CN113522364A - Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system - Google Patents
Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system Download PDFInfo
- Publication number
- CN113522364A CN113522364A CN202110815013.4A CN202110815013A CN113522364A CN 113522364 A CN113522364 A CN 113522364A CN 202110815013 A CN202110815013 A CN 202110815013A CN 113522364 A CN113522364 A CN 113522364A
- Authority
- CN
- China
- Prior art keywords
- chemiluminescence
- mofs
- naio
- bdc
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to the field of chemiluminescence, in particular to a chemiluminescence enhancer, a preparation method thereof and application thereof in a hydrogen peroxide-periodate system. Wherein the luminescence enhancer comprises a nano-thick rare earth metal organic framework material. The metal organic framework material is a nano rare earth metal organic framework material which is synthesized by taking one metal atom of terephthalic acid (BDC), trivalent cerium (Ce), gadolinium (Gd) and holmium (Ho) as a central atom through an ultrasonic method as a ligand. The molar ratio of the ligand to the metal central atom is 1: 1. The chemiluminescence reinforcing agent can enhance the chemiluminescence of a hydrogen peroxide-periodate system, thereby improving the detection effect of biochemical molecules.
Description
Technical Field
The invention relates to the field of chemiluminescence, in particular to a chemiluminescence enhancer, a preparation method thereof and application thereof in a hydrogen peroxide-periodate system.
Background
Chemiluminescence (CL), a phenomenon of luminescence produced by chemical reactions. The method has the outstanding advantages of high sensitivity, high reaction speed, convenient operation, low instrument cost, weak background signal and the like.
At present, chemiluminescence analysis methods are widely applied to a plurality of fields of environmental science, life science, food science, medical clinical diagnosis and the like. However, the chemiluminescence analysis method still has the problems of weak luminescence signal, luminescence time period and the like. Therefore, finding suitable chemiluminescence enhancers to obtain higher chemiluminescence signals has become a focus of research in the field of chemiluminescence. Researchers have tried various methods to obtain stronger chemiluminescent signals, thereby increasing the sensitivity of detection.
Among them, the metal organic framework material is expected to be used as a chemiluminescence enhancer because of its catalytic properties, and catalyzes and enhances chemiluminescence in a chemiluminescence reaction. So-called Metal-Organic Framework Materials (MOFs) are assembled by Metal ions and Organic linkers through strong coordination bonds. MOFs offer a number of unique properties by the design of cross-linking ligands and the adoption of diverse synthetic methods. Among them, the porous structure, higher surface area, more active sites and modifiability of MOFs provide them with better properties as catalysts. However, most of the existing MOFs have problems in certain permeability and stability, or the pore structure generates space obstruction to the metal active sites. These problems limit to some extent the effectiveness of existing MOFs as catalysts.
Disclosure of Invention
In view of the above problems, the embodiments of the present specification provide a nanosheet structure rare earth metal organic framework material as an enhancer of a chemiluminescence reaction, and a preparation method, a use and a reagent of the chemiluminescence enhancer.
In a first aspect, the present specification embodiments provide a chemiluminescence enhancer, which is a nanosheet structure of rare earth metal organic framework materials (Ln-MOFs). The metal-organic framework material takes terephthalic acid (BDC) as a ligand, and trivalent lanthanide metals of cerium (Ce), gadolinium (Gd) and holmium (Ho) as central atoms, wherein the molar ratio of the central atoms to the ligand is 1: 1.
In a second aspect, the present specification provides a method for preparing a chemiluminescence enhancer, the method comprising:
mixing N, N-Dimethylformamide (DMF), ethanol and water to prepare a solvent; adding to said solvent ligand terephthalic acid (BDC) and a trivalent lanthanide metal salt;
step (2), triethylamine is added into the solution prepared in the step (1) to prepare mixed solution;
step (3), transferring the mixed solution into a reaction bottle, and carrying out ultrasonic reaction for 8 hours; centrifuging the solution after the ultrasonic reaction is finished, and removing supernatant; adding ethanol for washing; adding water for dispersion, and freeze-drying to obtain the chemiluminescence enhancer.
