CN109439314B - Preparation method of magnetic nano fluorescent probe for specifically recognizing Fe (III) - Google Patents
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Abstract
The invention relates to a method for specifically recognizing Fe3+The preparation method of the magnetic nano fluorescent probe mainly solves the problems that the existing metal ion probe is difficult to recover and separate and is easy to cause pollution and the like. In the preparation process, 3-aminopropyltriethoxysilane, glyoxal and rhodamine hydrazide are sequentially used for coating the silicon dioxide on Fe3O4The nano particles are modified to finally obtain Fe capable of being specifically identified3+The magnetic nano fluorescent probe can be conveniently and quickly recovered by adopting magnetic separation.
Description
Technical Field
The invention relates to the technical field of fluorescent probes and metal ion detection, in particular to a method for specifically identifying Fe3+The magnetic nano fluorescent probe and the preparation method thereof.
Background
The detection and treatment of heavy metal ions has been one of the most serious problems facing the field of environmental protection for the past decades. Different types of metal ions can cause different degrees of influence on the environment and organisms, the accumulation of high-concentration heavy metal ions and transition element ions in the organisms can influence the normal functions of cells, generally, the harm is larger along with the increase of the accumulation concentration, and the heavy metal pollution in natural water body can also bring potential threat to the health of human bodies.
Fe3+(or Fe (III)) is one of the most basic elements in biological systems, and has great significance for maintaining the normal operation of various functions of organisms, for example, iron ions play an important role in the processes of hemoglobin transportation of oxygen, cell metabolism and the like, and when the concentration of iron ions in a human body is not at a normal level, diseases such as anemia, heart failure, senile dementia and the like can be caused. Is due to iron ion to organismThe great influence of the body and the environment makes qualitative and quantitative analysis and detection of the body and the environment more necessary. At present, methods commonly used for detecting iron ions include atomic absorption spectrometry, colorimetry and the like, and although the methods can detect iron ions, the methods have the defects of long detection period, poor specificity selectivity, complex and expensive equipment and the like, so that a new method for quickly and sensitively detecting iron ions needs to be designed to meet the large amount of detection requirements in the fields of environmental protection, biomedicine, analytical science and the like. The iron ion probe is an excellent solution, and attracts many scholars in recent years.
Rhodamine B and derivatives thereof are artificially synthesized dyes which have excellent optical properties and are often used for synthesizing metal ion probes. At present, a plurality of achievements are obtained in the field, Goswami synthesizes a fluorescent probe by taking rhodamine 6G and niazid as raw materials, and the probe and Fe are mixed in an acetonitrile/water system3+The color of the system changes from colorless to pink after combination, and Fe can be qualitatively detected through the change of the color3+Has high sensitivity and selectivity. Similar probes also comprise a rhodamine hydrazide derivative compound disclosed in CN106146526A, but the probes generally have the problems of difficult recovery and secondary pollution.
Disclosure of Invention
The present invention is to solve the above problems of the prior art and to provide a method for specifically recognizing Fe3+The magnetic nano fluorescent probe and the preparation method thereof. By coupling rhodamine hydrazide to Fe3O4Obtaining a magnetic nano fluorescent probe on the surface of the nano particle, wherein the magnetic nano fluorescent probe is used for detecting Fe in a water-acetonitrile mixed system3+The fluorescent probe has specific recognition capability, has good fluorescent response signals besides macroscopic color change, can be separated simply and quickly by a magnet after the fluorescent probe is used, is convenient to recover and cannot cause secondary pollution. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
(a) dispersing the magnetic nano particles coated by the silicon dioxide in an alcohol solvent, adding a silane coupling agent and ammonia water, and obtaining a product A after the reaction is finished;
(b) dispersing the product A in an alcohol solvent, and then adding an aldehyde reagent and an acid reagent for reflux reaction to obtain a product B;
(c) dispersing the product B in an alcohol solvent, adding rhodamine hydrazide and an acid reagent for reflux reaction to obtain a target product, namely the target product capable of specifically recognizing Fe3+The magnetic nano fluorescent probe.
Further, the magnetic nanoparticles are Fe3O4The alcohol solvent is ethanol, the silane coupling agent is 3-aminopropyltriethoxysilane, the aldehyde reagent is glyoxal, and the acid reagent is acetic acid.
Furthermore, the concentration of the magnetic nano particles coated by the silicon dioxide in the reaction liquid in the step (a) is 1-5g/L, and the dosage of the silane coupling agent and the ammonia water respectively corresponds to (0.5-2.0)% and (0.5-5)% of the volume of the reaction liquid.
Further, water is added in the step (a), and the volume ratio of the water to the alcohol solvent is 1: 4.
Further, the concentration of the product A in the reaction liquid in the step (b) is 1-5g/L, and the mass ratio of the aldehyde reagent to the product A is 10-30: 1.
Further, the concentration of the product B in the reaction liquid in the step (c) is 1-5g/L, and the mass ratio of the rhodamine hydrazide to the product B is 1-15: 1.
Further, the reaction time of the steps (a) - (c) is 8-16h, stirring is continuously carried out during the reaction, the obtained product is washed for multiple times after centrifugal separation, and the solvent used for washing is selected from at least one of water and alcohol solvent.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects: the traditional rhodamine metal ion probe is coupled on the surface of the magnetic nano particle, so that the problems of difficult probe recovery and easy secondary pollution are solved; the prepared magnetic nano fluorescent probe is used for detecting Fe in a water-acetonitrile system3+The specific recognition capability is shown, and the interference of other metal ions is basically avoided; the modification method of the metal probe is simple, low in cost and easy to realize.
Drawings
FIG. 1 is a comparison graph of IR spectra of a raw material, an intermediate product and a final product in example 1 of the present invention;
FIG. 2 is a diagram of the UV absorption spectra of the magnetic nano-fluorescence probe prepared in example 2 of the present invention in different metal ion solutions;
FIG. 3 is a fluorescence spectrum of the magnetic nano fluorescent probe prepared in example 3 of the present invention in different metal ion solutions.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The rhodamine hydrazide structure used in each example of the invention is as follows:
the preparation method of the magnetic nano particle coated by the silicon dioxide comprises the following steps: mixing Fe3O4Dispersing magnetic nano particles in an ethanol water solution, adding ammonia water, mechanically stirring in a sealed environment, slowly dropwise adding tetraethyl orthosilicate during the mechanical stirring, stirring and reacting for 8-16h at room temperature, attracting and settling by using a magnet, and washing and separating.
Example 1
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 2.5 g/L. Adding 1mL of 3-aminopropyltriethoxysilane and 2.5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion B. Adding 2.0g of glyoxal (40%, volume fraction, the same below) and 2 drops of glacial acetic acid, stirring, refluxing, reacting for 10h, centrifuging, washing the obtained product with ethanol for 3 times to obtain the surface modified productFe of aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion C. Then 0.75g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifuged, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Respectively carrying out surface modification on the intermediate product obtained in the first step, namely Fe with amino groups3O4The infrared spectroscopic analysis of the nanoparticles (a), the rhodamine hydrazide as the raw material (b), and the magnetic nanoprobes (c) was performed, and the results are shown in fig. 1. 1090cm in FIG. 1-a-1Is positioned at 1380cm and is an antisymmetric stretching vibration peak of Si-O-Si-1At 590cm of bending vibration peak of methyl-1The characteristic absorption peak of Fe-O-Fe bond indicates that the silane coupling agent has been successfully modified to the Fe coated by the silicon dioxide3O4The surface of the nanoparticles. 2970cm in FIG. 1-b-1And 2987cm-1Is positioned at a C-H stretching vibration peak of 1700-500cm-1A series of absorption peaks in the range belong to structures such as benzene rings in a rhodamine hydrazide structure; 1724cm of it-1The strong peak appeared here is C ═ O stretching vibration absorption peak. At 1587cm in FIG. 1-c-1The newly appeared absorption peak is C ═ N stretching vibration absorption peak. In conclusion, rhodamine hydrazide is coupled to Fe through glyoxal3O4@SiO2Of (2) is provided.
Example 2
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 5 g/L. Adding 2mL of 3-aminopropyltriethoxysilane and 5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a dispersion B having a concentration of 5 g/L. 6g of glyoxal (40%) and2 drops of glacial acetic acid are stirred, refluxed and reacted for 10 hours, and then centrifugally separated, and the obtained product is washed 3 times by ethanol, namely the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give dispersion C at a concentration of 5 g/L. And adding 3g of rhodamine hydrazide and 2 drops of glacial acetic acid, stirring, refluxing, reacting for 10 hours, then carrying out centrifugal separation, and washing the obtained product with ethanol to obtain the target product, namely the magnetic nano fluorescent probe.
Using acetonitrile-water mixed solution with volume ratio of 1:1 as solvent, respectively preparing BaCl with same concentration (within experimental range of 100 μ M)2、CaCl2、CuCl2、FeCl3、HgCl2、KCl、FeCl2、NaCl、MgCl2Metal ion solutions, 10mg of the prepared magnetic nano fluorescent probes were added, and after standing for 15min, samples were taken for ultraviolet absorption spectroscopy analysis, and the results are shown in fig. 2. During which the color of the iron ion solution gradually changed to a vivid pink color as observed by the naked eye, while the other metal ion solutions did not show any color change. The UV absorption spectrum shown in FIG. 2 further confirms the above phenomenon, Na+、K+、Mg2+、Ba2+、Ca2+、Cu2+、 Hg2+、Fe2+No obvious absorption peak exists in the ion solution spectrogram, and Fe3+The solution has obvious absorption peak at 560nm, which shows that the magnetic nano fluorescent probe indeed has the effect on Fe3+Has specific recognition ability. The adsorption and recovery of the probe can be completed by a magnet, and the probe is cleaned for standby.
Example 3
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a with a concentration of 1 g/L. Then adding 0.5mL of 3-aminopropyltriethoxysilane and 0.5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 1g/L dispersion B. Then 0.4g of glyoxal (40%) and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed, reacted for 10 hours and then centrifugally separated, and the obtained product is washed 3 times by ethanol, namely the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 1g/L dispersion C. Then 0.04g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifuged, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
BaCl was prepared according to the method of example 22、CaCl2、CuCl2、FeCl3、HgCl2、KCl、 FeCl2、NaCl、MgCl2The metal ion solutions were added with 10mg of each of the prepared magnetic nano fluorescent probes, and after standing for 15min, a sample was taken for fluorescence spectrum analysis, and the results are shown in fig. 3. FIG. 3 shows that Na+、 K+、Mg2+、Ba2+、Ca2+、Cu2+、Hg2+、Fe2+The metal ion solution has no obvious change of fluorescence signal, but Fe3+The result that the solution has strong fluorescence intensity at 586nm further proves that the magnetic nanoprobe prepared by the method of the invention can specifically identify Fe3+And the probe is in contact with Fe3+The complex product shows a strong fluorescent signal.
Example 4
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 1 g/L. Then adding 0.5mL of 3-aminopropyltriethoxysilane and 0.5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4Nanoparticle fractionDispersed in 40mL of ethanol to obtain a 1g/L dispersion B. Adding 2g of glyoxal (40%) and 2 drops of glacial acetic acid, stirring, refluxing, reacting for 10h, centrifuging, washing the obtained product with ethanol for 3 times to obtain the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 1g/L dispersion C. Then 0.75g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifuged, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Example 5
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 2.5 g/L. Adding 1mL of 3-aminopropyltriethoxysilane and 2.5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Fe surface-modified with amino group3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion B. Adding 6g of glyoxal (40%) and 2 drops of glacial acetic acid, stirring, refluxing, reacting for 10h, centrifuging, washing the obtained product with ethanol for 3 times to obtain the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion C. And then 3g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifugal separation is carried out, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Example 6
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 2.5 g/L. Then, 1mL of 3-aminopropyltriethoxysilane and 2.5mL of ammonia were addedStirring and reacting for 12h at room temperature, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion B. Then 0.4g of glyoxal (40%) and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed, reacted for 10 hours and then centrifugally separated, and the obtained product is washed 3 times by ethanol, namely the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a 2.5g/L dispersion C. Then 0.1g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifuged, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Example 7
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 5 g/L. Adding 2mL of 3-aminopropyltriethoxysilane and 5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a dispersion B having a concentration of 5 g/L. Then 0.4g of glyoxal (40%) and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed, reacted for 10 hours and then centrifugally separated, and the obtained product is washed 3 times by ethanol, namely the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give dispersion C at a concentration of 5 g/L. Then 0.1g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifugal separation is carried out, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Example 8
Silica coated Fe3O4Nanoparticles were dispersed in 100mL of a water-alcohol mixed solvent (V)Ethanol： VWater (W)4:1) to give a dispersion a having a concentration of 5 g/L. Adding 2mL of 3-aminopropyltriethoxysilane and 5mL of ammonia water, stirring at room temperature for 12h, centrifuging, washing the obtained product with water and ethanol for 3 times alternately to obtain the surface modified amino Fe3O4Nanoparticles.
Surface-modified Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give a dispersion B having a concentration of 5 g/L. Adding 2g of glyoxal (40%) and 2 drops of glacial acetic acid, stirring, refluxing, reacting for 10h, centrifuging, washing the obtained product with ethanol for 3 times to obtain the Fe with the surface modified aldehyde group3O4Nanoparticles.
Modifying aldehyde group on surface with Fe3O4The nanoparticles were dispersed in 40mL of ethanol to give dispersion C at a concentration of 5 g/L. Then 0.75g of rhodamine hydrazide and 2 drops of glacial acetic acid are added, the mixture is stirred, refluxed and reacted for 10 hours, and then centrifuged, and the obtained product is washed by ethanol, thus obtaining the target product, namely the magnetic nano fluorescent probe.
Claims (4)
1. A preparation method of a magnetic nano fluorescent probe for specifically recognizing Fe (III) is characterized by comprising the following steps:
(a) dispersing the magnetic nano particles coated by the silicon dioxide in an alcohol solvent, adding a silane coupling agent and ammonia water, and obtaining a product A after the reaction is finished;
(b) dispersing the product A in an alcohol solvent, and then adding an aldehyde reagent and an acid reagent for reflux reaction to obtain a product B;
(c) dispersing the product B in an alcohol solvent, adding rhodamine hydrazide and an acid reagent for reflux reaction, and carrying out solid-liquid separation and washing;
the concentration of the magnetic nano particles coated by the silicon dioxide in the reaction liquid in the step (a) is 1-5g/L, and the dosage of the silane coupling agent and the ammonia water is respectively equal to (0.5-2.0)% and (0.5-5)% of the volume of the reaction liquid; the concentration of the product A in the reaction liquid in the step (b) is 1-5g/L, and the mass ratio of the aldehyde reagent to the product A is 10-30: 1; the concentration of the product B in the reaction liquid in the step (c) is 1-5g/L, and the mass ratio of the rhodamine hydrazide to the product B is 1-15: 1;
the magnetic nanoparticles are Fe3O4The alcohol solvent is ethanol, the silane coupling agent is 3-aminopropyltriethoxysilane, the aldehyde agent is glyoxal, the acid agent is acetic acid, and the rhodamine hydrazide is rhodamine hydrazide
2. The method of claim 1, wherein: water is also added in the step (a), and the volume ratio of the water to the alcohol solvent is 1: 4.
3. The method of claim 1, wherein: the reaction time of the steps (a) - (c) is 8-16h, stirring is carried out continuously during the reaction period, the obtained product is washed for multiple times after centrifugal separation, and the solvent used for washing is selected from at least one of water and alcohol solvent.
4. The magnetic nano fluorescent probe for specifically recognizing Fe (III) prepared according to any one of the methods in claims 1 to 3.
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