CN116515475A - 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application - Google Patents

3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application Download PDF

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CN116515475A
CN116515475A CN202310486091.3A CN202310486091A CN116515475A CN 116515475 A CN116515475 A CN 116515475A CN 202310486091 A CN202310486091 A CN 202310486091A CN 116515475 A CN116515475 A CN 116515475A
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magnetic
mercapto
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曾晓丹
陈昕
陈杰
于世华
刘治刚
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Jilin Institute of Chemical Technology
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Jilin Institute of Chemical Technology
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Abstract

The invention relates to Fe modified by 3-mercapto-1-propane sodium sulfonate 3 O 4 The magnetic fluorescent nanosensor of the ZnS core-shell structure can be used for measuring, detecting, screening or separating silver ions. The invention synthesizes the magnetic fluorescent nano sensor, has simple operation, short synthesis time and rapid detection, can separate the magnetic fluorescent nano sensor by a magnetic separation method, and solves the problems of silver ion enrichment, detection, separation and realityThe problem of the thorough purification of silver ions and secondary pollution to the environment.

Description

3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application
Technical Field
The invention belongs to the field of fluorescent nanosensors, and in particular relates to Fe modified by 3-mercapto-1-propane sodium sulfonate 3 O 4 Magnetic fluorescent nano sensor with a ZnS core-shell structure and application thereof in measuring, detecting, screening or separating silver ions, and magnetic resonance imaging or fluorescent imaging; the invention also provides a method for preparing the magnetic fluorescent nano sensor.
Background
Silver is concerned by the unique chemical properties of strong corrosion resistance, high oxidation resistance and the like, is widely used for manufacturing articles for daily use due to rarity and good glossiness, is easy to influence the environment due to a large amount of general use, is likely to cause silver poisoning, slow growth and the like due to excessive contact of silver with human body, and can damage skin and eyes due to excessive intake. Thus, an appropriate detection method is required for analysis thereof.
In recent years, magnetic nanomaterials have attracted great attention in the fields of analytical chemistry and biosensors due to their excellent stability, high biocompatibility, low toxicity and strong magnetic responsiveness. Wherein superparamagnetic iron oxide (Fe 3 O 4 ) Because of the unique high coercivity and excellent controllable magnetic responsiveness, the multifunctional nano probe can be controlled by an external magnetic field, the size and the surface can be controlled easily, and researchers in various fields such as chemistry, biology, medicine, materials and the like can utilize MNPs to construct the multifunctional nano probe to make many researches on sewage treatment, biological imaging, drug delivery and the like.
However, due to strong magnetic dipole attraction between particles, fe 3 O 4 Nanoparticles tend to aggregate. Therefore, stabilizers such as organic compounds and oxides having specific functional groups are often modified on the surface thereof for the purpose of improving the stability. By using various biocompatible polymers for Fe 3 O 4 The surface of the nanoparticle is functionalized and modified to have the new function of being a hot spot of current research, and fluorescent materials are introduced under the condition of ensuring the stability of the nanoparticle so as to realize magnetic resonance imaging and fluorescent imaging, thereby better realizing magnetic separationOff and targeting movements.
The detection of silver species includes a variety of instrumentation techniques including flame atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, electrochemical detection, and the like. In addition to these techniques, extraction methods using molecular receptors or chelating ligands have also been used to detect Ag (I). However, fluorescence detection has a great advantage over conventional analysis in that it is rapid in reaction, simple in operation, low in cost and high in sensitivity. In addition, a higher three-dimensional space can be penetrated and selected deeper so that the distribution of silver ions is seen during cell processing. Therefore, the development of the magnetic fluorescent nano sensor which has high stability, high selectivity, high sensitivity and rapid detection and is applied to measuring, detecting, screening and separating silver ions has important effect.
Disclosure of Invention
In view of the above, the present invention provides a sodium 3-mercapto-1-propanesulfonate-modified Fe 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure has the advantages of simple synthesis, rapid detection and good selectivity, and can be separated by a magnetic separation method, so that the problems of enrichment, detection and separation of silver ions, thorough purification of silver ions and secondary pollution to the environment are solved.
In particular, the invention provides a 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nanosensor (I) with @ ZnS core-shell structure and modified by 3-mercapto-1-propane sodium sulfonate in Fe 3 O 4 Microsphere surface with @ ZnS core-shell structure, fe 3 O 4 The core of the microsphere with the @ ZnS core-shell structure is Fe 3 O 4 Wherein ZnS quantum dots are wrapped in Fe 3 O 4 A surface.
In some embodiments of the invention, sodium 3-mercapto-1-propanesulfonate modified Fe 3 O 4 The preparation method of the magnetic fluorescent nanosensor with the@ZnS core-shell structure comprises the following steps:
①Fe 3 O 4 preparation of magnetic microspheres
FeCl 3 ·6H 2 Placing O in a container, addingAdding ethylene glycol, heating and stirring to fully dissolve the ethylene glycol to obtain a clear black solution, adding sodium acetate and a surfactant into the solution, and stirring for a certain time to obtain a reddish brown viscous solution; transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a stainless steel jacket and sealing, placing the stainless steel jacket into a blast drying box for hydrothermal reaction for a certain time, taking out, naturally cooling for a certain time, removing supernatant after opening a reaction kettle cover, collecting black precipitate at the bottom, and washing with deionized water to obtain Fe 3 O 4 The nano magnetic microsphere particles are added with water to prepare dispersion liquid for the next step of magnetic microsphere surface modification;
②Fe 3 O 4 preparation of @ ZnS magnetic fluorescent nanoparticle
Taking Fe prepared in the step (1) 3 O 4 Adding deionized water into the nano magnetic microsphere particle dispersion, adding a small amount of ammonia water to keep the pH stable, and stirring for a certain time under constant-temperature heating water bath; zn (Ac) 2 ·2H 2 O is dissolved in deionized water and transferred to Fe 3 O 4 In the solution, na 2 S·9H 2 Slowly dripping O solution into Fe 3 O 4 In the mixed solution, when Na 2 S·9H 2 After O solution is added dropwise, znS quantum dots will be added in Fe 3 O 4 Is formed on the surface of the alloy, is stirred in a constant-temperature heating water bath for a certain time, and is magnetically absorbed and washed until the water solution is clear, thus obtaining Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(3) 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into ZnS magnetic fluorescent nano particles to prepare dispersion liquid, then adding 3-mercapto-1-propane sodium sulfonate acetic acid solution, heating in water bath, keeping away from light, stirring for a certain time, and then magnetically absorbing water until the water solution is clear to prepare 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor (II) with ZnS core-shell structure.
The invention also provides Fe modified by 3-mercapto-1-propane sodium sulfonate 3 O 4 The preparation method of the magnetic fluorescent nano sensor with the@ZnS core-shell structure comprises the following steps:
①Fe 3 O 4 preparation of magnetic microspheres
FeCl 3 ·6H 2 Placing O in a container, adding glycol, T 1 Heating and stirring at a temperature of below zero to fully dissolve the mixture to obtain a clear black solution, adding sodium acetate and surfactant into the solution, and stirring for t 1 After hours, a reddish brown viscous solution is obtained; then transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a stainless steel jacket, sealing, and placing into a blast drying box for T 2 Hydrothermal reaction at DEG C t 2 Taking out after hours, and naturally cooling t 3 After the reaction kettle cover is opened for hours, removing supernatant, collecting black precipitate at the bottom, and then washing with deionized water to obtain Fe 3 O 4 The nanometer magnetic microsphere particles are added with water to prepare dispersion liquid for the next Fe 3 O 4 Preparing a ZnS magnetic fluorescent nanoparticle;
②Fe 3 O 4 preparation of @ ZnS magnetic fluorescent nanoparticle
Taking Fe prepared in the step (1) 3 O 4 Adding deionized water into nanometer magnetic microsphere particle dispersion, adding small amount of ammonia water to maintain pH stable, T 3 Stirring t under constant-temperature heating water bath at the temperature of 4 Hours; zn (Ac) 2 ·2H 2 O is dissolved in deionized water and transferred to Fe 3 O 4 In the solution, na 2 S·9H 2 Slowly dripping O solution into Fe 3 O 4 In the mixed solution, when Na 2 S·9H 2 After O solution is added dropwise, znS quantum dots will be added in Fe 3 O 4 Is formed on the surface of T 4 Constant-temperature heating water bath stirring t at DEG C 5 For an hour, magnetically absorbing water and washing until the water solution is clear, and preparing Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(3) 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Magnetic fluorescence of @ ZnSAdding water into the nano particles to prepare dispersion liquid, then adding 3-mercapto-1-propane sodium sulfonate acetic acid solution, T 5 Stirring t in water bath in dark place at the temperature of 6 After the water is absorbed magnetically until the water solution is clear, the Fe modified by 3-mercapto-1-propane sodium sulfonate is prepared 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
In some embodiments of the invention, T 1 ＝80-90；t 1 ＝0.5-1；T 2 ＝160-200；t 2 ＝10-12；t 3 ＝12-13；T 3 ＝80；t 4 ＝0.5-1；T 4 ＝70-80；t 5 ＝6-7；T 5 ＝40；t 6 ＝4。
In some embodiments of the invention, T 1 ＝85；t 1 ＝0.5；T 2 ＝200；t 2 ＝12；t 3 ＝12；T 3 ＝80；t 4 ＝0.5；T 4 ＝80；t 5 ＝6；T 5 ＝40；t 6 ＝4。
In some embodiments of the invention, the sodium 3-mercapto-1-propanesulfonate modified Fe 3 O 4 In the preparation steps (1) - (3) of the preparation method of the magnetic fluorescent nanosensor with the ZnS core-shell structure, the mass ratio of the components is as follows: feCl 3 ·6H 2 O: sodium acetate = 1:0.3-1:0.8; zn (Ac) 2 ·2H 2 O：Na 2 S·9H 2 O＝1:0.5-1:2；Fe 3 O 4 @ ZnS: sodium 3-mercapto-1-propanesulfonate=1:1-1.5:1, fe 3 O 4 The amount of the @ ZnS material is based on the amount of zinc sulfide material, the concentration of the zinc sulfide can be adjusted according to the synthesized microspheres with different diameters by synthesizing the zinc sulfide on the surface of the microspheres, the optimal fluorescence intensity is selected, and the amount ratio of the 3-mercapto-1-propane sodium sulfonate to the zinc sulfide material can be adjusted according to the optimal fluorescence intensity.
In some embodiments of the invention, the surfactant is polyethylene glycol.
The invention also provides Fe modified by 3-mercapto-1-propane sodium sulfonate 3 O 4 Preparation method of magnetic fluorescent nanosensor with@ZnS core-shell structurePrepared 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is applied to measuring, detecting, screening, silver ion separation and magnetic resonance imaging or fluorescence imaging.
The invention also provides a magnetic fluorescent nanosensor composition for measuring, detecting, screening or separating silver ions comprising sodium 3-mercapto-1-propanesulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor (I) or (II) with ZnS core-shell structure.
In some embodiments of the invention, the magnetic fluorescent nanosensor composition further comprises a solvent, an acid, a base, a buffer solution, or a combination thereof.
The present invention also provides a method for detecting the presence of silver ions in a sample or determining the content of silver ions in a sample, comprising:
a) Fe modified by sodium 3-mercapto-1-propane sulfonate 3 O 4 Contacting the magnetic fluorescent nanosensor (I) or (II) with ZnS core-shell structure with a sample to form a fluorescence change product;
b) The fluorescence properties of the products were determined.
In some embodiments of the invention, the sample is a water sample, a chemical sample, or a biological sample.
The invention also provides a method for separating silver ions in a sample, comprising:
a) Fe modified by sodium 3-mercapto-1-propane sulfonate 3 O 4 The magnetic fluorescent nanosensor (I) or (II) with the ZnS core-shell structure is contacted with a sample;
b) Fe modified by 3-mercapto-1-propane sodium sulfonate under the environment of external magnetic field 3 O 4 Separation of magnetic fluorescent nanosensor of @ ZnS core-shell structure from sample.
In some embodiments of the invention, the sample is a water sample, a chemical sample, or a biological sample.
The invention also provides for detecting the presence of silver ions in a sample or determining the silver ion content in a sample or separating a sampleKit of silver ions comprising sodium 3-mercapto-1-propanesulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor (I) or (II) with ZnS core-shell structure.
Compared with the prior art, the invention has the following remarkable advantages and effects: sodium 3-mercapto-1-propanesulfonate-modified Fe of the present invention 3 O 4 Magnetic fluorescent nanosensor of@ZnS core-shell structure for simultaneously ultrasensitive detection and removal of Ag in aqueous solution + Exhibits significant fluorescence quenching and is specific for Ag + Is a high selectivity of (2). The magnetic fluorescent nano sensor is simple in synthesis, short in synthesis time and rapid in detection, and solves the problems of enrichment, detection and separation of silver ions, thorough purification of silver ions and secondary pollution to the environment.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of sodium 3-mercapto-1-propanesulfonate modified Fe 3 O 4 Preparing a magnetic fluorescent nano sensor with a ZnS core-shell structure;
FIG. 2 is Fe 3 O 4 Magnetic microspheres (a, c), fe 3 O 4 SEM and TEM images of ZnS-MPS (b, d);
FIG. 3 is Fe 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic nanoparticles @ ZnS and Fe 3 O 4 XRD spectrum of @ ZnS-MPS;
FIG. 4 is Fe 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic nano particles @ ZnS and Fe 3 O 4 Infrared spectra of ZnS-MPS and sodium 3-mercapto-1-propanesulfonate.
FIG. 5 is Fe 3 O 4 XPS (Spectrometry) analysis of @ ZnS-MPS (a), fe 3 O 4 Fe2p# of ZnS-MPSb) High resolution XPS spectrum of Zn2p (c), S2 p (d);
FIG. 6 is Fe 3 O 4 Magnetic microsphere and Fe 3 O 4 Hysteresis loop graph of @ ZnS-MPS;
FIG. 7 is Fe 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic nano particles @ ZnS and Fe 3 O 4 Thermal gravimetric curve @ ZnS-MPS;
FIG. 8 is Fe 3 O 4 Presence or absence of Ag at different pH values for @ ZnS-MPS + Fluorescence intensity in presence;
FIG. 9 is Ag + Before and after adding Fe 3 O 4 Comparison of fluorescence spectra of @ ZnS-MPS, wherein the inset is Ag + Before and after adding Fe 3 O 4 TEM image of @ ZnS-MPS;
FIG. 10 is Fe 3 O 4 Adding Ag with different concentrations into ZnS-MPS + (0-100. Mu.M), wherein the inset shows the fluorescence intensity at 425nm and Ag + (0-100. Mu.M);
FIG. 11 is a graph of silver ions versus Fe for other different ion analytes 3 O 4 Influence of fluorescence intensity of @ ZnS-MPS and Fe in the presence of different ionic analytes 3 O 4 Fluorescence intensity after silver ion identification by ZnS-MPS, wherein (a) bar graph shows the difference of metal ions (1, co 2+ ；2，Pb 2+ ；3，Ni 2+ ；4,Hg 2+ ；5，Al 3+ ；6，Cu 2+ ；7，Zn 2+ ；8，Cd 2+ ；9,Fe 3+ ；10,Fe 2+ ；11，K + ；12，Ca 2+ ；13，Na + ；14，Ag + ) The method comprises the steps of carrying out a first treatment on the surface of the (b) The bar graph shows the proportion of MFNS fluorescence quenching when 1 equivalent of ag+ was added to a solution containing 1 equivalent of other metal ions (1, co 2+ ；2，Pb 2+ ；3，Ni 2+ ；4,Hg 2+ ；5，Al 3+ ；6，Cu 2+ ；7，Zn 2+ ；8，Cd 2+ ；9,Fe 3+ ；10,Fe 2+ ；11，K + ；12，Ca 2+ ；13，Na + ；14，Blank)；
FIG. 12 is Ag + Initial initiationConcentration of Fe 3 O 4 Influence of the adsorption capacity and removal rate of ZnS-MPS.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it should be apparent that the described embodiments are only some of the embodiments of the present invention and should not be used to limit the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1: 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Preparation of 3-mercapto-1-propanesulfonic acid sodium salt modified Fe according to the following procedure 3 O 4 Magnetic fluorescent nanosensor of @ ZnS core-shell structure:
①Fe 3 O 4 preparation of magnetic microspheres
The preparation method adopts a solvothermal method to synthesize the magnetic nano ferroferric oxide, and comprises the following steps: 2.7g FeCl 3 ·6H 2 O is placed in a 100mL beaker, 60mL of ethylene glycol is added, the mixture is placed in a water bath kettle at 85 ℃ and is magnetically stirred to be fully dissolved to obtain a clear black solution, then 7.2g of sodium acetate trihydrate and 0.5g of surfactant are added into the solution, and the mixture is magnetically stirred for 30min to obtain a reddish brown viscous solution. Transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, putting the reaction kettle into a stainless steel jacket and sealing, putting the stainless steel jacket into a blast drying box for hydrothermal reaction at 200 ℃ for 12 hours, taking out, naturally cooling for 12 hours, removing supernatant after opening a reaction kettle cover, collecting black precipitate at the bottom, and washing with deionized water for 3-4 times to prepare Fe 3 O 4 The nano particles are added with water to prepare dispersion liquid for the next step of magnetic microsphere surface modification.
②Fe 3 O 4 Preparation of @ ZnS magnetic fluorescent nanoparticle
10mL of the Fe prepared above was taken 3 O 4 The dispersion is fixed to volume to 100mL by deionized water,a small amount of ammonia water was added to maintain the pH stable and stirred in a constant temperature water bath at 80 ℃ for half an hour. 2.5mmol of Zn (Ac) 2 ·2H 2 O was dissolved in 50mL deionized water and transferred to Fe 3 O 4 In solution, 50mL of Na 2 S·9H 2 A solution of O (2.5 mmol) was slowly added dropwise to the above mixed solution. When Na is 2 S·9H 2 ZnS quantum dot will be added in Fe after O solution is added dropwise 3 O 4 Is stirred in a constant temperature water bath at 80 ℃ for 6 hours, and is magnetically washed until the water solution is clear. Fe prepared 3 O 4 The @ ZnS microsphere is added with water to prepare a dispersion liquid for the next surface modification of the magnetic microsphere.
(3) Fe modified by sodium 3-mercapto-1-propanesulfonate (MPS) 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Taking 5mLFE 3 O 4 The @ ZnS ethanol solution was placed in a round bottom flask, and 5mL of an aqueous solution of sodium 3-mercapto-1-propanesulfonate (MPS) (89.105 mg,0.1 mmol/L) was added and stirred in a 40℃water bath in the absence of light for 4h. Magnetically absorbing water and washing until the water solution is clear, and preparing the 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
EXAMPLE 2 Fe 3 O 4 、Fe 3 O 4 SEM and TEM test of @ ZnS-MPS
SEM test conditions: at room temperature, a proper amount of sample is taken and dispersed by ethanol, and after the sample is dried, the sample is dripped on a sample table with conductive adhesive.
TEM test conditions: at room temperature, a proper amount of samples are taken and dispersed by ethanol, and one drop of samples is taken to be dried and tested.
Fe by SEM and TEM 3 O 4 The morphology and particle size of the magnetic microsphere and Fe3O4@ZnS-MPS core-shell nanocomposite were tested. FIGS. a, c are Fe 3 O 4 SEM and TEM images of magnetic microspheres revealing Fe 3 O 4 The magnetic microspheres have a regular and uniform distribution. In addition, fe 3 O 4 ZnS-MPS (referring to sodium 3-mercapto-1-propanesulfonate modified Fe prepared in example 1 3 O 4 Magnetic fluorescent nano-meter with @ ZnS core-shell structureSEM image of sensor) as shown in fig. b, comparing fig. a, b, it was found that ZnS particles after thiol modification were accumulated in Fe 3 O 4 Surface, fe 3 O 4 The surface of the magnetic microspheres becomes irregular and rough. In addition, fe 3 O 4 TEM image d of @ ZnS-MPS shows that ZnS particles after the modification of the thiol groups have been deposited on Fe 3 O 4 Magnetic microsphere surface.
Example 3: fe (Fe) 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic fluorescent nanoparticle @ ZnS and Fe 3 O 4 XRD test of @ ZnS-MPS
XRD test conditions: and (3) grinding and tabletting the sample at room temperature, and measuring at an angle of 5-80 degrees.
FIG. 3 is Fe 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic fluorescent nanoparticle @ ZnS and Fe 3 O 4 XRD pattern of @ ZnS-MPS. In XRD spectrum, fe 3 O 4 The magnetic microspheres exhibited six diffraction peaks near 2θ=30.1°, 35.6 °, 43.1 °, 53.7 °, 57.1 ° and 62.8 °, corresponding to Fe, respectively 3 O 4 The (220), (311), (400), (422), (511) and (440) planes of the cubic spinel crystal structure. Fe (Fe) 3 O 4 The presence of ZnS crystals in the composite was confirmed by the presence of 3 new diffraction peaks for the @ ZnS magnetic fluorescent nanoparticles around 2θ=28.9°, 47.7 ° and 57.0 °. Fe (Fe) 3 O 4 Fe at ZnS-MPS 3 O 4 The diffraction peak position is not changed when the quantum dot and the sulfhydryl are modified, which indicates that in the coating process, the magnetic core Fe 3 O 4 No chemical and structural changes occurred. It is clear that the diffraction peaks before and after functionalization are substantially identical, indicating that Fe is present during different functionalization processes 3 O 4 The crystal structure of (a) is not changed.
Example 4: fe (Fe) 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic fluorescent nanoparticle @ ZnS and Fe 3 O 4 Infrared test of sodium @ ZnS-MPS, 3-mercapto-1-propanesulfonate
FT-IR test: taking a proper amount of sample at room temperature, addingGrinding potassium bromide to obtain tablet with wave number (sigma) of 500-4000cm -1 。
FIG. 4 is Fe 3 O 4 Magnetic microsphere, fe 3 O 4 Magnetic fluorescent nanoparticle @ ZnS and Fe 3 O 4 Infrared spectra of ZnS-MPS, sodium 3-mercapto-1-propanesulfonate. Fe can be seen 3 O 4 Infrared spectrum of magnetic microsphere 584cm -1 The strong absorption peak of (2) is related to the stretching vibration of Fe-O bond. For Fe 3 O 4 The peak value corresponding to the stretching vibration of Fe-O and Zn-S of the @ ZnS magnetic fluorescent nanoparticle appears at 580cm -1 And 1018cm -1 . 3-mercapto-1-propane sodium sulfonate 2600-2500 cm -1 The absorption, i.e., -SH, peak of stretching vibration. For Fe 3 O 4 Magnetic fluorescent nanoparticle @ ZnS-MPS at 1018cm -1 The Zn-S stretching vibration peak modified by the sulfhydryl group is obviously covered up and is within 3000cm -1 At this time, a new C-H peak appears, and the peak corresponding to the new S-O stretching vibration is 1042cm -1 1178cm -1 The peak at this point is attributed to s=o=o symmetrical stretching vibration. This can prove that the thiol groups bind to the microsphere surface and that the ligand is successfully modified to the microsphere surface.
Example 5: fe (Fe) 3 O 4 XPS test of @ ZnS-MPS
XPS test: and (3) taking a proper amount of samples for grinding and measuring at room temperature.
Search for Fe by XPS analysis 3 O 4 The elemental composition of the @ ZnS-MPS nanocomposite (FIG. 5), five peaks at 1019.2eV, 709.8eV, 529.6eV, 282.7eV and 159.2eV consisted of Zn2p, fe 2p, O1S, C1S and S2 p, respectively, confirming Fe 3 O 4 Successful synthesis of ZnS-MPS nanocomposites. As can be seen from FIG. 5b, fe 3+ 2p 3/2 And Fe (Fe) 3+ 2p 1/2 Binding energy is at 710.8 and 725.0eV, respectively, and bimodal fitting of Fe 2p can result in Fe at 708.7 and 721.6eV, respectively 2+ 2p 3/2 And Fe (Fe) 2+ 2p 1/2 Binding energy, indicating the presence of Fe in the nanocomposite 3 O 4 . As can be seen from FIG. 5c, zn2p 3/2 With Zn2p 1/2 The binding energy difference between them was 22.5eV, indicating catalysisThe metal Zn loaded by the agent exists mainly in the +2 valence state. Peaks at 159.5eV and 160.7eV (FIG. 5 d) are attributed to metal sulfide S from ZnS, respectively 2- (2p 3/2 And S2 p 1/2 )。
EXAMPLE 6 Fe 3 O 4 Magnetic microsphere and Fe 3 O 4 Magnetic property test of @ ZnS-MPS
VSM test: at room temperature, a proper amount of sample is weighed out by a precision balance, and is tightly packed into a small sphere by soft paper for measurement.
FIG. 6 is Fe 3 O 4 Magnetic microsphere and Fe 3 O 4 Hysteresis loop plot of @ ZnS-MPS. Fe (Fe) 3 O 4 The saturation magnetization of the magnetic microsphere is 64.52emu/g, fe 3 O 4 The magnetic saturation value of the @ ZnS-MPS nanocomposite was 47.09emu/g. Due to Fe 3 O 4 The magnetization in the nanocomposite is reduced by the antimagnetic effect of the thick thiol-modified ZnS layer around the magnetic microsphere. Zn (zinc) 2+ The ion redistribution of (a) may also lead to a decrease in the saturation magnetization of the composite material. However, the material still has typical superparamagnetism, can meet the experimental requirements, and can remove Ag + And still exhibit excellent magnetic properties (see inset of figure 6).
EXAMPLE 7 Fe 3 O 4 Thermogravimetric analysis test of @ ZnS-MPS
In order to study the thermal properties of the samples, the samples are analyzed by a thermal weight loss analyzer, the thermal properties are an important index for measuring the hybrid materials, and the thermal properties of the hybrid materials are different according to different synthesis methods. Fe was measured at a heating rate of 10 ℃/min under a nitrogen atmosphere 3 O 4 TGA curve of @ ZnS-MPS and results are shown in FIG. 7. As shown in FIG. 7, the weight loss ratio of the product is not very large, fe 3 O 4 The weight loss rate is only about 8%, the weight loss after ZnS modification is reduced, the loss is the moisture contained in ZnS, and the weight loss rate after MPS modification reaches 17%, which indicates that the polymers in the sample are all removed. Thermogravimetric analysis therefore again indicated that the thiol group had been modified to Fe 3 O 4 Magnetic microsphere surface.
EXAMPLE 8 pH vs. Fe 3 O 4 Influence of the ability of ZnS-MPS to recognize silver ions
The pH of the solution is one of the important parameters affecting the detectability of the probe. As can be seen from FIG. 8, in the pH range of 4.8-9, the fluorescence intensity of the probe itself does not change greatly, and the degree of fluorescence intensity quenching is not affected by the pH value by the addition of silver ions, so that the invention selects the common neutral liquid with the pH value of 7.0 as an experimental standard.
EXAMPLE 9 Fe 3 O 4 Ag is added to ZnS-MPS + Front-to-back fluorescence test
Fluorescence intensity test: under the condition of room temperature, a proper amount of sample is taken and dissolved in phosphoric acid buffer solution, and the fluorescence spectrum test selects excitation wavelength of 370nm and the spectrum range of 400-500nm.
FIG. 9 is Fe 3 O 4 Fluorescence characteristic spectrum contrast diagrams before and after addition of Ag+ to ZnS-MPS. As can be seen from fig. 9, ag + Can obviously quench Fe by adding 3 O 4 ZnS-MPS; the illustration shows the addition of Ag + Front and rear Fe 3 O 4 Transmission electron microscopy image of @ ZnS-MPS, ag was clearly seen + Has been loaded and dispersed in Fe 3 O 4 The surface of the @ ZnS-MPS magnetic fluorescent nanoparticle. Fe (Fe) 3 O 4 The @ ZnS-MPS nanoparticle itself has good dispersibility and is almost spherical. Ag (silver) + With Fe 3 O 4 Complexing the sodium 3-mercapto-1-propanesulfonate at the ZnS surface resulted in probe aggregation, leading to significant fluorescence quenching.
Example 10 test of Fe 3 O 4 Response range and concentration gradient test of ZnS-MPS for silver ions
FIG. 10 shows that Ag in solution accompanies + Increasing concentration, gradually decreasing fluorescence intensity, and 0-100 μm of Ag + Within the concentration range, ag + The detection limit was 7.04. Mu.M in terms of the concentration and fluorescence intensity. Relevant regulations are made on the content of silver ions according to the World Health Organization (WHO): silver ions in the domestic drinking water cannot be higher than 0.05mg/L, and the concentration of silver ions in human bodies is required to be lower than 0.05mg/L (0.46 mu m/L), which is just in line with the magnetic fluorescent nanoparticleDetection range of the seed. Therefore, the nano particles can accurately determine the content of silver ions.
EXAMPLE 11 Fe testing 3 O 4 Selectivity and anti-interference capability test of @ ZnS-MPS
High selectivity is a necessary condition for the sensor, so that the prepared magnetic fluorescent composite material is examined for Ag by screening the reaction of related analytes under the same condition + Is selected from the group consisting of (1). The results show that Ag + Although other ions may be weakly quenched, this is clearly negligible compared to silver ions (fig. 11 a). To further investigate the ability of magnetic fluorescent nanoparticles to recognize silver ions in the presence of other metal ions and to simultaneously investigate the tamper resistance of the nanoparticles, when one equivalent of silver ions was added to a solution of one equivalent of other ions (400 μm of Ag + ，Co 2+ 、Ni 2+ 、Al 3+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Fe 3+ 、Fe 2+ 、K + 、Ca 2+ 、Na + 、Pb 2+ 、Hg 2+ ) The other ions have no influence on the detection of silver ions by the magnetic fluorescent nanoparticles. This is well demonstrated by fluorescence emission spectra (fig. 11 b), where common metal ions in the environment do not significantly interfere with the qualitative and quantitative detection of silver ions by the particles.
Example 12 testing of initial concentration of Ag+ versus Fe 3 O 4 Influence of adsorption Capacity and removal Rate of ZnS-MPS Ag + The effect of initial concentration on adsorption efficiency is shown in figure 12. Adsorption analysis showed that following initial Ag +
Concentration increase, fe 3 O 4 The adsorption amount of ZnS-MPS is gradually increased due to the increase of initial concentration, the adsorption driving force and the ion mass transfer rate are improved, and the binding sites on the surface of the adsorbent are gradually replaced by Ag + Occupancy, adsorption capacity is thereby increased. Ag in solution + The removal rate of (2) was gradually decreased after reaching 99.62% at 100. Mu.M, since the amount of adsorbent in the solution was constant and was Ag + The adsorption sites are also providedIn (3), almost all Ag is present when the heavy metal concentration is low + Can be combined with adsorption sites to achieve higher removal rate, and the adsorption gradually reaches equilibrium, so that the adsorption effect of the adsorbent on free metal ions in the solution is reduced, and the removal rate is reduced. When Ag is + When the concentration is changed from 300 mu M to 600 mu M, the removal rate is reduced from 99.54% to 93.54%, the adsorption capacity is increased from 322.496mg/g to 606.112mg/g, and the comprehensive consideration is that Ag + The concentration was about 400. Mu.M at the intersection point to obtain an optimized result.
While the invention has been described with reference to the above embodiments, it will be understood that the invention is capable of further modifications and variations without departing from the spirit of the invention, and these modifications and variations are within the scope of the invention.

Claims (10)

1. 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 The magnetic fluorescent nano sensor with the @ ZnS core-shell structure is characterized in that: fe is prepared by adopting a solvothermal method 3 O 4 Magnetic microsphere for Fe by chemical precipitation method 3 O 4 Coating quantum dot ZnS, and modifying Fe by using 3-mercapto-1-propane sodium sulfonate 3 O 4 And preparing the sulfhydryl functional magnetic fluorescent microsphere by using the @ ZnS.
2. Sodium 3-mercapto-1-propanesulfonate-modified Fe as claimed in claim 1 3 O 4 The magnetic fluorescent nano sensor with the @ ZnS core-shell structure is characterized in that:
3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 The preparation method of the magnetic fluorescent nanosensor with the@ZnS core-shell structure comprises the following steps:
①Fe 3 O 4 preparation of magnetic microspheres
FeCl 3 ·6H 2 Placing O in a container, adding glycol, heating and stirring to fully dissolve the O to obtain a clear black solution, adding sodium acetate and a surfactant into the solution, and stirring for a certain time to obtain a reddish brown viscous solution; then transferring the solution into a polytetrafluoroethylene reaction kettlePlacing the mixture in a stainless steel jacket and sealing, placing the stainless steel jacket into a blast drying oven for hydrothermal reaction for a certain time, taking out the mixture, naturally cooling the mixture for a certain time, opening a reaction kettle cover, removing supernatant, collecting black precipitate at the bottom, and washing the precipitate with deionized water to obtain Fe 3 O 4 The nano magnetic microsphere particles are added with water to prepare dispersion liquid for the next step of magnetic microsphere surface modification;
②Fe 3 O 4 preparation of @ ZnS magnetic fluorescent nanoparticle
Taking Fe prepared in the step (1) 3 O 4 Adding deionized water into the nano magnetic microsphere particle dispersion, adding a small amount of ammonia water to keep the pH stable, and stirring for a certain time under constant-temperature heating water bath; zn (Ac) 2 ·2H 2 O is dissolved in deionized water and transferred to Fe 3 O 4 In the solution, na 2 S·9H 2 Slowly dripping O solution into Fe 3 O 4 In the mixed solution, when Na 2 S·9H 2 After O solution is added dropwise, znS quantum dots will be added in Fe 3 O 4 Is formed on the surface of the alloy, is stirred in a constant-temperature heating water bath for a certain time, and is magnetically absorbed and washed until the water solution is clear, thus obtaining Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(3) 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into ZnS magnetic fluorescent nano particles to prepare dispersion liquid, then adding 3-mercapto-1-propane sodium sulfonate aqueous solution, heating in water bath, light-shielding and stirring for a certain time, and then magnetically absorbing water until the aqueous solution is clear to prepare the 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
3. 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 The preparation method of the magnetic fluorescent nano sensor with the ZnS core-shell structure is characterized by comprising the following steps:
①Fe 3 O 4 preparation of magnetic microspheres
FeCl 3 ·6H 2 Placing O in a container, adding glycol, T 1 Heating and stirring at a temperature of below zero to fully dissolve the mixture to obtain a clear black solution, adding sodium acetate and surfactant into the solution, and stirring for t 1 After hours, a reddish brown viscous solution is obtained; then transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a stainless steel jacket, sealing, and placing into a blast drying box for T 2 Hydrothermal reaction at DEG C t 2 Taking out after hours, and naturally cooling t 3 After the reaction kettle cover is opened for hours, removing supernatant, collecting black precipitate at the bottom, and then washing with deionized water to obtain Fe 3 O 4 The nanometer magnetic microsphere particles are added with water to prepare dispersion liquid for the next Fe 3 O 4 Preparing a ZnS magnetic fluorescent nanoparticle;
②Fe 3 O 4 preparation of @ ZnS magnetic fluorescent nanoparticle
Taking Fe prepared in the step (1) 3 O 4 Adding deionized water into nanometer magnetic microsphere particle dispersion, adding small amount of ammonia water to maintain pH stable, T 3 Stirring t under constant-temperature heating water bath at the temperature of 4 Hours; zn (Ac) 2 ·2H 2 O is dissolved in deionized water and transferred to Fe 3 O 4 In the solution, na 2 S·9H 2 Slowly dripping O solution into Fe 3 O 4 In the mixed solution, when Na 2 S·9H 2 After O solution is added dropwise, znS quantum dots will be added in Fe 3 O 4 Is formed on the surface of T 4 Constant-temperature heating water bath stirring t at DEG C 5 For an hour, magnetically absorbing water and washing until the water solution is clear, and preparing Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(3) 3-mercapto-1-propanesulfonic acid sodium salt modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into ZnS magnetic fluorescent nano particles to prepare dispersion liquid, then adding 3-mercapto-1-propane sodium sulfonate acetic acid solution, T 5 Stirring t in water bath in dark place at the temperature of 6 After the water is absorbed magnetically until the water solution is clear, the 3-mercapto-1-propane sodium sulfonate modification is preparedFe of (2) 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
4. The method for preparing the 3-mercapto-1-propane sodium sulfonate modified Fe3O4@ZnS core-shell structured magnetic fluorescent nanosensor as claimed in claim 3, wherein,
T 1 ＝80-90；t 1 ＝0.5-1；T 2 ＝160-200；t 2 ＝10-12；t 3 ＝12-13；T 3 ＝80；t 4 ＝0.5-1；
T 4 ＝70-80；t 5 ＝6-7；T 5 ＝40-60；t 6 ＝3-4。
5. a sodium 3-mercapto-1-propanesulfonate-modified Fe as claimed in claim 3 3 O 4 A method for preparing a magnetic fluorescent nano sensor with a ZnS core-shell structure is characterized in that,
in the steps (1) - (3), the mass ratio of the substances of each component is as follows: feCl 3 ·6H 2 O: sodium acetate = 1:0.3-1:0.8; zn (Ac) 2 ·2H 2 O：Na 2 S·9H 2 O＝1:0.5-1:2；Fe 3 O 4 @ ZnS: sodium 3-mercapto-1-propanesulfonate=1:1-1.5:1.
6. A sodium 3-mercapto-1-propanesulfonate-modified Fe as claimed in any one of claims 3-5 3 O 4 Fe modified by 3-mercapto-1-propane sodium sulfonate prepared by preparation method of magnetic fluorescent nanosensor with ZnS core-shell structure 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is applied to measuring, detecting, screening, silver ion separation and magnetic resonance imaging or fluorescence imaging.
7. A magnetic fluorescent nanosensor composition for measuring, detecting, screening or separating silver ions comprising the sodium 3-mercapto-1-propanesulfonate modified Fe of any one of claims 1-2 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
8. The fluorescent probe composition of claim 7, wherein the magnetic fluorescent nanosensor composition further comprises a solvent, an acid, a base, a buffer solution, or a combination thereof.
9. A method for detecting the presence of silver ions in a sample or determining the silver ion content in a sample, comprising:
a) Modification of sodium 3-mercapto-1-propanesulfonate according to any one of claims 1-2 3 O 4 Contacting the magnetic fluorescent nano sensor with the@ZnS core-shell structure with a sample to form a fluorescent change product;
b) The fluorescence properties of the products were determined.
10. A method for separating silver ions in a sample, comprising:
a) Modification of sodium 3-mercapto-1-propanesulfonate according to any one of claims 1-2 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is contacted with a sample;
b) Fe modified by 3-mercapto-1-propane sodium sulfonate under the environment of external magnetic field 3 O 4 Separation of magnetic fluorescent nanosensor of @ ZnS core-shell structure from sample.
CN202310486091.3A 2023-04-28 2023-04-28 3-mercapto-1-propane sodium sulfonate modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application Pending CN116515475A (en)

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