CN115895279B - 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 Frameworks (MOFs) material by a hydrothermal method, centrifuging a reaction product, washing, collecting precipitate, and drying in an oven to obtain the sulfonated polyaniline functionalized metal organic frameworks material; adding Luminol, magnetically stirring, reacting for a period of time, centrifuging, washing and precipitating to obtain the SPAN/MOFs@Luminol chemiluminescent material. The SPAN/MOFs@Luminol luminescent material prepared by the method has high chemiluminescent quantum yield, can generate remarkable chemiluminescent signals in the presence of hydrogen peroxide without adding any chemiluminescent substrate, and is easy to operate, stable in luminescent signals 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 luminescent phenomenon in which a specific chemical reaction produces light emission. Specifically, a certain molecule in the system is transited from a ground state to an excited state through oxidation-reduction reaction, and then is relaxed back to the ground state in the form of optical radiation, so that light with a wavelength ranging from near ultraviolet to near infrared, namely chemiluminescence, is generated. 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 is used as a typical chemiluminescent reagent and has the advantages of simple structure, simple synthesis, relatively high quantum efficiency and the like. However, luminol has poor solubility in water and cannot be used directly under physiological conditions. Thus, luminol generally needs to be dissolved in an alkaline solution, and its chemiluminescent signal must be measured under alkaline conditions. By functionalizing the luminol surface groups, the luminol can have higher solubility under neutral conditions, and stronger luminescent signals are 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 analytical assay. With the rise of nanotechnology in recent years, various nano materials including metal and metal oxide nano particles, metal Organic Frameworks (MOFs), graphene oxide, carbon dots and the like are also found to have good catalytic effects on luminol luminescence, and the catalytic reaction between the catalyst and luminol is mostly carried out between solid-liquid two phases, so that the catalyst and the luminol are heterogeneous catalytic processes. MOFs can be used as a carrier and have catalytic action due to the large specific surface area, wide porosity, adjustable structure and high-density active catalytic center. However, MOFs materials generally have poor dispersion characteristics in an 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 a luminescence signal. Although the dispersion performance of MOFs materials can be improved to a certain extent by reducing the size of the MOFs materials to the nanometer level, the preparation of the MOFs is complex, difficult to control and difficult to realize. And most MOFs materials have poor stability in the aqueous phase, and collapse of the lattice structure is easy to occur during long-term use, so that the performance of the MOFs materials is lost. Therefore, it is necessary to improve the dispersion performance of MOF materials in the water phase and improve the stability of the materials by adopting a simple surface functionalization method, and the method for preparing the novel high-efficiency chemiluminescent materials has great significance in improving the performance of chemiluminescent analysis and measurement.
Through the above analysis, the problems and defects existing in the prior art are as follows: 1) Because the chemiluminescent agent has the problems of limited quantum efficiency, weak luminous intensity and the like, the chemiluminescent analysis process of an actual sample is difficult to sensitively respond to low-concentration analytes; 2) The metal organic framework material is added into the chemiluminescent reaction system as a catalyst, but the existing metal organic framework material is difficult to prepare, has high cost and has poor stability in aqueous solution; 3) The luminol luminous reagent is limited in solubility under neutral conditions, and usually needs to be dissolved in alkaline solution, and luminous medium is regulated to be alkaline to obtain higher luminous efficiency, so that the luminol luminous reagent limits the application of a luminol system in the fields of biology and the like; therefore, developing a new luminescent material is one of the main problems that researchers have overcome at this 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 an application of the SPAN/MOFs@Luminol luminescent material in chemiluminescent detection, a biosensor and biological imaging.
In order to solve the technical problems, the technical scheme of the invention is implemented as follows: a preparation method of a SPAN/MOFs@Luminol luminescent material comprises the following steps:
s1, dispersing an aniline monomer, a surfactant and 3-aminobenzenesulfonic acid in a first solvent by ultrasonic 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 continuing to react for a certain time to obtain a sulfonated polyaniline mixed solution C;
s4, standing, centrifuging, washing, collecting sediment, and placing in an oven for drying and weighing the sulfonated polyaniline mixed C solution obtained in the step S3 in a low-temperature environment to obtain a SPAN material;
s5, adding the SPAN material obtained in the S4, metal ions and organic ligands into a second solvent, uniformly stirring, and transferring into a reaction kettle for reaction, and centrifuging, washing and drying a reaction liquid after the reaction is completed to obtain the SPAN/MOFs composite material;
s6, ultrasonically dispersing the SPAN/MOFs composite material obtained in the S5 in a solvent, adding Luminol, and magnetically stirring to enable the SPAN/MOFs@Luminol composite material to fully react to obtain the SPAN/MOFs@Luminol composite material.
