CN111999276B - Method for preparing luminous europium-based metal organic framework probe and application thereof - Google Patents
Method for preparing luminous europium-based metal organic framework probe and application thereof Download PDFInfo
- Publication number
- CN111999276B CN111999276B CN202010874260.7A CN202010874260A CN111999276B CN 111999276 B CN111999276 B CN 111999276B CN 202010874260 A CN202010874260 A CN 202010874260A CN 111999276 B CN111999276 B CN 111999276B
- Authority
- CN
- China
- Prior art keywords
- alpha
- europium
- probe
- based metal
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a method for preparing a luminescent europium-based metal organic framework probe and application thereof. And preparing the nano probe Eu-alpha-CD with high crystallinity at room temperature by using alpha-cyclodextrin as an organic ligand and bovine serum albumin as a mineralizer. Compared with the prior art, the method is simple, overcomes the limitation that lanthanide series metal organic framework materials need hydrothermal synthesis, and overcomes the defects of harsh material synthesis conditions, long time consumption and the like; bovine serum albumin is used as a mineralizer, so that the crystal phase of probe Eu-alpha-CD is improved, and the biocompatibility of Eu-alpha-CD is enhanced; the fluorescence intensity of the prepared luminescent Eu-alpha-CD probe is reduced along with the increase of the concentration of the dopamine, which shows that the probe specifically and specifically responds to the dopamine, and the phenomenon has good repeatability and can be used for efficiently and quickly detecting the content of the dopamine; the nitrocellulose membrane loaded with the probe Eu-alpha-CD is used for detecting dopamine, so that visual qualitative detection under an ultraviolet lamp can be realized, and possibility is provided for field test.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials and analytical chemistry, and particularly relates to a method for preparing a luminous europium-based metal organic framework probe Eu-alpha-CD and a method for detecting dopamine by using the luminous europium-based metal organic framework probe Eu-alpha-CD.
Background
Dopamine is an important neurotransmitter in hypothalamic dopamine and pituitary glands, is widely distributed in the central nervous system, the midbrain and body fluids, and has important significance in maintaining functional activities of the central nervous system, the cardiovascular system and the hormonal system. Abnormal dopamine levels are closely related to diseases such as Parkinson's disease and Alzheimer's disease. Lack of dopamine in the endocrine of the human body can cause loss of muscle control capability, and in severe cases, Parkinson's disease is caused. Therefore, the early monitoring of diseases such as the Parkinson and the like is of great significance by measuring the content of the dopamine in body fluid. At present, the detection of the dopamine content in body fluid becomes an essential biochemical detection index in the early detection of Parkinson patients.
In recent years, many methods for detecting dopamine have been developed, and the commonly used detection methods include spectrophotometry, chemiluminescence, liquid chromatography, electrochemical methods and the like, but all of the detection methods have certain disadvantages, such as long detection time, complex detection process, pretreatment of some samples, expensive instruments, poor interference resistance and the like. Therefore, it is very important to develop a simple, fast and easy-to-operate analysis and test method.
Disclosure of Invention
Technical problem to be solved
In order to solve at least one problem, the invention provides a method for preparing a luminescent europium-based metal organic framework probe Eu-alpha-CD and a method for detecting dopamine by using the luminescent europium-based metal organic framework probe Eu-alpha-CD.
(II) technical scheme
The invention adopts the following specific technical scheme:
in one embodiment of the present invention, the present invention provides a method for preparing a luminescent europium-based metal organic framework probe, which synthesizes the luminescent europium-based metal organic framework probe Eu- α -CD formed by europium salt and α -cyclodextrin at room temperature, and comprises:
dissolving solid europium salt powder and solid alpha-cyclodextrin powder in a solvent respectively, and stirring until the solid europium salt powder and the solid alpha-cyclodextrin powder are fully dissolved to obtain a europium salt solution and an alpha-cyclodextrin solution with volume ratios of 1: 1 respectively;
adding bovine serum albumin into the alpha-cyclodextrin solution, stirring until the bovine serum albumin is fully dissolved, then adding a europium salt solution, fully stirring and mixing, and dropwise adding ammonia water to adjust the pH value to 9 to obtain a suspension solution;
and continuously stirring the suspension solution at normal temperature, centrifugally washing the suspension solution by using ultrapure water, and drying a centrifugal product at the temperature of between 30 and 40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD.
In one embodiment of the present invention, in the step of separately dissolving the solid powder of europium salt and solid powder of α -cyclodextrin in the solvent, the europium salt is the europium salt Eu (NO) nitrate3)·6H2And O, wherein the solvent is ultrapure water.
