the protection of nitrogen to obtain the surface imprinting adsorption material. The invention not only realizes the recycling of agricultural wastes, but also has good stability and regeneration performance of the obtained adsorption material, and has high adsorption speed on heavy metal ions, thus being widely applied to the treatment of heavy metal ion wastewater. Somaye Akbari discloses that the method of invention patent （US20180345247）"Modification of halloysite mineral adsorbent by dendritic polymer in convergent synthetic route and its application", involves modifying halloysite nanotubes with dendrimers to treat wastewater containing ionic or nonionic water contaminants such as heavy metal ions, dyes, surfactants, high molecular weight coagulants, and mineral oils. This method increases the surface activity of the adsorbent and can be used to create a positive or negative charge on the adsorbent surface. The modified minerals can be used as: adsorbents for contaminants, such as dyes, heavy metal ions, aromatic substances in aqueous solutions, for removing cations from aqueous solutions, for removing anions from aqueous solutions, as fillers in nanocomposite materials, such as particles in nano-polymer films, soil adsorbents and special pharmaceutical applications. Jamie Lead, university of south carolina, discloses an invention patent (US 20190023591) "Collection of metal ions from water mixtures using nanotechnology" which provides a method for removing metal ions (Cd, cr, ni, zn and Pb ions) from water. The polyvinylpyrrolidone coated magnetic nanoparticles (PVP-Fe 3O4 NPs) can remove metal ions (Cd, cr, ni, zn and Pb ions) from synthetic soft water and seawater under acidic or non-acidic conditions. PVP-Fe 3O4 NPs can remove about 100% of Cd, cr, ni, zn and Pb metal ions at a concentration of 0.1 mg/L and can remove more than 80% of metal ions at a concentration of 1 mg/L. In addition, the majority of the adsorption of the metal by the nanoparticles can be completed within 3 hours. The invention discloses a preparation method of a highly selective adsorption material for different heavy metal ions, which is disclosed in an invention patent (CN 103285837A) of Lu Yuxian and the like of Wuhan family dream environmental engineering Co. The invention relates to a method for producing an adsorption material which has selectivity to certain heavy metal ions such as copper, chromium, lead, mercury and the like and can be repeatedly used by taking some inorganic minerals such as montmorillonite, silicon dioxide and the like as modified carriers and adopting 1) pretreatment and thermal activation of the carriers, 2) surface polymerization of a template ion carrier and 3) a crosslinking film coating process of carrier surface imprinting molecules. The material can be used for separating, removing and enriching specific heavy metal ions in mixed solution, process water and wastewater treatment process. The invention discloses an invention patent (CN 104262536A) of an active/controllable graphene oxide surface ion imprinted polymer and a preparation method and application thereof, provides an active/controllable graphene oxide surface ion imprinted polymer and a preparation method and application thereof, and belongs to the technical field of material preparation and separation; in particular to a method for preparing an ionic imprinting polymer on the surface of graphene oxide by taking graphene oxide as a substrate, metal ions as templates, a coupling agent, a functional monomer, a crosslinking agent and an initiator and adopting a reversible addition-fragmentation chain transfer polymerization as a polymerization mode; solves the problems that the thickness of the surface polymer layer is uncontrollable, the template molecules cannot be thoroughly eluted due to too deep embedding, the adsorption rate is slow, and the like; the method is mainly used for adsorbing corresponding metal ions in the aqueous solution, has good adsorption effect at room temperature, has obvious selective separation effect and is used repeatedly. The invention discloses a preparation method of an ion imprinted polymer film, which belongs to the field of preparation of electroactive functional polymer film materials and selective separation of ions, and is characterized by being a preparation method of an ion imprinted polymer film with an electric control cation exchange function, and discloses an invention patent (CN 103214689A) of Hao Xiaogang. The method comprises the steps of preparing an aqueous solution of a monomer for preparing a polymer, an electrolyte solution, protonic acid, imprinting ions and a doped ion solution, mixing the five solutions, and carrying out in-situ polymerization on a conductive matrix by a monopolar pulse electrodeposition method to obtain the iron cyanide doped polymer film from which the imprinting ions are removed by one-step synthesis. The method is simple and quick to operate, can remove imprinting ions in situ without an additional pickling step, and is mild in preparation condition and convenient to control. The ion imprinting polymer film prepared by the method has an electric control cation exchange function, and can be used for selectively removing heavy metal ions in water or separating and recovering rare earth ions. The invention discloses a method for preparing metal ion imprinted polymer microspheres in an aqueous medium, which belongs to the preparation technology of metal ion imprinted materials, and discloses a method for preparing metal ion imprinted polymer microspheres in an aqueous medium, namely, tianjin university Cheng Guoxiang and the like. The method comprises the steps of taking TRIM as a polymer skeleton monomer, toluene as a diluent, span-80 as an emulsifier, SDBS or PVA as a dispersing agent, MAA as a functional monomer, cu 2+ or Ni 2+ as imprinting ions, mg 2+ as an ionic strength control agent, preparing inverse emulsion, preparing an external aqueous phase solution, and performing polymerization post-treatment to obtain the imprinted polymer microsphere product of Cu 2+,Ni2+. The invention has the advantages that: the preparation process is simple, the period is short, the implementation is easy, the polymerization process is carried out in an aqueous medium, the imprinting requirement of water-soluble molecules can be met, the dispersibility and sphericity of the product are kept good, the most common and cheap reagent is used, and the production cost is low. The invention is widely applied to adsorption and separation of metal ions, and can also be used as a component of a chemical sensor for monitoring the change of the concentration of the metal ions in the aqueous solution. The invention discloses a preparation method and application of a magnetic metal ion surface imprinted polymer in an invention patent (CN 101905151A) disclosed by Nanchang aviation university Luo Xubiao and the like, and the invention discloses a preparation method of the magnetic metal ion surface imprinted polymer, which comprises the following steps: 1) Preparing nano ferroferric oxide magnetic fluid by adopting a coprecipitation method; 2) Pre-assembling the template ions and a nitrogenous silylation reagent to obtain a pre-assembled solution of the template ions and nitrogenous silylation; 3) Adding activated ferroferric oxide into a template ion and nitrogenous silanization pre-assembly solution (ion imprinting pre-polymerization solution) to obtain a magnetic ion imprinting polymer containing template ions; 4) After the reaction is finished, the magnetic ion imprinted polymer is obtained. The invention has the advantages that: 1) The post-treatment is convenient, and the applicability is wide; 2) After the adsorption is finished, the separation from the sample matrix can be realized rapidly; 3) The adsorption quantity of metal ions is relatively large; 4) The interference of the matrix can be well removed; 5) The method is suitable for treating heavy metal ions and recycling noble metal ions in various waste water. MA SHENGQIAN, et al, at university of south florida, disclose an invention patent (WO 2019140338) 'Multifunctional porous materials for water purification and remediation', which relates to various compositions for water purification and remediation that are effective in facilitating the removal of contaminants. The composition comprises a porous organic polymer having a pore size in the range of about 1 nm to 10 nm or greater. The porous organic polymer has one or more functional groups that bind the contaminant and may include one, two or more different functional groups, such as amines, halides, ammonium, pyridine, thiols, and the like. Contaminants may include antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, selenium, phosphate, and the like. The invention discloses a method for preparing a soil chromium pollution specific adsorption fiber membrane, which is disclosed in an invention patent (CN 108722364) Shang Anshun of Edison automation equipment limited company in Ulva, and is prepared from raw materials such as attapulgite, penicillium mycelium, chitosan, methylene dichloride, polyvinyl nitrile, polyurethane, ethyl orthosilicate and the like, wherein the attapulgite is modified, carboxyl-containing modified components are introduced through surface functionalization, the adsorption capacity of chromium ions is improved by utilizing the complexation of ethylenediamine tetraacetic acid and heavy metals, and meanwhile, molecular imprinting nano materials are combined, the invention has the advantages that the fiber membrane has high chromium ion adsorption removal rate, shorter repair period and no secondary pollution, can improve the soil quality, has simple operation, strong applicability and low cost, and meets the current repair requirement on the chromium pollution of the soil.