Preferably, 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.
Preferably, in the S2, the concentration of the oxidant is 0.01-0.15M, and the volume dosage is 5-30 mL; the oxidant is one or more of dichromate, persulfate, permanganate, peroxide and other inorganic oxidants.
Preferably, in S3, the reaction time is 10 to 30min.
Preferably, in the step 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, a step of; 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, preferably trimesic acid; the metal ion is one or more of nitrate, hydrochloride, sulfate and acetate of Cu, co, ni, fe metal ion.
Preferably, in the step S5, a hydrothermal reaction is performed in the reaction kettle, the temperature of the hydrothermal reaction is 100-150 ℃, and the time of the hydrothermal reaction 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 dosage 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 adopting the preparation method.
The third technical scheme of the invention is realized as follows: the SPAN/MOFs@Luminol luminescent material is applied to 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 method can automatically catalyze to generate a chemiluminescent signal in the presence of hydrogen peroxide, has higher chemiluminescent efficiency, does not need to additionally add a chemiluminescent substrate, and is easy to operate, stable in luminescent signal and easy to record.
The SPAN/MOFs@Luminol luminescent material provided by the invention is decorated on the surface of MOFs by 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 accords with the green chemical concept. The invention also provides the chemiluminescent characteristic of the SPAN/MOFs@Luminol luminescent material, the SPAN helps the luminescent material to show good dispersibility in water phase, and provides rich sites for the catalysis of MOFs and luminol, so that the luminescent signal is remarkably improved. The invention can utilize the synthesized SPAN/MOFs@Luminol luminescent material to catalyze H in alkaline environment 2 O 2 Generating enhanced chemiluminescent signals useful for testing H in the range of 30 to 600pmol 2 O 2 Concentration; and can enhance chemiluminescent signals in neutral environments, can be used to test H in the range of 0.1 μm to 30. Mu.M 2 O 2 Concentration. And the SPAN/MOFs@Luminol luminescent material prepared by the inventionThe material has good biocompatibility, and widens the application of the SPAN/MOFs@Luminol luminescent material in the field of chemiluminescence immunoassay.
Compared with the existing chemiluminescent reagents such as luminol, acridinium ester, lucigenin and the like in the market, 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 nontoxic and harmless; (2) The nano luminescent material has the dual functions of chemiluminescent substrate and nano catalysis, so that the conventional chemiluminescent reaction system can be omitted, and the chemiluminescent reaction can be realized only by adding the prepared SPAN/MOFs@Luminol luminescent material; (3) Compared with the traditional chemiluminescent reaction which needs to obtain a chemiluminescent signal under an alkaline condition, the chemiluminescent signal generated by the nano luminescent material can be stronger and more stable under the alkaline condition and the neutral condition, is easier to record by a detection instrument, and expands the application field of a chemiluminescent analysis method.
The SPAN/MOFs@Luminol luminescent material obtained by the invention is a novel chemiluminescent nanomaterial with luminescent substrates and catalysts, and H can be realized by the SPAN/MOFs@Luminol luminescent material 2 O 2 And no additional catalyst and luminescent reagent are needed in the detection system. Therefore, the application of SPAN/MOFs@Luminol luminescent material can overcome the problems that the existing chemiluminescence immunoassay needs multiple biological enzyme catalysis, the chemiluminescence reaction system is complex, the chemiluminescence immunoassay can only be used under alkaline conditions, 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 an ultraviolet-visible absorption spectrum of 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 graph of chemiluminescent signals generated by hydrogen peroxide catalyzed by SPAN/MOFs@Luminol luminescent material provided in example 5 of the present invention.
FIG. 5 is a graph showing chemiluminescent signals generated by hydrogen peroxide catalyzed by SPAN/MOFs@Luminol luminescent material provided in example 5 of the present invention at different pH values.
FIG. 6 shows SPAN/MOFs@Luminol luminescent material and Co according to example 6 of the present invention 2+ Comparison of chemiluminescent signals generated by HRP catalyzed hydrogen peroxide and the luminescent substrate lumineol.
FIG. 7 is a graph showing the detection of different concentrations of H under alkaline conditions using SPAN/MOFs@Luminol luminescent material according to example 7 of the present invention 2 O 2 At the time of chemiluminescence peak value and H 2 O 2 Concentration graph.
