CN115746320B - Synthesis method and application of lanthanide series metal organic framework material Eu-MOF - Google Patents
Synthesis method and application of lanthanide series metal organic framework material Eu-MOF Download PDFInfo
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Abstract
The invention discloses a novel synthesis method and application of lanthanide series metal organic framework material Eu-MOF, wherein the synthesis method comprises the following steps of preparing lanthanide series metal salt Eu (NO) 3 ) 3 ·6H 2 O、H 2 DCHB and phen in a molar ratio of 1-1.5): 1.5: (5-10) metering for use and adding H 2 O is dissolved, then potassium hydroxide solution is added to adjust the pH value of the system, the mixture is added into a high-temperature reaction kettle and stirred uniformly, the reaction is carried out for 72 hours at 160-185 ℃, the temperature is reduced to room temperature, the synthesized lanthanide metal organic framework material Eu-MOF is filtered and dried at room temperature, and colorless transparent blocky crystals are obtained. The lanthanide series metal organic framework material Eu-MOF can detect the pH value in the solution through the change of fluorescence color, has high specific selectivity on vanilla mandelic acid, and can rapidly and sensitively detect the vanilla mandelic acid in human urine.
Description
Technical field:
the invention relates to a lanthanide metal organic framework material Eu-MO, in particular to a novel synthesis method and application of the lanthanide metal organic framework material Eu-MOF.
The background technology is as follows:
pheochromocytoma (pheeo) is a rare neuroendocrine tumor, and clinical symptoms are not specific, so that the Pheochromocytoma is difficult to accurately locate in the early diagnosis process of diseases, and organs such as heart can be seriously damaged until the Pheochromocytoma is developed to the later stage, thereby endangering life. The PHEO patients secrete a great deal of catecholamines, and the final metabolite of the catecholamines is vanilloid (Vanillymandelic Acid, VMA) which can be metabolized out of the body along with urine, and the VMA content in the urine is usually used as an index for assisting in diagnosing pheochromocytoma. Therefore, the detection of VMA content in human urine is of great importance for early diagnosis and treatment of pheochromocytoma. At present, the detection of the vanilla mandelic acid in the blood and urine of a patient mainly depends on the detection of the vanilla mandelic acid content in the blood and urine of the patient, but the false negative rate of the blood detection is higher, the accuracy is lower than that of the urine detection, the urine detection needs to collect 24h urine of the patient, the whole collection process needs to be carried out in the hospital, the time consumption is long, and the detection is troublesome. The special vanilla mandelic acid detection kit is arranged in the scientific research laboratory, but needs experienced scientific research personnel to operate, the detection time can be shortened to 2 hours, but the kit has high price, can only be used in the experimental category, and cannot be widely applied to daily disease detection. In addition, there is also high performance liquid chromatography, which is the detection method with highest accuracy at present, but the equipment operation is very complex, the price is more expensive, and the method cannot be applied and popularized for disease detection.
Metal Organic Frameworks (MOFs) as a unique new porous crystalline material can create new topologies by altering the combination of different metal ions with multifunctional bridging ligands, which makes them excellent in structural adjustability and functional diversity, attracting the eye of many fields. Lanthanide metal organic frameworks, which are a unique branch in MOFs, are synthesized by coordination of lanthanide metals with organic ligands, and their unique electronic configuration and "antenna effect" contribute to their excellent photoluminescent properties (including narrow characteristic emission, large stokes shift, macroscopic color, long luminescence lifetime, and high quantum yield), and so have been widely used today for sensing of metal ions, volatile compounds, explosive substances, and the like. Compared with the high cost and complex operation of the conventional detection means (electrochemical method, high performance liquid chromatography, gas chromatography, inductively coupled plasma emission spectroscopy and the like), the lanthanide metal organic frame sensor has the advantages of low cost, simple manufacture, high sensitivity and high response speed, and obvious color change can make the detection result clear at a glance, so that the detection method is a very good means for simplifying the detection flow, but currently, the Eu-MOF of the known lanthanide metal organic frame material has not been disclosed as a technology for detecting vanilla mandelic acid, and the Eu-MOF prepared from the known lanthanide metal organic frame material can not be used for detecting vanilla mandelic acid.
The invention comprises the following steps:
the invention aims to solve the technical problems of providing a novel synthesis method and application of a lanthanide series metal organic framework material Eu-MOF, and the Eu-MOF synthesized by the method has good fluorescence performance, can detect the pH value in a solution through the change of fluorescence color, has high specific selectivity on vanilla mandelic acid, and can rapidly and sensitively detect the vanilla mandelic acid in human urine.
The technical proposal of the invention is to provide a method for synthesizing lanthanide series metal organic framework material Eu-MOF, which comprises the steps of, preparing lanthanide series metal salt Eu (NO) 3 ) 3 ·6H 2 O、H 2 DCHB and phen in molar ratio (1-1.5): 1.5: (5-10) metering for use and adding H 2 O is dissolved, then potassium hydroxide solution is added to adjust the pH value of the system, the mixture is added into a high-temperature reaction kettle and stirred uniformly, the reaction is carried out for 72 hours at 160-185 ℃, the temperature is reduced to room temperature, the synthesized lanthanide metal organic framework material Eu-MOF is filtered and dried at room temperature, and colorless transparent bulk crystals are obtained, and the crystals are the lanthanide metal organic framework material Eu-MOF. The structural chemical general formula of the lanthanide metal organic framework material Eu-MOF is [ Eu (DCHB) 1.5 phen] n Wherein n > 0 and is a positive integer; the crystal system is triclinic, and the space group isP -1 The unit cell parameters areα= 69.5652 ° (11), β= 85.3184 ° (14), γ= 62.3573 ° (13). During the actual synthesis, the lanthanide metal salt may be used in a relative excess, typically (1-1.5): 1.5, most preferably 1:1.5; and H is 2 The stoichiometric ratio of DCHB to phen is typically 1.5: (5-10), most preferably 1.5:10. the reaction temperature is selected within the range of 160-185 ℃, and the crystal quality of the product is obviously improved along with the increase of the reaction temperature, but the luminous performance and purity are greatly reduced, so that the most preferable temperature of the luminous performance is 160 ℃. The cooling speed is controlled to be 3-6 ℃/h, and the most preferable cooling speed is 3 ℃/h.
Preferably, the organic ligand H 2 The structural formula of DCHB is as follows
The structural formula of the organic ligand phen is as follows
Preferably, eu (NO 3 ) 3 ·6H 2 O(0.05mmol,22.3mg)、H 2 DCHB (0.075 mmol,32.1 mg), phen (0.5 mmol,100 mg) and H 2 O (8 ml) was mixed, and potassium hydroxide solution (0.05 ml,1mol L) was added -1 ) Regulating pH value of the system, adding the mixture into a high-temperature reaction kettle, stirring uniformly, reacting at 160-185 ℃ for 72 hours, and cooling to room temperature, wherein the composition is in water, and is required to be filtered and dried at room temperature to obtain colorless transparent blocky crystals.
Furthermore, the invention also provides an application of the lanthanide metal organic framework material Eu-MOF prepared by the synthesis method of the lanthanide metal organic framework material Eu-MOF, and the lanthanide metal organic framework material Eu-MOF detects the pH value of the solution through the change of fluorescence color, so that the Ph value of the solution is detected. The method for detecting the pH value of the aqueous solution comprises the steps of adding a certain amount of materials into the aqueous solutions with different pH values, uniformly dispersing by ultrasonic waves to form stable suspension, and measuring the fluorescence spectrum of the suspension by irradiating the suspension under an ultraviolet lamp with excitation wavelength of 365nm to find the macroscopic color change of the suspension.
Furthermore, the invention also provides an application of the lanthanide metal organic framework material Eu-MOF prepared by the synthesis method of the lanthanide metal organic framework material Eu-MOF, and the lanthanide metal organic framework material Eu-MOF is used for preparing a product for detecting and identifying vanillin in human urine.
The specific detection method comprises the following steps of dispersing a certain amount of lanthanide series metal organic framework material Eu-MOF into a urine sample to be detected, performing ultrasonic dispersion to form stable suspension, then irradiating under an ultraviolet lamp with excitation wavelength of 365nm, and irradiating under an ultraviolet lamp with excitation wavelength of 365nm to find the macroscopic color change of the suspension. Different levels of vanilla mandelic acid in the sample can quench Eu-MOF luminescence to different degrees, and can be easily observed and verified by measuring fluorescence spectra
Compared with the prior art, the invention has the following advantages: the Eu-MOF synthesized by the method has good fluorescence performance, can detect the pH value in the solution through the change of fluorescence color, has high specific selectivity on the vanilla mandelic acid, can rapidly and sensitively detect the vanilla mandelic acid in human urine, and is a few metal-organic framework materials capable of detecting the vanilla mandelic acid in urine at present;
meanwhile, the Eu-MOF is used for detecting vanilla mandelic acid in urine, which has the following advantages: (1) the Eu-MOF has low preparation cost and low price; (2) The operation is simple, the result is visual, the fluorescent change phenomenon can be observed only by arranging Eu-MOF in a urine sample and uniformly dispersing the Eu-MOF and then irradiating the Eu-MOF by an ultraviolet lamp, and the detection result is easy to understand. (3) The response speed is high, the whole reaction process can be completed within 300 seconds, and the detection speed and the detection efficiency are far higher than those of the VMA kit; (4) The specificity is good, the anti-interference performance is good, the detection result is inaccurate due to diet problems possibly occurring in the conventional detection method, but Eu-MOF has high specificity and specificity to VMA, and the result is inaccurate due to the interference of common chemical substances in urine.
Description of the drawings:
FIG. 1 is a diagram showing the coordination environment of Eu (III) as an organic framework material of lanthanide series metal in the present invention.
FIG. 2 is a three-dimensional extended structural view of the Eu-MOF of the present invention having one-dimensional rectangular channels.
FIG. 3 shows an organic ligand H for Eu-MOF synthesis according to the present invention 2 Structure of DCHB and phen.
FIG. 4 is a space-filling diagram of the Eu-MOF of the present invention.
FIG. 5 is a solid state spectrum of the Eu-MOF of the present invention.
FIG. 6 is a solid-state spectrum of an organic ligand for Eu-MOF synthesis according to the present invention.
FIG. 7 is a thermogravimetric analysis of the Eu-MOF of the present invention.
FIG. 8 is a PXRD pattern for the Eu-MOF of the present invention.
FIG. 9 is a photograph of the Eu-MOF of the present invention under ultraviolet excitation at 365nm in aqueous solutions of different pH values.
FIG. 10 is a graph showing fluorescence spectra of Eu-MOF of the present invention in aqueous solutions of different pH values.
FIG. 11 is a graph showing fluorescence spectra of Eu-MOF of the present invention under different components of interfering substances.
FIG. 12 is a graph showing fluorescence spectra of Eu-MOF of the present invention in different urine chemistries and photographs under ultraviolet excitation at 365 nm.
FIG. 13 is a graph showing fluorescence spectra of Eu-MOF of the present invention in simulated urine environments with different vanilla mandelic acid concentrations.
The specific embodiment is as follows:
the invention is further described with reference to the drawings and detailed description which follow:
a method for synthesizing a novel lanthanide series metal organic framework material Eu-MOF comprises the following steps: eu (NO) 3 ) 3 ·6H 2 O(0.05mmol,22.3mg)、H 2 DCHB (0.075 mmol,32.1 mg), phen (0.5 mmol,100 mg) and H 2 O (8 ml) was mixed, and potassium hydroxide solution (0.05 ml,1mol L) was added -1 ) Regulating the pH value of the system, adding the mixture into a high-temperature reaction kettle, uniformly stirring, reacting for 72 hours at 160-185 ℃, keeping the cooling speed of 3-5 ℃/h, cooling the high-temperature reaction kettle to room temperature, filtering the composition, and drying at room temperature to obtain colorless transparent blocky crystals, wherein the crystals are lanthanide series metal organic framework material Eu-MOF. The pH value of the system refers to the pH value of a mixed reaction solution in a hydrothermal kettle of a synthesis container, different pH values have influence on the single crystal formation and size of Eu-MOF, and the subsequent adding amount of the potassium hydroxide solution can be adjusted according to the observed morphology of the Eu-MOF product.
The structural chemical general formula of the Eu-MOF is [ Eu (DCHB) 1.5 phen] n Wherein n > 0 and is a positive integer; the crystal system is triclinic, and the space group is P -1 The unit cell parameters are α= 69.5652 ° (11), β= 85.3184 ° (14), γ= 62.3573 ° (13), the three-dimensional structure is shown in fig. 2, and the structure of the organic ligand used is shown in fig. 3.
The novel Eu-MOF material can detect the pH value in the solution and the presence of vanilla mandelic acid in human urine by observing the change of fluorescence color under ultraviolet excitation.
Example 1
(1) Detecting the pH value of the aqueous solution:
grinding Eu-MOF materials into powder, adding 3mg of each powder into aqueous solutions with different pH values, forming stable suspension after ultrasonic dispersion is uniform, and measuring the liquid fluorescence spectrum of each solution. The pH range selected is 2-13, measured at every 0.5 difference. As shown in fig. 10, the fluorescence spectrum changes in aqueous solutions at different pH values. The main emission peak of Eu-MOF at 612nm, within pH range 4.50-9.91, the emission peak at 612nm appears to fluctuate to different degrees, but the fluorescence intensity is basically normal and not affected too much, but the emission peak at 612nm starts to appear to have a significant fluorescence quenching between pH values of 2.03-4.50 and 9.91-12.99, increasing in proportion to the acidity and alkalinity value of the solution. FIG. 11 is a photograph of a portion of the solution with UV lamp excitation, from left to right, at pH values of 2.03, 2.51, 3.03, 3.53, 4.07, 4.50, 5.51, 6.86, 7.20, 8.77, 9.52, 10.46, 10.99, 11.52, 12.01, 12.45, 12.99, respectively, and it can be seen that the fluorescence colors of the solutions at the two sides are substantially consistent with each other, the fluorescence gradually decreases with increasing pH value until complete quenching, and the quenching rule is consistent with the fluorescence spectrum result.
Example 2
(1) Research on anti-interference performance of Eu-MOF material
Setting two groups of samples, namely a control group and an experimental group, wherein the control group is a chemical substance solution and a blank water solution in common urine, so that the mass concentration of each group is the same; the experimental group is to add vanilla mandelic acid with a certain concentration based on the control group and measure the fluorescence spectra of the two groups. As shown in FIG. 11, the fluorescence intensity of the emission peak of Eu-MOF at 612nm is obviously compared, the fluorescence intensity of the control group at 612nm is consistent with the trend shown in FIG. 12, and the experimental group added with vanillin completely shows a large-scale fluorescence quenching, which indicates that the common chemical substances in urine cannot interfere with the detection of Eu-MOF on vanillin, and the Eu-MOF has good anti-interference performance and selectivity.
Example 3
(1) Study of response of Eu-MOF Material to Vanilla mandelic acid in human urine Environment
Selecting common chemical components (urea, uric acid, creatinine, creatine, glucose, potassium chloride, ammonium chloride and sodium sulfate) and VMA in human urine, and preparing into a liquid with mass concentration of 10 -2 M, grinding Eu-MOF materials into powder, adding 3mg of each Eu-MOF material into corresponding solution, performing ultrasonic dispersion to prepare uniformly dispersed suspension, and measuring the fluorescence spectrum of each solution. As shown in FIG. 12, the fluorescence intensity of Eu-MOF is not excessively affected by common chemicals in urine, although there areThe fluorescence quenching was varied to different degrees, but the variation was small, and complete fluorescence quenching was only seen in vanilla mandelic acid solution, demonstrating that the common chemicals present in human urine did not interfere with the detection of vanilla mandelic acid by Eu-MOF. It can also be found from photographs of different aqueous solution samples under irradiation of ultraviolet lamp that only vanilla mandelic acid solution has no obvious fluorescence under ultraviolet excitation, which is consistent with the result of fluorescence spectrum measurement.
The milled Eu-MOF material was weighed and added to a simulated urine sample, and the mixture was sonicated to form a uniform suspension, the fluorescence spectrum of the original sample was measured, and then vanilla mandelic acid was gradually added to the original sample and the fluorescence spectrum after each addition was measured, as shown in FIG. 13. Eu-MOF has two obvious emission peaks at 590nm and 612nm, and along with the increase of the vanillin concentration in a sample, the fluorescence intensity of the two emission peaks starts to decrease until the fluorescence quenching efficiency reaches 85% when the vanillin concentration reaches about 0.017808M, and the fluorescence intensity of the vanillin concentration is not changed any more after the concentration of the vanillin is increased. Fitting calculation is carried out by using a Stern-Volmer equation according to the change relation between the concentration of vanilla mandelic acid in a sample and the fluorescence intensity of the sample, so that a linear relation between the two can be obtained: i0/i=269.955 [ c]-0.032,R 2 ＝0.987,K SV The concentration value of vanillic acid in the solution can be obtained by substituting the measured fluorescence intensity of the emission peak at 612nm into a formula (269.955 mol/L).
The Eu-MOF material has good selectivity and anti-interference performance, can detect the pH value of the solution and whether vanilla mandelic acid exists in a urine sample through simple fluorescence color change, and provides a new thought for an early diagnosis method of pheochromocytoma.
The foregoing is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the claims. All equivalent structures or equivalent flow path changes made by the specification and the drawings of the invention are included in the protection scope of the invention.
Claims (8)
1. Lanthanide metal hasThe synthesis method of the Eu-MOF (metal oxide semiconductor field effect transistor) frame material is characterized by comprising the following steps of: the synthesis method comprises the steps of adding lanthanide series metal salt Eu (NO 3 ) 3 ·6H 2 O、H 2 DCHB and phen in molar ratio (1-1.5): 1.5: (5-10) metering for use and adding H 2 O is dissolved, then potassium hydroxide solution is added to adjust the pH value of the system, the mixture is added into a high-temperature reaction kettle and stirred uniformly, the reaction is carried out for 72 hours at 160-185 ℃, the temperature is reduced to room temperature, and the filtered matter is dried at room temperature to obtain lanthanide metal organic framework material Eu-MOF;
organic ligand H 2 The structural formula of DCHB is as follows
The structural formula of the organic ligand phen is as follows
2. The method for synthesizing lanthanide-series metal-organic framework material Eu-MOF according to claim 1, characterized in that: the structural chemical general formula of the lanthanide metal organic framework material Eu-MOF is [ Eu (DCHB) 1.5 phen] n Wherein n > 0 and is a positive integer; the crystal system is triclinic, and the space group is P -1 The unit cell parameters areα＝69.5652°(11)，β＝85.3184°(14)，γ＝62.3573°(13)。
3. The method for synthesizing lanthanide-series metal-organic framework material Eu-MOF according to claim 1, characterized in that: the cooling speed after the reaction is finished is 3-5 ℃/h.
4. The method for synthesizing lanthanide-series metal-organic framework material Eu-MOF according to claim 1, characterized in that: will be0.05mmol,22.3mg Eu (NO) 3 ) 3 ·6H 2 O, 0.075mmol,32.1mg H 2 DCHB, 0.5mmol,100mg phen and 8m H 2 O was mixed and 0.05ml,1mol L was added -1 The pH value of the system is regulated by potassium hydroxide solution, the mixture is added into a high-temperature reaction kettle and stirred uniformly, the reaction is carried out for 72 hours at 160-185 ℃, the temperature is reduced to room temperature, and the filtered matter is dried at room temperature to obtain colorless transparent blocky crystals.
5. Use of a lanthanide metal organic framework material Eu-MOF prepared by a synthesis method of the lanthanide metal organic framework material Eu-MOF according to any of the claims 1-4, characterized in that: the lanthanide metal organic framework material Eu-MOF detects the pH value of the solution through the change of fluorescence color.
6. The use according to claim 5, characterized in that: dispersing a specific amount of lanthanide series metal organic framework material Eu-MOF in aqueous solutions with different pH values, performing ultrasonic dispersion to form stable suspension, irradiating under an ultraviolet lamp with excitation wavelength of 365nm, checking the color change of the suspension, and measuring fluorescence spectrum.
7. Use of a lanthanide metal organic framework material Eu-MOF prepared by a synthesis method of the lanthanide metal organic framework material Eu-MOF according to any of the claims 1-4, characterized in that: the lanthanide series metal organic framework material Eu-MOF is used for preparing a product for detecting and identifying vanillin in human urine.
8. The use according to claim 7, characterized in that: the detection method comprises dispersing Eu-MOF of lanthanide series metal organic frame material into urine sample to be detected, performing ultrasonic dispersion to form stable suspension, irradiating with ultraviolet lamp with excitation wavelength of 365nm, checking color change of suspension, and measuring fluorescence spectrum.
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| [Eu_2(BA)_6(bipy)_2]的晶体结构和荧光光谱;张颖, 金林培, 吕少哲;无机化学学报(03);全文 * |
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