CN106947018B - A high-performance and highly controllable core-shell type imprinted sensor and preparation method and use - Google Patents

A high-performance and highly controllable core-shell type imprinted sensor and preparation method and use Download PDF

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CN106947018B
CN106947018B CN201710136136.9A CN201710136136A CN106947018B CN 106947018 B CN106947018 B CN 106947018B CN 201710136136 A CN201710136136 A CN 201710136136A CN 106947018 B CN106947018 B CN 106947018B
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李洪吉
姜佳琪
徐叶青
卢凯
刘锡清
李春香
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Jiangsu University
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Abstract

The present invention provides a kind of high-performance and highly controllable hud typed trace sensor and preparation method and purposes, preparation step are as follows: the preparation of step 1, amino functional Nano particles of silicon dioxide；The preparation of step 2, functionalization SiO2/Ag nano-complex particle；The preparation of step 3, nucleocapsid SiO2/Ag/MIPs.The present invention combines SERS technology with surface molecule print technology, so that the product of preparation has both the highly sensitive and MIT highly selective of SERS Detection Techniques；The present invention selects molecular imprinted polymer on surface (SMIPs) to promote the selectivity of tradition SERS substrate material, expands the application range of SERS detection.

Description

A kind of high-performance and highly controllable hud typed trace sensor and preparation method and Purposes
Technical field
The present invention relates to the preparations and application of a kind of high-performance and highly controllable hud typed trace sensor, belong to new material Technical field.
Background technique
In recent years, organic pollutant seriously endangers global environment, threatens the health of the ecological balance and the mankind.However, mostly Number organic pollutant exists only in trace or ultra trace is horizontal, time-consuming using traditional detection method, complicated, and is extremely difficult to sensitive Degree demand carries out accurate detection relative difficulty.Therefore, it is badly in need of developing effective and sensitive detection method.
Surface enhanced Raman scattering (SERS) is a kind of effective analysis method, and tracing detection may be implemented.When probe point Son SERS stromal surface or it is neighbouring when, the Raman signal of probe molecule can significantly be enhanced.In general, SERS enhances There are two mechanism, respectively physics enhancing and Chemical enhancement.The former is since SERS active substrate surface plasmon oscillations are drawn The localized electromagnetic field enhancing risen, so that Raman signal is been significantly enhanced.The latter be then due to probe molecule and SERS substrate it Between chemical action so that probe molecule polarizability increase caused by Raman signal enhance.Under normal conditions, both enhance Mechanism acts on simultaneously causes Raman signal to enhance, and only there are different contribution proportions in different systems.
Currently, noble metal nano particles (such as gold, silver) are widely used in the preparation of SERS host material, mainly due to your gold Metal nano-particle has outstanding optics, electrical properties, and has strong characteristic absorption in visibility region, this is largely It is attributed to its surface plasma body resonant vibration.Wherein, silver-colored use is widest, is primarily due to the SERS signal enhancing of silver the most Obviously, and silver chemical property is stablized, and has broad-spectrum antibiotic property and potential anti-cancer applications.Currently, SERS technology is wide It is general to be applied to detection trace level chemical substance, in the identification of protein, Medicines, food additives and a variety of biotic components.So And mainly concentrated in the promotion of host material pattern or SERS performance about the research of SERS at present, and ignore biography Host material of uniting lacks specific selectivity.Therefore, the selectivity for promoting tradition SERS base material will be enlarged by answering for SERS detection With.
Recently, molecularly imprinted polymer (MIPs) is excellent by feat of specific recognition, structure effect precordainment and extensive practicability etc. Different characteristic is concerned in chromatographic isolation, UF membrane, Solid Phase Extraction, drug controlled release, chemical sensitisation, environment measuring.Point Sub- engram technology is to will form multiple action site when template molecule (microsphere) is contacted with polymer monomer, passes through polymerization Process generates specific recognition site, after template molecule removes, is formed and template molecule steric configuration phase in polymer Matched site hole, such hole will have selection evident characteristics to template molecule and the like.In MIPs material, Molecular imprinted polymer on surface (SMIPs) because can preferably solve the disadvantage that traditional MIPs, such as binding ability it is poor, in conjunction with moving Mechanical property is bad, active site embeds too deep, template molecule removal and is not thorough, and has gradually attracted more and more scientific works The favor of author.