FIG. 8 is a graph showing the detection of different concentrations of H under neutral conditions using SPAN/MOFs@Luminol luminescent material according to example 7 of the present invention 2 O 2 At the time of chemiluminescence peak value and H 2 O 2 Concentration graph.
FIG. 9 is a schematic illustration of the detection of stimulated cell release H using SPAN/MOFs@Luminol luminescent material in accordance with example 8 of the present invention 2 O 2 The content is as follows.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It should be noted that the raw materials used in the following specific examples can be obtained by purchase and self-preparation.
The embodiment of the invention provides a preparation method of a SPAN/MOFs@Luminol luminescent material, which comprises the following steps:
s1, dispersing an aniline monomer, a surfactant and 3-aminobenzenesulfonic acid in a first solvent by ultrasonic 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 dilute sulfuric acid solution, diluteOne or more of 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 dosage 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 continuing to react for 10-30 min to obtain a sulfonated polyaniline mixed solution C;
s4, standing the sulfonated polyaniline mixed C solution obtained in the step S3 for 10-30 hours in a low-temperature environment of 2-8 ℃, centrifuging, washing, collecting precipitate, and drying and weighing in an oven of 50-85 ℃ to obtain a SPAN material; wherein, the pH value of the filtrate is 5.5-6.0 after washing;
s5, adding the SPAN material obtained in the S4, metal ions and organic ligands into a second solvent, uniformly stirring, and transferring into a reaction kettle for reaction, and centrifuging, washing and drying a reaction liquid after the reaction is completed to obtain the SPAN/MOFs composite material; wherein the molar ratio of the metal ion to the organic ligand is (0.5-2): 1, the mass ratio of the organic ligand to the SPAN is (1-16): 1, a step of; 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 ion is one or more of nitrate, hydrochloride, sulfate and acetate of Cu, co, ni, fe metal ion; carrying out a hydrothermal reaction in the reaction kettle, wherein the temperature of the hydrothermal reaction is 100-150 ℃, and the time of the hydrothermal reaction 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 in a solvent, adding Luminol, and magnetically stirring to fully react the SPAN/MOFs@Luminol composite material; wherein the solvent is selected from water or ethanol water solution, preferably water; the concentration of the Luminol is 1-10 mM, and the volume dosage 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: dispersing aniline monomer, hexadecyl trimethyl ammonium bromide serving as a surfactant and 3-aminobenzenesulfonic acid in a first solvent dilute hydrochloric acid in an ultrasonic manner, wherein the mass ratio of the aniline monomer to the hexadecyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1:1:2, obtaining 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, continuing to react for 15min to obtain sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 24h at the temperature of 5 ℃;
s4: centrifuging, washing, filtering to pH 5.0-6.5, collecting precipitate, drying in 80 deg.c oven and weighing to obtain SPAN material;
s5: sulfonated polyaniline, cu (COOH) 2 ·H 2 Adding O and organic ligand terephthalic acid into a solvent obtained by mixing absolute ethyl alcohol serving as a second solvent and water according to the volume ratio of 1:0.9, and stirring, wherein the molar ratio of metal ions to organic ligand is 1:1, and the mass ratio of organic ligand to SPAN is 5:1, transferring 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 a SPAN/CuMOF composite material;
s6: the SPAN/CuMOF composite material is dispersed by distilled water to obtain 10mL of SPAN/CuMOF composite material dispersion liquid with the concentration of 4mg/mL, then 1mL of Luminol with the concentration of 5mM is added, and the mixture is stirred magnetically to enable the mixture and the Luminol to fully react for 10 hours, so that the SPAN/CuMOF@Luminol composite material is prepared, and the mixture is stored in an environment of 3-4 ℃.
As shown in FIG. 1, which is an SEM image of the SPAN/CuMOF@Luminol luminescent material prepared in the embodiment 1, the material has regular morphology and structure, is in an octahedral structure, is about 5 μm, and has good particle dispersibility; FIG. 2 is an ultraviolet-visible absorption spectrum analysis chart of a SPAN/CuMOF@Luminol luminescent material, and the prepared SPAN/CuMOF@Luminol luminescent material shows characteristic absorption peaks at 302nm, 349nm and 780 nm; FIG. 3 shows the XRD pattern of the SPAN/CuMOF@Luminol luminescent material, which is shown to be consistent with the crystal plane of the CuMOF, further illustrating the successful modification of Luminol and SPAN on the CuMOF.
Example 2
The SPAN/MOFs@Luminol luminescent material provided in the embodiment 2 of the invention is prepared by the following steps:
s1: dispersing aniline monomer, polyvinylpyrrolidone serving as a surfactant and 3-aminobenzenesulfonic acid in dilute hydrochloric acid serving as a first solvent in an ultrasonic manner, wherein the mass ratio of the aniline monomer to the polyvinylpyrrolidone to the 3-aminobenzenesulfonic acid is 1:1:1, so as to obtain a uniform solution A;
s2: dissolving 20mL of hydrogen peroxide oxidant with the concentration of 0.1M in 10mL of water to form solution B;
s3: slowly dripping the solution B into the solution A, continuing to react 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, filtering until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in a 60 ℃ oven, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline and CuSO 4 ·5H 2 Adding O and organic ligand terephthalic acid into a solvent obtained by mixing absolute ethyl alcohol of a second solvent and water according to the volume ratio of 1:0.9, and stirring, wherein the molar ratio of metal ions to organic ligand is 0.5:1, and the mass ratio of organic ligand to SPAN is 2:1, transferring the mixture into a reaction kettle, reacting for 12 hours at 140 ℃, centrifuging, washing with absolute ethyl alcohol and water, and drying in a 60 ℃ oven to obtain the SPAN/CuMOF composite material;
s6: the SPAN/CuMOF composite material is dispersed by distilled water to obtain 10mL of SPAN/CuMOF composite material dispersion liquid with the concentration of 3mg/mL, then 1mL of Luminol with the concentration of 10mM is added, and the mixture is stirred magnetically to enable the mixture and the Luminol to fully react for 12 hours, so that the SPAN/CuMOF@Luminol composite material is prepared, and the mixture is stored in the environment of 4 ℃.
Example 3
The SPAN/MOFs@Luminol luminescent material provided in the embodiment 3 of the invention is prepared by the following steps:
s1: dispersing aniline monomer, hexadecyl trimethyl ammonium bromide serving as a surfactant and 3-aminobenzenesulfonic acid in dilute hydrochloric acid serving as a first solvent in an ultrasonic manner, wherein the mass ratio of the aniline monomer to the hexadecyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1:1:2, so as to obtain uniform solution A;
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, continuing to react for 15min to obtain sulfonated polyaniline mixed solution C, and standing the sulfonated polyaniline mixed solution C for 24h at the temperature of 5 ℃;
s4: centrifuging, washing, filtering to pH 5.0-6.5, collecting precipitate, drying in 80 deg.c oven and weighing to obtain SPAN material;
s5: sulfonated polyaniline and FeCl 2 Adding organic ligand terephthalic acid into a solvent obtained by mixing absolute ethyl alcohol of a second solvent and water according to the volume ratio of 1:1, stirring, wherein the molar ratio of metal ions to organic ligands is 1:1, the mass ratio of organic ligands to SPAN is 5:1, transferring the mixture into a reaction kettle, reacting for 10 hours at 100 ℃, centrifuging, washing the mixture with absolute ethyl alcohol and water, and drying the mixture in an oven at 80 ℃ to obtain the SPAN/FeMOF composite material;
s6: the SPAN/FeMOF composite material is dispersed by distilled water to obtain 10mL of SPAN/FeMOF composite material dispersion liquid with the concentration of 4mg/mL, then 1mL of Luminol with the concentration of 5mM is added, and the mixture is stirred magnetically to enable the mixture and the Luminol to fully react for 8 hours, so that the SPAN/FeMOF@Luminol composite material is prepared and stored in the environment of 3-4 ℃.