However, in molecular surface imprinting, the target analyte entering the recognition site mostly has no signal output by itself, and thus, the sensitive signal output of the target analyte entering the recognition site becomes a hot spot of interest to researchers. Jilin university Lv Shaowu et al discloses an invention patent (CN 110180509A) 'a fluorescent molecularly imprinted polymer hollow microsphere, a preparation method and application thereof', a silica nanoparticle SiO 2 is prepared, and a polymer of which the surface is grafted with fluorescein isothiocyanate SiO 2 @FITC-APTES is prepared; fluorescent molecularly imprinted polymer SiO 2 @FITC-APTES@MIP was prepared and etched into hollow fluorescent molecularly imprinted polymer FITC-APTES@MIP. The advantages are that: the hollow fluorescent molecularly imprinted polymer which can rapidly and efficiently detect the target analyte in a specific manner and is safer and more environment-friendly in the synthesis process is prepared, and the hollow fluorescent molecularly imprinted polymer specifically adsorbs the target analyte and generates fluorescent quenching, and has a remarkable quenching effect in 20 min, so that the detection time is shortened. The institute of fertigation Gao Daming et al discloses an invention patent (CN 111426669A) of a preparation method of a fluorescence labeling molecularly imprinted silica probe array for catechol detection, which is characterized in that catechol molecules are imprinted on the surface of prepared SiO 2 nano particles, functional monomers and labeled fluorescein NBD are modified at a recognition site, and the probe array is self-assembled on the surface of glass fibers. The invention combines nano synthesis, molecular imprinting and plasma etching technologies with photoelectron induced transfer mechanisms, has a recognition site with a spatial structure matched with catechol on the surface of a silicon dioxide nanoparticle probe for eluting catechol molecules, realizes selective recognition of catechol, forms hydrogen bonds with lone pair electrons of nitrogen atoms on amino groups in APTS and hydrogen atoms in hydroxyl groups in catechol entering the recognition site, inhibits electron transfer of nitrogen atoms based on the photoelectron induced transfer principle, leads to NBD electron induced transfer, enhances the fluorescence intensity of a fluorescent probe marked at the recognition site, and realizes high-sensitivity detection of catechol as a target molecule. The above-described techniques address the issues of highly selective recognition and highly sensitive detection of specific target analytes entering the recognition site, but require the construction of specific fluorescent probes for specific target analytes to respond to target analytes. The invention discloses a research and field detection application of a high-selectivity multi-component printing molecularly imprinted paper chip fluorescence sensor disclosed in an invention patent (CN 103033495A) by Jinan university, beijing and the like, and discloses a high-selectivity multi-component printing molecularly imprinted paper chip fluorescence sensor and a method for detecting heavy metal ions by the same. The preparation method of the printing molecularly imprinted paper chip fluorescence sensor comprises the following steps: selecting a functional monomer corresponding to the metal ion; preparing quantum dots and preparing quantum dot molecular imprinting mixed solution according to literature; and printing the mixed solution of different metal ion quantum dot molecular imprinting on paper by using a printer, and performing ultraviolet irradiation to prepare the fluorescent sensor for the printed molecular imprinting paper chip. A method for simultaneously detecting heavy metal ion pollutants in a water body by high-selectivity multicomponent comprises the following steps: and immersing the prepared printing molecularly imprinted paper chip fluorescence sensor into a water body sample, then soaking a saturated fluorescent reagent emitted by short waves, and detecting heavy metal ions in the sample. The invention has strong specificity and high sensitivity; the detection time is short; the cost is low; is convenient to process. The method for detecting heavy metal ions by fluorescence is rapid and simple in operation, and the reaction and the result are automatically completed and recorded by an instrument. The invention discloses a preparation and application of a fluorescent ion imprinting probe in the invention patent (CN 104292381) published by Jiangsu university Zheng Xudong, which relates to a preparation method and application of the fluorescent ion imprinting probe, in particular to a preparation method of the fluorescent imprinting probe for detecting Cu 2+ and Cu 2+ applied to detecting trace amount in water, belonging to the technical field of material preparation and detection, in particular to a fluorescent ion imprinting probe which uses a metal europium ion complex as a luminous group, divalent Cu ion as a template molecule, methacrylic acid (MAA) as a functional monomer and Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent, the trace analysis and detection experiment and the selectivity experiment are used for researching the selectivity analysis performance of the prepared fluorescent probe, and the result shows that the fluorescent blotting probe obtained by the invention has excellent Cu ion recognition performance. The invention discloses a hexavalent chromium anion imprinting core-shell type magnetic fluorescent sensing microsphere, which is disclosed in an invention patent (CN 107573468) of Tianjin industrial university, namely Showa et al. The core-shell type magnetic fluorescent sensing microsphere takes Fe 3O4 magnetic material as an inner core, a layer of fluorescent material with hexavalent chromium anion imprinting is wrapped on the surface of the core as an outer shell, the fluorescent material has a selective adsorption effect on hexavalent chromium anions, the fluorescence intensity of the microsphere is reduced after the hexavalent chromium anions are adsorbed, the concentration of the hexavalent chromium anions in a system can be obtained by measuring the change of the fluorescence intensity of the microsphere, and the core-shell type magnetic fluorescent sensing microsphere obtained by the invention can be applied to the field of recovery or detection of the hexavalent chromium anions. The university of Yi Xu Shoufang et al discloses a preparation method of a fluorescent polymer for simultaneously detecting trivalent chromium ions and hexavalent chromium ions in the invention patent (CN 111088032), and the invention discloses a preparation method of a fluorescent polymer for simultaneously detecting trivalent chromium ions and hexavalent chromium ions, which comprises the following steps: (1) Preparing a blue carbon point and a red carbon point, wherein the excitation wavelength of the blue carbon point is about 370 nm, the emission wavelength is about 450 nm, the excitation spectrum of the blue carbon point is completely overlapped with the absorption spectrum of hexavalent chromium ions, and the blue carbon point is quenched by the hexavalent chromium ions through an internal filtering effect; the excitation wavelength of the red carbon point is about 570 nm, the emission wavelength is about 600 nm, and the red carbon point can be quenched by trivalent chromium ions based on electron transfer; (2) Coating blue carbon dots inside the silicon sphere; (3) And coating a fluorescent imprinting layer of trivalent chromium ions on the surface of the silicon sphere coated with the blue carbon dots, and finally forming a fluorescent polymer with a core-shell structure, wherein red carbon dots are doped in the fluorescent imprinting layer, and the fluorescent imprinting layer is of a mesoporous structure. The fluorescent polymer obtained by the method can be used for simultaneously detecting trivalent chromium ions and hexavalent chromium ions.
