CN111205468B - Dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and preparation method thereof - Google Patents
Dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and a preparation method thereof, wherein the chemical formula is [ M (L)x(G)y]·(R)nWherein M is a metal ion, L is a flexible symmetrical organic ligand containing a carboxylic acid group, G is a solvent molecule, and R represents a dye molecule in a pore channel. The material is prepared by a solvothermal method, can emit visible light of 500-700 nm under the action of exciting light, is sensitive to temperature (100-200 ℃) in maximum luminous intensity and strongest emission wavelength, and has a linear relation with temperature, so that double-parameter sensing of the material can be realized. The quantum efficiency and the thermal stability of the loaded dye are obviously improved. The sensor is expected to be practically applied to temperature sensing.
Description
Technical Field
The invention relates to a dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and a preparation method thereof.
Background
Temperature is a very important parameter in the fields of daily life, industrial production and scientific research, and how to realize accurate temperature sensing is a promising research topic. At present, commonly used thermometers, particularly thermocouple thermometers, are not suitable for environments with severe conditions, strong electromagnetic fields and high resolution requirements. In addition, a range of excellent-performance, fluorescent-color-diverse dyes are used for temperature sensing, which is one of the most interesting temperature measurement methods because of its non-invasiveness, short acquisition time, ability to operate in strong electromagnetic fields, high spatial resolution and temperature resolution. Most studies on fluorescence thermometer temperature sensing are based on the change in intensity of fluorescence, fluorescence lifetime, the strongest emission wavelength, and the ratio of fluorescence intensities. The strongest emission wavelength and intensity of the dye changes with increasing temperature, which can be applied simultaneously to temperature sensing. Compared with a single parameter method, the multi-parameter thermometer simultaneously uses various optical signals to sense the temperature, and further has higher precision.
The dye has excellent fluorescence property in a dilute solution, the quantum efficiency is high, and the fluorescence property of the powder is obviously reduced due to concentration quenching. However, due to the volatility of the solution and the difficulty of handling relative to the powder sample, it cannot be used as a detector at high temperatures. Therefore, it is possible to improve thermal stability and quantum efficiency of the dye by assembling the dye and the porous material into a composite material. Host-guest materials formed of dyes and host materials such as porous silicon, zeolite, and layered inorganic salts have been used in many fields such as fluorescent materials, lasers, and nonlinear optics. However, inorganic porous materials have many crystal defects, and the shape and size of the internal pores thereof cannot be designed. Metal-organic frameworks (MOFs) are a new crystalline material that self-assembles from metal ions and organic ligands. Due to the special porosity and structural diversity, the dye can be reasonably filled in the pores for functional application. MOFs are a promising temperature sensing platform because different guest molecules can be encapsulated and produce fluorescent emission that varies with temperature. To date, some MOFs-based fluorescence thermometers have been reported, but most have been prepared based on a mixed lanthanide MOFs strategy. Due to the emission characteristics of rare earth metals, the emission peak position hardly moves with the temperature change, which limits the temperature measurement parameters to fluorescence intensity.
Disclosure of Invention
The invention aims to provide a dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing and a preparation method thereof.
The dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing has a long-range ordered crystal structure and regular pore channels, and the chemical formula of the material is [ M (L) ]x(G)y]·(R)nWherein M is a metal ion comprising Zn, Cu, Cr, Co, Cd, or Zr; l is a flexible symmetrical organic ligand containing carboxylic acid groups and is 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy]Methyl radical]-1, 3-propanediol]Bis (oxygen)]-bis-2-naphthoic acid, x ═ 0.5 to 1; g represents a solvent molecule coordinated with the metal ion or in the pore channel of the crystal, and is water, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide; y is 0-60, R represents cation pyridine hemicyanine dye molecules in pore channels and comprises 4- [2- [4- (diethylamino) phenyl]Vinyl radical]-1-methylpyridine, 4- (4- (diethylamino) styryl) -1-ethylpyridine, 4- [2- [4- (dimethylamino) phenyl]Vinyl radical]-1-ethylpyridine, 4- [2- [4- (diphenylamino) phenyl]Vinyl radical]-1-methylpyridine, 1-methyl-4- [2- [4- (methylphenylamino) phenyl]Vinyl radical]-pyridine, n ═ 1 to 50.
The preparation method of the dye loaded metal-organic framework material for multi-parameter fluorescence temperature sensing comprises the following steps:
adding metal nitrate and an organic ligand into deionized water and an organic solvent together to obtain a mixed solution, putting the obtained solution into a liner of a reaction kettle, heating and reacting for 1-3 days at 100-120 ℃, centrifuging and washing to obtain a metal organic framework material; and soaking the obtained metal-organic framework material in an organic solution of cationic pyridine hemicyanine dye, and placing the metal-organic framework material in an oven at the temperature of 40-60 ℃ for heat preservation for 2-7 days to obtain the dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing.
In the present invention, the metal nitrate is zinc nitrate, copper nitrate, chromium nitrate, cobalt nitrate, cadmium nitrate, or zirconium nitrate.
In the present invention, the flexible symmetric organic ligand containing carboxylic acid groups is 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy ] methyl ] -1, 3-propanediol ] bis (oxy) ] -bis-2-naphthoic acid, having the following structural formula:
in the invention, the cationic pyridine hemicyanine dye has the following structural formula: (a)4- [2- [4- (diethylamino) phenyl ] vinyl ] -1-methylpyridine; (b)4- (4- (diethylamino) styryl) -1-ethylpyridine; (c)4- [2- [4- (dimethylamino) phenyl ] vinyl ] -1-ethylpyridine; (d)4- [2- [4- (diphenylamino) phenyl ] ethenyl ] -1-methylpyridine; or (e) 1-methyl-4- [2- [4- (methylphenylamino) phenyl ] vinyl ] -pyridine. The structural formula is as follows:
in the present invention, the organic solvent used is any one of N, N-dimethylformamide, N-dimethylacetamide, or N, N-diethylformamide.
In the invention, the molar ratio of metal ions to organic ligands is 1-3: 1.
in the invention, the volume ratio of the organic solvent to the deionized water is 2-5: 1.
in the present invention, in the ion exchange process, the solvent of the organic solution of the dye may be any one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
The detection method of the dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing can be used for emitting visible light of 500-700 nm under the excitation of ultraviolet and visible light, the maximum luminous intensity and the wavelength corresponding to the strongest emission are sensitive to temperature and have a linear relation with the temperature, and double-parameter sensing of the material can be realized.
The invention has the following specific beneficial effects:
1. the metal-organic framework material loaded by the dye and used for multi-parameter fluorescence temperature sensing is a novel metal-organic framework material, and the material width of MOFs is expanded.
2. The method is used for the dye-loaded metal-organic framework material of the multi-parameter fluorescence temperature sensing, and the visible light of 500-700 nm is emitted under the excitation of ultraviolet and visible light. The maximum luminous intensity is sensitive to temperature and has a linear relation with the temperature, and the detection sensitivity can reach 0.68-5.12% DEG C through calculation-1The above; the wavelength corresponding to the strongest emission also changes with temperature and exhibits a linear relationship, with a wavelength shift of about 0.06nm or less per degree celsius. Thus, two-parameter sensing of temperature can be achieved.
3. Compared with inorganic compounds, complexes or organic molecules, the metal-organic framework material is a crystalline material with ordered micropores, and has a long-range ordered crystal structure and regular pore channels. The dye molecules can be uniformly dispersed in the frame, so that the fluorescent quenching caused by molecular agglomeration is avoided, and the luminous efficiency is improved.
4. The dye is very easy to dissolve and poor in thermal stability, so that the dye is difficult to apply to biological tissues, and the thermal stability of the dye can be improved (by about 100 ℃) after the dye is loaded by a metal-organic framework material, so that the application range of the dye is expanded.
Drawings
FIG. 1 is (a) a metal coordination of the novel dye-loaded metal-organic framework material of the present invention; (b) coordinating a ligand; (c) a schematic diagram of a crystal structure;
FIG. 2 is the thermal stability of dye-loaded metal-organic framework materials useful for multiparameter fluorescence temperature sensing according to the present invention;
FIG. 3 shows the variation of the emission spectrum of the dye (4- [2- [4- (diethylamino) phenyl ] vinyl ] -1-methylpyridine) loaded metal-organic framework material (a) with temperature for multiparameter fluorescence temperature sensing according to the present invention; (b) maximum emission intensity (620 nm) versus temperature; (c) the variation of sensitivity with temperature; (d) the relationship of the strongest emission wavelength to temperature;
FIG. 4 is a graph of emission spectra of a dye (4- [2- [4- (dimethylamino) phenyl ] vinyl ] -1-ethylpyridine) loaded metal-organic framework material (a) useful for multiparameter fluorescence temperature sensing according to the present invention as a function of temperature; (b) maximum emission intensity (620 nm) versus temperature; (c) the variation of sensitivity with temperature; (d) the strongest emission wavelength is temperature dependent.
Detailed Description
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Example 1:
the metal-organic framework material is synthesized by a solvothermal method by utilizing zinc nitrate and 6,6' - [ [2, 2-bis [ (6-carboxyl-2-naphthyl) oxy ] methyl ] -1, 3-propanediol ] bis (oxy) ] -bis-2-naphthoic acid, and the specific synthetic route is as follows:
0.1mmol of zinc nitrate and 0.1mmol of 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy ] are added]Methyl radical]-1, 3-propanediol]Bis (oxygen)]-bis-2-naphthoic acid dissolved in 1.4mL DMF and 0.6mL H2O mixed solvent, then the solution is packaged in a 5mL glass bottle and placed in a 110 ℃ oven for reaction for 48 h. Cooling to room temperature, washing with DMF for 3 times to obtain colorless acicular metallo-organicFramework material Zn3(L)2·(DMF)5.5·(H2O)7. 100mg of the crystals are placed in 0.1mol L-1Cationic dye 4- [2- [4- (diethylamino) phenyl]Vinyl radical]-1-methylpyridine in DMF. Putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 7 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with DMF (dimethyl formamide) for 3 times, washing the glass bottle with ethanol for 3 times, and putting the glass bottle into the oven for drying at 60 ℃ to obtain the novel metal-organic framework material loaded with the dye, wherein the dye content is 3.4 wt%.
Under 467nm laser excitation, the peak value of the obtained emission spectrum is located at 620nm, the emission spectrum intensity is reduced along with the temperature rise, the emission spectrum intensity has good linear relation with the temperature, and the following formula can be used for fitting:
I＝-30.54T+7160.81
where I is the maximum luminescence intensity. When the temperature is low, the fluorescence intensity is strong, the fluorescence intensity is obviously reduced along with the temperature rise, and the detection sensitivity of the material can reach 0.68-5.12 percent DEG C through calculation-1(ii) a In addition, the strongest emission wavelength is also red-shifted with increasing temperature, and the corresponding peak position and temperature form the following linear fitting relation:
λmax＝0.0593T+615.3
wherein λmaxIs the wavelength corresponding to the strongest emission. The corresponding wavelength shift per degree celsius was calculated to be about 0.06nm (fig. 3).
The thermal stability of the material was characterized and after loading into the pores of the metal-organic framework material, the thermal stability of the dye was improved by about 100 ℃, thereby expanding the application range of the dye (fig. 2).
After the dye is loaded, the luminous quantum efficiency is obviously improved, and is increased from 2.73% of a pure dye to 30.4% of the pure dye in the composite material, so that the sensitivity of material temperature detection is improved to a certain extent.
Example 2:
the metal-organic framework material is synthesized by a solvothermal method by utilizing zinc nitrate and 6,6' - [ [2, 2-bis [ (6-carboxyl-2-naphthyl) oxy ] methyl ] -1, 3-propanediol ] bis (oxy) ] -bis-2-naphthoic acid, and the specific synthetic route is as follows:
0.1mmol of zinc nitrate and 0.1mmol of 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy ] are added]Methyl radical]-1, 3-propanediol]Bis (oxygen)]-bis-2-naphthoic acid dissolved in 1.4mL DMF and 0.6mL H2O mixed solvent, then the solution is packaged in a 5mL glass bottle and placed in a 110 ℃ oven for reaction for 48 h. Cooling to room temperature, washing with DMF for 3 times to obtain colorless needle-like metal-organic framework material Zn3(L)2·(DMF)5.5·(H2O)7. 100mg of the crystals are placed in 0.01mol L-1Cationic dye 4- [2- [4- (dimethylamino) phenyl]Vinyl radical]-1-ethylpyridine in DMF. Putting the mixture into a 15mL glass bottle, putting the glass bottle into a 60 ℃ oven for reaction for 7 days, taking out the glass bottle, filtering to remove the dye solution, washing the glass bottle with DMF (dimethyl formamide) for 3 times, washing the glass bottle with ethanol for 3 times, and putting the glass bottle into the oven for drying at 60 ℃ to obtain the novel metal-organic framework material loaded with the dye, wherein the dye content is 0.060 wt%.
Under the excitation of 466nm laser, the peak value of the obtained emission spectrum is located at 620nm, the emission spectrum intensity is reduced along with the temperature increase, the emission spectrum intensity has a good linear relation with the temperature, and the following formula can be used for fitting:
I＝-47.57T+10337.84
where I is the maximum luminescence intensity. When the temperature is low, the fluorescence intensity is strong and obviously reduced along with the temperature rise; in addition, the strongest emission wavelength is also red-shifted with increasing temperature, and the corresponding peak position and temperature form the following linear fitting relation:
λmax＝0.08334T+605.51
wherein λmaxIs the wavelength corresponding to the strongest emission (fig. 4). The thermal stability of the material is characterized, and after the material is loaded into the pores of the metal-organic framework material, the thermal stability of the dye is obviously improved, so that the application range of the dye is expanded.
After the dye is loaded, the luminous quantum efficiency is obviously improved, and is increased from 1.19% of a pure dye to 47.97% of the pure dye in the composite material, so that the sensitivity of material temperature detection is improved to a certain extent.
Claims (8)
1. A dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing, characterized in that the material has a long-range ordered crystal structure and regular channels, and the chemical formula is [ M (L) ]x(G)y]·(R)nWherein M is a metal ion Zn; l is a flexible symmetrical organic ligand containing carboxylic acid groups and is 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy]Methyl radical]-1, 3-propanediol]Bis (oxygen)]-bis-2-naphthoic acid, x ═ 0.5 to 1; g represents a solvent molecule coordinated with the metal ion or in the pore channel of the crystal, and is water, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide; y is 0-60, R represents cation pyridine hemicyanine dye molecules in pore channels and is 4- [2- [4- (diethylamino) phenyl]Vinyl radical]-1-methylpyridine, 4- (4- (diethylamino) styryl) -1-ethylpyridine, 4- [2- [4- (dimethylamino) phenyl]Vinyl radical]-1-ethylpyridine, 4- [2- [4- (diphenylamino) phenyl]Vinyl radical]-1-methylpyridine, or 1-methyl-4- [2- [4- (methylphenylamino) phenyl]Vinyl radical]-pyridine, n ═ 1 to 50; the flexible symmetrical organic ligand 6,6' - [ [2, 2-bis [ (6-carboxy-2-naphthyl) oxy ] containing carboxylic acid group]Methyl radical]-1, 3-propanediol]Bis (oxygen)]-bis-2-naphthoic acid, of formula:
2. the method for preparing the dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing according to claim 1, comprising the steps of:
adding metal nitrate and a flexible symmetrical organic ligand containing carboxylic acid groups into deionized water and an organic solvent together to obtain a mixed solution, putting the obtained solution into an inner container of a reaction kettle, heating and reacting for 1-3 days at 100-120 ℃, centrifuging and washing to obtain a metal organic framework material; and soaking the obtained metal-organic framework material in an organic solution of cationic pyridine hemicyanine dye, and placing the metal-organic framework material in an oven at the temperature of 40-60 ℃ for heat preservation for 2-7 days to obtain the dye-loaded metal-organic framework material for multi-parameter fluorescence temperature sensing.
3. The method for preparing the dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing according to claim 2, wherein the metal nitrate is zinc nitrate.
4. The method for preparing the dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing according to claim 2, wherein the organic solution of cationic pyridine hemicyanine dye is: (a)4- [2- [4- (diethylamino) phenyl ] vinyl ] -1-methylpyridine; (b)4- (4- (diethylamino) styryl) -1-ethylpyridine; (c)4- [2- [4- (dimethylamino) phenyl ] vinyl ] -1-ethylpyridine; (d)4- [2- [4- (diphenylamino) phenyl ] ethenyl ] -1-methylpyridine; or (e) 1-methyl-4- [2- [4- (methylphenylamino) phenyl ] vinyl ] -pyridine; the structural formula is as follows:
5. the method for preparing the dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing according to claim 2, wherein the organic solvent in the mixed solution is any one of N, N-dimethylformamide, N-dimethylacetamide, or N, N-diethylformamide; and the volume ratio of the organic solvent to the deionized water is 2-5: 1.
6. the preparation method of the dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing according to claim 2, wherein the metal nitrate contains metal ions and organic ligands in a molar ratio of 1-3: 1.
7. use of a dye-loaded metal-organic framework material for multiparameter fluorescence temperature sensing based on luminescence intensity and wavelength corresponding to the strongest emission, as defined in claim 1 or as prepared by the method according to any one of claims 2 to 6.
8. The use of the dye-loaded metal-organic framework material according to claim 7, wherein the material emits 500-700 nm visible light under the action of excitation light, and the maximum luminous intensity and the maximum emission wavelength are both temperature-sensitive and have a linear relationship with temperature, so that the double-parameter sensing of the material can be realized.
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