CN112592359B - Fluorescent probe for detecting concentration of 2, 6-pyridinedicarboxylic acid calcium, preparation method and application - Google Patents
Fluorescent probe for detecting concentration of 2, 6-pyridinedicarboxylic acid calcium, preparation method and application Download PDFInfo
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- 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
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Abstract
The invention discloses a fluorescent probe for detecting the concentration of 2, 6-pyridinedicarboxylic acid calcium, a preparation method and application thereof. The fluorescent probe is a rare earth-doxycycline complex, and the specific method comprises the following steps: dissolving soluble rare earth salt and doxycycline in water to obtain a uniform solution containing rare earth elements; and (3) adjusting the pH value of the solution containing the rare earth elements to be alkalescent, generating precipitates at the moment, and continuing to react until the precipitates are not increased any more, thereby obtaining the rare earth-doxycycline complex fluorescent probe. The application is that the fluorescent probe is used for detecting the concentration of the 2, 6-pyridine calcium dicarboxylate solution. The invention innovatively coordinates doxycycline and rare earth ions, and the obtained rare earth-doxycycline complex has the advantages of long fluorescence life, stable luminescent signal, large Storkes displacement, narrow peak, avoidance of background interference of organisms, strong binding property with calcium 2, 6-pyridinedicarboxylate, capability of being used for detecting the concentration of calcium 2, 6-pyridinedicarboxylate, and popularization to other sensors for detecting the concentrations of different biological micromolecules.
Description
Technical Field
The invention belongs to the technical field of biosensing, and particularly relates to a fluorescent probe for detecting the concentration of 2, 6-pyridinedicarboxylic acid calcium, a preparation method and application thereof.
Background
Anthrax is used as a fulminant infectious disease, and the pathogen bacillus anthracis belongs to the second category of pathogenic microorganisms (highly pathogenic microorganisms) in the pathogenic microorganism catalogue of interpersonal infection published in China. During spore germination, 2, 6-dipicolinic acid (DPA) and divalent cations (mainly Ca) combined with the DPA account for about 5-10% of dry weight of spore2+) Therefore, the germination condition of the spores can be judged by detecting the unique marker of the calcium 2, 6-pyridinedicarboxylate, thereby indirectly achieving the effect of identifying the anthrax virus.
Many methods for detecting calcium 2, 6-pyridinedicarboxylate have been developed so far, including colorimetric analysis, polymerase chain reaction analysis, immunoassay, fourier transform infrared spectroscopy, gas chromatography, surface enhanced raman spectroscopy, high pressure liquid chromatography, electrochemical analysis, fluorescence analysis, and the like. Because other detection technologies are complex in implementation process, related instruments are expensive, and detection results cannot be directly observed, the fluorescence analysis method is widely applied due to the advantages of intuition and the like of the detection results.
The substrates for constructing the rare earth ion doping in the fluorescent probe mainly comprise inorganic materials and organic ligands. In the aspect of inorganic materials, research is mainly focused on rare earth doped carbon/silicon quantum dots and other small-scale nano materials. In the aspect of organic ligands, the design and synthesis of ligands such as oxygen-containing organic matters, nitrogen-containing organic matters, supermolecule macrocycles, biomolecules and the like are focused. Tetracycline antibiotics, as a class of rapid bacteriostats, have been widely used in veterinary medicine since their first discovery in 1950. Doxycycline is an excellent ligand of rare earth because of its molecular structure of beta-diketone, which is one of tetracycline antibiotics.
As natural hosts of the bacillus anthracis comprise herbivorous wild animals and livestock, the detection of the calcium 2, 6-pyridinedicarboxylate of meat products and milk products produced by the animals as raw materials requires a quick, green and nontoxic detection means. In addition, the detection reagent should have good water solubility. However, the existing fluorescent probe, whether a rare earth complex or a rare earth modified nano material, has the following disadvantages: the preparation steps are complex, reagents with different degrees of toxicity are required to participate in the preparation, and the water solubility is general.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fluorescent probe for detecting the concentration of 2, 6-pyridinedicarboxylic acid calcium, a preparation method and application thereof.
The technical scheme for solving the technical problem of the fluorescent probe is to provide the fluorescent probe for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium, and the fluorescent probe is characterized by being a rare earth-doxycycline complex.
The technical scheme for solving the technical problem of the method is to provide a preparation method of the fluorescent probe for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium, which is characterized by comprising the following steps:
(1) dissolving soluble rare earth salt and doxycycline in water to obtain a uniform solution containing rare earth elements;
(2) and (3) adjusting the pH value of the solution containing the rare earth element to be alkalescent, then generating precipitates, and continuing to react until the precipitates are not increased any more, thus obtaining the rare earth-doxycycline complex fluorescent probe.
The technical scheme for solving the application technical problem is to provide an application of the fluorescent probe for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium, which is characterized in that the fluorescent probe is used for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution, and the specific steps are as follows:
(1) mixing the fluorescent probe with calcium 2, 6-dipicolinate solutions with different concentrations for reaction;
(2) measuring the spectrum by adopting a fluorescence method to obtain the fluorescence spectrum of the 2, 6-calcium dipicolinate solution with different concentrations;
(3) then, taking the concentration value of the calcium 2, 6-pyridinedicarboxylate as an abscissa, and taking the fluorescence intensity value of a characteristic peak in a fluorescence spectrum corresponding to different concentrations of the calcium 2, 6-pyridinedicarboxylate as an ordinate to draw a standard curve;
(4) and (3) measuring the fluorescence intensity of the 2, 6-pyridinedicarboxylic acid calcium solution with the concentration to be measured by a fluorescence method, and finding the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution corresponding to the fluorescence intensity in the standard curve to obtain the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution to be measured.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention innovatively coordinates doxycycline and rare earth ions, and the obtained rare earth-doxycycline complex has the advantages of long fluorescence life, stable luminescent signal, large Storkes displacement, narrow peak, avoidance of background interference of organisms, strong binding property with calcium 2, 6-pyridinedicarboxylate, capability of being used for detecting the concentration of calcium 2, 6-pyridinedicarboxylate, and popularization to other sensors for detecting the concentrations of different biological micromolecules.
2. The molecular structure of doxycycline has multiple ketone carbonyl and hydroxyl functional groups, and such functional groups can realize ketol tautomerism under alkaline conditions, so as to generate free oxygen ions. Rare earth elements, on the other hand, tend to have a tendency toward negatively charged or neutral oxygen and nitrogen atoms due to their own high lewis acidity. Therefore, the rare earth ions can better form complexes with carbonyl oxygen in the doxycycline and oxygen anions in carboxylate ions.
3. The fluorescent probe is synthesized by a one-pot method, the preparation process is simple, the raw materials are nontoxic and easy to obtain, the price is low, the environment is friendly, and the method is suitable for popularization and application.
4. According to the method for quantitatively analyzing the concentration of the 2, 6-pyridinedicarboxylic acid calcium, the europium/dysprosium-doxycycline complex fluorescent probe is combined with the standard curve, so that the method is simple and convenient, the detection steps are simplified, other precise and expensive instruments are not needed, the cost is reduced, the slope of the standard curve can visually reflect the relative sensitivity of the fluorescent probe, and the higher the slope is, the higher the relative sensitivity is.
Drawings
FIG. 1 is a scanning electron micrograph of a europium-doxycycline complex prepared in example 1 of the present invention;
FIG. 2 is a fluorescence emission spectrum of europium-doxycycline complex obtained in example 1 of the present invention;
FIG. 3 is a fluorescence emission spectrum of europium-doxycycline complex in calcium 2, 6-pyridinedicarboxylate solutions of different concentrations according to example 1 of the present invention;
FIG. 4 is a standard curve diagram of the europium-doxycycline complex provided in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of dysprosium-doxycycline complex obtained in example 2 of the present invention;
FIG. 6 is a fluorescence emission spectrum of dysprosium-doxycycline complex obtained in example 2 of the present invention;
FIG. 7 is a fluorescence emission spectrum of dysprosium-doxycycline complex in calcium 2, 6-pyridinedicarboxylate solutions of different concentrations provided in example 2 of the present invention;
FIG. 8 is a graph of a calibration curve for dysprosium-doxycycline complexes provided in example 2 of the invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a fluorescent probe (called fluorescent probe for short) for detecting the concentration of 2, 6-pyridine calcium dicarboxylate, which is characterized in that the fluorescent probe is a rare earth-doxycycline complex.
Wherein the europium-doxycycline complex fluorescent probe is a 60nm nanorod particle, and the dysprosium-doxycycline complex fluorescent probe is in an amorphous state.
The invention also provides a preparation method (method for short) of the fluorescent probe for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium, which is characterized by comprising the following steps:
(1) mixing soluble rare earth salt, doxycycline and water, and reacting for 0.5-1.5 h at 15-35 ℃ with stirring until the soluble rare earth salt and the doxycycline are dissolved in the water to obtain a uniform solution containing rare earth elements;
preferably, in step 1, the water is deionized water, distilled water or ultrapure water;
preferably, in step 1, the soluble rare earth salt is rare earth chloride or rare earth nitrate, and the rare earth element is dysprosium or europium;
preferably, in the step 1, the molar ratio of the soluble rare earth salt to the doxycycline is 1: 1-3; the ratio of the mol of the soluble rare earth salt to the volume of water is 1mol: 20-60L;
(2) and adjusting the pH value of the solution containing the rare earth elements to be alkaline (preferably alkalescence), allowing a tawny precipitate to appear, continuing to react for 0-5 hours under the stirring condition until the precipitate is not increased any more, and performing centrifugal separation, washing to remove impurities and drying to obtain the rare earth-doxycycline complex fluorescent probe.
Preferably, in the step 2, the alkalescence is 8-10; the method for adjusting the pH is to add ammonia water into the solution containing the rare earth elements, wherein the ammonia water has an alkaline effect.
Preferably, the stirring conditions in step 1 and step 2 are: magnetic stirring at a rotation speed of 200-800 r/min.
The invention also provides an application of the fluorescent probe, which is characterized in that the fluorescent probe is used for detecting the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution, and the specific steps are as follows:
(1) mixing the fluorescent probe with calcium 2, 6-dipicolinate solutions with different concentrations for reaction; the temperature of the mixing reaction is 15-35 ℃, and the time is 10-20 min;
(2) measuring the spectrum of 450-700 nm by adopting a fluorescence method to obtain the fluorescence spectrum of the 2, 6-calcium dipicolinate solution with different concentrations; the test conditions were: the spectra were measured in a fluorescence spectrometer with a voltage value of 700V, a scanning speed of 1200nm/min, a slit width of 10nm and an excitation wavelength of 340 nm.
(3) Then, taking the concentration value of the calcium 2, 6-pyridinedicarboxylate as an abscissa, and taking the fluorescence intensity value at the characteristic peak in the fluorescence spectrum corresponding to different concentrations of the calcium 2, 6-pyridinedicarboxylate as an ordinate, and drawing a standard curve similar to a straight line;
in the embodiment, 615nm of a europium-doxycycline complex fluorescent probe is a characteristic peak, and the fluorescence intensity changes along with the change of the concentration of calcium 2, 6-dipicolinate; the europium-doxycycline complex fluorescent probe is characterized by 480nm, and the fluorescence intensity changes along with the change of the concentration of the calcium 2, 6-pyridinedicarboxylate.
(4) And (3) measuring the fluorescence intensity of the 2, 6-pyridinedicarboxylic acid calcium solution with the concentration to be measured by a fluorescence method, and finding the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution corresponding to the fluorescence intensity in the standard curve to obtain the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution to be measured.
In the step 1), the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution is 1-100 mu M. The concentrations of the calcium 2, 6-pyridinedicarboxylate solutions corresponding to the europium-doxycycline complex fluorescent probe were 1. mu.M, 16. mu.M, 32. mu.M, 48. mu.M, 64. mu.M, 80. mu.M, and 100. mu.M. The concentrations of the 2, 6-dipicolinic acid calcium solution corresponding to the dysprosium-doxycycline complex fluorescent probe are 1 mu M, 20 mu M, 40 mu M, 60 mu M, 80 mu M and 100 mu M.
Under the assistance of an ultraviolet lamp, with the continuous increase of the concentration of the 2, 6-pyridine calcium dicarboxylate solution, the fluorescence of the rare earth-doxycycline complex fluorescent probe can be directly observed from weak to strong by eyes, wherein europium ions gradually change from colorless to red, and dysprosium ions gradually change from colorless to blue. Therefore, the europium/dysprosium-doxycycline complex fluorescent probe can be used for detecting the calcium 2, 6-pyridinedicarboxylate.
Example 1
(1) 0.5mmol of europium chloride (EuCl)3·6H2O,0.1382g) and 1mmol of doxycycline (C)22H24N2O80.18g) of the rare earth element is dissolved in 20mL of deionized water, and the solution is magnetically stirred for 40min at the room temperature under the condition that the rotating speed is 500r/min, so that uniform solution containing the rare earth element is obtained;
(2) adjusting the pH value of the solution containing the rare earth elements to 9 by using ammonia water, stirring and reacting for 2 hours under the condition that the rotating speed is 800r/min, centrifugally separating out precipitate under the condition that the rotating speed is 5000r/min, washing for 3 times by using absolute ethyl alcohol, and finally drying the separated precipitate in an oven at 60 ℃ for 24 hours to obtain the europium-doxycycline complex fluorescent probe.
As can be seen from FIG. 1, the europium-doxycycline complex fluorescent probe obtained in example 1 is a nano-rod-shaped particle with an average particle size of 60 nm.
As can be seen from FIG. 2, the europium-doxycycline complex obtained in example 1 has a distinct characteristic peak at 615nm, corresponding to europium ion5D0→7F2The emission peak generated by the transition shows that the doxycycline and the rare earth europium ion are matched in energy level, and energy transfer exists between the doxycycline and the rare earth europium ion, namely the rare earth europium ion is successfully coordinated with the doxycycline.
The method for detecting the concentration of the 2, 6-pyridine calcium dicarboxylate solution by using the europium-doxycycline complex fluorescent probe comprises the following steps:
(1) 0.0053g (1.0X 10)-5mol) mixing the europium-doxycycline complex fluorescent probe with a 2, 6-pyridinedicarboxylic acid calcium solution with standard concentration to perform specific reaction, and performing ultrasonic dispersion for 10min to obtain a solution to be detected;
the concentrations of standard concentration 2, 6-pyridine calcium dicarboxylate solutions are respectively 1 muM, 16 muM, 32 muM, 48 muM, 64 muM, 80 muM and 100 muM, and the volumes are all 100 mL;
(2) respectively taking 3mL of the solution to be detected by a pipette, placing the solution to be detected into a cuvette one by one, and detecting an emission spectrum of the solution by using a fluorescence spectrometer under the condition that the monitoring wavelength is 340nm (shown in figure 3);
(3) and then, taking the concentration value of the standard concentration calcium 2, 6-pyridinedicarboxylate solution as an abscissa and taking the fluorescence intensity value at 615nm in the fluorescence spectrum corresponding to the standard concentration calcium 2, 6-pyridinedicarboxylate solution as an ordinate, and drawing a standard curve of the calcium 2, 6-pyridinedicarboxylate under the europium-doxycycline complex fluorescent probe (as shown in fig. 4).
As can be seen from FIG. 3, the emission peak (i.e., characteristic peak) at 615nm corresponds to Eu in the europium-doxycycline complex3+Of ions5D0→7F2The intensity of these emission peaks increases (in a proportional relationship) with the increase of the concentration of the calcium 2, 6-pyridinedicarboxylate solution, wherein the intensity of the emission peak at about 615nm increases with the concentration of the calcium 2, 6-pyridinedicarboxylate solution (at 1.0X 10)6mol/L to 1.0X 10-4In the mol/L range).
As can be seen from FIG. 4, the standard curve shows a substantially linear relationship, which indicates that the europium-doxycycline complex has good selectivity for calcium 2, 6-pyridinedicarboxylate. And (3) measuring the fluorescence intensity of the 2, 6-pyridinedicarboxylic acid calcium solution with the concentration to be measured by a fluorescence method, and finding the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution corresponding to the fluorescence intensity in the standard curve to obtain the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution to be measured.
R in FIG. 42To determine the coefficients in statistics, the ratio at which all the variations in the dependent variables can be explained by the independent variables by regression relations.
Example 2
(1) Adding 0.5mmol dysprosium chloride (DyCl)3·6H2O,0.1435g) and 1mmol of doxycycline (C)22H24N2O80.18g) of the rare earth element is dissolved in 20mL of deionized water, and the solution is magnetically stirred for 40min at room temperature and the rotating speed of 500r/min to obtain a uniform solution containing the rare earth element;
(2) adjusting the pH value of the solution containing the rare earth elements to 9 by using ammonia water, stirring and reacting for 2 hours under the condition that the rotating speed is 800r/min, centrifugally separating out precipitate under the condition that the rotating speed is 5000r/min, washing for 3 times by using absolute ethyl alcohol, and finally drying the separated precipitate in an oven at 60 ℃ for 24 hours to obtain the dysprosium-doxycycline complex fluorescent probe.
As can be seen from FIG. 5, the dysprosium-doxycycline complex fluorescent probe obtained in example 2 is in an amorphous state.
As can be seen from FIG. 6, the dysprosium-doxycycline complex obtained in example 2 has a distinct characteristic peak at 480nm, which corresponds to dysprosium ion4F9/2→6H15/2The emission peak generated by the transition shows that the doxycycline and the rare earth dysprosium ions are matched in energy level, and energy transfer exists between the doxycycline and the rare earth dysprosium ions, namely the rare earth dysprosium ions are successfully coordinated with the doxycycline.
The method for detecting the concentration of the 2, 6-pyridine calcium dicarboxylate solution by the dysprosium-doxycycline complex fluorescent probe comprises the following steps:
(1) 0.0053g (1.0X 10)-5mol) mixing the dysprosium-doxycycline complex fluorescent probe with a 2, 6-pyridinedicarboxylic acid calcium solution with standard concentration to perform specific reaction, and performing ultrasonic dispersion for 10min to obtain a solution to be detected;
the concentrations of standard concentration 2, 6-pyridine calcium dicarboxylate solutions are respectively 1 muM, 20 muM, 40 muM, 60 muM, 80 muM and 100 muM, and the volumes are all 100 mL;
(2) respectively taking 3mL of the solution to be detected by a pipette, placing the solution to be detected into a cuvette one by one, and detecting an emission spectrum of the solution by using a fluorescence spectrometer under the condition that the monitoring wavelength is 340nm (as shown in figure 7);
(3) and then, taking the concentration value of the calcium 2, 6-pyridinedicarboxylate solution with the standard concentration as an abscissa and taking the fluorescence intensity value at 480nm in a fluorescence spectrum corresponding to the calcium 2, 6-pyridinedicarboxylate solution with the standard concentration as an ordinate, drawing a standard curve of the calcium 2, 6-pyridinedicarboxylate under the dysprosium-doxycycline complex fluorescent probe (as shown in FIG. 8).
As can be seen from FIG. 7, the emission peak (i.e., characteristic peak) at 480nm corresponds to Dy in the dysprosium-doxycycline complex3+Of ions4F9/2→6H15/2The intensity of these emission peaks increases (in a proportional relationship) with the increase of the concentration of the calcium 2, 6-pyridinedicarboxylate solution, wherein the intensity of the emission peak at about 480nm increases with the concentration of the calcium 2, 6-pyridinedicarboxylate solution (at 1.0X 10)6mol/L to 1.0X 10-4In the mol/L range) increaseBut is increased.
As can be seen from FIG. 8, the standard curve shows a substantially linear relationship, which indicates that the dysprosium-doxycycline complex has good selectivity for calcium 2, 6-pyridinedicarboxylate. And (3) measuring the fluorescence intensity of the 2, 6-pyridinedicarboxylic acid calcium solution with the concentration to be measured by a fluorescence method, and finding the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution corresponding to the fluorescence intensity in the standard curve to obtain the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution to be measured.
In addition, the comparison of the slopes of the standard curves shows that compared with the europium-doxycycline complex fluorescent probe, the dysprosium-doxycycline complex has better detection sensitivity to calcium 2, 6-pyridinedicarboxylate.
Claims (3)
1. The application of the rare earth-doxycycline complex in the fluorescent probe for detecting the concentration of 2, 6-calcium dipicolinate is characterized in that the rare earth element is dysprosium or europium, and the method comprises the following specific steps:
(1) mixing the fluorescent probe with calcium 2, 6-dipicolinate solutions with different concentrations for reaction;
(2) measuring the spectrum by adopting a fluorescence method to obtain the fluorescence spectrum of the 2, 6-calcium dipicolinate solution with different concentrations;
(3) then, taking the concentration value of the calcium 2, 6-pyridinedicarboxylate as an abscissa, and taking the fluorescence intensity value of a characteristic peak in a fluorescence spectrum corresponding to different concentrations of the calcium 2, 6-pyridinedicarboxylate as an ordinate to draw a standard curve;
(4) and (3) measuring the fluorescence intensity of the 2, 6-pyridinedicarboxylic acid calcium solution with the concentration to be measured by a fluorescence method, and finding the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution corresponding to the fluorescence intensity in the standard curve to obtain the concentration of the 2, 6-pyridinedicarboxylic acid calcium solution to be measured.
2. The use according to claim 1, wherein in the step (1), the temperature of the mixing reaction is 15-35 ℃ and the time is 10-20 min.
3. The use according to claim 1, wherein in step (2), the test conditions are: measuring the spectrum of 450-700 nm in a fluorescence spectrometer with the voltage value of 700V, the scanning speed of 1200nm/min, the slit width of 10nm and the excitation wavelength of 340 nm.
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