In summary, the existing imprinted polymers have some difficulties to be overcome in practical applications such as molecular recognition or signal output, and the existing imprinted polymers can be summarized as the following aspects: (1) Because the number of effective sites is small, the affinity to target molecules is small; (2) Molecularly imprinted polymers are typically irregularly shaped materials with poor compatibility with the sensing device. (3) The target analyte entering the recognition site itself cannot be output as a sensitive signal. Therefore, the molecular imprinting polymer material with high selectivity, high binding capacity, easy accessibility of sites, high binding kinetics speed, high sensitive signal output and regular morphology is synthesized, has important practical and theoretical significance for solving the problems of heavy metal residue recognition and trace detection in water, and has very wide application prospect in the fields of trace substance detection, environment monitoring and the like.
In the invention, we report an artificial antibody preparation method for detecting heavy metal ions. The surface of the nano SiO 2 ball in the synthesized artificial antibody is coated with an acrylamide and ethylene glycol dimethacrylate polymer shell layer to form a core-shell structure, and the method is characterized in that: the recognition site of the imprinting shell layer is modified with fluorescein, so that the recognition site in the heavy metal ion artificial antibody shell layer is eluted to form a hole structure matched with the space structure of the imprinting metal ion, heavy metal ions entering the recognition site again capture electrons on a fluorescent probe of the recognition site, and selective recognition and sensitive detection of the heavy metal ions are realized by utilizing the principle of fluorescence resonance energy transfer.
Disclosure of Invention
The invention aims to: aiming at the defects existing in the prior art, the invention synthesizes the preparation method of the fluorescent probe artificial antibody SiO 2 @MIPs with controllable shell thickness and sensitive recognition on heavy metal ions for the first time. The method is a chemical synthesis method, firstly preparing derivatives of fluorescein and a silanization reagent, then synthesizing a monodisperse nano SiO 2 fluorescent probe, then taking nano SiO 2 spheres modified with the fluorescent probe as a core, preparing a fluorescent probe artificial antibody SiO 2 @MIPs imprinted by heavy metal ions, forming the artificial antibody SiO 2 @MIPs with a core-shell structure, and finally removing imprinted heavy metal ions in a shell layer, wherein the fluorescent probe artificial antibody SiO 2 @MIPs selectively recognizes and detects heavy metal ions.
The technical scheme of the invention is as follows: the preparation method of the artificial antibody for detecting heavy metal ions comprises the steps of coating the surfaces of nano SiO 2 spheres in the synthesized artificial antibody with acrylamide and ethylene glycol dimethacrylate polymer shells to form a core-shell structure, and is characterized in that: the method comprises the following four steps:
1.1 the first step is the coupling of fluorescein with silylating agent: firstly, adding 1-3 mL of silanization reagent and 5-15 mL of absolute ethyl alcohol into a 100 mL conical flask with a grinding plug, after ultrasonic dispersion of 5-10 min, weighing 0.0100-0.0200 g of fluorescein by using an electronic balance with precision of ten-thousandth, adding the fluorescein into the mixed solution, sealing the conical flask, placing the sealed conical flask on a magnetic stirrer with controllable temperature, and carrying out polymerization reaction at a rotating speed of 500 rpm for 12-15 h at the temperature of 25 ℃ to obtain a derivative solution of the fluorescein and the silanization reagent, namely solution A;
1.2 the second step is the preparation of a nano SiO 2 fluorescent probe: firstly, adding 3-6 mL tetraethoxysilane and 80-200 mL absolute ethyl alcohol into a 250-mL conical flask with a grinding plug in sequence, performing ultrasonic dispersion on the mixture to form a mixed solution, then adding 6-12 mL solution A into the mixed solution, performing ultrasonic dispersion on the mixed solution again to obtain 5-10 min, rapidly adding 12-24 mL ammonia water into the mixed solution, sealing the conical flask, placing the conical flask on a magnetic stirrer with controllable temperature, stirring at a speed of 750-rpm for hydrolytic condensation reaction 2-5 min at 25 ℃, and performing hydrolytic condensation reaction at a speed of 500-rpm for 12-15 h; centrifuging the obtained reaction product by using a 50 mL centrifuge tube at a speed of 8500 rmp for 5 min to remove unreacted substrates, dispersing by using industrial ethanol in an ultrasonic manner, repeatedly washing for 3 times to obtain a nano SiO 2 fluorescent probe with surface modified fluorescein, adding 110-220 mL deionized water into the fluorescent probe, and performing ultrasonic dispersion to obtain a monodisperse round nano SiO 2 fluorescent probe suspension with surface modified fluorescein, which is called solution B;
1.3 the third step is the preparation of heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs: after solution B is subjected to ultrasonic dispersion of 5-10 min, 20mL of the solution is measured, centrifugal 5-min is carried out at 8500 rmp, deionized water is removed, then acetonitrile is used for ultrasonic dispersion, after the steps are repeated for 3 times, 50-mL acetonitrile is used for ultrasonic dispersion again, the solution is transferred to a conical flask of 250 mL, finally 0.0200 g heavy metal inorganic salt, 0.0150-0.0300. 0.0300 g acrylamide and 0.0100-0.0150 g azodiisobutyronitrile are respectively weighed with the accuracy of ten thousandth of an electronic day, the solution is added into the polymer suspension, after ultrasonic dispersion of 5-10 min, 170-220 mu L of ethylene glycol dimethacrylate is added, 10-15 min of high-purity nitrogen is introduced into the mixed solution, after oxygen in the mixed solution is removed, vacuum grease is smeared on a grinding mouth plug of a conical flask, the conical flask is sealed, the mouth plug is wrapped with a preservative film, the mouth plug is wrapped and wrapped, finally the sealed conical flask is placed in a shaking table with a programmed temperature, and the three steps of reaction time control are carried out as follows: (1) reaction at 60℃2 h; (2) reaction at 65℃10 h; (3) reaction curing at 70 ℃ for 2-3 h. Transferring the obtained polymerization reaction product into a 50 mL centrifuge tube, centrifuging at a speed of 8500 rpm to remove unreacted substrate, then performing ultrasonic dispersion with industrial ethanol, centrifuging again, repeating for 3 times to obtain heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs, adding 50 mL deionized water into the centrifugally washed artificial antibodies SiO 2 @MIPs, performing ultrasonic dispersion for later use, and obtaining a solution C;
1.4 the fourth step is the preparation method of the fluorescent probe artificial antibody SiO 2 @ MIPs with heavy metal ion identification and detection functions: and (3) weighing 0.0300-0.0600 g ethylenediamine tetraacetic acid-disodium with the precision of ten-thousandth of an electronic balance, placing the solution C, shaking the solution C at 25 ℃ at the rotation speed of 300 rpm for 4h, transferring the mixed solution into a 50mL centrifuge tube, centrifuging the mixed solution at the rotation speed of 8500 rpm, removing the supernatant, ultrasonically dispersing the precipitate with 30-40 mL deionized water, centrifuging the precipitate again, and repeating the process for 3 times to obtain the SiO 2 @MIPs of the fluorescent probe artificial antibody with the functions of selectively identifying and sensitively detecting heavy metal ions.
