CN116930133A - Mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application - Google Patents

Mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application Download PDF

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CN116930133A
CN116930133A CN202310777637.0A CN202310777637A CN116930133A CN 116930133 A CN116930133 A CN 116930133A CN 202310777637 A CN202310777637 A CN 202310777637A CN 116930133 A CN116930133 A CN 116930133A
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zns
magnetic
shell structure
mercaptosuccinic acid
magnetic fluorescent
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曾晓丹
陈昕
陈杰
马明硕
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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    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention relates to a mercaptosuccinic acid modified Fe 3 O 4 The magnetic fluorescent nanosensor of the ZnS core-shell structure can be used for measuring, detecting, screening or separating copper ions. The invention synthesizes the magnetic fluorescent nano sensor, has simple operation, short synthesis time and rapid detection, and can separate the magnetic fluorescent nano sensor by magnetismThe method solves the problems of enrichment, detection and separation of copper ions, complete purification of copper ions and secondary pollution to the environment.

Description

Mercaptosuccinic acid 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 particularly relates to mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure and application thereof in measuring, detecting, screening or separating copper ions; the invention also provides a method for preparing the magnetic fluorescent nano sensor.
Background
Copper ions are considered to be important trace minerals in organisms and also important components of many enzymes and proteins, playing a key role in cellular oxygen transport and activation, energy production and signal transduction. Excessive exposure to copper in humans is likely to cause gastrointestinal disturbances, liver damage, etc., and disruption of copper ion homeostasis can lead to a variety of diseases such as Wilson's disease, alzheimer's disease, and prion diseases. Thus, an appropriate detection method is required for analysis thereof.
Magnetic nanoparticle Fe 3 O 4 Is a novel functional nano material, and has wide application in catalysis, environmental protection, sensors, magnetic storage media, clinical diagnosis and treatment by virtue of the advantages of magnetism, chemical stability, biocompatibility, low toxicity and the like. However, due to strong magnetic dipole attraction between particles, fe 3 O 4 The nanoparticles have strong magnetic dipole attraction and tend to aggregate with each other. Thus, stability is enhanced by surface modification of certain specific functional group organic, oxide, etc. stabilizers. By using various biocompatible polymers for Fe 3 O 4 The surface of the nano particle is functionalized and modified, so that the nano particle has a new function of being a hot spot of current research, and magnetic separation and targeted movement can be better realized by introducing fluorescent materials under the condition of ensuring the stability of the nano particle.
The detection of copper species includes a variety of instrumentation techniques such as flame atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, electrochemical detection, and the like. However, fluorescence detection has a great advantage over conventional analysis in that it is simple to operate, has high sensitivity and selectivity, and has a low detection limit. In addition, a higher three-dimensional space can be penetrated and selected deeper so that the copper ion distribution 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 copper ions has important effect.
Disclosure of Invention
In view of the above, the present invention provides a mercaptosuccinic acid 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 copper ions, thorough purification of the copper ions and secondary pollution to the environment are solved.
In particular, the invention provides a mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nanosensor with@ZnS core-shell structure, and mercaptosuccinic acid modified 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, mercaptosuccinic acid 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 @ ZnS magnetic fluorescent nanoparticle
Fe is added to 3 O 4 Respectively dissolving ZnS and ZnS in deionized water, and then mixing the two solutions; stirring for reaction, and then carrying out ultrasonic treatment; subsequently, the resulting product was washed by centrifugation at 1500rpm using deionized water and ethanol; finally, heating and drying the collected black precipitate, and grinding the product into fine powder to prepare Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(2) mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into the magnetic fluorescent nano particles @ ZnS to prepare a dispersion liquid, then adding a mercaptosuccinic acid solution, heating in a water bath, stirring in a dark place, and then magnetically absorbing water until the water solution is clear to prepare the mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
The invention also provides Fe modified by mercaptosuccinic acid 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 @ ZnS magnetic fluorescent nanoparticle
Fe with a certain weight ratio 3 O 4 Respectively dissolving ZnS and ZnS in deionized water, and then mixing the two solutions; reaction at T 1 Continuously stirring at a temperature of t 1 Minute and then at T 2 Ultrasonic treatment at a temperature t 2 Minutes; subsequently, t is obtained by centrifugation at 1500rpm 3 Washing the resulting product at least once with deionized water and ethanol for a minute; finally, the collected black precipitate is subjected to T 3 Drying at C for t 4 For hours, then grinding the product into fine powder to prepare Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(2) mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into the magnetic ZnS fluorescent nanoparticle to prepare dispersion, and then adding a mercaptosuccinic acid solution T 4 Heating in water bath and light-shielding stirring t at DEG C 5 After the reaction for hours, the water is absorbed magnetically until the water solution is clear, and the Fe modified by the mercaptosuccinic acid is prepared 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
In some embodiments of the invention, the mercaptosuccinic acid modified Fe 3 O 4 @ZnS core-shell structureIn the preparation steps (1) - (2) in the preparation method of the magnetic fluorescent nanosensor of (2), fe 3 O 4 : the weight ratio of ZnS is as follows: fe (Fe) 3 O 4 ：ZnS＝1:2-1:3；Fe 3 O 4 @ ZnS: the mass ratio of the mercaptosuccinic acid is as follows: fe (Fe) 3 O 4 @ ZnS: mercaptosuccinic acid = 1:1-1.25:1.
In some embodiments of the invention, T 1 ＝80-90；t 1 ＝30-60；T 2 ＝40-60；t 2 ＝90-100；t 3 ＝12-15；T 3 ＝50-60；t 4 ＝12-15；T 4 ＝40-50；t 5 ＝4-5
The invention also provides Fe modified by mercaptosuccinic acid 3 O 4 Preparation method of magnetic fluorescent nano sensor with@ZnS core-shell structure prepares mercaptosuccinic acid modified Fe 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is applied to measuring, detecting, screening and separating copper ions.
The invention also provides a magnetic fluorescent nanosensor composition for measuring, detecting, screening or separating copper ions, comprising mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor 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 copper ions in a sample or determining the copper ion content in a sample, comprising:
a) Fe for modifying mercaptosuccinic acid 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.
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 copper ions in a sample, which comprises the following steps:
a) Fe for modifying mercaptosuccinic acid 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is contacted with a sample;
b) Fe for realizing mercaptosuccinic acid modification 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.
The invention also provides a kit for detecting the presence of copper ions in a sample or determining the content of copper ions in a sample or separating copper ions in a sample, comprising mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
Compared with the prior art, the invention has the following remarkable advantages and effects: mercaptosuccinic acid modified Fe of the invention 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure can be used for simultaneously detecting and removing Cu in aqueous solution 2 + Exhibits significant fluorescence quenching and is effective for Cu 2+ 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 copper ions, thorough purification of copper 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 mercaptosuccinic acid modified Fe 3 O 4 Schematic diagram of magnetic fluorescent nanosensor with ZnS core-shell structure and fluorescent response condition aiming at copper ions with different concentrations;
FIG. 2 is Fe 3 O 4 Magnetic microsphere @ ZnS (a, c), fe 3 O 4 SEM and TEM images of ZnS-COOH magnetic microspheres (b, d);
FIG. 3 is Fe 3 O 4 Magnetic microsphere (a), fe 3 O 4 XRD patterns of @ ZnS magnetic microspheres (b);
FIG. 4 is Fe 3 O 4 Magnetic microsphere (a) of @ ZnS and Fe 3 O 4 Infrared spectra of @ ZnS-COOH magnetic microspheres (b) and mercaptosuccinic acid (c).
FIG. 5 is Fe in the absence of (a) and in the presence of (b) copper ions 3 O 4 XPS (x-ray Spectroscopy) analysis of the@ZnS-COOH magnetic microspheres;
FIG. 6 is Fe 3 O 4 Magnetic microsphere (a), fe 3 O 4 Magnetic microsphere of @ ZnS (b) and Fe 3 O 4 Magnetic susceptibility curves of @ ZnS-COOH (c) magnetic microspheres;
FIG. 7 is Fe 3 O 4 Magnetic microsphere (a), fe 3 O 4 Magnetic microsphere (b) of @ ZnS and Fe 3 O 4 A thermogravimetric curve of @ ZnS-COOH magnetic microsphere (c);
FIG. 8 is Fe 3 O 4 Cu exists in the magnetic microsphere of @ ZnS-COOH under different pH values 2+ Fluorescence intensity in presence;
FIG. 9 is Fe 3 O 4 Cu with different concentrations is added into the @ ZnS-COOH magnetic microsphere 2+ (0-400. Mu.M), wherein the inset shows fluorescence intensity at 425nm and Cu 2+ (0-400. Mu.M);
FIG. 10 is a graph of copper ions versus Fe for other different ion analytes 3 O 4 Effect of fluorescence intensity of ZnS-COOH magnetic microspheres, bar graph shows the effect of different metal ions (1, cu 2+ ；2,Co 2+ ；3,Pb 2+ ；4,Ni 2+ ；5,Hg 2+ ；6,Al 3+ ；7,Zn 2+ ；8,Cd 2+ ；9,Fe 3+ ；10,Fe 2+ ；11,K + ；12,Ca 2+ ；13,Na + )；
FIG. 11 is a diagram of Fe with copper ions in the presence of different ion analytes 3 O 4 Fluorescent intensity of magnetic microsphere @ ZnS-COOH after copper ion identificationThe bar graph shows that 1 equivalent of Cu is added to a solution containing 1 equivalent of other metal ions 2+ Proportion of fluorescence quenching by MFNS (1, cu) 2+ ；2,Co 2+ ；3,Pb 2+ ；4,Ni 2+ ；5,Hg 2+ ；6,Al 3+ ；7,Zn 2+ ；8,Cd 2+ ；9,Fe 3+ ；10,Fe 2+ ；11,K + ；12,Ca 2+ ；13,Na + )。
FIG. 12 is Cu 2+ Initial concentration vs. Fe 3 O 4 Influence of adsorption capacity and removal rate of ZnS-COOH.
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: mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Preparation of mercaptosuccinic acid modified Fe according to the following procedure 3 O 4 Magnetic fluorescent nanosensor of @ ZnS core-shell structure:
①Fe 3 O 4 preparation of @ ZnS magnetic fluorescent nanoparticle
By Fe 3 O 4 And ZnS are used as raw materials, fe3O4@ZnS nano microsphere is synthesized according to the weight ratio of 1:2, and Fe is added into the nano microsphere 3 O 4 And ZnS were dissolved in 25 ml deionized water, respectively, and then the two solutions were mixed. The reaction was allowed to stir continuously at 80℃for 30 minutes and then sonicated at 40℃for 90 minutes. Subsequently, the resulting product was washed three times with deionized water and ethanol by centrifugation at 1500rpm for 12 minutes. Finally, the collected black precipitate was dried at 50 ℃ for 12 hours, and then the product was ground into fine powder.
(2) Mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into the magnetic fluorescent nano particles @ ZnS to prepare a dispersion liquid, and then adding Fe and the dispersion liquid 3 O 4 The preparation method comprises the steps of heating a mercaptosuccinic acid solution with the mass ratio of the magnetic fluorescent nano particles of ZnS being 1:1 in a water bath at 40 ℃ and stirring for 4 hours in a dark place, and then magnetically absorbing water until the water solution is clear, so as to prepare the mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
EXAMPLE 2 Fe 3 O 4 Magnetic microsphere @ ZnS (a, c), fe 3 O 4 SEM and TEM testing of @ ZnS-COOH magnetic microspheres (b, d);
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.
The test results are shown in fig. 2. Fe by SEM and TEM 3 O 4 Magnetic microsphere of @ ZnS and Fe 3 O 4 The morphology and particle size of the magnetic particles @ ZnS-COOH were studied, and in FIG. 2 a and c are Fe respectively 3 O 4 SEM and TEM images of the @ ZnS magnetic microspheres revealing Fe 3 O 4 The @ ZnS magnetic microspheres had a regular and uniform distribution. In addition, fe 3 O 4 SEM images of the magnetic particles @ ZnS-COOH are shown as b in FIG. 2, and comparing a and b in FIG. 2, it can be found that the surface pores of the particles become larger after carboxyl modification, and the contact area is obviously increased. In addition, fe 3 O 4 TEM image of the magnetic microsphere at ZnS-COOH is d in fig. 2, and the core-shell structure of the microsphere after carboxyl modification is more obvious.
Example 3: fe (Fe) 3 O 4 Magnetic microsphere (a), fe 3 O 4 XRD test of @ ZnS magnetic microsphere (b) in the 20-80 DEG range
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 (a), fe 3 O 4 XRD pattern of @ ZnS magnetic microsphere (b).
In XRD spectrum, fe 3 O 4 Six diffraction peaks appear 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. The presence of 3 new diffraction peaks near 2θ=28.9°, 47.7 ° and 57.0 ° confirm the presence of ZnS crystals in the composite. From XRD spectra, it can be concluded that ZnS has been successfully encapsulated into Fe 3 O 4 A surface.
Example 4: fe (Fe) 3 O 4 Magnetic microsphere (a) of @ ZnS and Fe 3 O 4 Infrared test of magnetic microspheres (b) and mercaptosuccinic acid (c) of ZnS-COOH
FT-IR test: taking a proper amount of sample, adding potassium bromide, grinding and tabletting under room temperature, wherein the wave number (sigma) is 500-4000cm -1 。
FIG. 4 is Fe 3 O 4 Magnetic microsphere @ ZnS and Fe 3 O 4 Infrared spectrograms of @ ZnS-COOH magnetic microspheres and mercaptosuccinic acid. The infrared spectrum of the magnetic microspheres can be seen, 584cm in FIG. 4 (a), (b) -1 The strong absorption peak of (2) is related to the stretching vibration of Fe-O bond. For Fe 3 O 4 The @ ZnS magnetic microsphere (a) has a peak value corresponding to the stretching vibration of Zn-S of 1018cm -1 . For Fe 3 O 4 Magnetic microsphere of @ ZnS-COOH at 1018cm -1 The Zn-S stretching vibration peak is obviously covered after the sulfhydryl group is modified, and at the moment, the Zn-S stretching vibration peak is at 1728cm -1 A new C-H peak appears at the position, and the corresponding peak value of the new carboxyl stretching vibration is 2930cm -1 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 in the absence of (a) and in the presence of (b) copper ions 3 O 4 XPS test of@ZnS-COOH magnetic microspheres
XPS test: and (3) taking a proper amount of samples for grinding and measuring at room temperature.
The absence of (a) and presence of (b) copper ion was explored by XPS analysis for Fe 3 O 4 The elemental composition of the @ ZnS-COOH microspheres (FIG. 5), five peaks at 1019.2eV, 709.8eV, 529.6eV, 282.7eV and 159.2eV consisted of Zn 2p, fe 2p, O1S, C1S and S2 p, respectively, confirming Fe 3 O 4 Successful synthesis of ZnS-COOH nanocomposite. As can be seen from fig. 5b, the peak at 932.6eV is Cu 2p, confirming that the prepared magnetic microsphere has the ability to adsorb copper ions.
EXAMPLE 6 Fe 3 O 4 Magnetic microsphere (a), fe 3 O 4 Magnetic microsphere of @ ZnS (b) and Fe 3 O 4 Magnetic susceptibility curve of @ ZnS-COOH magnetic microsphere (c)
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 、Fe 3 O 4 @ZnS and Fe 3 O 4 Hysteresis loop graph of @ ZnS-COOH. Original Fe 3 O 4 The saturation magnetization of the magnetic microsphere is 64.52emu/g, and the higher saturation magnetization indicates Fe 3 O 4 A very good crystal structure. Fe (Fe) 3 O 4 Saturation magnetization of the @ ZnS magnetic microsphere was 34.73emu/g, which was higher than that of the original Fe 3 O 4 Is low due to ZnS modification in Fe 3 O 4 The reason for the surface. Fe (Fe) 3 O 4 The saturation magnetization of the magnetic microsphere @ ZnS-COOH was 16.25emu/g. Therefore, the result shows that the nano magnetic microsphere prepared by the technical scheme of the invention has typical superparamagnetism and Cu in water is removed 2+ Is provided).
EXAMPLE 7 Fe 3 O 4 Magnetic microsphere (a), fe 3 O 4 Magnetic microsphere of @ ZnS (b) and Fe 3 O 4 Thermal gravimetric curve of @ ZnS-COOH (c) magnetic microspheres;
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. The TGA profile of the nanomicrospheres was measured at a rate of 20 ℃/min in a nitrogen atmosphere and the results are shown in fig. 6. As a whole in fig. 7The weight loss rate of the material 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 that the water contained in ZnS is contained, and the weight loss rate after carboxyl modification reaches 21%, which indicates that the polymers in the sample are all removed. Thermogravimetric analysis therefore again indicated that mercaptosuccinic acid has been modified to Fe 3 O 4 Magnetic microsphere surface.
EXAMPLE 8 pH vs. Fe 3 O 4 Influence of magnetic microsphere @ ZnS-COOH on ability to recognize copper 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 quenching of the fluorescence intensity is not affected by the pH value by the addition of copper ions, so that the invention selects the common neutral liquid with the pH value of 7.0 as an experimental standard.
EXAMPLE 9 testing Fe 3 O 4 Response range and concentration gradient test of@ZnS-COOH magnetic microspheres to copper ions
FIG. 9 shows that Cu in solution is accompanied 2+ Increasing concentration, gradually decreasing fluorescence intensity, and Cu in 0-400 μm 2+ Within the concentration range, cu 2+ The detection limit was 0.489. Mu.M in a linear relationship between the concentration and the fluorescence intensity. The maximum value (20 mu M) of the allowable copper ion concentration specified by the U.S. environmental protection agency can be met, and the detection range of the magnetic fluorescent nanoparticle is exactly met. Therefore, the nano particles can accurately determine the content of copper ions.
Example 10 test of Fe 3 O 4 Selectivity and anti-interference capability test of ZnS-COOH magnetic microsphere
High selectivity is a necessary condition for the sensor, and therefore, under the same condition, the prepared magnetic fluorescent composite material is examined on Cu by screening the reaction of related analytes 2+ Is selected from the group consisting of (1). The results show that Cu 2+ Although other ions showed a weak quenching, this was clearly negligible compared to copper ions (fig. 10). To further study in other metalsThe ability to recognize copper ions for magnetic fluorescent nanoparticles in the presence of ions, and the anti-interference ability of the nanoparticles was examined at the same time. When one equivalent of copper ions is added to a solution of the other ions in a volume of one equivalent (400. Mu.M Cu 2+ 、Co 2+ 、Ni 2+ 、Al 3+ 、Zn 2+ 、Cd 2+ 、Fe 3+ 、Fe 2+ 、K + 、Ca 2+ 、Na + 、Pb 2+ 、Hg 2+ ) Other ions have no influence on the detection of copper ions by the magnetic fluorescent nanoparticles; this is well demonstrated by fluorescence emission spectra (fig. 11), where common metal ions in the environment do not significantly interfere with qualitative and quantitative detection of copper ions by the particles.
EXAMPLE 11 test Cu 2+ Initial concentration vs. Fe 3 O 4 Influence of adsorption Capacity and removal Rate of @ ZnS-COOH magnetic microspheres
Cu 2+ The effect of initial concentration on adsorption efficiency is shown in figure 12. Adsorption analysis showed that with initial Cu 2+ Concentration increase, fe 3 O 4 The adsorption amount of ZnS-COOH also gradually increases due to the increase of the initial concentration, the adsorption driving force and the ion mass transfer rate are improved, and the binding sites on the adsorbent surface are gradually replaced by Cu 2+ Occupancy, adsorption capacity is thereby increased. Cu in solution 2+ The removal rate of (2) was gradually decreased after reaching 99.88% at 100. Mu.M, since the amount of the adsorbent in the solution was constant and was Cu 2+ The adsorption sites provided are also defined, almost all Cu being present when the heavy metal concentration is low 2+ 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.
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. Mercaptosuccinic acid modificationFe of (2) 3 O 4 The magnetic fluorescent nano sensor with the @ ZnS core-shell structure is characterized in that: mercaptosuccinic acid is modified 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.
2. Mercaptosuccinic acid modified Fe of claim 1 3 O 4 The magnetic fluorescent nano sensor with the @ ZnS core-shell structure is characterized in that:
mercaptosuccinic acid 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 @ ZnS magnetic fluorescent nanoparticle
Fe is added to 3 O 4 Respectively dissolving ZnS and ZnS in deionized water, and then mixing the two solutions; stirring for reaction, and then carrying out ultrasonic treatment; subsequently, the resulting product was washed by centrifugation at 1500rpm using deionized water and ethanol; finally, heating and drying the collected black precipitate, and grinding the product into fine powder to prepare Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(2) mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into the magnetic fluorescent nano particles @ ZnS to prepare a dispersion liquid, then adding a mercaptosuccinic acid solution, heating in a water bath, stirring in a dark place, and then magnetically absorbing water until the water solution is clear to prepare the mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
3. Mercaptosuccinic acid 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 @ ZnS magnetic fluorescent nanoparticle
Fe with a certain weight ratio 3 O 4 Respectively dissolving ZnS and ZnS in deionized water, and then mixing the two solutions; reaction at T 1 Continuously stirring at a temperature of t 1 Minute and then at T 2 Ultrasonic treatment at a temperature t 2 Minutes; subsequently, t is obtained by centrifugation at 1500rpm 3 Washing the resulting product at least once with deionized water and ethanol for a minute; finally, the collected black precipitate is subjected to T 3 Drying at C for t 4 For hours, then grinding the product into fine powder to prepare Fe 3 O 4 Magnetic fluorescent nanoparticles of @ ZnS;
(2) mercaptosuccinic acid modified Fe 3 O 4 Preparation of magnetic fluorescent nanosensor with@ZnS core-shell structure
Fe 3 O 4 Adding water into the magnetic ZnS fluorescent nanoparticle to prepare dispersion, and then adding a mercaptosuccinic acid solution T 4 Heating in water bath and light-shielding stirring t at DEG C 5 After the reaction for hours, the water is absorbed magnetically until the water solution is clear, and the Fe modified by the mercaptosuccinic acid is prepared 3 O 4 Magnetic fluorescent nano sensor with ZnS core-shell structure.
4. The preparation method of the mercaptosuccinic acid modified Fe3O4@ZnS core-shell structured magnetic fluorescent nanosensor as claimed in claim 3 is characterized by comprising the following steps:
T 1 ＝80-90；t 1 ＝30-60；T 2 ＝40-60；t 2 ＝90-100；t 3 ＝12-15；T 3 ＝50-60；t 4 ＝12-15；
T 4 ＝40-50；t 5 ＝4-5。
5. a mercaptosuccinic acid 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) - (2), fe 3 O 4 : the weight ratio of ZnS is as follows: fe (Fe) 3 O 4 ：ZnS＝1:2-1:3；Fe 3 O 4 @ ZnS: mercapto groupThe mass ratio of the succinic acid is as follows: fe (Fe) 3 O 4 @ ZnS: mercaptosuccinic acid = 1:1-1.25:1.
6. A mercaptosuccinic acid modified Fe as claimed in any one of claims 3 to 5 3 O 4 Preparation method of magnetic fluorescent nano sensor with@ZnS core-shell structure prepares mercaptosuccinic acid modified Fe 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is applied to measuring, detecting, screening and separating copper ions and magnetic resonance imaging or fluorescent imaging.
7. A magnetic fluorescent nanosensor composition for measuring, detecting, screening or separating copper ions, comprising the mercaptosuccinic acid 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 copper ions in a sample or determining the copper ion content in a sample, comprising:
a) Modification of mercaptosuccinic acid of any one of claims 1-2 with Fe 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 copper ions in a sample, comprising:
a) Modification of mercaptosuccinic acid of any one of claims 1-2 with Fe 3 O 4 The magnetic fluorescent nano sensor with the@ZnS core-shell structure is contacted with a sample;
b) Fe for realizing mercaptosuccinic acid modification under the environment of external magnetic field 3 O 4 Separation of magnetic fluorescent nanosensor of @ ZnS core-shell structure from sample.
CN202310777637.0A 2023-06-28 2023-06-28 Mercaptosuccinic acid modified Fe 3 O 4 Magnetic fluorescent nano sensor with@ZnS core-shell structure, preparation method and application Pending CN116930133A (en)

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