In order to improve the selectivity of SERS substrate material, SERS technology and molecular imprinting technology (MIT) are combined, preparation MIPs-SERS sensor.For example, Kamra et al. is prepared for a novel biosensor, their binding molecule trace polymerizations Object and Surface enhanced Raman spectroscopy (MIPs-SERS) have determined melamine in whole milk.Xiao et al. establishes MIP- Based chemical sensor detects nicotine by SERS.These methods present the Optimality of MIPs-SERS technology Energy.Therefore, highly sensitive SERS Detection Techniques and highly selective MIT are combined, prepares MIPs-SERS sensor, inspection Surveying organic pollutants has feasibility.
Summary of the invention
The sensor is mainly synthesized by three-step reaction.Firstly, synthesizing amino functionalized SiO 2 nanoparticle.By second Alcohol, water and NH3·H2O is equably mixed, and ethyl orthosilicate (TEOS) and mechanical stirring is slowly added dropwise.Again by three second of 3- aminopropyl Oxysilane (APTES) is added in solution, and continues to be stirred liquid.After reaction, centrifugation is cleaned with ethyl alcohol, is dried；Then, Amino functional Nano particles of silicon dioxide is distributed in the mixed solution of ethanol/water, silver nitrate solution is added, is then added dropwise Polyvinylpyrrolidone (PVP) solution continues magnetic agitation in a dark environment.Then, ethanol amine is added into mixed system, And increase temperature, continue to stir.Centrifugation, is cleaned with water and ethyl alcohol repeatedly, removes unreacted reactant.Final product is in room The lower vacuum drying of temperature；Finally, acrylamide (AM) and ethylene glycol dimethacrylate (EGDMA) are added by rhodamine (R6G) Into solution above, N is used2Thoroughly remove oxygen.It adds azodiisobutyronitrile (AIBN), hybrid system is sealed, perseverance is put into Tepidarium oscillator, after 50 DEG C of reaction a few hours, then be increased to 60 DEG C reaction the reaction was continued.Product uses second by being collected by centrifugation Alcohol repeatedly washs, and removes unreacted reactant, then further washed with Soxhlet extraction.
The present invention is achieved through the following technical solutions:
A kind of high-performance and highly controllable hud typed trace sensor, the sensor are by amino functional titanium dioxide Silicon, Ag, imprinted layer are combined, and the Ag is carried on amino functional silica, form SiO2The nano combined grain of/Ag Son；The imprinted layer is by acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) and azodiisobutyronitrile (AIBN) It is polymerized, the imprinted layer is coated on functionalization SiO2Outside/Ag nano-complex particle, the imprinted layer with a thickness of 40~ 170nm。
A kind of preparation method of high-performance and highly controllable hud typed trace sensor, steps are as follows:
The preparation of step 1, amino functional Nano particles of silicon dioxide
It is added ammonium hydroxide into ethanol/water mixed solution, under stirring condition, TEOS is added, stirring adds APTES, continues It is stirred to react；Product is centrifugated, washing and drying, obtains amino functional Nano particles of silicon dioxide, for use；
Step 2, functionalization SiO2The preparation of/Ag nano-complex particle
Disperse amino functional Nano particles of silicon dioxide in ethanol/water mixed solution, be added silver nitrate solution and PVP solution, in a dark environment magnetic agitation；Then, EA is added, promotes temperature and continues to be stirred to react；Solid product is centrifuged Separation is washed, dry, obtains functionalization SiO2/ Ag nano-complex particle, for use；
Step 3, nucleocapsid SiO2The preparation of/Ag/MIPs
By functionalization SiO2/ Ag nano-complex particle is distributed in acetonitrile, and rhodamine 6G, AM and EGDMA is added, uses inertia Gas clean-up oxygen；Then, AIBN is added, sealing is placed in thermostatic control oscillator vibration, it is anti-to be set in 50 DEG C of progress prepolymerizations It answers, then heating to 60 DEG C, the reaction was continued；Solid product centrifuge separation, is washed, dry, obtains nucleocapsid SiO2/ Ag/MIPs, i.e., The high-performance and highly controllable hud typed trace sensor.