As a further improvement over the prior art, the silylating agent in the prepared artificial antibody is 3-aminopropyl triethoxysilane. The heavy metal ions imprinted in the prepared artificial antibody are suitable for Pb 2+,Cd2+,Hg2+ and Cu 2+. The acrylamide in the prepared artificial antibody is a functional monomer. The ethylene glycol dimethacrylate in the prepared artificial antibody is a cross-linking agent. The azo-bis-isobutyronitrile in the prepared artificial antibody is an initiator. The fluorescein in the prepared artificial antibody is a probe. The fluorescent group modified in the prepared artificial antibody has part of excited state fluorescence absorbed by heavy metal ions, so that the fluorescence intensity of the fluorescent group is reduced, a sensitive recognition signal combined with a target substance is obtained, and the selective and sensitive detection of the heavy metal ions is achieved. The thickness of the imprinted polymer shell layer of the prepared artificial antibody can be controlled by adjusting the amount of acrylamide and ethylene glycol dimethacrylate.
Compared with the prior art, the beneficial effects are that:
The current molecular imprinting technology for detecting heavy metal ions is transited from a traditional molecular imprinting synthetic material to a surface molecular imprinting material, then transited to a fluorescent probe modified and marked at a recognition site of the molecular imprinting material, and finally to a nano-structure molecular imprinting material, thereby reflecting the continuous innovation and change of the molecular imprinting technology. However, the imprinted polymers prepared by the conventional method currently face a plurality of difficulties to be overcome in practical application of molecular recognition and signal output, and can be summarized in the following aspects: (1) Because the molecular imprinting polymer has high crosslinking density, template molecules in the crosslinked network cannot be completely removed, and target molecules are difficult to diffuse into imprinting points in the network, the binding kinetics of the target molecules is slow （Markowitz, M. A.; Kust, P. R.; Deng, G.; Schoen, P. E.; Gaber, B. P. Langmuir2000, 16,.1759.;Rao, M. S.; Dave, B. C. J. Am. Chem. Soc.1998, 120, 13270.）;（2）, and because the number of effective sites is small, the affinity of the target molecules is small; (3) Molecularly imprinted polymers are typically irregularly shaped materials with poor compatibility with the sensing device. (4) The target analyte entering the recognition site itself cannot be output as a sensitive signal. In view of this, the aim （Hayden, O.; Mann, K. J.; Krassnig, S.; Dickert, F. L. Angew. Chem. Int. Ed. 2006, 45, 2626.;Schmidt, R. H.; Mosbach, K.; Haupt, K. Adv. Mater.2004, 16, 719.）. pursued for synthesizing the molecularly imprinted polymer material with high selectivity, high binding capacity, easy accessibility of sites, high binding kinetics speed and high sensitive signal output and with regular morphology has been to synthesize the molecularly imprinted polymer material with high selectivity, high binding capacity, easy accessibility of sites, high binding kinetics speed and high sensitive signal output and with regular morphology, has important practical and theoretical significance for developing highly selective, highly integrated and miniaturized chemical biological sensing devices, and has very wide application prospects in the fields of trace substance detection, environment monitoring and the like.
In recent years, development of a preparation technology of nano materials and an optical signal sensing method brings new opportunities for solving difficulties faced by a molecularly imprinted material. The nanostructured molecularly imprinted material has the following distinct advantages over conventional imprinted materials: (1) The imprinting polymerization on the surface of the nano material reduces the phenomenon that imprinting sites are embedded too deeply, template molecules are almost all positioned on the surface or near the surface of the nano structure, so that the template molecules can be almost completely removed, thereby generating high-density effective imprinting points, realizing high affinity （GUO Z H, FLOREA A, CRISTEA C, et al. Sensors & Actuators B Chemical, 2015 , 207 ,960 -966.）;（2） for target molecules, being beneficial to the adsorption-desorption process of the template molecules, and increasing the bonding speed of the imprinting molecules and the bonding sites, so that the molecular imprinting material with the （BOUGRINI M, FLOREA A, CRISTEA C, et al. Food Control, 2016, 59, 424 - 429.;S. Tokonami, H. Shiigi, T. Nagaoka, Anal. Chim. Acta, 641, 2009, 7–13.）;（3） nano structure has huge specific surface area, regular shape and high mechanical stability, and the specific recognition sites are not easy to damage, and can be assembled on a sensor in practical application (Gao, D.M.; zhang, Z.P.; wu, M.H.J. Am. chem. Soc.2007, 129 and 7859.); (4) The fluorescent probe modification is easy to be carried out on the molecular imprinting surface of the nano structure, so that the signal output is convenient; (5) Meanwhile, the imprinting process is carried out on the nano surface, the sensitivity of the material is greatly improved due to the large specific surface, and trace substance detection is facilitated (ALIZADEH T, ANALYTICA CHIMICAACTA, 2010, 669 (1), 94-101).
The method comprises the following steps: compared with the prior art, the nano SiO 2 sphere surface with good dispersibility is coated with a layer of nano shell layer of acrylamide and ethylene glycol dimethacrylate, so that the specific surface area of the polymer is increased, all recognition sites are positioned on the nano shell layer surface, and the number, the combination amount and the selectivity of the recognition sites are increased.
And two,: in the method provided by the invention, the shell thickness of the core-shell structure SiO 2 @MIPs with controllable shell thickness can be controlled by adjusting the amounts of acrylamide and ethylene glycol dimethacrylate. I.e. the thickness of the nanoshell with the recognition property is controllable, thus, the composite nanospheres suitable for the required nanoshell can be obtained by optimizing the reaction conditions.
And thirdly,: compared with the traditional molecularly imprinted polymer, the artificial antibody SiO 2 @MIPs has the surface modified with the fluorescent group, has the advantages of fluorescent recognition performance, high sensitivity, simple and convenient operation, high response speed and improvement of molecular recognition performance, selectivity and recognition efficiency.
Fourth, it is: the synthetic SiO 2 ball surface is coated with acrylamide and glycol dimethacrylate nano shell layers, and has the following advantages: (1) The thickness of the shell layer of the synthesized composite microsphere is controllable, the SiO 2 spherical particle size is about 180: 180 nm, the surface area is large, and the synthesis process is simple; (2) The chemical and thermal stability of the catalyst is not reacted with the organic solvent in the reaction process; (3) easy grafting organic functional groups on the surface; (4) is environmentally friendly; (5) The imprinting shell recognition site has the advantages of strong rigidity, difficult collapse and good selectivity.
Fifth, it is: the prepared artificial antibody for detecting heavy metal ions is applicable to Pb 2 +、Cd2+、Hg2+ and Cu 2+, and has a certain broad spectrum.
Drawings
FIG. 1 is a schematic diagram showing that the fluorescent probe artificial antibody SiO 2 @ MIPs prepared by the invention has selective recognition and detection on target molecules.
FIG. 2 is a graph showing the ultraviolet-visible spectrum of the association of fluorescein and 3-aminopropyl triethoxysilane derivatives prepared by the invention with different concentrations of Cd 2+、Cu2+、Pb2+ and Hg 2+ ions.
FIG. 3 is a graph of association constants of the interactions of derivatives of fluorescein and 3-aminopropyl triethoxysilane prepared in accordance with the present invention with Cd 2+、Cu2+、Pb2+ and Hg 2+ ions.
FIG. 4 is a fluorescence spectrum of the fluorescent probe of the surface modified fluorescein nano SiO 2 and the derivative of the fluorescein and the 3-aminopropyl triethoxy silane prepared by the invention.
FIG. 5 is an infrared spectrogram of SiO 2 ball, fluorescein, nano SiO 2 fluorescent probe with surface modified fluorescein, fluorescent probe artificial antibody SiO 2 @MIPs with heavy metal ion imprinting removed and fluorescent probe artificial antibody SiO 2 @MIPs with Cd 2+ ion imprinting adsorbed prepared by the invention.
FIG. 6 is an SEM image of a fluorescent probe artificial antibody SiO 2 @MIP prepared by the invention and having selective recognition and sensitivity detection on Cu 2+,Cd2+,Hg2+ and Pb 2+ ions.
FIG. 7 is a TEM image and MAP image of a fluorescent probe artificial antibody SiO 2 @MIP with selective recognition and sensitivity detection on Pb 2+ ions prepared by the invention.
FIG. 8 is a graph of Hg 2+ ion molecular imprinting and non-imprinting SiO 2 @MIPs isothermal adsorption prepared by the invention.
FIG. 9 is a kinetic profile of Hg 2+ ion molecularly imprinted and non-imprinted SiO 2 @MIPs prepared by the present invention.
FIG. 10 is a graph showing the relationship between the intensity of a fluorescent probe prepared by the present invention and the concentration change of heavy metal ions.
FIG. 11 is a Stern-Volmer equation for a fluorescent probe prepared according to the present invention fitted to metal ions of different concentrations.
FIG. 12 shows the detection limits of the fluorescence-labeled artificial antibodies prepared according to the present invention for metal ions of different concentrations.
The detailed description will be further explained with reference to the drawings
FIG. 1 is a schematic diagram showing that the fluorescent probe artificial antibody SiO 2 @ MIPs prepared by the invention has selective recognition and detection on target molecules. The specific process is as follows: 1-2, preparation of a nano SiO 2 fluorescent probe represented by the process: the nano SiO 2 and fluorescein are hydrolyzed and condensed to obtain a nano SiO 2 fluorescent probe with surface modified fluorescein; the process of 2-3 shows that the preparation of the fluorescent probe artificial antibody SiO 2 @MIPs imprinted by heavy metal ions comprises the following steps: dispersing a nano SiO 2 fluorescent probe with surface modified fluorescein in acetonitrile, adding a template molecule, a functional monomer, an initiator and a crosslinking agent, and carrying out polymerization reaction in a nitrogen atmosphere to obtain a heavy metal ion imprinted fluorescent probe artificial antibody SiO 2 @MIPs; and 3-4, namely eluting the target molecule and re-combining the target molecule to form the fluorescent-labeled artificial antibody for identifying and detecting the target analyte.
FIG. 2 is a graph showing the ultraviolet-visible spectrum of the association of fluorescein and 3-aminopropyl triethoxysilane derivatives prepared by the invention with different concentrations of Cd 2+、Cu2+、Pb2+ and Hg 2+ ions. (A), (B), (C) and (D) show the UV-visible absorption in ethanol solutions at Cd 2+、Cu2+、Pb2+ and Hg 2+ cation addition levels of 0, 1.0X10. 10 -6、2.0×10-6、3.0×10-6、4.0×10-6 and 5.0X10. 10 -6 mol/L, respectively. It was observed that the absorbance spectrum was significantly changed with the increase in the amount of heavy metal ions added, and the absorbance was in a regularly increased state. When the added heavy metal ions are Cu 2+ ions, the blue shift phenomenon is obvious, and the other metal ions have the red shift phenomenon. This indicates that a complex is formed between the fluorescent probe and the heavy metal ion.
FIG. 3 is a graph of association constants of the interactions of derivatives of fluorescein and 3-aminopropyl triethoxysilane prepared in accordance with the present invention with Cd 2+、Cu2+、Pb2+ and Hg 2+ ions. As is known from calculation, the association constants of Cd 2+、Cu2+、Pb2+ and Hg 2+ ions with the fluorescent probe are 3.9174 × 4、1.2092×106、2.7481×106 and 8.7643 × 4 L/moL, respectively, which indicates that complexes are formed between the four metal ions and the fluorescent probe.
FIG. 4 is a fluorescence spectrum of a nano SiO 2 fluorescent probe of fluorescein and 3-aminopropyl triethoxysilane derivatives and surface modified fluorescein prepared by the invention. The inset shows photographs of APTS-NBD and SiO 2-NH2 -NBD under 312 nm natural light (a, c) and ultraviolet light (b, d), respectively, and the result shows that the fluorescent probe formed by fluorescein modification on nano SiO 2 has higher fluorescence brightness.
FIG. 5 is an infrared spectrogram of SiO 2 ball, fluorescein, nano SiO 2 fluorescent probe with surface modified fluorescein, fluorescent probe artificial antibody SiO 2 @MIPs with heavy metal ion imprinting removed and fluorescent probe artificial antibody SiO 2 @MIPs with Cd 2+ ion imprinting adsorbed prepared by the invention. Compared with the infrared spectrum data of pure SiO 2, the surface modified fluorescent probe SiO 2 nano-particle shows an amino characteristic peak near 1460 cm -1, and the artificial antibody SiO 2 @MIPs nano-particle coated with the shell layer of acrylamide and ethylene glycol dimethacrylate shows a stronger carbonyl baseband at 1720 cm -1.
FIG. 6 is an SEM image of the artificial antibodies SiO 2 @MIPs prepared by the invention and having selective recognition and sensitivity detection on Cu 2+,Cd2+,Hg2+ and Pb 2+ ions. SEM image shows that the synthesized metal ion imprinted SiO 2 @MIPs nano particles have a core-shell structure, the particle size of SiO 2 is about 180 nm, and the surface is rough, which indicates that the polymer shell layer is coated on the surface of SiO 2.
FIG. 7 is a TEM image and MAP image of a fluorescent probe artificial antibody SiO 2 @MIP with selective recognition and sensitivity detection on Pb 2+ ions prepared by the invention. It can be seen that the thickness of the shell layer of the polymer of the acrylamide and the ethylene glycol dimethacrylate coated on the surface of the synthesized SiO 2 ball is about 10-20: 20 nm, and the synthesized SiO 2 ball forms a core-shell structure. The Map graph shows that three elements Pb, si and O are respectively arranged on the polymer shell layers of the acrylamide and the ethylene glycol dimethacrylate, and again shows that metal Pb 2+ ions are imprinted in the polymer shell layers.
FIG. 8 is a graph of Hg 2+ ion molecular imprinting and non-imprinting SiO 2 @MIPs isothermal adsorption prepared by the invention. The maximum saturation binding capacity of the artificial antibody material of SiO 2 @MIPs with Hg 2+ ion imprinting to Hg 2+ ion is 60 mg/g, and the maximum saturation binding capacity of the artificial antibody material of non-imprinting material to Hg 2+ ion is 4 mg/g. The amount of adsorption of the blotting material was 15 times that of the non-blotting material.
FIG. 9 is a kinetic profile of Hg 2+ ion molecularly imprinted and non-imprinted SiO 2 @MIPs prepared in accordance with the present invention. The adsorption quantity of Hg 2+ ion imprinted SiO 2 @MIPs artificial antibody material to Hg 2+ ions is increased along with the time, and the adsorption balance is achieved at 240 min. The adsorption kinetics of the blotting material is significantly better than that of the non-blotting material.
FIG. 10 is a graph showing the relationship between the intensity of a fluorescent probe prepared by the present invention and the concentration change of heavy metal ions. When the concentrations of Cu 2+,Cd2+,Hg2+ and Pb 2+ ions are increased from 0 to 5.0X10. 10 -6 mol/L, the prepared fluorescent probes have obvious descending trend in intensity because heavy metal ions capture electrons on the recognition sites of the fluorescent probes, and the fluorescence intensity of the fluorescent probes is reduced according to a fluorescence resonance energy transfer mechanism. The degree of decrease in fluorescence intensity becomes more remarkable with an increase in the concentration of heavy metal ions.
FIG. 11 is a Stern-Volmer equation for a fluorescent probe prepared according to the present invention fitted to metal ions of different concentrations. According to the Stern-Volmer equation: (I 0/I) -1=ksv [ C ], wherein I 0 represents the fluorescence intensity in the fluorescent probe without added metal ion, wherein I represents the fluorescence intensity in the fluorescent probe with added metal ion, ksv represents the quenching constant, that is, the slope of the straight line of the stew-Volmer equation, and the quenching constants of Pb 2+,Cd2+,Hg+ and Cu 2+ in the figure are 87143, 81495, 83470 and 74886L/mol, respectively, and the concentration of metal ion represented by [ C ]. Among them, pb 2+ has the highest quenching constant and best effect.
FIG. 12 shows the detection limits of the fluorescence-labeled artificial antibodies prepared according to the present invention for metal ions of different concentrations. FIGS. 12 (A), (B), (C) and (D) show the quenching curves of Cu 2+,Cd2+,Hg2+ and Pb 2+, respectively, at different concentrations for the fluorescent probe in the fluorescently labeled artificial antibody, with a minimum detection limit of 10 -10 mol/L.
Detailed Description
1. The preparation method of the artificial antibody for detecting heavy metal ions comprises the steps of coating the surfaces of nano SiO 2 spheres in the synthesized artificial antibody with acrylamide and ethylene glycol dimethacrylate polymer shells to form a core-shell structure, and is characterized in that: the recognition site of the imprinting shell layer is modified with fluorescein, so that the recognition site in the heavy metal ion artificial antibody shell layer is eluted to form a hole structure matched with the heavy metal space structure of the imprinting metal ion, heavy metal ions entering the recognition site again capture electrons on a fluorescent probe of the recognition site, and selective recognition of the heavy metal ions is realized by utilizing a fluorescence resonance energy transfer mechanism.
1.1 The first step is the coupling of fluorescein with silylating agent: firstly, adding 1-3 mL of silanization reagent and 5-15 mL of absolute ethyl alcohol into a 100 mL conical flask with a grinding plug, after ultrasonic dispersion of 5-10 min, weighing 0.0100-0.0200 g of fluorescein by using an electronic balance with precision of ten-thousandth, adding the fluorescein into the mixed solution, sealing the conical flask, placing the sealed conical flask on a magnetic stirrer with controllable temperature, and carrying out polymerization reaction at a rotating speed of 500 rpm for 12-15 h at the temperature of 25 ℃ to obtain a derivative solution of the fluorescein and the silanization reagent, namely solution A;
1.2 the second step is the preparation of a nano SiO 2 fluorescent probe: firstly, adding 3-6 mL tetraethoxysilane and 80-200 mL absolute ethyl alcohol into a 250-mL conical flask with a grinding plug in sequence, performing ultrasonic dispersion on the mixture to form a mixed solution, then adding 6-12 mL solution A into the mixed solution, performing ultrasonic dispersion on the mixed solution again to obtain 5-10 min, rapidly adding 12-24 mL ammonia water into the mixed solution, sealing the conical flask, placing the conical flask on a magnetic stirrer with controllable temperature, stirring at a speed of 750-rpm for hydrolytic condensation reaction 2-5 min at 25 ℃, and performing hydrolytic condensation reaction at a speed of 500-rpm for 12-15 h; centrifuging the obtained reaction product by using a 50 mL centrifuge tube at a speed of 8500 rmp for 5 min to remove unreacted substrates, dispersing by using industrial ethanol in an ultrasonic manner, repeatedly washing for 3 times to obtain a nano SiO 2 fluorescent probe with surface modified fluorescein, adding 110-220 mL deionized water into the fluorescent probe, and performing ultrasonic dispersion to obtain a monodisperse round nano SiO 2 fluorescent probe suspension with surface modified fluorescein, which is called solution B;
1.3 the third step is the preparation of heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs: after solution B is subjected to ultrasonic dispersion of 5-10 min, 20mL of the solution is measured, centrifugal 5-min is carried out at 8500 rmp, deionized water is removed, then acetonitrile is used for ultrasonic dispersion, after the steps are repeated for 3 times, 50-mL acetonitrile is used for ultrasonic dispersion again, the solution is transferred to a conical flask of 250 mL, finally 0.0200 g heavy metal inorganic salt, 0.0150-0.0300. 0.0300 g acrylamide and 0.0100-0.0150 g azodiisobutyronitrile are respectively weighed with the accuracy of ten thousandth of an electronic day, the solution is added into the polymer suspension, after ultrasonic dispersion of 5-10 min, 170-220 mu L of ethylene glycol dimethacrylate is added, 10-15 min of high-purity nitrogen is introduced into the mixed solution, after oxygen in the mixed solution is removed, vacuum grease is smeared on a grinding mouth plug of a conical flask, the conical flask is sealed, the mouth plug is wrapped with a preservative film, the mouth plug is wrapped and wrapped, finally the sealed conical flask is placed in a shaking table with a programmed temperature, and the three steps of reaction time control are carried out as follows: (1) reaction at 60℃2 h; (2) reaction at 65℃10 h; (3) reaction curing at 70 ℃ for 2-3 h. Transferring the obtained polymerization reaction product into a 50 mL centrifuge tube, centrifuging at a speed of 8500 rpm to remove unreacted substrate, then performing ultrasonic dispersion with industrial ethanol, centrifuging again, repeating for 3 times to obtain heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs, adding 50 mL deionized water into the centrifugally washed artificial antibodies SiO 2 @MIPs, performing ultrasonic dispersion for later use, and obtaining a solution C;
1.4 the fourth step is the preparation method of the fluorescent probe artificial antibody SiO 2 @ MIPs with heavy metal ion identification and detection functions: and (3) weighing 0.0300-0.0600 g ethylenediamine tetraacetic acid-disodium with the precision of ten-thousandth of an electronic balance, placing the solution C, shaking the solution C at 25 ℃ at the rotation speed of 300 rpm for 4h, transferring the mixed solution into a 50mL centrifuge tube, centrifuging the mixed solution at the rotation speed of 8500 rpm, removing the supernatant, ultrasonically dispersing the precipitate with 30-40 mL deionized water, centrifuging the precipitate again, and repeating the process for 3 times to obtain the SiO 2 @MIPs of the fluorescent probe artificial antibody with the functions of selectively identifying and sensitively detecting heavy metal ions.
Examples:
Firstly, adding 1 mL of 3-aminopropyl triethoxysilane and 5 mL of absolute ethyl alcohol into a 100 mL conical flask with a grinding plug, after ultrasonic dispersion for 5 min, weighing 0.0010 g of fluorescein with an electronic balance with precision, adding the fluorescein into the mixed solution, sealing the conical flask, placing the conical flask on a magnetic stirrer with controllable temperature, and carrying out polymerization reaction for 12h at the temperature of 25 ℃ at the rotation speed of 500 rpm to obtain a fluorescent probe solution.
Adding 3 mL tetraethoxysilane and 89.1 mL absolute ethyl alcohol into a 250 mL conical flask with a grinding plug in sequence, performing ultrasonic dispersion for 5 min to form a mixed solution, then adding 6 mL fluorescent probe solution into the mixed solution, performing ultrasonic dispersion for 5 min again, rapidly adding 12 mL ammonia water into the mixed solution, sealing the conical flask, placing the sealed conical flask on a magnetic stirrer with controllable temperature, performing hydrolytic condensation reaction for 2 min at a speed of 750 rpm at 25 ℃, and performing hydrolytic condensation reaction for 12h at a speed of 500 rpm; centrifuging the obtained reaction product by using a 50 mL centrifuge tube at a speed of 8500 rmp for 5 min to remove unreacted substrates, dispersing by using industrial ethanol in an ultrasonic manner, repeatedly washing for 3 times to obtain a nano SiO 2 fluorescent probe with surface modified fluorescein, adding 110-220 mL deionized water into the fluorescent probe, and dispersing by using ultrasonic manner to obtain a monodisperse round nano SiO 2 fluorescent probe suspension with surface modified fluorescein.
Measuring 20 mL of nano SiO 2 fluorescent probe suspension with surface modified fluorescein, performing ultrasonic dispersion for 5 min, centrifuging for 5 min at a speed of 8500 rmp, removing deionized water, performing ultrasonic dispersion with acetonitrile, repeating for 3 times, performing ultrasonic dispersion again with 50 mL acetonitrile, and transferring to a conical flask of 250 mL. 0.0200 g lead nitrate, 0.0172 g acrylamide and 0.0104 g azodiisobutyronitrile are weighed equally and evenly in one ten thousandth of electronic days, added into the polymer suspension, subjected to ultrasonic dispersion for 5 min, 170 mu L of ethylene glycol dimethacrylate is added, 10 min high-purity nitrogen is introduced into the mixed solution, oxygen in the mixed solution is removed, a grinding plug of a conical flask is smeared with vacuum grease, the conical flask is sealed, the grinding plug is wrapped by a preservative film, and finally the sealing conical flask is wrapped by a rubber band, and is placed in a shaking table with programmed temperature, and the programmed temperature and the reaction time are set, wherein the steps are as follows: (1) reaction at 60℃2 h; (2) reaction at 65℃10 h; (3) reaction curing at 70 ℃ 2h. Transferring the obtained polymerization reaction product into a 50 mL centrifuge tube, centrifuging at 8500 rpm speed to remove unreacted substrate, then performing ultrasonic dispersion with industrial ethanol, centrifuging again, repeating for 3 times to obtain a fluorescent probe artificial antibody SiO 2 @MIPs with Pb 2+ print, adding 50 mL deionized water into the artificial antibody SiO 2 @MIPs after centrifugal washing, and performing ultrasonic dispersion for later use.
And (3) weighing 0.0500 g ethylenediamine tetraacetic acid-disodium by using an electronic balance with the precision of ten-thousandth, and placing the disodium ethylenediamine tetraacetic acid-disodium in the artificial antibody SiO 2 @MIPs solution after centrifugal washing. 25. Shaking at 300-rpm deg.C for 4-h, transferring the mixed solution into a 50-mL centrifuge tube, centrifuging at 8500-rpm, removing supernatant, ultrasonically dispersing the precipitate with 40-mL deionized water, centrifuging again, and repeating for 3 times to obtain SiO 2 @MIPs with fluorescent probe artificial antibodies for selectively recognizing and sensitively detecting Pb 2+ ions.
Claims (9)
1. The preparation method of the artificial antibody for detecting heavy metal ions comprises the steps of coating the surfaces of nano SiO 2 spheres in the synthesized artificial antibody with acrylamide and ethylene glycol dimethacrylate polymer shells to form a core-shell structure, and is characterized in that: the method comprises the following four steps of:
1.1 the first step is the coupling of fluorescein with silylating agent: firstly, adding 1-3 mL of silanization reagent and 5-15 mL of absolute ethyl alcohol into a 100mL conical flask with a grinding plug, after ultrasonic dispersion for 5-10 min, weighing 0.0100-0.0200 g of fluorescein with an electronic balance with precision, adding the fluorescein into a conical flask mixed solution, sealing the conical flask, placing the conical flask on a magnetic stirrer with controllable temperature, and carrying out polymerization reaction at a rotating speed of 500rpm for 12-15 h at 25 ℃ to obtain a derivative solution of the fluorescein and the silanization reagent, namely solution A;
1.2 the second step is the preparation of a nano SiO 2 fluorescent probe: firstly, adding 3-6 mL of tetraethoxysilane and 80-200 mL of absolute ethyl alcohol into 250mL of conical flask with a grinding plug in sequence, performing ultrasonic dispersion for 5-10 min to form a mixed solution, then adding 6-12 mL of solution A into the mixed solution, performing ultrasonic dispersion again for 5-10 min, rapidly adding 12-24 mL of ammonia water into the mixed solution, sealing the conical flask, placing the conical flask on a magnetic stirrer with controllable temperature, performing hydrolytic condensation reaction at 25 ℃ at 750rpm for 2-5 min, and performing hydrolytic condensation reaction at 500rpm for 12-15 h; centrifuging the obtained reaction product with a 50mL centrifuge tube at a speed of 8500rmp for 5min to remove unreacted substrate, dispersing with industrial ethanol by ultrasonic, repeatedly washing for 3 times to obtain a nano SiO 2 fluorescent probe with surface modified fluorescein, adding 110-220 mL deionized water into the fluorescent probe, and performing ultrasonic dispersion to obtain a monodisperse round nano SiO 2 fluorescent probe suspension with surface modified fluorescein, which is called solution B;
1.3 the third step is the preparation of heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs: after solution B is dispersed for 5-10 min by ultrasonic, 20mL of dispersed solution B is measured, centrifugal is carried out for 5min at 8500rmp, deionized water is removed, then acetonitrile is used for ultrasonic dispersion, after the ultrasonic dispersion is carried out for 3 times, 50mL of acetonitrile is used again, the solution B is transferred into a 250mL conical flask, finally 0.0200g of heavy metal inorganic salt, 0.0150-0.0300 g of acrylamide and 0.0100-0.0150 g of azodiisobutyronitrile are respectively weighed by equal parts per million of electronic days, the solution B is added into a conical flask polymer suspension, ultrasonic dispersion is carried out for 5-10 min, 170-220 mu L of ethylene glycol dimethacrylate is added into the mixed solution, high-purity nitrogen is introduced into the mixed solution, oxygen in the mixed solution is removed, the conical flask is coated with vacuum grease by a grinding mouth plug, the conical flask is sealed, the conical flask is wrapped with a preservative film, the sealing conical flask is wrapped by using a rubber band, and finally the sealed conical flask is placed into a programmed heating table, and the programmed heating table is set with temperature control and reaction time is divided into three stages, and the following steps: (1) reacting for 2 hours at 60 ℃; (2) reacting for 10 hours at 65 ℃; (3) reaction curing for 2-3 h at 70 ℃;
Transferring the obtained polymerization reaction product into a 50mL centrifuge tube, centrifuging at 8500rpm to remove unreacted substrate, then performing ultrasonic dispersion and re-centrifuging with industrial ethanol for 3 times, finally obtaining heavy metal ion imprinted fluorescent probe artificial antibodies SiO 2 @MIPs, adding 50mL deionized water into the centrifugally washed artificial antibodies SiO 2 @MIPs, performing ultrasonic dispersion for later use, and obtaining a solution C;
1.4 the fourth step is the preparation method of the fluorescent probe artificial antibody SiO 2 @ MIPs with heavy metal ion identification and detection functions: and (3) weighing 0.0300-0.0600 g of ethylene diamine tetraacetic acid-disodium by using an electronic balance with the precision of ten-thousandth, placing the solution C, shaking at the temperature of 25 ℃ for 4 hours at the speed of 300rpm, transferring the mixed solution into a 50mL centrifuge tube, centrifuging at the speed of 8500rpm, removing the supernatant, ultrasonically dispersing the precipitate by using 30-40 mL deionized water, centrifuging again, and repeating for 3 times to obtain the SiO 2 @MIPs of the fluorescent probe artificial antibody with the functions of selectively identifying and sensitively detecting heavy metal ions.
2. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the silylation agent in the prepared artificial antibody is 3-aminopropyl triethoxysilane.
3. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the heavy metal ions imprinted in the prepared artificial antibody are suitable for Pb 2+,Cd2+,Hg2+ and Cu 2+.
4. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the acrylamide in the prepared artificial antibody is a functional monomer.
5. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the ethylene glycol dimethacrylate in the prepared artificial antibody is a cross-linking agent.
6. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the azo-bis-isobutyronitrile in the prepared artificial antibody is an initiator.
7. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the fluorescein in the prepared artificial antibody is a probe.
8. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the fluorescent group molecules modified in the prepared artificial antibodies have part of excited state fluorescence absorbed by heavy metal ions, so that the fluorescence intensity of the fluorescent group is reduced, a sensitive recognition signal combined with a target substance is obtained, and the selective and sensitive detection of the heavy metal ions is achieved.
9. The method for preparing the artificial antibody for detecting the heavy metal ions, which is characterized by comprising the following steps of: the thickness of the imprinted polymer shell layer of the prepared fluorescent probe artificial antibody SiO 2 @MIPs can be controlled by adjusting the amount of acrylamide and ethylene glycol dimethacrylate.
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