In a third aspect, the present specification examples provide the use of such a chemiluminescence enhancer, which can be used to increase the luminescence intensity of a chemiluminescent system, particularly a hydroperoxide-periodate system.
In a fourth aspect, the present specification provides a method of using a chemiluminescent enhancer in a hydrogen peroxide-periodate system, comprising the steps of: adding the chemiluminescence enhancing reagent prepared in the second aspect into NaIO4Obtaining a mixed solution; adding H into the mixed solution2O2H of (A) to (B)2SO4And (3) solution.
The chemiluminescence reinforcing agent provided by the invention can improve the chemiluminescence intensity of a hydrogen peroxide-periodate system, thereby improving the detection sensitivity and accuracy, and can be used for the detection effect of a biomolecule chemiluminescence analysis method of the hydrogen peroxide-periodate system.
Meanwhile, the metal framework material is synthesized by the ultrasonic method, the method is simpler and safer than a hydrothermal method and a solution heating method, and the product has the advantages of fluffy structure, thinner thickness, lower density and better material permeability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1a is a Scanning Electron Microscope (SEM) photograph of a Ce-BDC metal-organic frame material;
FIG. 1b is a Scanning Electron Microscope (SEM) photograph of Gd-BDC as a metal organic framework material;
FIG. 1c is a Scanning Electron Microscope (SEM) photograph of a metal organic framework material Ho-BDC;
FIG. 2a is a Transmission Electron Microscope (TEM) photograph of the metal-organic framework material Ce-BDC;
FIG. 2b is a Transmission Electron Microscope (TEM) photograph of the metal organic framework material Gd-BDC;
FIG. 2c is a Transmission Electron Microscope (TEM) photograph of the metal organic framework material Ho-BDC
FIG. 3 is an XRD spectrum of Ce-BDC, Gd-BDC, Ho-BDC metal organic framework materials;
FIG. 4 is an infrared spectrum of Ce-BDC, Gd-BDC, Ho-BDC of the metal organic framework material;
FIG. 5 shows the metal organic frame materials Ce-BDC, Gd-BDC and Ho-BDC in NaIO4-H2O2Absorption spectra in the system;
FIG. 6 shows the catalysis of NaIO by Ce-BDC, Gd-BDC and Ho-BDC metal organic frame materials4-H2O2The chemiluminescence intensity of the system;
FIG. 7 shows the metal organic frame material Ce-BDC, Gd-BDC, Ho-BDC with NaIO added4-H2O2The chemiluminescence spectrum of the system;
FIG. 8 shows Ln-MOFs-NaIO in different sample-adding sequences4-H2O2The luminous intensity of the system chemistry;
FIG. 9 shows different NaIO4Ln-MOFs-NaIO at concentration4-H2O2The luminous intensity of the system chemistry;
FIG. 10 shows a case of a variation H2O2Ln-MOFs-NaIO at concentration4-H2O2The luminous intensity of the system chemistry;
FIG. 11 shows a case of a variation H2SO4Ln-MOFs-NaIO at concentration4-H2O2The luminous intensity of the system chemistry;
FIG. 12 is a diagram of Ln-MOFs enhanced NaIO4-H2O2The principle of chemiluminescence of the system;
FIG. 13 is a schematic diagram of preparation of Ln-MOFs and the application of Ln-MOFs in NaIO4-H2O2The system is a catalytic chemiluminescence reaction scheme.
Detailed Description
Based on the defects of low permeability, space obstruction of an organic ligand to an active metal space and the like existing in the MOFs, the inventors adopt the following solution ideas. Firstly, the catalytic efficiency is improved by selecting ultrathin MOFs. The nanometer thickness of the ultrathin MOFs can realize rapid mass transmission, and can solve the problem of low permeability of the existing MOFs. Meanwhile, the proportion of the exposed catalytic active surface of the ultrathin MOFs is extremely high, and the ultrathin MOFs have unsaturated metal points, so that the catalytic effect can be improved. Secondly, the inventors chose terephthalic acid (BDC) as ligand. The molecular structure of terephthalic acid (BDC) can reduce the problem of space obstruction of metal active sites.
Therefore, the invention uses ultra-thin MOFs prepared by an ultrasonic method with terephthalic acid (BDC) as a ligand and lanthanide metal as a central atom as a chemiluminescence enhancer, can effectively improve chemiluminescence intensity, and is especially suitable for a hydrogen peroxide-periodate system.
It is to be understood that the scope of the present application is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present application; in the specification and claims of this application, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected from the group consisting of the endpoints unless otherwise indicated herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the present application, in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and the description of the present application.
Through a large number of experiments, the inventor of the application finds that metal organic framework materials (Ln-MOFs) with lanthanide metals as central atoms and terephthalic acid (BDC) as ligands can promote NaIO4-H2O2The system generates active oxygen species, thereby enhancing NaIO4-H2O2The chemiluminescence property of the system.
The inventors of the present application have also found that the nano-sheet structured Ln-MOFs, i.e., ultra-thin MOFs, has an exposed catalytic active surface higher than that of the general MOFs due to its ability to realize rapid material transport, and has unsaturated metal sites, and that the nano-sheet structured Ln-MOFs catalyzes NaIO4-H2O2The system is more efficient in generating reactive oxygen species. Therefore, the Ln-MOFs of the nanosheet structure is more suitable as a chemiluminescence enhancer.
Based on the above findings, the present application further selects three lanthanide metals, namely cerium (Ce), gadolinium (Gd), and holmium (Ho), as central atoms of Ln-MOFs. Three Ln-MOFs are obtained through preparation, namely metal organic frame materials Ce-BDC, Gd-BDC and Ho-BDC.
The above is a description of the chemiluminescence enhancer provided by the present solution. The method of preparing the above described chemiluminescent enhancing agent will be described next.
The present embodiments provide a method for preparing the nanosheet layer structure Ln-MOFs described above. Particularly, terephthalic acid (BDC) is used as a ligand, one of trivalent cerium (Ce), gadolinium (Gd) and holmium (Ho) is used as a metal central atom, and an ultrasonic method is used for preparing the ultrathin MOFs. The method comprises the following steps:
step 3, transferring the mixed solution into a reaction bottle, and carrying out ultrasonic reaction for 8 hours; centrifuging the solution after the ultrasonic reaction is finished, and removing supernatant; adding ethanol for washing; adding water for dispersion, and freeze-drying to obtain the chemiluminescence enhancer.
In a preferred embodiment, the mass of reactants, reaction time, and centrifugation speed, etc. are as follows:
32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of water were added to a reaction flask and mixed well to obtain a mixed solution. 0.75mmol of terephthalic acid (BDC) and 0.75mmol of a trivalent rare earth salt were dissolved in succession in the mixed solution to obtain a reaction solution. Wherein the trivalent rare earth salt is CeCl3·7H2O、GdCl3·6H2O、HoCl3·6H2And O is one of the compounds.
To the reaction solution was added 0.8mL of triethylamine, and the mixture was stirred rapidly for 5 min.
The reaction flask was subjected to sonication for 8h and maintained at a steady temperature. After the ultrasonic reaction is finished, centrifuging the reaction solution for 5min at the speed of 8000rpm, and removing supernatant in a reaction bottle; adding ethanol into the residual precipitate in the reaction bottle, washing and dispersing, centrifuging at 8000rpm for 5min, and removing the supernatant; the washing step was repeated 4 times; adding a proper amount of water into the precipitate washed by the ethanol, and dispersing the precipitate into a culture dish; putting the culture dish into a refrigerator for freezing for more than 6 hours; the frozen precipitate was dried to obtain the chemiluminescence enhancer described above.
FIG. 1 is a Scanning Electron Micrograph (SEM) of Ln-MOFs prepared according to the above method, and FIG. 2 is a Transmission Electron Micrograph (TEM) of Ln-MOFs prepared according to the above method. Wherein FIGS. 1.a, 2.a correspond to Ce-BDC, FIGS. 1.b, 2.b correspond to Gd-BDC, FIGS. 1.c, 2.c correspond to Ho-BDC. From the images shown by SEM and TEM, it can be seen that the Ln-MOFs nano-lamellar structure, i.e., ultra-thin MOFs, is prepared according to the above steps.
FIG. 3 is an X-ray diffraction (XRD) pattern of Ln-MOFs prepared by the above method, and it can be seen from comparison with the simulated peak described in the reference document that the Ln-MOFs prepared by the above steps is a triclinic nanosheet.
FIG. 4 shows the IR spectrum of Ln-MOFs prepared according to the above method. Wherein, 3512cm-1Is a stretching vibration peak of-OH in BDC of a ligand synthesized by Ln-MOFs, the peak is 1424cm-1Bending vibration peak of-OH, 1587cm-1Is the stretching vibration peak of C ═ O, 1670cm-1The peak of bending vibration is C ═ O. Compared with the peak value of C-O in-COOH of the Ln-MOFs material synthesized BDC, the peak value is 1670cm-1Bathochromic shift value 1587cm-1. The successful synthesis of Ln-MOFs can be proved by combining the characteristic peak of the 200 crystal face in the XDR diagram of FIG. 3.
Next, it will be verified through experiments whether the chemiluminescence enhancer obtained according to the preparation method described above is capable of catalyzing a hydrogen peroxide-periodate chemiluminescence system, and how to obtain a better luminous effect by adjusting the order of addition of hydrogen peroxide and periodate, and the concentrations of hydrogen peroxide and periodate. See description below for details.
(1) The chemiluminescence reinforcing agent is proved to be capable of catalyzing the reaction of hydrogen peroxide and periodate by detecting the change of an absorption spectrum of a hydrogen peroxide-periodate system
Determination of the Ln-MOF produced by the above-described preparation method for NaIO by measuring the absorption spectra of the following substances for ultraviolet-visible light4And H2O2Whether or not the reaction(s) is catalytic. Separately detecting sodium periodate (NaIO)4) Hydrogen peroxide (H)2O2)、NaIO4Mixture with Ln-MOF, H2O2Mixture with Ln-MOF, NaIO4And H2O2Mixture of (2), and NaIO4-H2O2Mixtures with Ln-MOF. Wherein, NaIO4And H2O2The mixture of (a) shows a weak absorption peak at 450nm, which becomes strong after addition of Ln-MOF, and the position of the absorption peak is not substantially changed. It can be shown that the addition of Ln-MOF can catalyze NaIO4And H2O2The reaction of (1).
(2) The chemiluminescence reinforcing agent can be proved to be capable of enhancing the luminescence of the hydrogen peroxide-periodate system by detecting the change of the luminescence intensity of the system
Separately detect NaIO4-H2O2System and NaIO with three Ln-MOFs added4-H2O2The chemiluminescence intensity of the system is examined to investigate the effect of Ln-MOFs on NaIO4-H2O2Whether the chemiluminescence of the system has enhancement effect or not.
The experimental conditions were: 0.3M of H2O2Dissolved in 0.01M H2SO4In (1), 0.1M NaIO4Adding the solution to obtain NaIO4-H2O2And (4) preparing the system. Another 0.3M H2O2Dissolved in 0.01M H2SO4Adding 2mg Ln-MOFs, mixing, and adding 0.1M NaIO into the above solution4To obtain Ln-MOFs-NaIO4-H2O2And (4) preparing the system. Wherein Ln-MOFs are Ce-BDC, Gd-BDC and Ho-BDC respectively. For NaIO4-H2O2System and three Ln-MOFs-NaIO4-H2O2The luminous intensity of the system is detected.
As shown in FIG. 6, in NaIO4-H2O2After Ln-MOFs is added into the system, the luminous intensity is obviously improved. Among them, the luminous intensity of the added Ho-BDC is the highest, about 20000 (counts). NaIO added with Ce-BDC and Gd-BDC4-H2O2The system luminescence intensity was about 8750 (counts) and 10000 (counts), respectively.
Measuring Ln-MOFs-NaIO by using optical filter at intervals of 25nm4-H2O2And determining the chemiluminescence intensity of the system.
As shown in FIG. 7, Ln-MOFs-NaIO4-H2O2The peak value of the luminescence spectrum of the system is about 550 nm.
(3) The optimal sample adding sequence of the luminescent system is obtained by detecting the luminous intensity of hydrogen peroxide and periodate under different adding sequences
By adjusting NaIO4And H2O2In the order of addition of Ln-MOFs-NaIO4-H2O2System ofThe kinetics of luminescence of (a) was investigated. Under static conditions, the following two different addition sequences were adopted respectively:
Ln-MOFs-NaIO obtained by the two sample adding sequences4-H2O2The systems all comprise 0.01M of H2SO40.3M H2O20.1M NaIO4And 2mg Ln-MOFs.
According to the above experiment, it was found that the order of adding reagents affects Ln-MOFs-NaIO4-H2O2The luminous intensity of the system.
As shown in FIG. 7, sequence 1 obtains Ln-MOFs-NaIO4-H2O2The luminous intensity of the system is far lower than that of Ln-MOFs-NaIO obtained by the sequence 24-H2O2The luminous intensity of the system.
From this it can be seen that H2O2Adding Ln-MOFs and NaIO4Obtained in the mixed solution of Ln-MOFs-NaIO4-H2O2The system has the strongest luminous intensity, and the sequence is the optimal sample adding sequence.
(4) The optimal reaction concentration of the luminescent system is obtained by adjusting the concentrations of the hydrogen peroxide, the periodate and the sulfuric acid
Under the determined optimal sample adding sequence, the chemiluminescence intensity and NaIO of the system4And H2O2Shows a certain correlation. To obtain the best linear relationship, this example separately examines NaIO4、H2O2And H2SO4Effect of concentration on chemiluminescence.
Fix 0.1 mol. L-1H2O2、0.04mol·L-1H2SO4And 2mg of Ln-MOFs. NaIO4The concentration is observed in the range of 0 to 0.15 mol.L-1。
Fix 0.1 mol. L-1NaIO4、0.04mol·L-1H2SO4And 2mg of Ln-MOFs. H2O2The concentration is observed in the range of 0 to 1.0 mol.L-1。
Fix 0.1 mol. L-1NaIO4、0.3mol·L-1H2O2And 2mg of Ln-MOFs. H2SO4The concentration is observed in the range of 0 to 0.3 mol.L-1。
The concentrations of the respective components are those before mixing.
As shown in FIG. 9, when other conditions are fixed, in NaIO4The chemiluminescence intensity is strongest when the concentration is 0.1M. Continue to increase NaIO4Concentration, then, results in a gradual decrease in the intensity of the emitted light.
As shown in fig. 10, when other conditions are fixed, at H2O2The chemiluminescence intensity is strongest when the concentration is 0.3M. Continuously increasing H2O2Concentration, then, results in a gradual decrease in the intensity of the emitted light.
As shown in fig. 11, when other conditions are fixed, at H2SO4The chemiluminescence intensity is strongest when the concentration is 0.02M. Continuously increasing H2SO4Concentration, then, results in a gradual decrease in the intensity of the emitted light.
When NaIO4And H2O2When the concentration is too small, sufficient active oxygen cannot be produced, thus resulting in a weak luminescence signal. When NaIO is used4And H2O2At too high a concentration, the higher concentration will quench the luminescence. For H2SO4To said end, no H is added2SO4The time-intensity is weaker, so that Ln-MOFs-NaIO4-H2O2The system is acidified by emitting light.
The above experiment shows that the optimal reaction condition is 0.1M NaIO4、0.3M H2O2、0.02M H2SO4Which isThe amount of Ln-MOFs added was 2 mg. The order of addition is to2O2H of (A) to (B)2SO4Solution, adding to Ln-MOFs and NaIO4In the mixed solution to obtain Ln-MOFs-NaIO4-H2O2And (4) preparing the system.
The chemiluminescence enhancer described above is capable of catalyzing the reaction of the hydrogen peroxide-periodate system, which is reflected in an increase in the luminous intensity of the hydrogen peroxide-periodate system. Next, the reaction mechanism of the chemiluminescence enhancer for enhancing the luminescence of the hydrogen peroxide-periodate system will be described.
Based on experimental research and literature investigation, the inventors found that Ln-MOFs-NaIO4-H2O2The chemiluminescence principle of the system is shown in fig. 12. Namely NaIO4And acidification H2O2Generation of active oxygen1O2. When Ln-MOFs are added, the catalytic performance of the Ln-MOFs can accelerate NaIO4-H2O2The electron transfer process in the system further improves the generation rate of a plurality of free radicals in the system.
As a catalyst, Ln-MOFs can catalyze NaIO4-H2O2In the system H2O2O-O bond of (A) is broken to form OH and O2And1O2. At the same time, Ln-MOFs can also make OH and O2Stabilized on the surface or in the pores, formed by recombination1O2。
1O2Very actively, very easily forming excited states: (1O2)2 *. Ln-MOFs-NaIO measured according to the above4-H2O2The luminescence spectrum wavelength of the system is 525-600nm, and the wavelength can be regarded as (1O2)2 *(578 nm).
Ln-MOFs-NaIO4-H2O2The reaction process of the chemiluminescence system is as follows:
IO4 -+H2O2→·O2 -+IO3 -+H2O (1)
2IO4 -+·O2 -→21O2+2IO3 - (2)
2·OH+2H++·O2→1O2+2H2O (6)
1O2+ 1O2→(1O2)2*→hv (7)
the above embodiments are merely illustrative of the principles and utilities of the present application and are not intended to limit the application. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present application. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical concepts disclosed in the present application shall be covered by the claims of the present application.
Claims (7)
1.A chemiluminescent enhancer characterized by: the chemiluminescence reinforcing agent is a rare earth metal organic framework material (Ln-MOF) with a nanosheet structure, and consists of ligand terephthalic acid (BDC) and central atoms of lanthanide metals of cerium (Ce), gadolinium (Gd) and holmium (Ho), wherein the molar ratio of the central atoms to the ligands is 1: 1.
2.A chemiluminescent enhancer of claim 1 wherein: the central atom is one of trivalent lanthanide metals of cerium (Ce), gadolinium (Gd) and holmium (Ho).
3. A method of preparing a chemiluminescent enhancer of claim 1 comprises the steps of:
mixing N, N-Dimethylformamide (DMF), ethanol and water to obtain a solvent; adding terephthalic acid (BDC) and trivalent rare earth metal salt into the solvent to obtain a reaction solution; wherein the trivalent rare earth salt is one of trivalent cerium (Ce), gadolinium (Gd) and holmium (Ho) salt; the molar ratio of the trivalent rare earth metal atoms to terephthalic acid (BDC) ligands is 1: 1;
mixing the reaction solution with triethylamine to obtain a mixed solution;
carrying out ultrasonic reaction on the mixed solution; after the reaction is finished, centrifuging to obtain a precipitate, and adding ethanol into the precipitate for washing; and dispersing the washed precipitate into water, and freeze-drying to obtain the chemiluminescence reinforcing agent.
4. A method of preparing a chemiluminescent enhancer of claim 3 wherein:
the trivalent rare earth salt is CeCl3·7H2O、GdCl3·6H2O、HoCl3·6H2And O is one of the compounds.
5. Use of a chemiluminescent enhancer of claim 1 or 2 in a chemiluminescent system.
6. Use according to claim 5, wherein the chemiluminescent system is a hydrogen peroxide periodate system.
7. The use according to claim 6, wherein the use of the chemiluminescence enhancer for enhancing the luminescence of a hydrogen peroxide periodate system comprises the steps of:
configuring NaIO4Adding the chemiluminescence reinforcing agent into the solution to obtain a mixed solution;
adding H to the mixture2O2H of (A) to (B)2SO4Solution of H in the mixture2O2Has a concentration of 0.3mol/L, H2SO4Is 0.1mol/L, and 1mg of the chemiluminescence enhancing reagent is contained in 1mL of the mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110815013.4A CN113522364B (en) | 2021-07-19 | 2021-07-19 | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110815013.4A CN113522364B (en) | 2021-07-19 | 2021-07-19 | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113522364A true CN113522364A (en) | 2021-10-22 |
| CN113522364B CN113522364B (en) | 2022-05-06 |
Family
ID=78100228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110815013.4A Active CN113522364B (en) | 2021-07-19 | 2021-07-19 | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113522364B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163995A (en) * | 2021-12-02 | 2022-03-11 | 中国地质大学（北京） | Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid |
| CN115895279A (en) * | 2022-11-24 | 2023-04-04 | 西北大学 | SPAN/MOFs @ Luminol luminescent material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989004302A1 (en) * | 1987-11-04 | 1989-05-18 | Igen, Inc. | Electrochemiluminescent rhenium moieties and methods |
| CN102362182A (en) * | 2010-03-03 | 2012-02-22 | 中国科学技术大学 | N-(4-aminobutyl)-n-ethylisoluminol functionalized gold nanoparticles, preparation method and application thereof |
| CN104062288A (en) * | 2014-07-09 | 2014-09-24 | 北京师范大学 | Chemiluminiscence-based detection method of naphthylamine compound |
| GB201621817D0 (en) * | 2016-12-21 | 2017-02-01 | Wista Lab Ltd | Methods of chemical synthesis |
| CN109589334A (en) * | 2018-11-28 | 2019-04-09 | 内蒙古大学 | A kind of nano enzyme antioxidant and preparation method thereof |
| CN111330643A (en) * | 2020-02-25 | 2020-06-26 | 青岛农业大学 | Ultrasonic synthesis method and application of different single-metal and double-metal two-dimensional MOFs nanoenzymes |
| CN111450894A (en) * | 2020-05-02 | 2020-07-28 | 桂林理工大学 | Ce-based organic metal complex catalytic material and preparation and application thereof |
-
2021
- 2021-07-19 CN CN202110815013.4A patent/CN113522364B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989004302A1 (en) * | 1987-11-04 | 1989-05-18 | Igen, Inc. | Electrochemiluminescent rhenium moieties and methods |
| CN102362182A (en) * | 2010-03-03 | 2012-02-22 | 中国科学技术大学 | N-(4-aminobutyl)-n-ethylisoluminol functionalized gold nanoparticles, preparation method and application thereof |
| CN104062288A (en) * | 2014-07-09 | 2014-09-24 | 北京师范大学 | Chemiluminiscence-based detection method of naphthylamine compound |
| GB201621817D0 (en) * | 2016-12-21 | 2017-02-01 | Wista Lab Ltd | Methods of chemical synthesis |
| CN109589334A (en) * | 2018-11-28 | 2019-04-09 | 内蒙古大学 | A kind of nano enzyme antioxidant and preparation method thereof |
| CN111330643A (en) * | 2020-02-25 | 2020-06-26 | 青岛农业大学 | Ultrasonic synthesis method and application of different single-metal and double-metal two-dimensional MOFs nanoenzymes |
| CN111450894A (en) * | 2020-05-02 | 2020-07-28 | 桂林理工大学 | Ce-based organic metal complex catalytic material and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHENLONG ZHAO等: "Ultrathin metal–organic framework nanosheets", 《NATURE ENERGY》 * |
| 石文兵: "CeO2纳米粒子催化鲁米诺-过氧化氢的化学发光特性", 《中国测试》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163995A (en) * | 2021-12-02 | 2022-03-11 | 中国地质大学（北京） | Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid |
| CN115895279A (en) * | 2022-11-24 | 2023-04-04 | 西北大学 | SPAN/MOFs @ Luminol luminescent material and preparation method and application thereof |
| CN115895279B (en) * | 2022-11-24 | 2023-07-21 | 西北大学 | SPAN/MOFs@Luminol luminescent material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113522364B (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113522364B (en) | Chemiluminescence reinforcing agent, preparation and application in hydrogen peroxide periodate system | |
| Chao et al. | Ultrastable and ultrasensitive pH-switchable carbon dots with high quantum yield for water quality identification, glucose detection, and two starch-based solid-state fluorescence materials | |
| CN105949473B (en) | The preparation method and its H of rare earth coordination polymer fluorescence probe2O2With glucose detection application | |
| CN108816268A (en) | Composite photocatalyst nano material and preparation method thereof and degradation of contaminant method | |
| CN107335460B (en) | A kind of preparation method and applications of composite photocatalyst material | |
| Li et al. | An ultrasensitive electrochemiluminescence aptasensor for the detection of diethylstilbestrol based on the enhancing mechanism of the metal–organic framework NH 2-MIL-125 (Ti) in a 3, 4, 9, 10-perylenetetracarboxylic acid/K 2 S 2 O 8 system | |
| CN109317176A (en) | A kind of azotized carbon nano piece that Fe (III) is modified and its application in photocatalysis fixed nitrogen | |
| CN109806900A (en) | A kind of molecular imprinting Ag/Ag3VO4The preparation method and application of/CN nanometer sheet composite photo-catalyst | |
| Dong et al. | Carbon dots with tailor-made chelating ligands for specific metal ions recognition: Target synthesis and prediction of metal ions selectivity | |
| CN105833913A (en) | Chemical modified titanium dioxide photocatalyst and preparation method thereof | |
| Huang et al. | Ultraweak chemiluminescence enhanced on the surface of lanthanide metal–organic framework nanosheets synthesized by ultrasonic wave | |
| CN106001598A (en) | Method for synthesizing piece-shaped gold nanoparticles through hydrotalcite interlamination | |
| CN106378195A (en) | Ag-POPD embedded magnetic imprinted light photocatalyst and preparation method thereof | |
| Wang et al. | Constructing a high concentration CuO/CeO2 interface for complete oxidation of toluene: The fantastic application of spatial confinement strategy | |
| CN110819338B (en) | Composite fluorescent particle protected by super-hydrophobic shell layer and preparation method thereof | |
| Ahmadi et al. | Novel strategies for the formulation and processing of aluminum metal-organic framework-based sensing systems toward environmental monitoring of metal ions | |
| Lakhera et al. | Pivotal role of oxygen during the synthesis of Cu (OH) 2/TiO2 and its effect on photocatalytic hydrogen production activity | |
| Xue et al. | Covalent organic frameworks decorated by rare earth ions | |
| CN115322771A (en) | Cerium-doped copper nano material and preparation method thereof | |
| Qin et al. | An electrochemically deposited ordered hierarchical metal–organic framework-based dual-module sensor for decoding organic vapors | |
| CN112321833B (en) | Preparation method and application of fluorescent molecularly imprinted silica gel nanoparticles | |
| Chinigar et al. | Boron/Nitrogen Co-doped carbon quantum dots as a high sensitive and selective fluorescent sensor for PO 4 3-detection. | |
| CN111690406B (en) | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots | |
| CN108745308A (en) | A kind of conductive traces Ag@PANI/CoFe2O4The preparation method and applications of/C | |
| CN108067268A (en) | A kind of preparation and its application of 1-dimention nano tubulose Ag/AgCl/AgBr composite heterogenous junction visible light catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |