CN115895279A - SPAN/MOFs @ Luminol luminescent material and preparation method and application thereof - Google Patents
SPAN/MOFs @ Luminol luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano material preparation and chemiluminescence analysis, and discloses a preparation method and application of a sulfonated polyaniline functionalized metal organic framework @ Luminol (SPAN/MOFs @ Luminol) luminescent material, wherein the preparation method of the SPAN/MOFs @ Luminol luminescent material comprises the following steps: preparing Sulfonated Polyaniline (SPAN) by controlling synthesis conditions, modifying the SPAN on the surface of a Metal Organic Framework (MOFs) material by a hydrothermal method, centrifuging a reaction product, washing, collecting precipitate, and drying in a drying oven to obtain a sulfonated polyaniline functionalized metal organic framework material; adding Luminol, magnetically stirring for reaction for a while, centrifuging, washing and precipitating to obtain SPAN/MOFs @ Luminol chemiluminescent material. The SPAN/MOFs @ Luminol luminescent material prepared by the invention has high chemiluminescence quantum yield, can generate a significant chemiluminescence signal in the presence of hydrogen peroxide without adding a chemiluminescence substrate, and is easy to operate in reaction, stable in luminescence signal and easy to record.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a SPAN/MOFs @ Luminol luminescent material, and a preparation method and application thereof.
Background
Chemiluminescence is a light-emitting phenomenon in which a particular chemical reaction produces light emission. Specifically, a certain molecule in a system is transited from a ground state to an excited state through a redox reaction, and then relaxes back to the ground state in the form of light radiation to generate light with a wavelength from near ultraviolet to near infrared, that is, chemiluminescence. The chemiluminescence analysis has the advantages of simple instrument, high analysis speed, low background signal and the like, and has wide application in the aspects of clinical diagnosis, environmental evaluation, food safety and the like. Luminol, as a typical chemiluminescent reagent, has the advantages of simple structure, simple synthesis, relatively high quantum efficiency and the like. However, luminol is poorly soluble in water and cannot be used directly under physiological conditions. Therefore, luminol usually needs to be dissolved in an alkaline solution, and its chemiluminescent signal must be measured under alkaline conditions. By functionalizing the luminol surface group, the luminol surface group has higher solubility under neutral conditions, and a stronger luminescent signal is obtained. In practical applications, it is often desirable to use a catalyst to further enhance the luminol luminescence signal to increase the sensitivity of the assay. With the rise of nanotechnology in recent years, various nanomaterials including metal and metal oxide nanoparticles, metal Organic Frameworks (MOFs), graphene oxide, carbon dots and the like are also found to have good catalytic effects on luminol luminescence, and catalytic reactions between these catalysts and luminol are mostly carried out between solid and liquid phases, which is a heterogeneous catalytic process. MOFs can be used as a carrier and has catalytic action due to large specific surface area, wide porosity, adjustable structure and high-density active catalytic centers. However, the MOFs material generally has poor dispersion characteristics in the aqueous phase, and it is difficult to uniformly disperse the luminol-immobilized MOFs luminescent complex in a solvent when performing luminescence measurement in the aqueous phase, thereby affecting the stability of luminescent signal. Although the size of the MOFs material is reduced to the nanometer level, the dispersion performance of the MOFs material can be improved to a certain extent, the preparation of the nanometer MOFs is complex and difficult to control and realize. And most MOFs are not very stable in an aqueous phase, and the collapse of a lattice structure is easy to occur in long-term use, so that the performance of the MOFs is lost. Therefore, it is necessary to improve the dispersion performance of the MOF material in the aqueous phase and the stability of the material by a simple surface functionalization method, and it is important to explore a novel high-efficiency chemiluminescent material for improving the performance of chemiluminescence analysis and determination.
Through the above analysis, the problems and defects of the prior art are as follows: 1) Due to the problems of limited quantum efficiency, weak luminous intensity and the like of the chemiluminescence agent, the chemiluminescence analysis process of an actual sample has difficulty in sensitively responding to a low-concentration analyte; 2) The metal organic framework material is added in a chemiluminescence reaction system to be used as a catalyst, but the existing metal organic framework material is difficult to prepare, high in cost and poor in stability in aqueous solution; 3) Under the neutral condition, because the solubility of the luminol luminescent reagent is limited, the luminol luminescent reagent is usually dissolved in an alkaline solution, and a luminescent medium is adjusted to be alkaline, so that higher luminescent efficiency can be obtained, and the application of a luminol system in the fields of biology and the like is limited; therefore, developing a new luminescent material is one of the main problems that researchers have overcome at the present stage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a SPAN/MOFs @ Luminol luminescent material.
The invention also aims to provide the SPAN/MOFs @ Luminol luminescent material obtained by the preparation method.
The invention also aims to provide the application of the SPAN/MOFs @ Luminol luminescent material in chemiluminescence detection, biosensors and biological imaging.
In order to solve the technical problem, the technical scheme of the invention is implemented as follows: a preparation method of SPAN/MOFs @ Luminol luminescent material comprises the following steps:
s1, ultrasonically dispersing an aniline monomer, a surfactant and 3-aminobenzenesulfonic acid in a first solvent to obtain a uniform mixed solution A;
s2, dissolving an oxidant in water to form a mixed solution B;
s3, slowly dripping the mixed solution B obtained in the step S2 into the mixed solution A obtained in the step S1, and continuously reacting for a certain time to obtain a sulfonated polyaniline mixed solution C;
s4, standing, centrifuging, washing and collecting the sulfonated polyaniline mixed solution C obtained in the S3 in a low-temperature environment, and drying and weighing the solution in an oven to obtain the SPAN material;
s5, adding the SPAN material obtained in the S4, metal ions and an organic ligand into a second solvent, uniformly stirring, transferring into a reaction kettle for reaction, and after the reaction is completed, centrifuging, washing and drying a reaction solution to obtain the SPAN/MOFs composite material;
and S6, ultrasonically dispersing the SPAN/MOFs composite material obtained in the S5 into a solvent, adding Luminol, and magnetically stirring to enable the SPAN/MOFs @ Luminol composite material to be fully reacted to obtain the SPAN/MOFs @ Luminol composite material.
Preferably, in S1, the mass ratio of the aniline monomer to the surfactant to the 3-aminobenzenesulfonic acid is 1: (0.5-1.5): (1-4); the surfactant is cetyl trimethyl ammonium bromide 、 One or more of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; the first solvent is one or more of dilute sulfuric acid solution, dilute nitric acid solution, dilute hydrochloric acid solution, citric acid solution, oxalic acid solution and acetic acid solution.
Preferably, in the S2, the concentration of the oxidant is 0.01-0.15M, and the volume consumption is 5-30 mL; the oxidant is one or more of inorganic oxidants such as dichromate, persulfate, permanganate, peroxide and the like.
Preferably, in the step S3, the reaction time is 10 to 30min.
Preferably, in the S4, the standing temperature is 2-8 ℃, and the standing time is 10-30 h; washing until the pH value of the filtrate is 5.5-6.0; the drying temperature is 50-85 ℃.
Preferably, in S5, the molar ratio of the metal ion to the organic ligand is (0.5 to 2): 1, the mass ratio of the organic ligand to the SPAN is (1-16): 1; the second solvent is a mixed solution of absolute ethyl alcohol and water, and the volume ratio of the absolute ethyl alcohol to the water is 1 (0.8-1.2); the organic ligand is one or more of trimesic acid, 2-aminoterephthalic acid, terephthalic acid and 1, 10-phenanthroline-2,9-dicarboxylic acid, and is preferably trimesic acid; the metal ions are one or more of nitrate, hydrochloride, sulfate and acetate of Cu, co, ni and Fe metal ions.
Preferably, in the step S5, a hydrothermal reaction is performed in the reaction kettle, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-10 hours; the solvent for washing is distilled water and absolute ethyl alcohol; the drying temperature is 50-85 ℃.
Preferably, in the S6, the concentration of the Luminol is 1-10 mM, and the volume usage of the Luminol is 0.8-1.5 mL; the concentration of the SPAN/MOFs is 1-4 mg/mL, and the volume dosage of the SPAN/MOFs is 7-11 mL; the reaction time is 4-12 h.
The second technical scheme of the invention is realized as follows: SPAN/MOFs @ Luminol chemiluminescent material prepared by the preparation method is provided.
The third technical scheme of the invention is realized as follows: the SPAN/MOFs @ Luminol luminescent material is applied to the aspects of chemiluminescence detection, biosensing analysis and chemiluminescence imaging.
Compared with the prior art, the invention has the following beneficial effects:
the SPAN/MOFs @ Luminol luminescent material prepared by the invention can generate a chemiluminescence signal by autocatalysis in the presence of hydrogen peroxide, has higher chemiluminescence efficiency, does not need to additionally add a chemiluminescence substrate, and has the advantages of easy reaction operation, stable luminescence signal and easy recording.
The SPAN/MOFs @ Luminol luminescent material provided by the invention is decorated on the surface of MOFs by using sulfonated polyaniline, and has good water stability and dispersibility. Luminol is effectively immobilized on the complex by interaction with SPAN. The invention has simple preparation, good preparation effect, no toxicity and no pollution, and conforms to the concept of green chemistry. The invention also provides the chemiluminescence characteristics of the SPAN/MOFs @ Luminol luminescent material, the SPAN helps the luminescent material to show good dispersibility in a water phase, and provides rich sites for the catalytic action of the MOFs and luminol, thereby obviously improving the luminescent signal. The invention can utilize the synthesized SPAN/MOFs @ Luminol luminescent material to catalyze H in alkaline environment 2 O 2 Generating enhanced chemiluminescent signal for testing H in the range of 30 to 600pmol 2 O 2 Concentration; and enhanced chemiluminescent signal in neutral environment, useful for testing H in the range of 0.1 μ M to 30 μ M 2 O 2 And (4) concentration. The SPAN/MOFs @ Luminol luminescent material prepared by the invention has good biocompatibility, and the application of the SPAN/MOFs @ Luminol luminescent material in the field of chemiluminescence immunoassay is widened.
Compared with the existing chemiluminescence reagents in the market, such as luminol, acridinium ester, lucinol and the like, the SPAN/MOFs @ Luminol luminescent material provided by the invention has the following special properties: (1) The SPAN/MOFs @ Luminol luminescent material is simple in preparation method, is a hydrothermal method, and is non-toxic and harmless; (2) The nano luminescent material has dual functions of a chemiluminescent substrate and nano catalysis, so that the conventional chemiluminescent reaction system can be saved by adding the chemiluminescent substrate and the catalyst at the same time, and the chemiluminescent reaction can be realized only by adding the prepared SPAN/MOFs @ Luminol luminescent material; (3) Compared with the traditional chemiluminescence reaction which needs to obtain a chemiluminescence signal under an alkaline condition, the nanometer luminescent material can generate the chemiluminescence signal under the alkaline condition and the neutral condition, has stronger and stable chemiluminescence signal, is easier to record by a detection instrument, and expands the application field of chemiluminescence analysis methods.
The SPAN/MOFs @ Luminol luminescent material obtained by the invention is a novel chemiluminescent nano material with luminescent substrate and catalyst, and H can be realized by the SPAN/MOFs @ Luminol luminescent material 2 O 2 The detection system does not need additional catalysts and luminescent reagents. Therefore, the application of the SPAN/MOFs @ Luminol luminescent material can overcome the problems that the prior chemiluminescence immunoassay mostly needs biological enzyme catalysis, a chemiluminescence reaction system is complex, the chemiluminescence immunoassay can only be used under an alkaline condition and the like.
Drawings
FIG. 1 is an SEM image of SPAN/CuMOF @ Luminol luminescent material obtained in example 1 of the present invention.
FIG. 2 is a diagram of the UV-VIS absorption spectrum of the SPAN/CuMOF @ Luminol luminescent material obtained in example 1 of the present invention.
FIG. 3 is an XRD pattern of SPAN/CuMOF @ Luminol luminescent material obtained in example 1 of the present invention.
FIG. 4 is a chemiluminescent signal diagram generated by catalyzing hydrogen peroxide by the SPAN/MOFs @ Luminol luminescent material provided in embodiment 5 of the present invention.
FIG. 5 is a diagram of the chemiluminescence signals generated by the SPAN/MOFs @ Luminol luminescent material provided in embodiment 5 of the present invention catalyzing hydrogen peroxide at different pH.
FIG. 6 shows SPAN/MOFs @ Luminol phosphor and Co provided in embodiment 6 of the present invention 2+ Comparison of chemiluminescent signals generated by HRP catalyzed hydrogen peroxide and luminescent substrate lumineol.
FIG. 7 shows that the SPAN/MOFs @ Luminol luminescent material provided in embodiment 7 of the present invention is applied to detect H with different concentrations under alkaline conditions 2 O 2 Time, chemiluminescence peak and H 2 O 2 Graph of concentration dependence.
FIG. 8 shows that SPAN/MOFs @ Luminol luminescent material is applied to detect H with different concentrations under neutral condition in embodiment 7 of the present invention 2 O 2 Time, chemiluminescence peak and H 2 O 2 Graph of the relationship of concentration.
FIG. 9 is a diagram of example 8 of the present invention for detecting H released from stimulated cells by applying SPAN/MOFs @ Luminol luminescent material 2 O 2 And (4) content.
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 the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
It is to be noted that the raw materials used in the following examples are commercially available and may be prepared by the self-service method.
The embodiment of the invention provides a preparation method of SPAN/MOFs @ Luminol luminescent material, which comprises the following steps:
s1, ultrasonically dispersing aniline monomer, surfactant and 3-aminobenzene sulfonic acid in a first solvent to obtain a uniform mixed solution A; the mass ratio of the aniline monomer to the surfactant to the 3-aminobenzenesulfonic acid is 1: (0.5-1.5): (1-4); the surfactant is cetyl trimethyl ammonium bromide 、 One or more of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; the first solvent is one or more of dilute sulfuric acid solution, dilute nitric acid solution, dilute hydrochloric acid solution, citric acid solution, oxalic acid solution and acetic acid solution;
s2, dissolving an oxidant in water to form a mixed solution B; the concentration of the oxidant is 0.01-0.15M, and the volume consumption is 5-30 mL; the oxidant is one or more of inorganic oxidants such as dichromate, persulfate, permanganate, peroxide and the like;
s3, slowly dripping the mixed solution B obtained in the step S2 into the mixed solution A obtained in the step S1, and continuously reacting for 10-30 min to obtain a sulfonated polyaniline mixed solution C;
s4, standing the sulfonated polyaniline mixed C solution obtained in the S3 for 10-30 h at a low temperature of 2-8 ℃, centrifuging, washing, collecting precipitates, placing in a drying oven at a temperature of 50-85 ℃, drying and weighing to obtain the SPAN material; wherein, the pH value of the filtrate is 5.5 to 6.0 after the washing;
s5, adding the SPAN material obtained in the S4, metal ions and an organic ligand into a second solvent, uniformly stirring, transferring into a reaction kettle for reaction, and after the reaction is completed, centrifuging, washing and drying a reaction solution to obtain the SPAN/MOFs composite material; wherein the molar ratio of the metal ions to the organic ligands is (0.5-2): 1, the mass ratio of the organic ligand to the SPAN is (1-16): 1; the second solvent is a mixed solution of absolute ethyl alcohol and water, and the volume ratio of the absolute ethyl alcohol to the water is 1 (0.8-1.2); the organic ligand is one or more of trimesic acid, 2-amino terephthalic acid, terephthalic acid and 1, 10-phenanthroline-2,9-dicarboxylic acid, and the metal ions are one or more of nitrates, hydrochlorides, sulfates and acetates of Cu, co, ni and Fe metal ions; carrying out hydrothermal reaction in the reaction kettle, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-10 h; the solvent for washing is distilled water and absolute ethyl alcohol; the drying temperature is 50-85 ℃;
s6, ultrasonically dispersing the SPAN/MOFs composite material obtained in the S5 into a solvent, adding Luminol, and magnetically stirring to enable the SPAN/MOFs @ Luminol composite material to be fully reacted to obtain the SPAN/MOFs @ Luminol composite material; wherein, the solvent can be selected from water or ethanol water solution, and is preferably water; the concentration of the Luminol is 1-10 mM, and the volume consumption of the Luminol is 0.8-1.5 mL; the concentration of the SPAN/MOFs is 1-4 mg/mL, and the volume dosage of the SPAN/MOFs is 7-11 mL; the reaction time is 4-12 h.
The embodiment also provides the SPAN/MOFs @ Luminol chemiluminescent material prepared by the preparation method.
The embodiment also provides application of the SPAN/MOFs @ Luminol luminescent material in chemiluminescence detection, biosensing analysis and chemiluminescence imaging.
The following are specific examples
Example 1
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 1 of the invention is prepared by the following steps:
s1: ultrasonically dispersing aniline monomer, surfactant cetyl trimethyl ammonium bromide and 3-aminobenzenesulfonic acid in a first solvent dilute hydrochloric acid, wherein the mass ratio of the aniline monomer to the surfactant cetyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1:1:2, obtaining a uniform solution A;
s2: dissolving 20mL of ammonium persulfate oxidant with the concentration of 0.05M in 10mL of water to form solution B;
s3: slowly dripping the solution B into the solution A, continuously reacting for 15min to obtain a sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 24h at the temperature of 5 ℃;
s4: centrifuging, washing and filtering the reaction product until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in an oven at 80 ℃, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline, cu (COOH) 2 ·H 2 Adding terephthalic acid serving as an organic ligand into a solvent obtained by mixing anhydrous ethanol serving as a second solvent and water according to a volume ratio of 1:1, transferring the mixture into a reaction kettle, reacting for 10 hours at 100 ℃, centrifuging, washing with absolute ethyl alcohol and water, and drying in an oven at 80 ℃ to obtain the SPAN/CuMOF composite material;
s6: dispersing the SPAN/CuMOF composite material by distilled water to obtain 10mL of SPAN/CuMOF composite material dispersion liquid with the concentration of 4mg/mL, then adding 1mL of Luminol with the concentration of 5mM, fully reacting the SPAN/CuMOF @ Luminol composite material for 10 hours by magnetic stirring to prepare the SPAN/CuMOF @ Luminol composite material, and storing in an environment at 3-4 ℃.
As shown in FIG. 1, which is an SEM image of the SPAN/CuMOF @ Luminol luminescent material prepared in this example 1, it can be clearly seen that the material has a regular morphology structure, is in an octahedral structure, is about 5 μm, and has good particle dispersibility; FIG. 2 is a diagram showing the ultraviolet-visible absorption spectrum analysis of SPAN/CuMOF @ Luminol luminescent material, and it can be seen that the prepared SPAN/CuMOF @ Luminol luminescent material shows characteristic absorption peaks at 302nm, 349nm and 780 nm; FIG. 3 shows the XRD pattern of SPAN/CuMOF @ Luminol luminescent material, from which it can be seen that the material is consistent with the crystal plane of CuMOF, further illustrating the successful modification of Luminol and SPAN on CuMOF.
Example 2
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 2 of the invention is prepared by the following steps:
s1: ultrasonically dispersing aniline monomer, surfactant polyvinylpyrrolidone and 3-aminobenzenesulfonic acid in a first solvent of dilute hydrochloric acid, wherein the mass ratio of the aniline monomer to the surfactant polyvinylpyrrolidone to the first solvent is 1;
s2: dissolving 20mL of 0.1M hydrogen peroxide oxidant in 10mL of water to form solution B;
s3: slowly dripping the solution B into the solution A, continuously reacting for 30min to obtain sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 20h at the temperature of 5 ℃;
s4: centrifuging, washing and filtering the reaction product until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in an oven at 60 ℃, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline and CuSO 4 ·5H 2 Adding terephthalic acid serving as an organic ligand into a solvent obtained by mixing anhydrous ethanol serving as a second solvent and water according to a volume ratio of 1:1, transferring the mixture into a reaction kettle, reacting for 12 hours at 140 ℃, centrifuging, washing with absolute ethyl alcohol and water, and drying in an oven at 60 ℃ to obtain the SPAN/CuMOF composite material;
s6: dispersing the SPAN/CuMOF composite material by distilled water to obtain 10mL of SPAN/CuMOF composite material dispersion liquid with the concentration of 3mg/mL, then adding 1mL of Luminol with the concentration of 10mM, fully reacting the SPAN/CuMOF @ Luminol composite material for 12h by magnetic stirring to prepare the SPAN/CuMOF @ Luminol composite material, and storing the SPAN/CuMOF @ Luminol composite material at the temperature of 4 ℃.
Example 3
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 3 of the invention is prepared by the following steps:
s1: ultrasonically dispersing an aniline monomer, a surfactant cetyl trimethyl ammonium bromide and 3-aminobenzenesulfonic acid in a first solvent dilute hydrochloric acid, wherein the mass ratio of the aniline monomer to the surfactant cetyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1;
s2: dissolving 20mL of potassium persulfate oxidant with the concentration of 0.05M in 10mL of water to form solution B;
s3: slowly dripping the solution B into the solution A, continuously reacting for 15min to obtain a sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 24h at the temperature of 5 ℃;
s4: centrifuging, washing and filtering the reaction product until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in an oven at 80 ℃, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline and FeCl 2 Adding terephthalic acid serving as an organic ligand into a solvent obtained by mixing anhydrous ethanol serving as a second solvent and water according to a volume ratio of 1:1, stirring, transferring the mixture into a reaction kettle, reacting for 10 hours at 100 ℃, centrifuging, washing with anhydrous ethanol and water, and drying in an oven at 80 ℃, wherein the molar ratio of the metal ions to the organic ligand is 1:1, and the mass ratio of the organic ligand to SPAN is 5:1;
s6: dispersing the SPAN/FeMOF composite material by distilled water to obtain 10mL of SPAN/FeMOF composite material dispersion liquid with the concentration of 4mg/mL, then adding 1mL of Luminol with the concentration of 5mM, fully reacting the SPAN/FeMOF @ Luminol composite material for 8 hours by magnetic stirring to prepare the SPAN/FeMOF @ Luminol composite material, and storing the SPAN/FeMOF @ Luminol composite material at the temperature of 3-4 ℃.
Example 4
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 4 of the invention is prepared by the following steps:
s1: ultrasonically dispersing an aniline monomer, a surfactant cetyl trimethyl ammonium bromide and 3-aminobenzenesulfonic acid in a first solvent dilute hydrochloric acid, wherein the mass ratio of the aniline monomer to the surfactant cetyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1;
s2: dissolving 5mL of potassium persulfate oxidant with the concentration of 0.15M in 10mL of water to form solution B;
s3: slowly dripping the solution B into the solution A, continuously reacting for 10min to obtain sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 30h at the temperature of 5 ℃;
s4: centrifuging, washing and filtering the reaction product until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in an oven at 60 ℃, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline and FeCl 2 Adding organic ligand trimesic acid into a solvent obtained by mixing anhydrous ethanol and water according to the volume ratio of 1;
s6: dispersing the SPAN/FeMOF composite material by distilled water to obtain 10mL of SPAN/FeMOF composite material dispersion liquid with the concentration of 1mg/mL, then adding 1mL of Luminol with the concentration of 10mM, fully reacting the SPAN/FeMOF @ Luminol composite material and the Luminol composite material for 6 hours by magnetic stirring to prepare the SPAN/FeMOF @ Luminol composite material, and storing the SPAN/FeMOF @ Luminol composite material in an environment at 3-4 ℃.
Example 5
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 5 of the invention is applied to the aspect of chemiluminescence detection, and the specific application method and the comparison result are as follows:
1) Taking 5mL reaction tube, adding 50 μ L SPAN/CuMOF @ Luminol luminescent material and 150 μ L H in reaction system 2 O 2 Mixing the solutions immediately, and recording a chemiluminescence dynamic curve by using a chemiluminescence detector;
2) 150 mu L H 2 O 2 The mixture was injected into 50. Mu.L of SPAN/CuMOF @ Luminol in Tris-HCl buffer (pH 6-11) and sodium hydroxide solution (pH 12-13), and a chemiluminescence detector was used to record a chemiluminescence kinetic curve.
FIG. 4 shows that SPAN/CuMOF @ Luminol luminescent material generates a chemiluminescent signal 36 times higher than that generated by luminol of the same concentration. CuMOF has peroxidase-like catalytic activity and can catalyze H 2 O 2 OH is generated by decomposition, the efficiency of the chemiluminescence reaction is improved, the chemiluminescence intensity is enhanced, and excellent chemiluminescence performance is presented. FIG. 5 shows the use of SPAN/CuMOF @ LuThe minol luminescent materials produce strong chemiluminescent signals over a relatively wide pH range.
Example 6
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 6 of the invention is compared with the traditional luminescent catalyst, and the specific method for application and the comparison result are as follows:
conventional catalyst Co 2+ HRP catalyzes Luminol to generate a chemiluminescent signal, a 5mL reaction tube is taken, and 30 mu L (10 mu M) of Co is added into a reaction system 2+ 30 μ L (20 μ g/mL) of HRP,20 μ L (50 μ M) of Luminol solution, 150 μ L of H 2 O 2 The solutions were mixed immediately and the chemiluminescence kinetic curve was recorded using a chemiluminescence detector.
FIG. 6 shows a more conventional catalyst Co 2+ The HRP catalyzed chemiluminescence reaction, and the SPAN/MOF @ Luminol luminescent material can generate strong chemiluminescence signals which are easy to record; and because the catalyst and the chemiluminescent substrate are doped in the material, the step of adding the chemiluminescent substrate in the reaction can be omitted, and the operation is simpler.
Example 7
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 7 of the invention is applied to biological immunoassay, and the specific method of the application is as follows: the SPAN/CuMOF @ Luminol luminescent material is used for detecting hydrogen peroxide, and the method specifically comprises the following steps:
step 1) at 30% H 2 O 2 Adding deionized water for dilution to prepare H 2 O 2 Standard solution 10mM;
step 2) taking 50 mu L of prepared SPAN/HKUST-1@ Luminol luminescent material solution, adding sodium hydroxide buffer solutions with different volumes and pH values of 12.0, and mixing or mixing with PBS solution with pH value of 7.0;
step 3) adding different volumes of H containing 10mM prepared in step 1 2 O 2 Solutions of the corresponding H 2 O 2 The final concentration is 30pmol,50pmol,70pmol,100pmol,200pmol,300pmol,600pmol, or 0.1. Mu.M, 0.7. Mu.M, 1. Mu.M, 2. Mu.M, 3. Mu.M, 7. Mu.M, 15. Mu.M, 30. Mu.M, respectively, and the final reaction volume is 150. Mu.L;
step 4) addition of H 2 O 2 After the solution, a chemiluminescence detector is used for recording a chemiluminescence power curve, the highest value of a chemiluminescence signal is recorded, and H is added 2 O 2 And (4) drawing a reaction linear relation curve.
SPAN/CuMOF @ Luminol luminescent materials and H 2 O 2 Generating chemiluminescence signal after reaction, recording time kinetic curve of the chemiluminescence signal, and corresponding luminescence signal and H 2 O 2 The concentration is positively correlated. From the results in FIG. 7,8, the chemiluminescence signals were analyzed by linear regression with H 2 O 2 The concentration shows a good linear relationship (basic: R) 2 =0.995, neutral: r is 2 = 0.994), the linear regression equation is:
basic, y =12.77C-34.01; and (3) neutrality: y =246.6C +173.8
Therefore, the plateau chemiluminescence signal and H can be obtained from this equation 2 O 2 The linear relationship of the concentrations was calculated to give H in the range of 30 to 600pmol concentration 2 O 2 Concentration (basic); obtaining H in the concentration range of 0.1 to 30 mu M 2 O 2 Concentration (neutral).
Example 8
The SPAN/MOFs @ Luminol luminescent material provided by the embodiment 8 of the invention is applied to the aspect of biosensing analysis, and the specific method of the application is as follows: the SPAN/CuMOF @ Luminol luminescent material is used for detecting hydrogen peroxide released by cells, and the method specifically comprises the following steps:
1) Cells were harvested by centrifugation and injected with 30. Mu.L (5. Mu.M, 10. Mu.M) ascorbic acid to stimulate hydrogen peroxide production using 1mL (pH 7.4) of PBS;
2) 150 μ L of cell solution was mixed with 50 μ L of SPAN/HKUST-1@ Luminol luminescent material to obtain a chemiluminescent signal.
As shown in fig. 9, the material can be used to determine the amount of hydrogen peroxide released by the cells.
In summary, the significance of solving the problems existing in the prior art by adopting the method of the present application is as follows:
1) The problem of weak luminous intensity of the existing chemiluminescence agent is solved, a response signal in a chemiluminescence analysis process can be improved, and the detection sensitivity is improved; 2) It is necessary to adopt a simple surface functionalization method to improve the dispersion performance of the MOFs material in a water phase and improve the stability of the material; 3) The catalyst and the luminescent reagent are prepared into a complex, and the complex shows excellent chemiluminescence activity and good stability. The composite material not only can make up the defect of low catalytic activity of certain single materials, but also can provide more response sites to improve the selectivity of sample detection, thereby enhancing the value of chemiluminescence analysis.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of SPAN/MOFs @ Luminol luminescent material is characterized by comprising the following steps:
s1, ultrasonically dispersing an aniline monomer, a surfactant and 3-aminobenzenesulfonic acid in a first solvent to obtain a uniform mixed solution A;
s2, dissolving an oxidant in water to form a mixed solution B;
s3, slowly dripping the mixed solution B obtained in the step S2 into the mixed solution A obtained in the step S1, and continuously reacting for a certain time to obtain a sulfonated polyaniline mixed solution C;
s4, standing, centrifuging, washing and collecting the sulfonated polyaniline mixed solution C obtained in the S3 in a low-temperature environment, and drying and weighing the solution in an oven to obtain the SPAN material;
s5, adding the SPAN material obtained in the S4, metal ions and an organic ligand into a second solvent, uniformly stirring, transferring into a reaction kettle for reaction, and after the reaction is completed, centrifuging, washing and drying a reaction solution to obtain the SPAN/MOFs composite material;
and S6, ultrasonically dispersing the SPAN/MOFs composite material obtained in the S5 into a solvent, adding Luminol, and magnetically stirring to enable the SPAN/MOFs @ Luminol composite material to be fully reacted to obtain the SPAN/MOFs @ Luminol composite material.
2. The method according to claim 1, wherein in the S1, the mass ratio of the aniline monomer to the surfactant to the 3-aminobenzenesulfonic acid is 1: (0.5-1.5): (1-4); the surfactant is cetyl trimethyl ammonium bromide 、 One or more of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; the first solvent is one or more of dilute sulfuric acid solution, dilute nitric acid solution, dilute hydrochloric acid solution, citric acid solution, oxalic acid solution and acetic acid solution.
3. The method for preparing SPAN/MOFs @ Luminol luminescent material according to claim 1, wherein in S2, the concentration of said oxidant is 0.01-0.15M, and the volume dosage is 5-30 mL; the oxidant is one or more of inorganic oxidants such as dichromate, persulfate, permanganate, peroxide and the like.
4. The method for preparing SPAN/MOFs @ Luminol luminescent material according to claim 1, wherein in S3, the reaction time is 10-30 min.
5. The method for preparing SPAN/MOFs @ Luminol luminescent material according to claim 1, wherein in S4, the standing temperature is 2-8 ℃, and the standing time is 10-30 h; washing until the pH value of the filtrate is 5.5-6.0; the drying temperature is 50-85 ℃.
6. The method according to claim 1, wherein in S5, the molar ratio of the metal ions to the organic ligand is (0.5-2): 1, the mass ratio of the organic ligand to the SPAN is (1-16): 1; the second solvent is a mixed solution of absolute ethyl alcohol and water, and the volume ratio of the absolute ethyl alcohol to the water is 1 (0.8-1.2); the organic ligand is one or more of trimesic acid, 2-amino terephthalic acid, terephthalic acid and 1, 10-phenanthroline-2,9-dicarboxylic acid, and the metal ions are one or more of nitrates, hydrochlorides, sulfates and acetates of Cu, co, ni and Fe metal ions.
7. The method for preparing SPAN/MOFs @ Luminol luminescent material according to claim 6, wherein in S5, hydrothermal reaction is carried out in said reaction kettle, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-10 h; the solvent for washing is distilled water and absolute ethyl alcohol; the drying temperature is 50-85 ℃.
8. The method of claim 1, wherein the Luminol concentration in S6 is 1-10 mM, and the volume of Luminol is 0.8-1.5 mL; the concentration of the SPAN/MOFs is 1-4 mg/mL, and the volume dosage of the SPAN/MOFs is 7-11 mL; the reaction time is 4-12 h.
9. SPAN/MOFs @ Luminol chemiluminescent material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the SPAN/mofs @ lumineol luminescent material of claim 9 in chemiluminescence detection, in biosensor analysis, and in chemiluminescence imaging.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001035100A2 (en) * | 1999-11-12 | 2001-05-17 | Clinical Micro Sensors, Inc. | Binding acceleration techniques for the detection of analytes |
| JP2004319305A (en) * | 2003-04-17 | 2004-11-11 | Dainippon Printing Co Ltd | Electroluminescent element and polymer compound |
| CN109651621A (en) * | 2019-01-08 | 2019-04-19 | 安徽师范大学 | A kind of zirconium-based metallic organic frame composite material and preparation method and application |
| CN111318310A (en) * | 2020-03-17 | 2020-06-23 | 山东师范大学 | FePc-loaded metal-organic framework composite nanomaterial, preparation method thereof and application of composite nanomaterial in chemiluminescence detection |
| CN111474167A (en) * | 2020-04-29 | 2020-07-31 | 中晋环境科技有限公司 | Cu-MOF-luminol-H2O2Detection of Pb by chemiluminescence system2+Method (2) |
| CN112538296A (en) * | 2020-12-17 | 2021-03-23 | 成都新柯力化工科技有限公司 | Graphene network conductive coating for flexible circuit and preparation method thereof |
| WO2021112694A2 (en) * | 2019-12-03 | 2021-06-10 | Sultan Qaboos University | System and method for detecting analyte in food sample |
| CN113030217A (en) * | 2021-03-19 | 2021-06-25 | 山东理工大学 | Enzyme biosensor for detecting inosinic acid, preparation method and application thereof |
| CN113125422A (en) * | 2021-04-16 | 2021-07-16 | 合肥工业大学 | Preparation method of chemiluminescent hydrogel microspheres, prepared hydrogel microspheres and application thereof |
| CN113444371A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学 | Preparation method and application of metal organic framework/polyaniline composite material |
| CN113522364A (en) * | 2021-07-19 | 2021-10-22 | 中国地质大学（北京） | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system |
| CN113970580A (en) * | 2021-09-23 | 2022-01-25 | 济南大学 | Double-amplification electrochemiluminescence sensor and method for determining chlorpyrifos |
| CN114350207A (en) * | 2022-02-11 | 2022-04-15 | 西北大学 | Fluorescent MOFs ink and preparation method and application thereof |
-
2022
- 2022-11-24 CN CN202211485652.XA patent/CN115895279B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001035100A2 (en) * | 1999-11-12 | 2001-05-17 | Clinical Micro Sensors, Inc. | Binding acceleration techniques for the detection of analytes |
| JP2004319305A (en) * | 2003-04-17 | 2004-11-11 | Dainippon Printing Co Ltd | Electroluminescent element and polymer compound |
| CN109651621A (en) * | 2019-01-08 | 2019-04-19 | 安徽师范大学 | A kind of zirconium-based metallic organic frame composite material and preparation method and application |
| WO2021112694A2 (en) * | 2019-12-03 | 2021-06-10 | Sultan Qaboos University | System and method for detecting analyte in food sample |
| CN111318310A (en) * | 2020-03-17 | 2020-06-23 | 山东师范大学 | FePc-loaded metal-organic framework composite nanomaterial, preparation method thereof and application of composite nanomaterial in chemiluminescence detection |
| CN111474167A (en) * | 2020-04-29 | 2020-07-31 | 中晋环境科技有限公司 | Cu-MOF-luminol-H2O2Detection of Pb by chemiluminescence system2+Method (2) |
| CN112538296A (en) * | 2020-12-17 | 2021-03-23 | 成都新柯力化工科技有限公司 | Graphene network conductive coating for flexible circuit and preparation method thereof |
| CN113030217A (en) * | 2021-03-19 | 2021-06-25 | 山东理工大学 | Enzyme biosensor for detecting inosinic acid, preparation method and application thereof |
| CN113125422A (en) * | 2021-04-16 | 2021-07-16 | 合肥工业大学 | Preparation method of chemiluminescent hydrogel microspheres, prepared hydrogel microspheres and application thereof |
| CN113444371A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学 | Preparation method and application of metal organic framework/polyaniline composite material |
| CN113522364A (en) * | 2021-07-19 | 2021-10-22 | 中国地质大学（北京） | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system |
| CN113970580A (en) * | 2021-09-23 | 2022-01-25 | 济南大学 | Double-amplification electrochemiluminescence sensor and method for determining chlorpyrifos |
| CN114350207A (en) * | 2022-02-11 | 2022-04-15 | 西北大学 | Fluorescent MOFs ink and preparation method and application thereof |
Non-Patent Citations (7)
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