In step 1, the ethanol/water mixed solution, ammonium hydroxide, TEOS, APTES volume ratio be 80~100:10~20: 9:1~3；In the ethanol/water mixed solution, ethyl alcohol, water volume ratio be 4:5；The time of the stirring A is 4~6h, described Continuing the time being stirred to react is 10~14h.
In step 2, the amino functional Nano particles of silicon dioxide, ethanol/water mixed solution, silver nitrate solution, PVP Solution, EA amount ratio be 100mg:50mL:5mL:4~6mL:0.4~0.6mL；The concentration of the silver nitrate solution is 0.1mol/L, the concentration of the PVP solution are 0.2mol/L, in the ethanol/water mixed solution, ethyl alcohol, water volume ratio be 4:1；The time of the magnetic agitation in a dark environment is 4~6h, and the time for continuing stirring is 3~5h.
In step 3, the functionalization SiO2The use of/Ag nano-complex particle, acetonitrile, rhodamine 6G, AM, EGDMA, AIBN Amount is than being 100mg:50~70mL:0.05~0.15mmol:0.3~0.5mmol:0.237~0.396mL:9~11mg；It is described Inert gas is nitrogen.
In step 1~3, the washing is that ethyl alcohol and water wash 3 times respectively.
Prepared high-performance and highly controllable hud typed trace sensor are used for selective absorption rhodamine 6G.
The preparation method of the corresponding non-imprinted polymer of the present invention is as above similar to synthetic method, but R6G is not added.
Technological merit of the invention:
The present invention combines SERS technology with surface molecule print technology, so that the product of preparation has both SERS detection skill The high sensitivity of art is highly selective with MIT's；The present invention selects molecular imprinted polymer on surface (SMIPs) to promote tradition SERS lining The selectivity of bottom material expands the application range of SERS detection；In the present invention, it can control shell by changing dosage of crosslinking agent Thickness.In recent years, molecularly imprinted polymer (MIPs) was concerned.Because material avoids the disadvantage of traditional MIPs, can bind Template molecule, specific identification hole, by it in conjunction with SERS Detection Techniques, development to SERS technology has highly important Meaning.The present invention shows Surface enhanced Raman scattering detection and has broad application prospects in new material technology field.
Detailed description of the invention
Fig. 1: the SiO of the different imprinted layer thickness of preparation2The TEM image of/Ag/MIPs: 40nm (a), 100nm (b), 170nm(c)；
Fig. 2: SiO2/ Ag/MPS and SiO2The Fourier Transform Infrared Spectroscopy of/Ag/MIPs, curve a are SiO2/ Ag/MPS, Curve b is SiO2/Ag/MIPs；
Fig. 3: the SiO of different-thickness2/ Ag/MIPs absorption 10-6The SERS of mol/L R6G is detected: 40nm (a), 100nm (b), 170nm (c)；
Fig. 4: SiO2/ Ag/MIPs adsorbs the SERS spectra figure (a) and its raman scattering intensity and R6G concentration of various concentration R6G Linear relationship (b)；
Fig. 5: SiO2/ Ag/MIPs is 10–6SERS spectra selective enumeration method in mol/L R6G (a), RB (b) and CV (c).
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
(1) synthesis of amino functional Nano particles of silicon dioxide:
In 100mL single-necked flask, 90mL ethyl alcohol, water mixed solvent (volume ratio 4:5) is added, and 15mL NH is added3· H2O.Under stirring condition, 9mLTEOS is added, persistently stirs 5h.2mL APTES is added, continues to stir 12h.By product centrifugation point From, washing and drying, for use.
(2) functionalization SiO2The synthesis of/Ag nano-complex particle:
In 100mL single-necked flask, 100mg amino functional Nano particles of silicon dioxide is dispersed in 50mL ethanol/water Mixed solvent (v/v=4:1) in, addition 5mL concentration be 0.1mol/L silver nitrate solution, then be added 5mL concentration be 0.2mol/L PVP solution continues magnetic agitation 4h in a dark environment.Then, 500 μ L EA are added, and temperature is increased to 50 DEG C are continued to stir 5h.Centrifugation, wash the unreacted reactant of removing with water and ethyl alcohol repeatedly, final product vacuum at room temperature It is dry.
(3) nucleocapsid SiO2The preparation of/Ag/MIPs
In 100mL single-necked flask, by the modified SiO of 100mg MPS2/ Ag nanoparticle is dispersed in 60mL acetonitrile.It is added The EGDMA of 0.1mmol R6G, 0.4mmol AM and 237 μ L, are passed through N at room temperature215 minutes, thoroughly remove oxygen.Then, 10mg AIBN is added, sealing is put into thermostatic control oscillator vibration, and reaction temperature is set in 50 DEG C, reacts duration 6h.Then 60 DEG C are increased to, then is reacted for 24 hours.The product that is collected by centrifugation and with ethanol washing, removes unreacted reactant, further uses The washing of Soxhlet extraction liquid
In reaction system described in step (1), the volume ratio of TEOS and mixed solvent is 9mL:90mL, TEOS and ammonium hydroxide Volume ratio be the volume ratio of 9mL:15mL, TEOS and APTES be 9mL:2mL.Washing described in step is second alcohol and water It washs 3 times respectively.
In reaction system described in step (2), the volume ratio of silver nitrate solution and PVP is 1mL:1mL, silver nitrate solution with The volume ratio of EA solution is 1mL:100 μ L.
In reaction system described in step (3), SiO2The mass volume ratio of/Ag nanoparticle and acetonitrile solution is 100mg: 60mL, SiO2The mass ratio of/Ag nanoparticle and AIBN are 100mg:10mg, SiO2The quality mole of/Ag nanoparticle and R6G solution Than for 100mg:0.1mmol, SiO2The quality molar ratio of/Ag nanoparticle and AM solution is 100mg:0.4mmol, SiO2/ Ag nanometers The mass volume ratio of grain and EGDMA solution is 100mg:237 μ L.Washing described in step is that ethyl alcohol and water wash 3 respectively It is secondary.
The preparation method of the corresponding non-imprinted polymer of the present invention is as above similar to synthetic method, but R6G is not added.
Embodiment 2:
(1) synthesis of amino functional Nano particles of silicon dioxide:
In 100mL single-necked flask, 80mL ethyl alcohol, water mixed solvent (volume ratio 4:5) is added, and 10mL NH is added3· H2O.Under stirring condition, 8mL TEOS is added, persistently stirs 4h.1mL APTES is added, continues to stir 10h.By product centrifugation point From, washing and drying, for use.
(2) functionalization SiO2The synthesis of/Ag nano-complex particle:
In 100mL single-necked flask, 100mg amino functional Nano particles of silicon dioxide is dispersed in 50mL ethanol/water Mixed solvent (v/v=4:1) in, addition 4mL concentration be 0.1mol/L silver nitrate solution, then be added 4mL concentration be 0.2mol/L PVP solution continues magnetic agitation 3h in a dark environment.Then, 400 μ L EA are added, and temperature is increased to 50 DEG C are continued to stir 4h.Centrifugation, wash the unreacted reactant of removing with water and ethyl alcohol repeatedly, final product vacuum at room temperature It is dry.
(3) nucleocapsid SiO2The preparation of/Ag/MIPs
In 100mL single-necked flask, by the modified SiO of 100mg MPS2/ Ag nanoparticle is dispersed in 50mL acetonitrile.It is added The EGDMA of 0.05mmol R6G, 0.3mmol AM and 316 μ L, are passed through N at room temperature215 minutes, thoroughly remove oxygen.With Afterwards, 9mg AIBN is added, sealing is put into thermostatic control oscillator vibration, and reaction temperature is set in 50 DEG C, reacts duration 5h.With After be increased to 60 DEG C, then react 20h.The product that is collected by centrifugation and with ethanol washing, removes unreacted reactant, further makes It is washed with Soxhlet extraction liquid
In reaction system described in step (1), the volume ratio of TEOS and mixed solvent is 8mL:80mL, TEOS and ammonium hydroxide Volume ratio be the volume ratio of 8mL:10mL, TEOS and APTES be 8mL:1mL.Washing described in step is second alcohol and water It washs 3 times respectively.
In reaction system described in step (2), the volume ratio of silver nitrate solution and PVP is 1mL:1mL, silver nitrate solution with The volume ratio of EA solution is 1mL:100 μ L.
In reaction system described in step (3), SiO2The mass volume ratio of/Ag nanoparticle and acetonitrile solution is 100mg: 50mL, SiO2The mass ratio of/Ag nanoparticle and AIBN are 100mg:9mg, SiO2The quality molar ratio of/Ag nanoparticle and R6G solution For 100mg:0.05mmol, SiO2The quality molar ratio of/Ag nanoparticle and AM solution is 100mg:0.3mmol, SiO2/ Ag nanometers The mass volume ratio of grain and EGDMA solution is 100mg:316 μ L.Washing described in step is that ethyl alcohol and water wash 3 respectively It is secondary.
The preparation method of the corresponding non-imprinted polymer of the present invention is as above similar to synthetic method, but R6G is not added.
Embodiment 3:
(1) synthesis of amino functional Nano particles of silicon dioxide:
In 100mL single-necked flask, 100mL ethyl alcohol, water mixed solvent (volume ratio 4:5) is added, and 20mL is added NH3·H2O.Under stirring condition, 10mL TEOS is added, persistently stirs 6h.3mL APTES is added, continues to stir 14h.By product Centrifuge separation, washing and drying, for use.
(2) functionalization SiO2The synthesis of/Ag nano-complex particle:
In 100mL single-necked flask, 100mg amino functional Nano particles of silicon dioxide is dispersed in 50mL ethanol/water Mixed solvent (v/v=4:1) in, addition 6mL concentration be 0.1mol/L silver nitrate solution, then be added 6mL concentration be 0.2mol/L PVP solution continues magnetic agitation 5h in a dark environment.Then, 600 μ L EA are added, and temperature is increased to 50 DEG C are continued to stir 6h.Centrifugation, wash the unreacted reactant of removing with water and ethyl alcohol repeatedly, final product vacuum at room temperature It is dry.
(3) nucleocapsid SiO2The preparation of/Ag/MIPs
In 100mL single-necked flask, by the modified SiO of 100mg MPS2/ Ag nanoparticle is dispersed in 70mL acetonitrile.It is added The EGDMA of 0.15mmol R6G, 0.5mmol AM and 396 μ L, are passed through N at room temperature215 minutes, thoroughly remove oxygen.With Afterwards, 11mg AIBN is added, sealing is put into thermostatic control oscillator vibration, and reaction temperature is set in 50 DEG C, reacts duration 7h.With After be increased to 60 DEG C, then react 28h.The product that is collected by centrifugation and with ethanol washing, removes unreacted reactant, further makes It is washed with Soxhlet extraction liquid
In reaction system described in step (1), the volume ratio of TEOS and mixed solvent is 10mL:100mL, TEOS and ammonia The volume ratio of water is that the volume ratio of 10mL:20mL, TEOS and APTES are 10mL:3mL.Washing described in step is ethyl alcohol It is washed respectively with water 3 times.
In reaction system described in step (2), the volume ratio of silver nitrate solution and PVP is 1mL:1mL, silver nitrate solution with The volume ratio of EA solution is 1mL:100 μ L.
In reaction system described in step (3), SiO2The mass volume ratio of/Ag nanoparticle and acetonitrile solution is 100mg: 70mL, SiO2The mass ratio of/Ag nanoparticle and AIBN are 100mg:11mg, SiO2The quality mole of/Ag nanoparticle and R6G solution Than for 100mg:0.15mmol, SiO2The quality molar ratio of/Ag nanoparticle and AM solution is 100mg:0.5mmol, SiO2/ Ag receives The mass volume ratio of the grain of rice and EGDMA solution is 100mg:396 μ L.Washing described in step is that ethyl alcohol and water are washed respectively It washs 3 times.
The preparation method of the corresponding non-imprinted polymer of the present invention is as above similar to synthetic method, but R6G is not added.
Fig. 1: the SiO of preparation2The TEM image of/Ag/MIPs.The Ag is carried on amino functional silica, is formed SiO2/ Ag nano-complex particle；The imprinted layer be by acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) and Azodiisobutyronitrile (AIBN) is polymerized, and the imprinted layer is coated on functionalization SiO2It is described outside/Ag nano-complex particle Imprinted layer with a thickness of 40~170nm.By in figure we can see that different imprinted layer thickness: 40nm (a), 100nm (b), 170nm(c)；
Fig. 2: SiO2/ Ag/MPS and SiO2The Fourier Transform Infrared Spectroscopy of/Ag/MIPs.By in figure we can see that print Mark polymer layer is successfully wrapped in SiO2The surface /Ag；
Fig. 3: the SiO of different-thickness2/ Ag/MIPs absorption 10-6The SERS of mol/L R6G is detected.By in figure we can see The SiO of 40nm (a) polymer layer thickness out2The SERS maximum intensity of/Ag/MIPs, 100nm (b) take second place, and 170nm (c) is minimum；
Fig. 4: SiO2/ Ag/MIPs adsorbs the SERS spectra figure (a) and its raman scattering intensity and R6G concentration of various concentration R6G Linear relationship (b).By in figure we can see that in 1505cm-1Place, gradually decreases with R6G concentration, and raman scattering intensity reduces, and two Person has functional relation；
Fig. 5: SiO2/ Ag/MIPs is 10–6SERS spectra selective enumeration method in mol/L R6G (a), RB (b) and CV (c). By in figure we can see that peak value the ratio RB, CV of R6G are big.
Detectability evaluation carries out by the following method in the specific embodiment of the invention: the institute of absorption various concentration R6G Some SERS matrix is all dripped in glass slide, natural air drying.Excite 633nm, the time for exposure 10s of the spectra collection of each sample and The 0.25mW of incident laser power, SERS spectra, which is collected, uses 50 × nikon lens.With the concentration [c] of R6G for abscissa, SERS Intensity is that ordinate draws curve.
Test example 1:
SiO is had detected first2/ Ag/MIPs absorption various concentration R6G raman scattering intensity then investigated raman scattering intensity with Linear relationship between R6G concentration.Configuration 10-6-10-14The R6G solution of mol/L divides and takes 5 10mg SiO2/ Ag/MIPs is added It into centrifuge tube, is separately added into various concentration R6G and is adsorbed, drip substrate in glass slide, natural air drying after the completion of to be adsorbed, It is placed under object lens, adjusts object lens, then detect the raman scattering intensity of solution.In 1505cm-1Place can be observed, gradually with R6G concentration It reduces, raman scattering intensity reduces, and the two has functional relation.
Test example 2:
SiO is investigated2/ Ag/MIPs is to the selectivity of R6G, RB and CV (as shown in figure 5, obtained SiO2/Ag/MIPs 10–6It is stronger to the selectivity of R6G under the concentration of mol/L, also selective with CV to RB but compare to weaker).By R6G, RB 10 are configured to CV-6The solution of mol/L.10mL R6G, RB, CV solution and 10mg SiO are taken respectively2/ Ag/MIPs be added to from It in heart pipe, is adsorbed, is dripped substrate in glass slide after the completion of to be adsorbed, natural air drying is placed under object lens, adjusts object lens, so The raman scattering intensity of solution is detected afterwards.Can be using wavelength as abscissa, opposite raman scattering intensity is that ordinate draws Raman curve.As a result table It is bright, SiO2/ Ag/MIPs has good selectivity to R6G.

Claims (7)

1.一种高性能和高度可控的核壳型印迹传感器，其特征在于，所述传感器是由氨基功能化二氧化硅、Ag、印迹层复合而成的，所述Ag负载于氨基功能化二氧化硅上，形成SiO2/Ag纳米复合粒子；所述印迹层是由丙烯酰胺、二甲基丙烯酸乙二醇酯和偶氮二异丁腈聚合而成的，所述印迹层包覆于功能化SiO2/Ag纳米复合粒子外，所述印迹层的厚度为40～170nm。1. a high-performance and highly controllable core-shell type imprinted sensor, is characterized in that, described sensor is compounded by amino-functionalized silica, Ag, imprinted layer, and described Ag is loaded on amino-functionalized silica On the silica, SiO 2 /Ag nanocomposite particles are formed; the imprinting layer is polymerized by acrylamide, ethylene glycol dimethacrylate and azobisisobutyronitrile, and the imprinting layer is coated on Except for the functionalized SiO 2 /Ag nanocomposite particles, the thickness of the imprinted layer is 40-170 nm. 2.一种如权利要求1所述的高性能和高度可控的核壳型印迹传感器的制备方法，其特征在于，步骤如下：2. a preparation method of high performance and highly controllable core-shell type imprinted sensor as claimed in claim 1, is characterized in that, step is as follows: 步骤1、氨基功能化二氧化硅纳米粒子的制备Step 1. Preparation of amino-functionalized silica nanoparticles 向乙醇/水混合溶液中加入氨水，搅拌条件下，加入正硅酸乙酯，搅拌，再加入3-氨基丙基三乙氧基硅烷，继续搅拌反应；将产物离心分离，洗涤烘干，得到氨基功能化二氧化硅纳米粒子，待用；Ammonia water is added to the ethanol/water mixed solution, under stirring, ethyl orthosilicate is added, stirred, and then 3-aminopropyltriethoxysilane is added, and the stirring reaction is continued; the product is centrifuged, washed and dried to obtain Amino-functionalized silica nanoparticles, for use; 步骤2、功能化SiO2/Ag纳米复合粒子的制备Step 2. Preparation of functionalized SiO 2 /Ag nanocomposite particles 将氨基功能化二氧化硅纳米粒子分散于乙醇/水混合溶液中，加入硝酸银溶液和聚乙烯吡咯烷酮溶液，在黑暗环境中磁力搅拌；随后，加入乙醇胺，提升温度继续搅拌反应；将固体产物离心分离，洗涤，干燥，得到功能化SiO2/Ag纳米复合粒子，待用；The amino-functionalized silica nanoparticles were dispersed in an ethanol/water mixed solution, silver nitrate solution and polyvinylpyrrolidone solution were added, and magnetic stirring was performed in a dark environment; then, ethanolamine was added, and the temperature was raised to continue the stirring reaction; the solid product was centrifuged Separate, wash, and dry to obtain functionalized SiO 2 /Ag nanocomposite particles, which are ready for use; 步骤3、核壳SiO2/Ag/MIPs的制备Step 3. Preparation of core-shell SiO 2 /Ag/MIPs 将功能化SiO2/Ag纳米复合粒子分散到乙腈中，加入罗丹明6G、丙烯酰胺和乙二醇二甲基丙烯酸酯，用惰性气体清除氧气；随后，加入偶氮二异丁腈，密封，置于恒温水浴振荡器中，设定在50℃进行预聚合反应，然后升温至60℃继续反应；固体产物离心分离，洗涤，干燥，得到核壳SiO2/Ag/MIPs，即所述高性能和高度可控的核壳型印迹传感器。The functionalized SiO 2 /Ag nanocomposite particles were dispersed in acetonitrile, rhodamine 6G, acrylamide and ethylene glycol dimethacrylate were added, and oxygen was purged with inert gas; then, azobisisobutyronitrile was added, sealed, It was placed in a constant temperature water bath shaker, set at 50°C for pre-polymerization reaction, and then heated to 60°C to continue the reaction; the solid product was centrifuged, washed, and dried to obtain core-shell SiO 2 /Ag/MIPs, namely the high-performance and highly controllable core-shell imprinted sensors. 3.如权利要求2所述的高性能和高度可控的核壳型印迹传感器的制备方法，其特征在于，步骤1中，所述乙醇/水混合溶液、氨水、正硅酸乙酯、3-氨基丙基三乙氧基硅烷的体积比为80～100：10～20：9：1～3；所述乙醇/水混合溶液中，乙醇、水的体积比为4：5；所述搅拌的时间为4～6h，所述继续搅拌反应的时间为10～14h。3. The method for preparing a high-performance and highly controllable core-shell type imprinted sensor according to claim 2, wherein in step 1, the ethanol/water mixed solution, ammonia water, ethyl orthosilicate, 3 - The volume ratio of aminopropyltriethoxysilane is 80-100:10-20:9:1-3; in the ethanol/water mixed solution, the volume ratio of ethanol and water is 4:5; the stirring The time for the reaction is 4-6h, and the time for the continuous stirring reaction is 10-14h. 4.如权利要求2所述的高性能和高度可控的核壳型印迹传感器的制备方法，其特征在于，步骤2中，所述氨基功能化二氧化硅纳米粒子、乙醇/水混合溶液、硝酸银溶液、聚乙烯吡咯烷酮溶液、乙醇胺的用量比为100mg：50mL：5mL：4～6mL：0.4～0.6mL；所述硝酸银溶液的浓度为0.1mol/L，所述聚乙烯吡咯烷酮溶液的浓度为0.2mol/L，所述乙醇/水混合溶液中，乙醇、水的体积比为4：1；所述在黑暗环境中磁力搅拌的时间为4～6h，所述继续搅拌的时间为3～5h。4. The method for preparing a high-performance and highly controllable core-shell type imprinted sensor according to claim 2, wherein in step 2, the amino-functionalized silica nanoparticles, ethanol/water mixed solution, The dosage ratio of silver nitrate solution, polyvinylpyrrolidone solution and ethanolamine is 100mg: 50mL: 5mL: 4-6mL: 0.4-0.6mL; the concentration of the silver nitrate solution is 0.1mol/L, and the concentration of the polyvinylpyrrolidone solution is 0.2mol/L, and in the ethanol/water mixed solution, the volume ratio of ethanol and water is 4:1; the time of magnetic stirring in the dark environment is 4～6h, and the time of continuing stirring is 3～6h 5h. 5.如权利要求2所述的高性能和高度可控的核壳型印迹传感器的制备方法，其特征在于，步骤3中，所述功能化SiO2/Ag纳米复合粒子、乙腈、罗丹明6G、丙烯酰胺、乙二醇二甲基丙烯酸酯、偶氮二异丁腈的用量比为100mg：50～70mL：0.05～0.15mmol：0.3～0.5mmol：0.237～0.396mL：9～11mg；所述惰性气体为氮气。5. The method for preparing a high-performance and highly controllable core-shell type imprinted sensor according to claim 2, wherein in step 3, the functionalized SiO 2 /Ag nanocomposite particles, acetonitrile, rhodamine 6G The dosage ratio of acrylamide, ethylene glycol dimethacrylate and azobisisobutyronitrile is 100mg: 50-70mL: 0.05-0.15mmol: 0.3-0.5mmol: 0.237-0.396mL: 9-11mg; the The inert gas is nitrogen. 6.如权利要求2所述的高性能和高度可控的核壳型印迹传感器的制备方法，其特征在于，步骤1～3中，所述的洗涤，均为乙醇和水分别洗涤3次。6 . The method for preparing a high-performance and highly controllable core-shell type imprinted sensor according to claim 2 , wherein, in steps 1 to 3, the washings are washed three times with ethanol and water, respectively. 7 . 7.权利要求1所述的高性能和高度可控的核壳型印迹传感器用于选择性吸附罗丹明6G的用途。7. Use of the high-performance and highly controllable core-shell type imprinted sensor of claim 1 for selectively adsorbing rhodamine 6G.
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