In one embodiment of the present invention, in the step of adding bovine serum albumin to the alpha-cyclodextrin solution, the bovine serum albumin has a mass volume concentration of 0.5mg mL-1。
In one embodiment of the present invention, in the step of continuously stirring the suspension solution at room temperature and centrifugally washing with ultrapure water, the suspension solution is continuously stirred at room temperature for 1 to 2 hours and centrifugally washed with ultrapure water for 2 to 3 times.
In an embodiment of the present invention, the present invention further provides a method for detecting dopamine by using the luminescent europium-based metal organic framework probe, comprising:
dispersing the luminescent europium-based metal organic framework probe Eu-alpha-CD in ultrapure water, and measuring the emission spectrum of the luminescent europium-based metal organic framework probe Eu-alpha-CD; and
adding a standard dopamine solution into the ultrapure water dispersed with the luminescent europium-based metal organic frame probe Eu-alpha-CD for fluorescence titration to draw a standard curve, calculating quenching efficiency according to fluorescence intensity change, and further obtaining the concentration of the dopamine solution in the sample to be detected
In another embodiment of the present invention, the present invention provides a method for preparing a luminescent europium-based metal organic framework probe, wherein the luminescent europium-based metal organic framework probe is loaded on a nitrocellulose membrane in situ, and the method comprises the following steps:
preparing a bovine serum albumin solution with the mass percentage of 5%, soaking the cut nitrocellulose membrane in the bovine serum albumin solution, and incubating for 1 hour at 37 ℃;
taking out the incubated nitrocellulose membrane, placing the nitrocellulose membrane in an antibody incubation wet box, and drying the nitrocellulose membrane in an oven at the temperature of 30-40 ℃;
dissolving solid europium salt powder and solid alpha-cyclodextrin powder in a solvent simultaneously, and stirring until the solid europium salt powder and the solid alpha-cyclodextrin powder are fully dissolved and mixed to obtain a mixed solution of europium salt and alpha-cyclodextrin;
soaking the dried cellulose nitrate membrane in the mixed solution of europium salt and alpha-cyclodextrin, shaking and dropwise adding ammonia water to adjust the pH value to 9;
and taking out the soaked cellulose nitrate membrane, and drying in a drying oven at the temperature of 30-40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD loaded on the cellulose nitrate membrane in situ.
In another embodiment of the present invention, in the step of preparing a 5% bovine serum albumin solution, a phosphate buffer solution with a pH of 7.4 is used as a solvent.
In another embodiment of the present invention, in the step of simultaneously dissolving the solid powder of europium salt and the solid powder of α -cyclodextrin in the solvent, the europium salt is the europium salt Eu (NO) nitrate3)·6H2And O, wherein the solvent is ultrapure water.
In another embodiment of the present invention, the obtained mixed solution of Eu salt and α -cyclodextrin is Eu (NO)3)·6H2The molar ratio of O to alpha-cyclodextrin is 2: 1.
In another embodiment of the present invention, the present invention further provides a method for detecting dopamine by using the luminescent europium-based metal organic framework probe, comprising:
a plurality of luminous europium-based metal organic frame probes Eu-alpha-CD which are loaded on a nitrocellulose membrane in situ are soaked in dopamine solutions with different concentrations, and then are taken out and dried at the temperature of 30-40 ℃; and
and (3) placing the plurality of dried nitrocellulose membranes under an ultraviolet lamp to observe visual colors and measuring corresponding spectral signals of the nitrocellulose membranes, wherein different spectral signals correspond to the concentration of dopamine in different samples.
(III) advantageous effects
The preparation and application of the luminescent metal organic framework probe Eu-alpha-CD provided by the invention have the following advantages and effects: the invention discloses a preparation method for quickly synthesizing a luminescent metal organic framework probe Eu-alpha-CD at normal temperature by taking bovine serum albumin as a mineralizer, which can simply and quickly synthesize the probe Eu-alpha-CD with a crystalline structure; meanwhile, the defects of harsh synthesis conditions, long time consumption and the like of the lanthanide luminescent metal frame material are overcome; and by utilizing the high adsorbability of the nitrocellulose membrane to protein, the probe Eu-alpha-CD is grown on the nitrocellulose membrane in situ, so that the dopamine can be detected by visualization under ultraviolet and the like, and the aim of on-site detection is fulfilled.
Drawings
In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings:
FIG. 1 is a graph showing the luminescence property of probe Eu- α -CD measured by a fluorescence spectrometer according to example 1 of the present invention, wherein A is a three-dimensional fluorescence spectrum of probe Eu- α -CD; b is the position of the emission color of probe Eu-alpha-CD in CIE.
FIG. 2 is a scanning electron micrograph of probe Eu- α -CD according to example 1 of the present invention, wherein A is Eu- α -CD; b is an infrared spectrogram of Eu-alpha-CD; c is Eu-alpha-CD element analysis diagram.
FIG. 3 is a graph showing the effect of detecting dopamine by the probe Eu- α -CD according to example 1 of the present invention, wherein A is a fluorescence spectrum of the probe Eu- α -CD in response to different concentrations of dopamine; and B is a dopamine detection specificity experiment.
FIG. 4 is a representation before and after loading a probe Eu- α -CD on a nitrocellulose membrane according to example 2 of the present invention, wherein A is a scanning electron micrograph of the nitrocellulose membrane; b is a scanning electron microscope image of the nitrocellulose membrane loaded with a probe Eu-alpha-CD; c is an atomic force microscope surface topography picture of the nitrocellulose membrane; d is a surface topography diagram of the nitrocellulose membrane loaded probe Eu-alpha-CD before and after an atomic force microscope.
FIG. 5 is a graph showing the effect of detecting dopamine by using Eu-alpha-CD membrane in example 2 of the present invention, wherein A is dopamine concentration under UV lamp (0, 10 in order from left to right)2，103，104，105nM) visual map of the corresponding Eu- α -CD film; b is the spectrum corresponding to the A picture.
FIG. 6 is a standard operating curve between the dopamine concentration and the fluorescence intensity of Eu-. alpha. -CD according to example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
The invention provides a preparation method for preparing a nanoprobe Eu-alpha-CD with high crystallinity under room temperature by taking alpha-cyclodextrin (alpha-CD) as an organic ligand and bovine serum albumin as a mineralizer, and application of the nanoprobe Eu-alpha-CD in dopamine detection. The synthesis method disclosed by the invention is simple to operate, overcomes the limitation that the lanthanide series metal organic framework material needs hydrothermal synthesis, and overcomes the defects of harsh synthesis conditions, long time consumption and the like of the material.
In one embodiment of the present invention, there is provided a method for preparing a luminescent europium-based metal organic framework probe, which synthesizes a luminescent europium-based metal organic framework probe Eu- α -CD formed from europium salt and α -cyclodextrin at room temperature, including:
step 101: dissolving solid europium salt powder and solid alpha-cyclodextrin powder in a solvent respectively, and stirring until the solid europium salt powder and the solid alpha-cyclodextrin powder are fully dissolved to obtain a europium salt solution and an alpha-cyclodextrin solution with volume ratios of 1: 1 respectively;
step 102: adding bovine serum albumin into the alpha-cyclodextrin solution, stirring until the bovine serum albumin is fully dissolved, then adding a europium salt solution, fully stirring and mixing, and dropwise adding ammonia water to adjust the pH value to 9 to obtain a suspension solution;
step 103: and continuously stirring the suspension solution at normal temperature, centrifugally washing the suspension solution by using ultrapure water, and drying a centrifugal product at the temperature of between 30 and 40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD.
In one embodiment of the present invention, the europium salt solid powder and the alpha-cyclodextrin solid powder described in step 101 are respectively dissolved in a solvent, and the europium salt is europium nitrate Eu (NO)3)·6H2And O, wherein the solvent is ultrapure water.
In one embodiment of the invention, bovine serum albumin is added to the alpha-cyclodextrin solution as described in step 102In the step (b), the bovine serum albumin has a mass volume concentration of 0.5mg mL-1。
In one embodiment of the present invention, in the step of continuously stirring the suspension solution at room temperature and centrifugally washing with ultrapure water in step 103, the suspension solution is continuously stirred at room temperature for 1 to 2 hours and centrifugally washed with ultrapure water for 2 to 3 times.
Example 1: preparing luminescent europium-based metal organic frame probe Eu-alpha-CD at normal temperature
Weighing 0.223g of Eu (NO)3)·6H2O solid powder and 0.27g of alpha-cyclodextrin solid powder were dissolved in 5mL of ultrapure water, respectively, to obtain Eu (NO) in a volume ratio of 1: 13)·6H2O solution and alpha-cyclodextrin solution; adding 5mg of bovine serum albumin into the alpha-cyclodextrin solution, stirring to fully dissolve, and then adding Eu (NO)3)·6H2And fully stirring and mixing the solution O, dropwise adding concentrated ammonia water to adjust the pH value, testing by using pH test paper until the pH value is about 9, changing the solution from clear to milky white, continuously stirring the solution at normal temperature for 1h, centrifugally washing the solution for 2 to 3 times by using ultrapure water, and drying a centrifugal product in an environment at 37 ℃ to obtain the luminescent probe Eu-alpha-CD.
The optical performance of the Eu-alpha-CD luminescent probe is measured by a fluorescence spectrometer, and the test result is shown in figure 1. And reading corresponding horizontal and vertical coordinates at two obvious contour line aggregation positions in the three-dimensional fluorescence spectrum of the luminescent probe Eu-alpha-CD, wherein the excitation wavelength of the luminescent probe Eu-alpha-CD is 390nm, and the emission wavelengths are 591nm and 615 nm. The emission spectrum of the luminescence probe Eu-. alpha. -CD was converted into color coordinates, CIE coordinates (0.5764, 0.3493).
The characterization result of the Eu-alpha-CD of the luminescence probe is shown in figure 2, wherein the surface topography test is measured by using a field emission scanning electron microscope, the infrared spectrum is collected by a ThermoFisher-nicolet is50 Fourier transform infrared spectrometer, and A is a scanning electron microscope image of the Eu-alpha-CD; b is an infrared spectrogram of Eu-alpha-CD; c is Eu-alpha-CD element analysis diagram.
Based on the luminescent europium-based metal organic framework probe prepared in the embodiment 1, the embodiment 1 of the invention provides a method for detecting dopamine by using the luminescent europium-based metal organic framework probe, which comprises the following steps:
step 201: dispersing the luminescent europium-based metal organic framework probe Eu-alpha-CD in ultrapure water, and measuring the emission spectrum of the luminescent europium-based metal organic framework probe Eu-alpha-CD; and
step 202: and adding a standard dopamine solution into the ultrapure water dispersed with the luminescent europium-based metal organic frame probe Eu-alpha-CD to perform fluorescence titration to draw a standard curve, and calculating according to the change of fluorescence intensity to obtain the concentration of dopamine in the sample.
The following provides a detailed description of a method for detecting dopamine by using the luminescent europium-based metal organic framework probe in accordance with two specific applications.
Application 1: detection of dopamine by using luminescent europium-based metal organic framework probe Eu-alpha-CD
Response efficiency test of the luminescent probe Eu-alpha-CD to dopamine: dissolving dried Eu-alpha-CD in water, dissolving completely, taking 2mL homogeneous solution to test fluorescence intensity F0, adding 20 muL dopamine into F0 solution to make final solubility of dopamine be 0, 10 in sequence0，101，102，103，104，105nM, the fluorescence spectra were scanned separately, and the results are shown as a in fig. 3. Sequentially adding 10 to the Eu-alpha-CD aqueous solution5nM bovine serum albumin, tyrosine, potassium chloride, sodium chloride, glucose, human serum albumin, serine, cysteine, and uric acid, and their fluorescence intensities were measured, respectively. B in FIG. 3 shows that Eu-. alpha. -CD has a specific response to dopamine. Wherein, glucose, tyrosine, serine, lysine, cysteine, human serum albumin, sodium chloride, potassium chloride, etc. can be used as interfering molecules.
Application 2: the invention discloses a method for visually detecting dopamine by applying a luminous europium-based metal organic framework probe Eu-alpha-CD (europium-activated carbon) loaded on a nitrocellulose membrane in situ, which comprises the following steps: immersing the cellulose nitrate film loaded with Eu-alpha-CD in a solution of an object to be detected, taking out and drying the cellulose nitrate film, and carrying out visual observation under an ultraviolet lamp, wherein the color of the cellulose nitrate film is changed from bright red to pink till colorless along with the increase of the concentration of dopamine. In addition, the fluorescence intensity of the nitrocellulose membrane can be accurately measured by a fluorescence spectrometer.
In another embodiment of the present invention, the present invention further provides a method for preparing a luminescent europium-based metal organic framework probe, wherein the luminescent europium-based metal organic framework probe is loaded on a nitrocellulose membrane in situ, and the method comprises the following steps:
step 301: preparing a bovine serum albumin solution with the mass percentage of 5%, soaking the cut nitrocellulose membrane in the bovine serum albumin solution, and incubating for 1 hour at 37 ℃;
step 302: taking out the incubated nitrocellulose membrane, placing the nitrocellulose membrane in an antibody incubation wet box, and drying the nitrocellulose membrane in an oven at the temperature of 30-40 ℃;
step 303: dissolving solid europium salt powder and solid alpha-cyclodextrin powder in a solvent simultaneously, and stirring until the solid europium salt powder and the solid alpha-cyclodextrin powder are fully dissolved and mixed to obtain a mixed solution of europium salt and alpha-cyclodextrin;
step 304: soaking the dried cellulose nitrate membrane in the mixed solution of europium salt and alpha-cyclodextrin, shaking and dropwise adding ammonia water to adjust the pH value to 9;
step 305: and taking out the soaked cellulose nitrate membrane, and drying in a drying oven at the temperature of 30-40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD loaded on the cellulose nitrate membrane in situ.
In another embodiment of the present invention, a 5% bovine serum albumin solution is prepared in step 301, and the solvent is phosphate buffered saline with pH 7.4.
In another embodiment of the present invention as set forth above, the solid powder of europium salt and the solid powder of α -cyclodextrin as described in step 303 are simultaneously dissolved in the solvent, the europium salt being europium nitrate Eu (NO)3)·6H2And O, wherein the solvent is ultrapure water.
In another embodiment of the present invention as described above, Eu (NO) in the mixed solution of europium salt and α -cyclodextrin obtained as described in step 3033)·6H2The molar ratio of O to alpha-cyclodextrin is 2: 1.
Example 2: preparing luminescent europium-based metal organic framework probe Eu-alpha-CD supported on nitrocellulose membrane in situ
Adsorbing bovine serum albumin on the nitrocellulose membrane by utilizing the high adsorbability of the nitrocellulose membrane to protein; taking bovine serum albumin as a mineralizer, and growing a luminescent probe Eu-alpha-CD on a nitrocellulose membrane in situ, wherein the method comprises the following specific steps: weighing 200mg of bovine serum albumin, and dissolving the bovine serum albumin in 4mL of phosphate buffer (pH 7.4) to obtain a 5% bovine serum albumin solution; soaking the cut nitrocellulose membrane in the 5% bovine serum albumin solution, and incubating for 1 hour at 37 ℃; taking out the incubated nitrocellulose membrane, placing the nitrocellulose membrane in an incubation wet box, keeping a certain humidity to avoid inactivation of the nitrocellulose membrane, and placing the wet box in a 37 ℃ drying oven for drying to obtain the nitrocellulose membrane loaded with bovine serum albumin; weighing 0.223g of Eu (NO)3)·6H2Dissolving O solid powder and 0.27g alpha-cyclodextrin solid powder in 10mL ultrapure water, and sufficiently dissolving to obtain Eu (NO)3)·6H2A mixed solution of O and alpha-cyclodextrin; soaking the cellulose nitrate membrane loaded with bovine serum albumin in Eu (NO)3)·6H2And (3) placing the mixed solution of O and alpha-cyclodextrin on a shaker, dropwise adding ammonia water to adjust the pH value to about 9, taking out the nitrocellulose membrane, placing the nitrocellulose membrane in a wet incubation box, drying the nitrocellulose membrane in a drying oven at 37 ℃, and drying the nitrocellulose membrane to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD loaded on the nitrocellulose membrane in situ.
And the surface appearance of the nitrocellulose membrane loaded with the probe Eu-alpha-CD in situ is characterized by adopting a scanning electron microscope and an atomic force microscope. FIG. 4 is a schematic representation of a nitrocellulose membrane according to example 2 of the present invention before and after loading with probe Eu-. alpha. -CD, wherein A is a scanning electron micrograph of the nitrocellulose membrane; b is a scanning electron microscope image of the nitrocellulose membrane loaded with a probe Eu-alpha-CD; c is an atomic force microscope surface topography picture of the nitrocellulose membrane; d is a surface topography diagram of the nitrocellulose membrane loaded probe Eu-alpha-CD before and after an atomic force microscope.
Based on the luminescent europium-based metal organic framework probe loaded on the nitrocellulose membrane in situ prepared in the embodiment 2, the embodiment 2 of the invention also provides a method for detecting dopamine by using the luminescent europium-based metal organic framework probe, which comprises the following steps:
step 401: a plurality of luminous europium-based metal organic frame probes Eu-alpha-CD which are loaded on a nitrocellulose membrane in situ are soaked in dopamine solutions with different concentrations, and then are taken out and dried at the temperature of 30-40 ℃; and
step 402: and (3) placing the plurality of dried nitrocellulose membranes under an ultraviolet lamp to observe visual colors and measuring corresponding spectral signals of the nitrocellulose membranes, wherein different spectral signals correspond to the concentration of dopamine in a non-sample.
The following provides a detailed description of a method for detecting dopamine by using the luminescent europium-based metal organic framework probe loaded on the nitrocellulose membrane in situ, in accordance with example 2 of the present invention.
Application 3: detecting dopamine by using a luminous europium-based metal organic framework probe Eu-alpha-CD (europium-doped-cadmium-doped-lithium) loaded on a nitrocellulose membrane in situ:
weighing dopamine powder reagent with the preparation concentrations of 0 and 10 respectively2，103，104，105Soaking the nitrocellulose membrane loaded with the probe Eu-alpha-CD in the dopamine solution for reaction, taking out the nitrocellulose membrane, placing the nitrocellulose membrane in an incubation wet box, and drying the nitrocellulose membrane in a drying oven at 37 ℃; the color change of the dried nitrocellulose membrane was observed under an ultraviolet lamp, and the fluorescence spectrum was measured, and the results are shown in fig. 5, in which different spectrum signals correspond to different concentrations of dopamine solution.
FIG. 5 is a graph showing the effect of detecting dopamine by using Eu-alpha-CD membrane in example 2 of the present invention, wherein A is dopamine concentration under UV lamp (0, 10 in order from left to right)2，103，104，105nM) visual map of the corresponding Eu- α -CD film; b is the spectrum corresponding to the A picture.
Application 4: detecting dopamine by using a luminous europium-based metal organic framework probe Eu-alpha-CD (europium-doped-cadmium-doped-lithium) loaded on a nitrocellulose membrane in situ:
(1) drawing a standard working curve of Eu-alpha-CD fluorescence intensity and dopamine concentration: firstly, measuring the fluorescence intensity of Eu-alpha-CD when no dopamine exists, then adding dopamine standard solution with gradient concentration, measuring the fluorescence intensity of Eu-alpha-CD when dopamine exists, drawing a standard working curve, and obtaining a standard working curve equation by utilizing a fitting function: y 432.022 × exp (-x/1398.546) + 48.075; as shown in FIG. 6, FIG. 6 is a standard operation curve between the dopamine concentration and the fluorescence intensity of Eu-. alpha. -CD according to example 2 of the present invention.
(2) And (3) determining the concentration of dopamine in the substance to be detected: and under the same experimental conditions, measuring the fluorescence intensity of Eu-alpha-CD when the object to be detected exists, and obtaining the concentration of dopamine in the object to be detected according to the drawn standard working curve.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a luminescent europium-based metal organic framework probe is characterized in that the luminescent europium-based metal organic framework probe Eu-alpha-CD formed by europium salt and alpha-cyclodextrin is synthesized at room temperature, and the method comprises the following steps:
dissolving europium salt solid powder and alpha-cyclodextrin solid powder in a solvent respectively, and stirring until the europium salt solid powder and the alpha-cyclodextrin solid powder are fully dissolved to obtain a mixture with a volume ratio of 1: 1 europium salt solution and alpha-cyclodextrin solution;
adding bovine serum albumin into the alpha-cyclodextrin solution, stirring until the bovine serum albumin is fully dissolved, then adding a europium salt solution, fully stirring and mixing, and dropwise adding ammonia water to adjust the pH value to 9 to obtain a suspension solution;
and continuously stirring the suspension solution at normal temperature, centrifugally washing the suspension solution by using ultrapure water, and drying a centrifugal product at the temperature of between 30 and 40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD.
2. The luminescent europium-based metal-organic framework of claim 1The method for preparing the probe is characterized in that, in the step of respectively dissolving the solid powder of europium salt and the solid powder of alpha-cyclodextrin in the solvent, the europium salt is the europium salt Eu (NO) nitrate3)·6H2And O, wherein the solvent is ultrapure water.
3. The method of claim 1, wherein in the step of adding bovine serum albumin to the α -cyclodextrin solution, the bovine serum albumin has a concentration of 0.5mg mL/v-1。
4. The method of claim 1, wherein the step of stirring the suspension solution at room temperature and washing the suspension solution with ultrapure water by centrifugation comprises stirring the suspension solution at room temperature for 1 to 2 hours and washing the suspension solution with ultrapure water by centrifugation for 2 to 3 times.
5. A method for detecting dopamine using the luminescent europium-based metal-organic framework probe of any one of claims 1 to 4, comprising:
dispersing the luminescent europium-based metal organic framework probe Eu-alpha-CD in ultrapure water, and measuring the emission spectrum of the luminescent europium-based metal organic framework probe Eu-alpha-CD; and
and adding a standard dopamine solution into the ultrapure water dispersed with the luminescent europium-based metal organic frame probe Eu-alpha-CD to perform fluorescence titration to draw a standard curve, and calculating according to the change of fluorescence intensity to obtain the concentration of the dopamine solution in the sample to be detected.
6. A preparation method of a luminous europium-based metal organic framework probe is characterized in that the luminous europium-based metal organic framework probe is loaded on a nitrocellulose membrane in situ, and the preparation method comprises the following steps:
preparing a bovine serum albumin solution with the mass percentage of 5%, soaking the cut nitrocellulose membrane in the bovine serum albumin solution, and incubating for 1 hour at 37 ℃;
taking out the incubated nitrocellulose membrane, placing the nitrocellulose membrane in an antibody incubation wet box, and drying the nitrocellulose membrane in an oven at the temperature of 30-40 ℃;
dissolving solid europium salt powder and solid alpha-cyclodextrin powder in a solvent simultaneously, and stirring until the solid europium salt powder and the solid alpha-cyclodextrin powder are fully dissolved and mixed to obtain a mixed solution of europium salt and alpha-cyclodextrin;
soaking the dried cellulose nitrate membrane in the mixed solution of europium salt and alpha-cyclodextrin, shaking and dropwise adding ammonia water to adjust the pH value to 9;
and taking out the soaked cellulose nitrate membrane, and drying in a drying oven at the temperature of 30-40 ℃ to obtain the luminescent europium-based metal organic framework probe Eu-alpha-CD loaded on the cellulose nitrate membrane in situ.
7. The method of claim 6, wherein the step of preparing a 5% bovine serum albumin solution is performed in a pH 7.4 phosphate buffer.
8. The method of preparing a light-emitting europium-based metal organic frame probe of claim 6, wherein, in said step of dissolving simultaneously a solid powder of europium salt and a solid powder of α -cyclodextrin in a solvent, the europium salt is the europium salt Eu Nitrate (NO)3)·6H2And O, wherein the solvent is ultrapure water.
9. The method of claim 8, wherein the obtained mixed solution of europium salt and α -cyclodextrin is Eu (NO) in the form of a mixed solution3) The molar ratio of 6H2O to α -cyclodextrin was 2: 1.
10. A method of detecting dopamine using a luminescent europium-based metal-organic framework probe as claimed in any one of claims 6 to 9, comprising:
a plurality of luminous europium-based metal organic frame probes Eu-alpha-CD which are loaded on a nitrocellulose membrane in situ are soaked in dopamine solutions with different concentrations, and then are taken out and dried at the temperature of 30-40 ℃; and
and (3) placing the plurality of dried nitrocellulose membranes under an ultraviolet lamp to observe visual colors and measuring corresponding spectral signals of the nitrocellulose membranes, wherein different spectral signals correspond to the dopamine concentrations in different samples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010874260.7A CN111999276B (en) | 2020-08-26 | 2020-08-26 | Method for preparing luminous europium-based metal organic framework probe and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010874260.7A CN111999276B (en) | 2020-08-26 | 2020-08-26 | Method for preparing luminous europium-based metal organic framework probe and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111999276A CN111999276A (en) | 2020-11-27 |
| CN111999276B true CN111999276B (en) | 2021-06-08 |
Family
ID=73471186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010874260.7A Active CN111999276B (en) | 2020-08-26 | 2020-08-26 | Method for preparing luminous europium-based metal organic framework probe and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111999276B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774118B (en) * | 2022-03-28 | 2023-03-14 | 河南理工大学 | Preparation and detection method of two-channel visual multicolor fluorescent probe |
| CN115266663B (en) * | 2022-06-30 | 2023-06-16 | 四川省医学科学院·四川省人民医院 | Biological probe for non-invasive diagnosis of parkinsonism triggered by intestinal microenvironment as well as preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984276A (en) * | 2017-05-08 | 2017-07-28 | 中国农业科学院蔬菜花卉研究所 | Metal-organic framework material, its preparation method and application |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| CN109400937A (en) * | 2018-10-30 | 2019-03-01 | 武汉纺织大学 | The preparation method of highly conductive gas sensor material based on nanofiber |
| CN110031527A (en) * | 2019-04-30 | 2019-07-19 | 福建师范大学 | A kind of double reading biosensors of human thyroglobulin |
| CN110025592A (en) * | 2018-12-21 | 2019-07-19 | 中山大学 | Cyclodextrin-metal-organic framework materials complex microsphere and preparation method thereof |
| CN110452688A (en) * | 2019-08-19 | 2019-11-15 | 盐城工学院 | A kind of group of the lanthanides MOFs fluorescence membrane and preparation method thereof, application |
| CN110731961A (en) * | 2014-10-14 | 2020-01-31 | 芝加哥大学 | Metal organic framework, pharmaceutical preparation and use thereof in preparing medicament |
| CN110813253A (en) * | 2019-11-22 | 2020-02-21 | 山东农业大学 | Preparation method and application of hydrophilic metal organic framework surface bisphenol A molecular imprinting high-selectivity nanocomposite |
| CN111100304A (en) * | 2019-12-26 | 2020-05-05 | 烟台大学 | Preparation method of dopamine content detection material in human body |
| CN111545223A (en) * | 2020-05-11 | 2020-08-18 | 浙江工业大学 | Inclusion type metal fluoride catalyst based on cyclodextrin and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10736967B2 (en) * | 2016-01-05 | 2020-08-11 | Panaceanano, Inc. | Method of preparing cyclodextrin complexes |
| WO2017164822A1 (en) * | 2016-03-24 | 2017-09-28 | Nanyang Technological University | Core-shell plasmonic nanogapped nanostructured material |
-
2020
- 2020-08-26 CN CN202010874260.7A patent/CN111999276B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110731961A (en) * | 2014-10-14 | 2020-01-31 | 芝加哥大学 | Metal organic framework, pharmaceutical preparation and use thereof in preparing medicament |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| CN106984276A (en) * | 2017-05-08 | 2017-07-28 | 中国农业科学院蔬菜花卉研究所 | Metal-organic framework material, its preparation method and application |
| CN109400937A (en) * | 2018-10-30 | 2019-03-01 | 武汉纺织大学 | The preparation method of highly conductive gas sensor material based on nanofiber |
| CN110025592A (en) * | 2018-12-21 | 2019-07-19 | 中山大学 | Cyclodextrin-metal-organic framework materials complex microsphere and preparation method thereof |
| CN110031527A (en) * | 2019-04-30 | 2019-07-19 | 福建师范大学 | A kind of double reading biosensors of human thyroglobulin |
| CN110452688A (en) * | 2019-08-19 | 2019-11-15 | 盐城工学院 | A kind of group of the lanthanides MOFs fluorescence membrane and preparation method thereof, application |
| CN110813253A (en) * | 2019-11-22 | 2020-02-21 | 山东农业大学 | Preparation method and application of hydrophilic metal organic framework surface bisphenol A molecular imprinting high-selectivity nanocomposite |
| CN111100304A (en) * | 2019-12-26 | 2020-05-05 | 烟台大学 | Preparation method of dopamine content detection material in human body |
| CN111545223A (en) * | 2020-05-11 | 2020-08-18 | 浙江工业大学 | Inclusion type metal fluoride catalyst based on cyclodextrin and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| One-step fabrication of a boric acid-functionalized lanthanide metal-organic framework as a ratiometric fluorescence sensor for the selective recognition of dopamine;Qiuzheng Du 等;《NEW JOURNAL OF CHEMISTRY》;20181203;第43卷;44499-44507 * |
| 基于手性MOF与乙炔黑修饰电极对多巴胺和尿酸的同时检测;方智利 等;《无机化学学报》;20200131;第36卷(第1期);139-147 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111999276A (en) | 2020-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111999276B (en) | Method for preparing luminous europium-based metal organic framework probe and application thereof | |
| CN111269715B (en) | Ratiometric fluorescent probe and application thereof in visual detection of glutathione | |
| CN106959290A (en) | A kind of Ratio-type rare-earth fluorescent probe and the application for detecting bacillus anthracis biomarker | |
| CN107014787B (en) | Application of glutathione template gold nanocluster in detection of cysteine and lysine | |
| CN105928914A (en) | Hydrogen sulfide detection sensor, preparation method thereof, quantitative detection method of hydrogen sulfide, and qualitative detection method of hydrogen sulfide in cells | |
| CN109030456A (en) | A kind of Surface enhanced Raman spectroscopy detection substrate and its preparation method and application | |
| CN112816414B (en) | Alkaline phosphatase detection kit based on dual-emission lanthanide MOF and detection method | |
| He et al. | Two isomeric and distinguishable H 2 S fluorescence probes for monitoring spoilage of eggs and visualizing exogenous and endogenous H 2 S in living cells | |
| CN110243791B (en) | Method for detecting chloride ions in sweat through visual sensing | |
| CN113249115B (en) | Preparation of metal organic framework composite material and application of metal organic framework composite material as ratio type fluorescent probe in detection of hydrogen peroxide and Pi | |
| CN113138185B (en) | Method for detecting sodium thiocyanate in milk by using SERS (surface enhanced Raman Scattering) technology based on MOF (metal-organic framework) | |
| CN111363542B (en) | Full-color fluorescent CaF 2 And use of CaF 2 Prepared furfural molecular imprinting ratio fluorescence sensor and preparation method thereof | |
| CN110964044B (en) | Peroxynitrite fluorescent probe based on dicoumarin derivative, preparation method and application | |
| CN110372681B (en) | Application of self-assembled nano fluorescent probe for selectively detecting human serum albumin | |
| CN110411990A (en) | A method of hydrogen peroxide and related objective object are detected based on nano-probe | |
| CN110669503B (en) | Preparation and application of carbon monoxide near-infrared fluorescent probe | |
| CN108760695B (en) | Method for quantitatively detecting thrombin by using phosphorescence probe based on PRET | |
| Song et al. | A novel ratiometric fluorescence probe based on flower ball-like metal–organic frameworks for detecting carcinoid biomarker in urine | |
| CN109975268A (en) | A method of nitrite ion is detected based on gold and silver core shell nanoparticles SERS technology | |
| CN113150772B (en) | Zn/H 2 aip fluorescent probe, preparation and application thereof in detection of tetracycline antibiotics | |
| CN114989806A (en) | Composite probe for rapidly detecting malachite green and detection method thereof | |
| CN109632732B (en) | Near-infrared fluorescence sensitization method for determining glucose | |
| CN105647516B (en) | A kind of pH value is luminous to indicate material and its preparation method and application | |
| CN111087362A (en) | Fluorescent probe for detecting formaldehyde with high selectivity, and synthetic method and application thereof | |
| CN113666822A (en) | Small molecule fluorescent probe for aluminum ion detection and cell imaging and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |