CN107236538B - Noble metal nanoparticle-metal organic framework fluorescent probe molecule and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a metal nanoparticle-metal organic framework fluorescent probe molecule for selectively detecting glutathione, and a preparation method and application thereof. Compared with the prior art, the fluorescent probe molecule has high combination and complexation capacity with glutathione, and the fluorescence is obviously enhanced after complexation. The result of a cytotoxicity experiment shows that the probe has almost no toxicity to cells, has good biocompatibility and cell permeability, is simple, convenient, rapid and visual in method application, low in toxicity, high in sensitivity and simple in method, and provides an efficient and feasible method for detecting the glutathione.
Description
Technical Field
The invention relates to a noble metal nanoparticle-metal organic framework fluorescent probe molecule, a preparation method and application thereof, and belongs to the technical field of biological analysis and detection.
Background
Biological sulfhydryl molecules such as cysteine, cystine and glutathione play important roles in human physiological processes. Wherein, the glutathione is a sulfhydryl compound with the most abundant intracellular content (0.5-10 mmol/L), is tripeptide consisting of glutamic acid, glycine and cysteine, can maintain the redox balance in cells, and has the detoxification effect on heavy metals such as hydrogen peroxide, mercury, lead and the like. The concentration of cysteine in the cells is 50-200 mu mol/L, and the concentration is far lower than that of glutathione. Research shows that various diseases are related to the abnormality of glutathione content in cells, such as cancer, cardiovascular diseases, AIDS and the like. Therefore, quantitative detection of intracellular glutathione is of great significance for diagnosis and treatment of diseases. At present, methods for detecting GSH mainly include liquid chromatography, capillary electrophoresis, surface enhanced raman spectroscopy, electrochemical methods, fluorescence methods, colorimetric methods and the like, wherein expensive instruments are required for the methods such as the liquid chromatography, the capillary electrophoresis, the surface enhanced raman spectroscopy and the like. Compared with other methods, the fluorescence analysis method has the advantages of simple and convenient operation, high sensitivity, visual observation and the like, and can convert the molecular recognition process on the microcosmic scale into the change of a fluorescence signal on the macroscopical scale, thereby realizing the detection of the target.
The metal organic framework is a coordination polymer which is rapidly developed in recent decades and generally has a three-dimensional pore structure, namely, a metal ion is taken as a central atom, and one or more organic ligands are taken as supports to form a spatial three-dimensional extension, so that the metal organic framework becomes another novel important porous material besides zeolite molecular sieves, macroporous resins and carbon materials and has wide application in catalysis, energy storage and separation. The metal central ions can be used as nodes in the framework to provide a central center of the framework, and can also expand a network structure to form infinite branches in the central center, so that the unique physicochemical properties (such as porosity, chirality and the like) of the metal organic framework are provided. The specific surface area of the material is far larger than that of zeolite materials with similar channels, and the framework structure can still be maintained without being damaged after residual solvent small molecules in the channels are removed. Therefore, the metal organic framework has many special properties and needs to be developed.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects and problems of the existing glutathione detection method, the invention discovers and provides a fluorescent probe with good selectivity to carry out rapid, simple and convenient quantitative detection on glutathione; and provides the application of the fluorescent probe in detecting glutathione.
The technical scheme is as follows: the invention discloses a noble metal nanoparticle-metal organic framework fluorescent probe molecule for selectively detecting glutathione, which is formed by taking a metal organic framework as a matrix and loading noble metal nanoparticles and can selectively identify glutathione.
Preferably, the metal organic framework is NH 2 -MIL-53 or NH 2 -UiO-66.
Preferably, the noble metal nanoparticles are gold nanoparticles, silver nanoparticles, or platinum nanoparticles.
Preferably, the noble metal nanoparticles have a size of 3 to 15 nm.
Preferably, the fluorescent probe molecule has a fluorescence excitation wavelength of 343nm or 488nm and an emission wavelength of 435nm or 517nm, and does not change according to the change of the excitation wavelength.
The invention also provides a preparation method of the fluorescent probe molecule, which is characterized by comprising the following steps:
Firstly, preparing a metal organic framework by utilizing a matrix compound and 2-amino terephthalic acid through high-pressure reaction, then dispersing the metal organic framework in methanol, adding a noble metal compound solution, and finally adding a sodium borohydride aqueous solution for reaction to obtain the fluorescent probe molecule.
The matrix compound is zirconium tetrachloride, titanium tetrachloride or aluminum chloride; the noble metal compound is chloroauric acid, silver nitrate or chloroplatinic acid.
The invention finally provides the application of the fluorescent probe molecule in selectively recognizing glutathione and/or detecting the concentration of glutathione.
the invention can accurately adjust the linear range of the fluorescent probe for detecting the glutathione by adjusting the type of the metal organic framework and the size of the loaded noble metal nano-particles, thereby laying a good foundation for detecting the glutathione in the cells. Further, we also find that the noble metal nanoparticle-metal organic framework fluorescent probe has good biocompatibility, selectivity and lower detection limit.
The noble metal nanoparticle-metal organic framework fluorescent probe molecule has the following advantages:
Firstly, the noble metal-metal organic framework fluorescent probe for selectively detecting glutathione has good molecular dispersibility and stable fluorescence, and can selectively identify glutathione well.
Secondly, the noble metal-metal organic framework fluorescent probe molecule for selectively detecting glutathione can obtain different excitation and emission wavelengths by adjusting the types of metal centers (such as aluminum and zirconium) and ligands.
Thirdly, the noble metal-metal organic framework fluorescent probe molecule for selectively detecting the glutathione has good selectivity on the glutathione, and the interference of amino acids such as cysteine, arginine, glutamic acid, glycine, tyrosine, phenylalanine and the like on the detection is very small.
fourthly, the invention selectively detects the noble metal-metal organic framework fluorescent probe molecule of the glutathione, and the detection of the glutathione can reach nanomole per upgrade.
Fifthly, the noble metal-metal organic framework fluorescent probe molecule for selectively detecting glutathione has good biocompatibility and low cytotoxicity, and can be used for detecting the concentration change of glutathione in cells.
Sixth, the invention selectively detects the noble metal-metal organic framework fluorescent probe molecule of glutathione, through adjusting the kind of gold particle and the particle size of metal organic framework, can effectively adjust its linear range of detection, and lay the foundation for the quantitative detection of glutathione in cells.
The metal-metal organic framework fluorescent probe molecule provided by the invention has the following specific characteristics:
The noble metal-metal organic framework fluorescent probe molecule has selectivity on glutathione, and only glutathione can obviously enhance the fluorescence intensity of the noble metal-metal organic framework fluorescent probe molecule; the linear range of detection can be accurately adjusted by changing the size of the noble metal nano-particles and the type of the metal organic framework. By connecting with a fluorophore, the noble metal-metal organic framework probe molecule has different excitation and emission wavelengths and is photostable. Other amino acids such as cysteine, arginine, glutamic acid, glycine, tyrosine, phenylalanine and the like have little interference on detection; the detection of the fluorescent probe molecules on the glutathione can reach nanomolar level.
The technical effects are as follows: compared with the prior art, the fluorescent probe molecule has high combination and complexation capacity with glutathione, and the fluorescence is obviously enhanced after complexation. The result of a cytotoxicity experiment shows that the probe has almost no toxicity to cells, has good biocompatibility and cell permeability, is simple, convenient, rapid and visual in method application, low in toxicity, high in sensitivity and simple in method, and provides an efficient and feasible method for detecting the glutathione.
Description of the drawings:
FIG. 1 is the X-ray diffraction, scanning electron microscope, Fourier transform infrared and fluorescence spectrum of the gold nanoparticle-metal organic framework fluorescent probe molecule of the invention.
FIG. 2 is a graph of the ultraviolet-visible diffuse reflection, Fourier transform infrared and fluorescence spectra of the gold nanoparticle-metal organic framework fluorescent probe molecule of the invention after being connected with fluorescein isothiocyanate.
FIG. 3 is the relationship between the fluorescence intensity of the gold nanoparticle-metal organic framework fluorescent probe molecule and the concentration of glutathione. The abscissa is the concentration of glutathione and the ordinate is the fluorescence intensity. The sizes of the noble metal nano particles loaded in the A, B and C are respectively 15, 6 and 3 nm. The top to bottom lines correspond to the fluorescence of 6% (squares), 3% (circles), 2% (upper triangles), 1% (inverted triangles) gold loaded probes at the concentrations used of 50. mu.g/mL, 150. mu.g/mL, 250. mu.g/mL, respectively.
FIG. 4 shows fluorescence intensity of the gold nanoparticle-metal organic framework fluorescent probe molecule of the present invention after reacting with various amino acids. The spectrum result obviously shows that only glutathione obviously enhances the fluorescence of the noble metal-metal organic framework probe molecule, and other amino acids such as cysteine, arginine, glutamic acid, glycine, tyrosine, phenylalanine and the like have little interference on detection.
FIG. 5 shows the toxicity of the gold nanoparticle-metal organic framework fluorescent probe molecule of the present invention to cells. The abscissa is the concentration of the added noble metal-metal organic framework probe molecule and the ordinate is the cell viability.
FIG. 6 shows the application of the gold nanoparticle-metal organic framework fluorescent probe molecule in intracellular glutathione detection. FIG. 6A is Hela cells in bright field; FIG. 6B is an image of intracellular fluorescence after addition of fluorescent probe molecules, and the cells exhibit strong fluorescence.
Detailed Description
The invention will be better understood from the following examples. And those skilled in the art will readily appreciate that the specific test results described in the examples are merely illustrative of the invention and should not be construed to limit the invention described in the claims.
Example 1
Preparing gold nanoparticle-metal organic framework fluorescent probe molecules:
56.25 mg of zirconium tetrachloride and 161.25 mg of 2-amino terephthalic acid were dissolved in 15 ml of N, N-dimethylformamide, and 1.125 ml of glacial acetic acid was added thereto, and the mixture was placed in a 25 ml autoclave and reacted at 120 ℃ for 8 hours. The product was washed 3 times with 20 ml of N, N-dimethylformamide, then soaked for 24 hours with 20 ml of methanol and dried to give a yellow powder. 0.4 mg of the above powder was dispersed ultrasonically in 1.87 ml of methanol, 15. mu.l of a 200 mmol/l chloroauric acid solution were added, and after 6 hours, 30. mu.l of a 100 mmol/l aqueous sodium borohydride solution were added to the suspension. After half an hour of reaction, centrifugation was carried out, the supernatant was discarded, and washing with methanol was carried out three times.
the obtained fluorescent probe molecule is formed by taking NH 2 -UiO-66 as a metal organic framework and loading gold nanoparticles.
Example 2
The structure, the morphology and the fluorescence characteristic of the gold nanoparticle-metal organic framework fluorescent probe molecule. The powder of the sample is placed on a sample stage of an X-ray powder diffractometer to keep the surface smooth, and is scanned at 5 to 60 degrees. And (3) the sample is added to the surface of a smooth and clean silicon wafer in a dropwise manner after being subjected to ultrasonic treatment, and the appearance of the sample is observed under a scanning electron microscope. Noble metal-metal organic framework powder and potassium bromide powder were mixed and then sufficiently ground, and pressed into a sheet under a pressure of 25MPa to test the infrared spectrum thereof. The gold nanoparticle-metal organic framework powder was ultrasonically dispersed in ultrapure water or a phosphoric acid buffer solution (pH7.4,7mM) for 30 minutes to prepare a mother liquor having a concentration of 10 mg/mL. A certain amount of the mother liquor was diluted with a corresponding solvent such as ultrapure water or phosphoric acid buffer solution to a concentration of 50. mu.g/mL for the experiment. The diluted suspension was added to a clean 4mL quartz cuvette, setting the excitation wavelength at 343 nm. As shown in FIG. 1, the metal-organic framework showed a diffraction peak of UiO-66, and the particle size was about 90 nm. The excitation wavelength is 343nm and the emission wavelength is 435 nm.
Example 3
The structure and the optical performance of the isothiocyanate fluorescein connected gold nanoparticle-metal organic framework fluorescent probe molecule. The gold nanoparticle-metal organic framework powder connected with fluorescein isothiocyanate and potassium bromide powder are mixed and then fully ground, and the mixture is pressed into a sheet shape under the pressure of 25MPa to test the infrared spectrum of the mixture. Isothiocyanate fluorescein-linked noble metal-metal organic framework powders were pressed into barium sulfate substrates to test their uv-visible diffuse reflectance spectra. The isothiocyanate fluorescein-linked gold nanoparticle-metal organic framework was sonicated for 30 minutes to be dispersed in ultrapure water or a phosphoric acid buffer solution (pH7.4,7mM) to prepare a mother liquor having a concentration of 10 mg/mL. A certain amount of the mother liquor was diluted with a corresponding solvent such as ultrapure water or phosphoric acid buffer solution to a concentration of 50. mu.g/mL for the experiment. The diluted suspension was added to a clean 4mL quartz cuvette and excitation wavelengths were set at 343nm and 488 nm. The experimental results are shown in FIG. 2, from which it can be seen that fluorescein isothiocyanate was successfully attached to the metal-organic framework and maintained the excitation wavelength of 488nm and the emission wavelength of 517 nm.
Example 4
And the gold nanoparticle-metal organic framework fluorescent probe molecule responds to the fluorescence of glutathione.
the fluorescent response to glutathione was evaluated using gold nanoparticle-metal organic framework fluorescent probe molecules. A certain amount of the prepared mother liquor is diluted by phosphoric acid buffer solution to the concentration of 50, 150 or 250 mu g/mL used in the experiment. Add to a clean 4mL quartz cuvette and measure with the corresponding excitation wavelength. 200mM glutathione solution is dripped into the suspension by a micro-syringe to be uniformly mixed, and fluorescence spectra under different glutathione concentrations are detected. The fluorescence responses of different gold loads (6%, 3%, 2%, 1%) and different probe dosages were tested, and the experimental results are shown in fig. 3, from which it can be seen that the fluorescence intensity is continuously enhanced with the increase of glutathione concentration, and different probes have different linear ranges.
Example 5
The selectivity to glutathione was evaluated using gold nanoparticle-metal organic framework fluorescent probe molecules.
A certain amount of the prepared mother liquor is diluted to the concentration of 50 mug/mL used in the experiment by using a corresponding solvent such as ultrapure water or phosphoric acid buffer solution. A50. mu.g/mL concentration of gold nanoparticle-metal organic framework probe molecule suspension was added to a clean 4mL quartz cuvette and measured with either 343 or 488nm excitation wavelength. Firstly, detecting the fluorescence spectrum of gold nanoparticle-metal organic framework probe molecules, then respectively adding interfering amino acids with the concentration of 10mM such as cysteine, arginine, glutamic acid, glycine, tyrosine and phenylalanine by using a micro-injector, uniformly mixing, and detecting the fluorescence spectrum in the presence of various interfering amino acids. The fluorescence spectrum after glutathione addition was measured in the same manner. The results of the experiment are shown in FIG. 4. The emission peak position of all spectra is 435nm or 517nm, and for the fluorescence intensity of the ordinate, the fluorescence intensity when the interfering amino acid is added is not obviously enhanced compared with the fluorescence intensity of the gold nanoparticle-metal organic framework fluorescent probe. After the glutathione is added, the fluorescence intensity is obviously enhanced. As can be seen from the figure, the gold nanoparticle-metal organic framework probe molecule has obvious selective recognition capability on glutathione.
Example 6
Cytotoxicity test
L02, Hela, U87 and HepG2 cells in logarithmic growth phase are digested by trypsin to prepare single cell suspension with the concentration of 1 × 10 5/mL, the single cell suspension is inoculated in a 96-well plate, after 24h of culture, gold nanoparticle-metal organic framework probe molecules (10, 20, 30, 40, 50, 100, 200 μ g/mL) with different concentrations are processed, then the single cell suspension is continuously cultured in an incubator with the temperature of 37 ℃ and the humidity of 5% and the humidity of 95% for 24h, five repeated wells are arranged at each experimental point, the survival rate of the cells is detected by MTT colorimetry, 20 μ L of MTT solution with 5mg/mL of MTT solution is added into each well after the culture time is over and the culture is continuously cultured for 4h, then supernatant is aspirated, 150 μ L of dimethyl sulfoxide (DMSO) is added into each well, the reaction is stopped, the plate shaker is moved, the MTT reduction product is completely dissolved by horizontal shaking for 10min, then the absorbance (blank value) of each well is measured by an enzyme-linked immunosorbent assay detector, the control result is adjusted to zero, the average OD value of each well is expressed by the average OD 5, and the survival rate of each group is expressed by the standard cell survival rate:
Cell survival (%) ═ ODExperimental values-ODBlank value]492nm/[ODControl value-ODBlank value]×100％
The experimental result is shown in fig. 5, and the result shows that the survival rate of the cell is still above 90% when the porphyrin concentration reaches 200 μ M, which indicates that the gold nanoparticle-metal organic framework fluorescent probe has good molecular biocompatibility and very low toxicity to the cell.
Example 7
And detecting glutathione in the cells by using the gold nanoparticle-metal organic framework fluorescent probe molecules.
Hela human cervical cancer cell strain is placed in a DMEM (streptomycin 100 mu g/mL penicillin 100IU/mL) culture medium containing 10% fetal calf serum, cultured in an incubator containing 5% CO 2 at 37 ℃ and 95% humidity, before imaging, the cells are placed in a culture dish for culturing, after the cells are attached to the wall, gold nanoparticle-metal organic framework probe molecules with a certain concentration are added, after culturing for 0.5h with the final concentration of 50 mu g/mL, the cells are gently washed by sterile phosphate buffer solution, and fluorescence confocal microscope imaging is carried out.
The experimental result is shown in fig. 6, and the result shows that the Hela cells marked by the gold nanoparticle-metal organic framework fluorescent probe molecules can see that the fluorescence in the cytoplasm is obviously enhanced (fig. 6B). The gold nanoparticle-metal organic framework probe molecule can detect the change of the concentration of the glutathione in the cell through the confocal fluorescence intensity.
The results from the above specific examples show that: the gold nanoparticle-metal organic framework probe molecule has good biocompatibility and chemical light stability, and can be used for selectively identifying glutathione and detecting the change of the concentration of glutathione in cells. The method for detecting by using fluorescence is simple, convenient, easy, rapid and visual, has low toxicity, high sensitivity and simple method, and provides an efficient and feasible method for detecting the glutathione.
Example 8
Preparing a metal organic framework by utilizing matrix compounds of titanium tetrachloride and 2-amino terephthalic acid through high-pressure reaction, dispersing the metal organic framework in methanol, adding a noble metal compound of chloroauric acid solution, and finally adding a sodium borohydride aqueous solution for reaction, wherein other conditions are the same as those in example 1, and the fluorescent probe molecule is formed by taking UiO-66 as the metal organic framework and loading gold nanoparticles.
The detection results of the method are basically the same as the performances of the gold nanoparticle-metal organic framework probe molecule through the detection methods of the embodiments 2 to 7.
Example 9
Preparing a metal organic framework by utilizing a matrix compound of zirconium tetrachloride and 2-amino terephthalic acid through high-pressure reaction, dispersing the metal organic framework in methanol, adding a noble metal compound of silver nitrate solution, and finally adding a sodium borohydride aqueous solution for reaction, wherein other conditions are the same as those in example 1, and finally the obtained fluorescent probe molecule is formed by taking NH 2 -UiO-66 as the metal organic framework and loading silver nanoparticles.
The detection results of the method are basically the same as the performances of the gold nanoparticle-metal organic framework probe molecule through the detection methods of the embodiments 2 to 7.
Example 9
The preparation method comprises the steps of preparing a metal organic framework by utilizing matrix compounds of zirconium tetrachloride and 2-amino terephthalic acid through high-pressure reaction, dispersing the metal organic framework in methanol, adding a noble metal compound of chloroplatinic acid solution, and finally adding a sodium borohydride aqueous solution for reaction, wherein other conditions are the same as those in example 1, and finally the obtained fluorescent probe molecule is formed by taking NH 2 -UiO-66 as the metal organic framework and loading platinum nanoparticles.
The detection results of the method are basically the same as the performances of the gold nanoparticle-metal organic framework probe molecule through the detection methods of the embodiments 2 to 7.
Claims (3)
1. A preparation method of a noble metal nanoparticle-metal organic framework fluorescent probe molecule for selectively detecting glutathione is characterized by comprising the following steps:
Firstly, preparing a metal organic framework by utilizing a matrix compound and 2-amino terephthalic acid through high-pressure reaction, then dispersing the metal organic framework in methanol, adding a noble metal compound solution, and finally adding a sodium borohydride aqueous solution for reaction to obtain the fluorescent probe molecule;
The fluorescent probe molecule is formed by taking a metal organic framework as a matrix and loading noble metal nanoparticles, the metal organic framework can selectively identify glutathione, the metal organic framework is NH 2 -MIL-53 or NH 2 -UiO-66, and the noble metal nanoparticles are gold nanoparticles, silver nanoparticles or platinum nanoparticles.
2. The method for preparing a fluorescent probe molecule according to claim 1, wherein the base compound is zirconium tetrachloride, titanium tetrachloride or aluminum chloride; the noble metal compound is chloroauric acid, silver nitrate or chloroplatinic acid.
3. The method of claim 1, wherein the fluorescent probe molecule has a fluorescence excitation wavelength of 343nm or 488nm and an emission wavelength of 435nm or 517nm, and does not change according to the change of the excitation wavelength.
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| CN110964330B (en) * | 2019-11-15 | 2022-07-05 | 东莞理工学院 | UiO-66(NH2) Preparation process of silver sulfide composite material |
| CN111876147B (en) * | 2020-08-03 | 2023-04-21 | 青岛大学 | Preparation method of silver nanoparticle/sulfur quantum dot double-doped MOF (metal oxide fiber) compound ratio fluorescent exosome aptamer probe |
| CN114149801B (en) * | 2020-09-07 | 2023-12-08 | 中国科学院大连化学物理研究所 | Metal organic framework fluorescent probe, preparation method and application thereof |
| CN112946038B (en) * | 2021-01-25 | 2022-03-25 | 华南理工大学 | Gold nanoparticle/MIL-53 (Fe) composite material, cysteine sensor, preparation method and application |
| CN113030079B (en) * | 2021-04-23 | 2022-05-20 | 中南民族大学 | Method for detecting pesticide carbaryl based on nanogold etching |
| CN113466205B (en) * | 2021-06-23 | 2022-08-09 | 上海交通大学 | Preparation method of surface enhanced Raman sensor based on metal organic framework structure |
| CN113621687A (en) * | 2021-08-24 | 2021-11-09 | 青岛科技大学 | Method for detecting miRNA-21 |
| CN113995854B (en) * | 2021-11-09 | 2023-04-14 | 中山大学 | Glutathione-sensitive nano drug delivery system and preparation method and application thereof |
| CN115594856B (en) * | 2021-11-30 | 2023-06-23 | 青岛大学 | Preparation method and application of ratio fluorescent probe |
| CN115290612A (en) * | 2022-01-06 | 2022-11-04 | 深圳大学 | Hydrogen nanoprobe and hydrogen detection method |
| CN116818730B (en) * | 2023-06-20 | 2024-07-19 | 江南大学 | Fluorescence-SERS dual-mode sensor and preparation method and application thereof |
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