Example 4
The SPAN/MOFs@Luminol luminescent material provided in the embodiment 4 of the invention is prepared by the following steps:
s1: dispersing aniline monomer, hexadecyl trimethyl ammonium bromide serving as a surfactant and 3-aminobenzenesulfonic acid in dilute hydrochloric acid serving as a first solvent in an ultrasonic manner, wherein the mass ratio of the aniline monomer to the hexadecyl trimethyl ammonium bromide to the 3-aminobenzenesulfonic acid is 1:1:1, so as to obtain uniform solution A;
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, continuing to react 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, filtering until the pH value of the filtrate is 5.0-6.5, collecting the precipitate, drying in a 60 ℃ oven, and weighing to obtain the SPAN material;
s5: sulfonated polyaniline and FeCl 2 Adding organic ligand trimesic acid into a solvent obtained by mixing absolute ethyl alcohol of a second solvent and water according to the volume ratio of 1:1.2, stirring, wherein the molar ratio of metal ions to the organic ligand is 1:1, the mass ratio of the organic ligand to SPAN is 5:1, transferring the mixture into a reaction kettle, reacting for 10 hours at 100 ℃, centrifuging, washing the mixture with absolute ethyl alcohol and water, and drying the mixture in an oven at 80 ℃ to obtain the SPAN/FeMOF composite material;
s6: the SPAN/FeMOF composite material is dispersed by distilled water to obtain 10mL of SPAN/FeMOF composite material dispersion liquid with the concentration of 1mg/mL, then 1mL of Luminol with the concentration of 10mM is added, and the mixture is magnetically stirred to enable the mixture and the Luminol to fully react for 6 hours, so that the SPAN/FeMOF@Luminol composite material is prepared, and the mixture is stored in the environment of 3-4 ℃.
Example 5
The application of the SPAN/MOFs@Luminol luminescent material provided by the embodiment 5 of the invention in the aspect of chemiluminescence detection is as follows:
1) Taking a 5mL reaction test tube, adding 50 mu L of SPAN/CuMOF@Luminol luminescent material and 150 mu L of H into a reaction system 2 O 2 Immediately mixing the solutions, and recording a chemiluminescent dynamic curve by using a chemiluminescent detector;
2) Will be 150 mu L H 2 O 2 Into 50. Mu.L of SPAN/CuMOF@Luminol Tris-HCl buffer (pH 6-11) and sodium hydroxide solution (pH 12-13) and chemiluminescent kinetics were recorded using a chemiluminescent detector.
The SPAN/cumofr lumineol luminescent material shown in fig. 4 produced a chemiluminescent signal which was 36 times higher than that produced by the same concentration of luminol. CuMOF has peroxidase-like catalytic activity and can catalyze H 2 O 2 The decomposition generates OH, improves the efficiency of the chemiluminescent reaction, further enhances the chemiluminescent intensity and shows excellent chemiluminescent performance. FIG. 5 shows that strong chemiluminescent signals can be generated over a relatively wide pH range using SPAN/CuMOF@Luminol luminescent materials.
Example 6
The specific method and comparison result of the comparison of SPAN/MOFs@Luminol luminescent material provided in example 6 of the invention with the conventional luminescent catalyst are as follows:
traditional catalyst Co 2+ HRP catalyzed Luminol to produce chemiluminescent signal, 5mL reaction tube is taken, and 30. Mu.L (10. Mu.M) Co is added into the reaction system 2+ 30. Mu.L (20. Mu.g/mL) of HRP, 20. Mu.L (50. Mu.M) of Luminol solution, 150. Mu.L of H 2 O 2 The solutions were mixed immediately and the chemiluminescent kinetics profile was recorded using a chemiluminescent detector.
FIG. 6 shows a more conventional catalyst Co 2+ The HRP catalyzed chemiluminescent reaction can generate a strong chemiluminescent signal by utilizing the SPAN/MOF@Luminol luminescent material, and is easy to record; and the material of the invention is doped with the catalyst and the chemiluminescent substrate, so that the step of adding the chemiluminescent substrate in the reaction can be omitted, and the operation is simpler.
Example 7
The application of the SPAN/MOFs@Luminol luminescent material provided by the embodiment 7 of the invention in the aspect of biological immunoassay comprises the following specific methods: the SPAN/CuMOF@Luminol luminescent material is used for detecting hydrogen peroxide, and the method specifically comprises the following steps of:
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 the prepared SPAN/HKUST-1@Luminol luminescent material solution, adding different volumes of sodium hydroxide buffer solution with pH of 12.0 for mixing or PBS solution with pH of 7.0 for mixing;
step 3) adding different volumes of H comprising 10mM prepared in step (1) respectively 2 O 2 Solution, corresponding H 2 O 2 Final concentrations were 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, and final reaction volumes of 150. Mu.L, respectively;
step 4) adding H 2 O 2 After the solution is prepared, a chemiluminescent dynamic curve is recorded by using a chemiluminescent detector, the highest value of chemiluminescent signals is recorded, and H is added 2 O 2 And (3) drawing a reaction linear relation curve.
SPAN/CuMOF@Luminol luminescent material and H 2 O 2 Generating chemiluminescent signals after the reaction, recording the time dynamics curve of the chemiluminescent signals, and recording the corresponding luminescent signals and H 2 O 2 The concentrations were positively correlated. As can be seen from the results in FIGS. 7 and 8, the chemiluminescent signal was analyzed by linear regression with H 2 O 2 The concentration showed a good linear relationship (basicity: R 2 =0.995, neutral: r is R 2 =0.994), the linear regression equation is:
basicity y=12.77C-34.01; and (3) neutral: y=246.6c+173.8
Thus, the platform chemiluminescent signal and H can be derived from this equation 2 O 2 Linear relationship of concentration, H in the concentration range of 30pmol to 600pmol is calculated 2 O 2 Concentration (alkaline); h was obtained in a concentration range of 0.1. Mu.M to 30. Mu.M 2 O 2 Concentration (neutral).
Example 8
The application of the SPAN/MOFs@Luminol luminescent material provided by the embodiment 8 of the invention in the aspect of biosensing analysis comprises the following specific methods: detecting the release of hydrogen peroxide by cells by using the SPAN/CuMOF@Luminol luminescent material, and specifically comprising the following steps:
1) Cells were collected by centrifugation, and cells were stimulated to produce hydrogen peroxide by injection of 30. Mu.L (5. Mu.M, 10. Mu.M) of ascorbic acid with 1mL (pH 7.4) of PBS;
2) mu.L of cell solution was mixed with 50. Mu.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 hydrogen peroxide content released by cells.
In summary, the method for solving the problems in the prior art by adopting the method has the following meanings:
1) The problem of weak luminous intensity of the existing chemiluminescent agent is solved, the response signal in the chemiluminescent analysis process can be improved, and the detection sensitivity is improved; 2) It is necessary to improve the dispersion performance of MOFs materials in the water phase and improve the stability of the materials by adopting a simpler surface functionalization method; 3) The catalyst and the luminous reagent are prepared into a complex, and the complex has excellent chemiluminescent activity and good stability. The composite material not only can make up for 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.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a SPAN/MOFs@Luminol luminescent material is characterized by comprising the following steps:
s1, dispersing an aniline monomer, a surfactant and 3-aminobenzenesulfonic acid in a first solvent by ultrasonic 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 continuing to react for a certain time to obtain a sulfonated polyaniline mixed solution C;
s4, standing, centrifuging, washing, collecting sediment in an environment of 2-8 ℃ of the sulfonated polyaniline mixed C solution obtained in the step S3, and placing the sediment in an oven for drying and weighing to obtain a SPAN material;
s5, adding the SPAN material obtained in the S4, metal ions and organic ligands into a second solvent, uniformly stirring, and transferring into a reaction kettle for reaction, and centrifuging, washing and drying a reaction liquid after the reaction is completed to obtain the SPAN/MOFs composite material;
in the step S5, 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, a step of; 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 ion is one or more of nitrate, hydrochloride, sulfate and acetate of Cu, co, ni, fe metal ion;
s6, ultrasonically dispersing the SPAN/MOFs composite material obtained in the S5 in a solvent, adding Luminol, and magnetically stirring to fully react the SPAN/MOFs@Luminol composite material;
in the step S6, the concentration of the Luminol is 1-10 mM, and the volume dosage of the Luminol is 0.8-1.5 mL; the concentration of the SPAN/MOFs is 1-4 mg/mL, and the volume consumption of the SPAN/MOFs is 7-11 mL; the reaction time is 4-12 h.
2. The preparation method of the SPAN/MOFs@Luminol luminescent material 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 to 1.5): (1-4); the surfactant is one or more of cetyltrimethylammonium bromide, 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 preparation method of the SPAN/MOFs@Luminol luminescent material according to claim 1, wherein 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 dichromate, persulfate, permanganate and peroxide.
4. The preparation method of the SPAN/MOFs@Luminol luminescent material according to claim 1, wherein in the step S3, the reaction time is 10-30 min.
5. The preparation method of the SPAN/MOFs@Luminol luminescent material according to claim 1, wherein in the step S4, the standing time is 10-30 hours; washing until the pH value of the filtrate is 5.5-6.0; the drying temperature is 50-85 ℃.
6. The preparation method of the SPAN/MOFs@Luminol luminescent material is characterized in that in S5, a hydrothermal reaction is carried out in the reaction kettle, 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 ℃.
7. A SPAN/mofs@lumineol chemiluminescent material prepared by the preparation method as claimed in any one of claims 1-6.
8. Use of the SPAN/mofs@luminel luminescent material of claim 7 in chemiluminescent detection, in biosensing analysis and in chemiluminescent imaging.
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