CN114133581B - Mg-MOFs, preparation method thereof and application thereof in iron ion detection - Google Patents
Mg-MOFs, preparation method thereof and application thereof in iron ion detection Download PDFInfo
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Abstract
The invention relates to novel Mg-MOFs, a preparation method thereof and application thereof in iron ion detection, wherein the structural formula of the Mg-MOFs is [ Mg (L) xG ], wherein L is a quadrilateral symmetric ligand containing a tetracarboxylic acid group, and G is a solvent molecule coordinated with magnesium ions or in a crystal pore channel. The preparation method of the Mg-MOFs comprises the following steps: dissolving a metal magnesium salt and a ligand L in a mixed solution of an organic solvent and water; after ultrasonic homogenization, the mixture is sealed and placed in an oven at 100-120 ℃ for 24-72 hours; naturally cooling to room temperature, washing, filtering and drying to obtain the Mg-MOFs material. Due to the unique structure, the Mg-MOFs material prepared by the invention has obvious fluorescent response to the metal iron ions, so that the Mg-MOFs material has potential application prospect in the aspect of metal iron ion detection.
Description
Technical Field
The invention relates to preparation and application of Mg-MOFs, in particular to a fluorescent probe for detecting metal ions.
Background
Ferric ions are widely present in organisms and play an important role in biochemical processes such as oxygen transport, hemoglobin formation, cellular metabolism, and DNA replication. The lack or excess of ferric ions can lead to physical diseases such as anemia, mental deterioration, arthritis, diabetes, cancer, and the like. Therefore, the method has great significance for the selective and sensitive detection of ferric ions relative to other metal ions. At present, the conventional methods for detecting metal ions mainly include Ion Mobility Spectrometry (IMS), high Performance Liquid Chromatography (HPLC), liquid chromatography-mass spectrometry (LCMS), and the like, although the operation processes of these detection methods are complicated and time-consuming. Therefore, there is a strong need for a rapid and efficient detection technique for this particular environmental contaminant.
In recent years, luminescent metal-organic frameworks (LMOFs) have attracted increasing attention for their application in sensing due to their diverse structures and topologies, outstanding optical properties and emission wavelengths. Currently, most LMOFs used for fluorescence detection are mostly based on transition or lanthanide metal ions, while LMOFs constructed from alkaline earth metal ions are rarely used for fluorescence detection, possibly because of the difficult and unpredictable coordination patterns in their crystallization process. Indeed, alkaline earth metal-organic framework materials have many unparalleled advantages, such as low density, bio-friendliness, non-toxicity, and low cost, among others; more importantly, when the alkaline earth metal-organic framework material is used as a fluorescent probe in some biological systems, secondary pollution caused by heavy metal ions can be effectively avoided. Therefore, the alkaline earth metal-organic framework material is a fluorescent material with very potential application to metal ion detection.
Disclosure of Invention
The invention aims to provide Mg-MOFs, a preparation method thereof and application thereof in metal ion detection, wherein the Mg-MOFs has high selectivity and high sensitivity on ferric ions and can be used as a fluorescent probe for monitoring the ferric ions.
The Mg-MOFs for detecting metal ions has a long-range ordered crystal structure and regular pores, and has a chemical formula of [ Mg (L) xG ], wherein L is N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine, tetra (4-carboxyphenyl) methane, 4',5' -bis (4-carboxyphenyl) -3',6' -dimethyl- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid, 4',5' -bis (4-carboxyphenyl) -3',6' -dihydroxy- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid, and x =1-4; g represents a solvent molecule coordinated with magnesium ions or in the pore channels of the crystal, and is N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide.
The preparation method of the Mg-MOFs for detecting the metal ions comprises the following steps: dissolving a metal magnesium salt and a quadrilateral symmetric ligand containing a tetracarboxylic acid group in water, ethanol and an organic solvent to obtain a mixed solution, putting the obtained solution into a glass bottle, heating to react for 24-72 hours at 100-120 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain Mg-MOFs.
Further, the metal magnesium salt is one or more of magnesium nitrate, magnesium sulfate, magnesium acetate or magnesium chloride.
Further, the tetragonally symmetrical ligands containing tetracarboxylic acid groups used are (a) N, N, N ', N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine, (b) tetrakis (4-carboxyphenyl) methane, (c) 4',5' -bis (4-carboxyphenyl) -3',6' -dimethyl- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid or (d) 4',5' -bis (4-carboxyphenyl) -3',6' -dihydroxy- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid, the formulae for the four being respectively as follows:
further, the organic solvent used is any one of N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide. And wherein the volume ratio of water, ethanol and organic solvent is 1.
Furthermore, the molar ratio of the metal magnesium ions in the metal magnesium salt to the organic ligand is 1-4.
The application of the Mg-MOFs for detecting the metal ions is characterized in that the Mg-MOFs is used as a fluorescent probe for detecting the ferric ions contained in a system.
Further, the detection method comprises the following steps: and ultrasonically dispersing the prepared Mg-MOFs in the solution, and then dropwise adding the solution to be detected in situ for fluorescence detection.
The invention has the following specific beneficial effects:
1. the preparation method of the Mg-MOFs is a solvothermal method, the synthesis method is simple in process and mild in condition, and the yield is up to 60% -65%. Dissolving the raw materials, and reacting at 100-120 deg.C to obtain the desired substance. No toxic and harmful substances and catalysts are contained in all the used raw materials, and no toxic and harmful substances are generated in the preparation process. The obtained porous material has a novel structure, a long-range ordered crystal structure and regular pore channels. The porous material belongs to an orthorhombic system, the space group is Imma, and the unit cell parameter is
a = β = γ =90 °, cell volume is
Z＝2，D c ＝0.851。
2. The Mg-MOFs are three-dimensional infinite network structures formed by connecting magnesium chains consisting of four magnesium ions and quadrilateral symmetrical ligands of deprotonated tetracarboxylic acid groups, each magnesium chain is connected with 8 quadrilateral symmetrical ligands of deprotonated tetracarboxylic acid groups, and each quadrilateral symmetrical ligand of deprotonated tetracarboxylic acid groups is connected with 4 magnesium chains.
3. Compared with other rare earth organic frameworks and transition metal organic frameworks, the Mg-MOFs prepared by the invention is a crystalline material with an ordered microporous structure, has a long-range ordered crystal structure and regular pore channels, and can obtain larger ion spacing through the design of the framework structure and the adjustment of the pore channel size, so that metal ions can enter the pore channels, and the detection efficiency is improved; and the coordination of the carboxyl oxygen of the ligand in the structure remains uncoordinated, thus providing additional benefits for selective sensing of trace metals.
4. The Mg-MOFs prepared by the method has excellent stability, and after the Mg-MOFs are soaked in the solution of iron ions for 12 hours, the powder X-ray spectrum can still well correspond to that before the Mg-MOFs are soaked, so that the Mg-MOFs have good stability, and the application of the Mg-MOFs in the field of fluorescence detection is ensured.
5. The Mg-MOFs prepared by the method has excellent luminescence property, and can realize specific recognition on ions immersed in the molten metal iron. When the material is used for detecting metallic iron ions, the material is not interfered by copper ions, zinc ions, potassium ions, lithium ions, barium ions, cadmium ions, nickel ions, sodium ions, chloride ions, calcium ions, lead ions and cobalt ions, and the material shows excellent selectivity on the detection of ferric ions.
6. Compared with other technologies for detecting ferric ions, the quenching type detection method for the magnesium-metal organic frameworks has the advantages that quenching type detection can be realized on the ferric ions by using the Mg-MOFs, the method is high in sensitivity, small in sampling amount and relatively cheaper in equipment, and can be conveniently applied to direct detection, marking and identification of biological systems, so that the quenching type detection method has important significance and prospect on metal ions.
Drawings
FIG. 1 is a crystal structure diagram of Mg-MOFs of the present invention;
FIG. 2 is a graph showing the relationship between the concentration of the Mg-MOFs and the ferric ion in example 1 of the present invention;
FIG. 3 shows the results of experiments on the selectivity of Mg-MOFs to other metal ion interferents in example 1 of the present invention;
FIG. 4 shows the stability results of Mg-MOFs in example 1 of the present invention after being soaked in ferric ion solution for 12 hours.
Detailed Description
Example 1:
Mg-MOFs (named ZJU-118) is synthesized by using magnesium nitrate and N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine through a solvothermal method, and the specific synthetic route is as follows:
0.06mmol of magnesium nitrate and 0.02mmol of N, N, N ', N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine were dissolved in water, ethanol and N, N-Dimethylformamide (DMF) in a volume ratio of water, ethanol and DMF of 1:1:4, putting the obtained mixed solution into a glass bottle, heating and reacting for 24 hours at 110 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain Mg (L) 1 ) 4 DMF in a yield of 65.1%
Mg (L) obtained by single crystal X-ray diffraction analysis 1 ) 4 DMF has a long-range ordered crystal structure and a regular three-dimensional pore structure with a pore size of about
The size of the pore channel is about C-axis
Under the excitation of 370nm, the peak value of the obtained emission spectrum is about 450nm, the intensity of the emission spectrum is reduced along with the increase of the content of ferric ions, the ratio of the intensity of the emission spectrum to the addition amount of the ferric ions has a good linear relation, and the following formula can be used for fitting
I＝0.852+0.253[AA]
Wherein [ AA ] is the addition amount of iron ions (taking M as a unit), and I is the luminous intensity. As can be seen from FIG. 2, the fluorescence intensity of the Mg-MOFs is reduced when the concentration of added iron ions is very low, which indicates that the detection lower limit of the Mg-MOFs for iron ions is low and can reach 6.75 μ M by testing.
In order to examine the selective response of the Mg-MOFs to iron ions, different interfering substances are added into the system, and the fluorescence change of the system is detected. Addition of other interferents: after copper ions, zinc ions, potassium ions, lithium ions, barium ions, cadmium ions, nickel ions, sodium ions, chloride ions, calcium ions, lead ions and cobalt ions are added, 200 muL and 400 muL of iron ion solutions with the same concentration are respectively added, the change of the fluorescence intensity emitted at 450nm is not influenced by other interferents, so that the specific identification of the iron ions is realized, and the result is shown in figure 3.
Newly synthesized Mg (L) 1 ) 4 The powder X-ray diffraction pattern of DMF can be well matched with the single crystal simulated X-ray diffraction pattern, and the material is proved to have a long-range ordered crystal structure and good crystallinity. Mixing Mg (L) 1 ) 4 After DMF is soaked in ferric ion solution for 12h, the powder X-ray diffraction pattern can still be well matched with the single crystal simulated X-ray diffraction pattern, which proves that DMF has better stability (figure 4), the structural integrity is still maintained in the process of detecting ferric ions, and the DMF can be recycled.
Example 2:
Mg-MOFs are synthesized by utilizing magnesium chloride and tetra (4-carboxyphenyl) methane through a solvothermal method, and the specific synthetic route is as follows:
0.08mmol of magnesium chloride and 0.02mmol of tetrakis (4-carboxyphenyl) methane were dissolved in water, ethanol and N, N-Dimethylacetamide (DMA) in a volume ratio of 1:1:2, putting the obtained mixed solution into a glass bottle, heating and reacting for 48 hours at 100 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain Mg (L) 2 ) 2 DMA, yield 62.4%
Mg (L) obtained by single crystal X-ray diffraction analysis 2 ) 2 DMA has a long-range ordered crystal structure and a regular three-dimensional pore structure, and the size of a pore channel is about
The size of the channel is about
Under the excitation of 370nm, the peak value of the obtained emission spectrum is about 450nm, the intensity of the emission spectrum is reduced along with the increase of the content of ferric ions, and the ratio of the intensity of the emission spectrum to the addition amount of the ferric ions has a good linear relationship.
In order to examine the selective response of the Mg-MOFs to iron ions, different interfering substances are added into the system, and the fluorescence change of the system is detected. Addition of other interferents: after copper ions, zinc ions, potassium ions, lithium ions, barium ions, cadmium ions, nickel ions, sodium ions, chloride ions, calcium ions, lead ions and cobalt ions, respectively adding 200 mu L and 400 mu L of iron ion solutions with the same concentration in sequence, wherein the change of the fluorescence intensity emitted at 450nm is not influenced by other interferents, thereby realizing the specific identification of the iron ions.
Newly synthesized Mg (L) 2 ) 2 The powder X-ray diffraction pattern of the DMA can be well matched with the single crystal simulated X-ray diffraction pattern of the DMA, and the material is proved to have a long-range ordered crystal structure and good crystallinity.
Mixing Mg (L) 2 ) 2 After the DMA is soaked in the ferric ion solution for 12 hours, the powder X-ray diffraction pattern can still be well matched with the single crystal simulated X-ray diffraction pattern, so that the DMA has better stability, the integrity of the structure is still maintained in the process of detecting the ferric ions, and the DMA can be recycled.
Example 3:
magnesium sulfate and 4',5' -bis (4-carboxyphenyl) -3',6' -dimethyl- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid are utilized to synthesize Mg-MOFs by a solvothermal method, and the specific synthetic route is as follows:
0.02mmol of magnesium sulfate and0.02mmol of 4',5' -bis (4-carboxyphenyl) -3',6' -dimethyl- [1,1':2', 1' -terphenyl]-4,4 "-dicarboxylic acid was dissolved in water, ethanol and N, N-Diethylformamide (DEF) in a volume ratio of water, ethanol and DEF of 1:1:3, putting the obtained mixed solution into a glass bottle, heating and reacting for 72 hours at 120 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain MgL 3 DEF, yield 60.3%
MgL is obtained by single crystal X-ray diffraction analysis 3 DEF has a long-range ordered crystal structure and a regular three-dimensional pore structure with a pore channel size of about the order of the A-axis
The size of the pore channel is about C-axis
Under the excitation of 370nm, the peak value of the obtained emission spectrum is about 450nm, the intensity of the emission spectrum is reduced along with the increase of the content of ferric ions, and the ratio of the intensity of the emission spectrum to the addition amount of the ferric ions has a good linear relationship.
In order to examine the selective response of the Mg-MOFs to iron ions, different interfering substances are added into the system, and the fluorescence change of the system is detected. Addition of other interferents: after copper ions, zinc ions, potassium ions, lithium ions, barium ions, cadmium ions, nickel ions, sodium ions, chloride ions, calcium ions, lead ions and cobalt ions, respectively adding 200 mu L and 400 mu L of iron ion solutions with the same concentration in sequence, wherein the change of the fluorescence intensity emitted at 450nm is not influenced by other interferents, thereby realizing the specific identification of the iron ions.
Newly synthesized MgL 3 The powder X-ray diffraction pattern of DEF can be well matched with the single crystal simulated X-ray diffraction pattern of DEF, and the material is proved to have a long-range ordered crystal structure and good crystallinity.
MgL is added 3 After DEF is soaked in ferric ion solution for 12 hours, the powder X-ray diffraction pattern can still be well matched with the single crystal simulated X-ray diffraction pattern, and the demonstration that the powder X-ray diffraction pattern is well matched with the single crystal simulated X-ray diffraction pattern proves that the powder X-ray diffraction patternHas better stability, still keeps the integrity of the structure in the process of detecting iron ions, and can realize recycling.
Example 4:
Mg-MOFs are synthesized by a solvothermal method by utilizing magnesium acetate and 4',5' -bis (4-carboxyphenyl) -3',6' -dihydroxy- [1,1':2',1 '-terphenyl ] -4, 4' -dicarboxylic acid, and the specific synthetic route is as follows:
0.04mmol of magnesium sulfate and 0.02mmol of 4',5' -bis (4-carboxyphenyl) -3',6' -dihydroxy- [1,1':2', 1' -terphenyl were added]-4,4 "-dicarboxylic acid was dissolved in water, ethanol and N, N-Dimethylacetamide (DMF) in a volume ratio of 1:1:5, putting the obtained mixed solution into a glass bottle, heating and reacting for 72 hours at 115 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain Mg (L) 4 ) 3 DEF, yield 63.2%
Mg (L) obtained by single crystal X-ray diffraction analysis 4 ) 3 DMF has a long-range ordered crystal structure and a regular three-dimensional pore structure with pore channel dimensions of about
The size of the pore channel is about C-axis
Under the excitation of 370nm, the peak value of the obtained emission spectrum is about 450nm, the intensity of the emission spectrum is reduced along with the increase of the content of ferric ions, and the ratio of the intensity of the emission spectrum to the addition amount of the ferric ions has a good linear relationship.
In order to examine the selective response of the Mg-MOFs to iron ions, different interfering substances are added into the system, and the fluorescence change of the system is detected. Addition of other interferents: after copper ions, zinc ions, potassium ions, lithium ions, barium ions, cadmium ions, nickel ions, sodium ions, chloride ions, calcium ions, lead ions and cobalt ions are added, 200 mu L and 400 mu L of iron ion solutions with the same concentration are respectively added, and the change of the fluorescence intensity emitted at 450nm is not influenced by other interferents, so that the specific identification of the iron ions is realized.
Newly synthesized Mg (L) 4 ) 3 The powder X-ray diffraction pattern of DMF can be well matched with the single crystal simulated X-ray diffraction pattern, and the material is proved to have a long-range ordered crystal structure and good crystallinity.
Mixing Mg (L) 4 ) 3 After DMF is soaked in ferric ion solution for 12h, the powder X-ray diffraction pattern can still be well matched with the single crystal simulated X-ray diffraction pattern, so that the stability is better, the structural integrity is still maintained in the process of detecting ferric ions, and the repeated utilization can be realized.
Claims (8)
1. Mg-MOFs, characterized in that: the Mg-MOFs have a long-range ordered crystal structure and regular channels, and the chemical formula is [ Mg (L) xG ], wherein L is N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine, and the structural formula is as follows:
x =1-4; g represents a solvent molecule coordinated with magnesium ions or in the pore channels of the crystal, and is N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide; the lower limit of detection of the Mg-MOFs on iron ions reaches 6.75 mu M.
2. Process for the preparation of Mg-MOFs according to claim 1, characterized in that it comprises the following steps:
dissolving a metal magnesium salt and a quadrilateral symmetric ligand containing a tetracarboxylic acid group in a mixed solvent of water, ethanol and an organic solvent to obtain a mixed solution, putting the mixed solution into a container, heating to react for 24-72 hours at 100-120 ℃, naturally cooling to room temperature, centrifugally separating, washing, filtering and drying to obtain Mg-MOFs; the tetragon symmetric ligand containing tetracarboxylic acid group is N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine.
3. The process of claim 2, wherein the magnesium metal salt is one or more of magnesium nitrate, magnesium sulfate, magnesium acetate, and magnesium chloride.
4. The process for preparing Mg-MOFs according to claim 2, wherein said organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
5. The preparation method of Mg-MOFs according to claim 2, wherein the volume ratio of water, ethanol and organic solvent in said mixed solvent is 1.
6. The process of claim 2, wherein the molar ratio of magnesium metal ions to tetragonally symmetric ligands in the magnesium metal salt is 1-4.
7. The use of Mg-MOFs according to claim 1 for the detection of ferric ions, characterized in that they are used as fluorescent probes for the detection of ferric ions contained in the system.
8. The use of Mg-MOFs in the detection of iron ions according to claim 7, wherein the specific method for detecting trivalent iron ions is as follows: and (3) dropwise adding the solution to be detected into the solution containing Mg-MOFs in situ for fluorescence detection.
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