CN114163995A - Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid - Google Patents

Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid Download PDF

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CN114163995A
CN114163995A CN202111462517.9A CN202111462517A CN114163995A CN 114163995 A CN114163995 A CN 114163995A CN 202111462517 A CN202111462517 A CN 202111462517A CN 114163995 A CN114163995 A CN 114163995A
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chemiluminescence
mofs
mixed solution
naio
acid
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吴静
王嫣然
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni

Abstract

The embodiment of the specification relates to the technical field of pyrogallic acid detection, in particular to a chemiluminescence reinforcing agent, a preparation method thereof and application thereof in pyrogallic acid detection. Wherein the chemiluminescence enhancer is: the metal-organic framework (MOFs) material is formed by assembling positive divalent cobalt element serving as a central atom and 2-aminoterephthalic acid serving as an organic ligand. The chemiluminescence reinforcing agent can linearly reinforce NaIO4‑H2O2The chemiluminescence intensity of the system and the detection sensitivity of the gallic acid can reach 1 × 10‑7mol·L‑1。

Description

Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid
Technical Field
The embodiment of the specification relates to the technical field of pyrogallic acid detection, in particular to a chemiluminescence reinforcing agent, a preparation method thereof and application thereof in pyrogallic acid detection.
Background
Pyrogallic acid is an important polyphenol and has strong reducing property. Pyrogallic acid is widely used in many industries including pharmaceutical, plastic and cosmetic industries as an industrial raw material such as a preservative and a dyeing material. Pyrogallic acid is generally present in industrial waste, and in view of toxicity and environmental hazard inherent in pyrogallic acid, it is necessary to develop a highly sensitive method for detecting pyrogallic acid.
The pyrogallic acid is detected by a conventional method such as chromatography, spectrophotometry, electrochemical method and chemiluminescence method. The chromatographic method and the spectrophotometry have large errors and complicated procedures. Although the electrochemical method has fast response and simple operation, the instrument required for detection is expensive, thereby limiting the wide application of the electrochemical method.
Chemiluminescence is a powerful analysis technique and has the advantages of wide linear range, low background signal, simple instrument and equipment and the like. Therefore, detection technology of pyrogallic acid based on chemiluminescence is a worthy direction to be studied.
Disclosure of Invention
In view of the above problems, embodiments of the present specification provide a chemiluminescence enhancer, a chemiluminescence enhancing reagent, and a preparation method, a use and a kit thereof, which can enhance the chemiluminescence intensity in the detection process of pyrogallic acid, thereby improving the detection effect of pyrogallic acid by using a chemiluminescence method.
In a first aspect, there is provided a method of enhancing NaIO4-H2O2A chemiluminescence enhancer of the chemiluminescence intensity of the system, wherein the chemiluminescence enhancer is: the metal-organic framework (MOFs) material is formed by assembling positive divalent cobalt element serving as a central atom and 2-aminoterephthalic acid serving as an organic ligand. The chemiluminescence reinforcing agent is in a flower-shaped structure stacked by nanosheets.
In one embodiment, the molar ratio of the divalent cobalt element to the 2-aminoterephthalic acid in the chemiluminescence enhancer is 1:1 to 1: 3.
In a second aspect, a chemiluminescence enhancing reagent for detecting pyrogallic acid is provided, which is prepared from the chemiluminescence enhancing agent of the first aspect and water, wherein 1-10mg of the chemiluminescence enhancing agent is matched with 1mL of water; the chemiluminescence enhancing reagent is used for enhancing NaIO4-H2O2The chemiluminescence intensity of the system.
In one embodiment, 4mg of the chemiluminescence enhancer is combined per 1mL of water.
In a third aspect, there is provided a method for preparing the chemiluminescence enhancer of the first aspect, comprising the following steps:
step (1), preparing a reaction solution, and dissolving 2-amino terephthalic acid and a divalent cobalt salt in a solvent in sequence to obtain the reaction solution; wherein the solvent is a mixed solution of N, N-Dimethylformamide (DMF), ethanol and water; in the reaction solution, the mole ratio of the divalent cobalt salt to the 2-amino terephthalic acid is (1:1) - (1: 3);
step (2), adding triethylamine into the reaction solution, mixing, and oscillating to obtain a first mixed solution;
step (3), transferring the first mixed solution into a reaction bottle for ultrasonic treatment; and after the ultrasonic treatment is finished, centrifuging and removing supernatant, washing the precipitate with ethanol, dispersing the precipitate into water, and freeze-drying to obtain the chemiluminescence reinforcing agent.
In one embodiment, in the step (1), 32mL of DMF, 2mL of ethanol and 2mL of water are mixed uniformly to obtain the solvent; dissolving 0.75mmol of 2-amino terephthalic acid and 0.75mmol of divalent cobalt salt in the solvent in sequence to obtain a reaction solution;
in the step (2), 0.8mL of triethylamine is added into the reaction solution, and the mixture is rapidly oscillated for 5min to obtain the first mixed solution;
in the step (3), the first mixed solution is subjected to ultrasonic treatment at room temperature, wherein the frequency of the ultrasonic treatment is 80kHz, and the time is 8 h; and then, centrifuging the first mixed solution for 5min at 10000rpm, washing the centrifuged precipitate with ethanol, dispersing the precipitate into water, freezing the precipitate until the precipitate is completely frozen, and freeze-drying the frozen precipitate to obtain the chemiluminescence reinforcing agent.
In one embodiment, the divalent cobalt salt is CoCl2·6H2O。
In a fourth aspect, there is provided a use of the chemiluminescence enhancing reagent according to the second aspect in detecting pyrogallic acid.
In one embodiment, the use is the chemiluminescence enhancing agent in combination with NaIO4And H2O2The application in detecting pyrogallic acid; wherein the chemiluminescence enhancing reagent is used for enhancing NaIO4-H2O2The chemiluminescence intensity of the system.
In a fifth aspect, a pyrogallic acid detection method is provided, which comprises the following steps:
(1) preparing a solution to be detected;
(2) adding the chemiluminescence enhancing reagent according to claim 3 or 4 to a solution to be detected to obtain a first mixed solution;
(3) adding H into the first mixed solution obtained in the step (2)2O2H of (A) to (B)2SO4Dissolving to obtain a second mixed solution, wherein H in the second mixed solution2O2The final concentration is 0.12 mol.L-1，H2SO4The final concentration is 0.006 mol.L-1And every 1200 mul of the second mixed solution contains 100 mul of the chemiluminescence enhancing reagent;
(4) detecting the luminous intensity of the second mixed solution;
(5) and determining the pyrogallic acid concentration in the solution to be detected according to the luminous intensity and the standard curve.
A sixth aspect, a pyrogallic acid detection kit, wherein the detection limit of pyrogallic acid by the kit is equal to or less than 1.0 × 10-7mol·L-1；
The kit comprises: a chemiluminescent enhancer of the first aspect; alternatively, a chemiluminescent enhancing agent according to the second aspect.
The chemiluminescence reinforcing agent provided by the specification can linearly reinforce NaIO4-H2O2The chemiluminescence intensity of the system. The detection sensitivity of the gallic acid can reach 1 × 10-7mol·L-1. Therefore, the chemiluminescence enhancer, the detection method and the kit provided by the embodiment of the specification can be used for detecting pyrogallic acid by a chemiluminescence method, and have a good detection effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, 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 disclosure, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, 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 disclosure, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows a Scanning Electron Microscope (SEM) photograph of Co-MOF provided in the examples herein;
FIG. 2 shows a Transmission Electron Microscope (TEM) photograph of Co-MOF provided in the examples herein;
FIG. 3A shows an XPS spectrum of Co-MOF provided in the examples herein;
FIG. 3B shows an XPS spectrum of Co-MOF provided in the examples herein;
FIG. 4A shows a Fourier transform infrared spectrum of a Co-MOF provided in an example of the present specification;
FIG. 4B shows a Fourier transform infrared spectrum of a Co-MOF provided in an example of the present disclosure;
FIG. 5 shows fluorescence emission spectra (λ) of Co-MOFs provided in the examples of the present specificationex＝425nm)；
FIG. 6 shows an absorption spectrum of Co-MOF provided in examples herein;
FIG. 7 shows a comparison at NaIO4-H2O2Whether the chemiluminescence intensity of Co-MOF provided by the specification example is added in the system;
FIG. 8 shows the addition of Co-MOF to NaIO provided in the examples of the present specification4-H2O2Post-system chemiluminescence spectroscopy;
FIG. 9 shows Co-MOF-NaIO4-H2O2In the system H2SO4Optimization of concentration (experiment was repeated 3 times);
FIG. 10 shows Co-MOF-NaIO4-H2O2NaIO in the system4Optimization of concentration (experiment was repeated 3 times);
FIG. 11 shows Co-MOF-NaIO4-H2O2Optimization of Co-MOF concentration in the system (experiment was repeated 3 times);
FIG. 12 shows Co-MOF-NaIO4-H2O2In the system H2O2Optimization of concentration (experiment was repeated 3 times);
FIG. 13 shows a standard curve obtained for detection of pyrogallol solutions of different concentrations using a chemiluminescent system constructed according to the present embodiments;
FIG. 14 shows a Co-MOF enhanced NaIO provided in the examples of the present specification4-H2O2The principle of chemiluminescence of the system;
FIG. 15 shows a process for preparing Co-MOF provided in the examples herein.
Detailed Description
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.
The embodiment of the specification prepares a metal-organic framework (MOFs) material which is formed by assembling a positive divalent cobalt element as a center and 2-aminoterephthalic acid as an organic ligand and can be used for detecting the gallic acid in NaIO4-H2O2Used as a chemiluminescence enhancer in the system. The metal-organic framework materials may be referred to as Co-MOFs, and may also be referred to as Co-MOFs.
The metal-organic framework material is simple to prepare, has low cost and is beneficial to industrial production. The metal-organic framework material can reinforce NaIO4-H2O2The chemiluminescence of the system improves the detection effect of detecting the pyrogallic acid by using a chemiluminescence method, so the method has good application value in the field of pyrogallic acid detection.
Next, the scheme provided in the present specification will be specifically described with reference to different embodiments.
Example 1
The inventors of the present invention have found, through a large number of experiments, that 2-aminoterephthalic acid (NH) is used as a central atom of cobalt2·H2BDC) as ligand can promote NaIO (metal organic frameworks) (Co-MOFs, also called metal-organic frameworks, Co-MOFs)4-H2O2The system generates active oxygen species which can significantly enhance NaIO4-H2O2The chemiluminescence of the system is linearly related to the pyrogallic acid concentration in a certain range. Also, the inventors of the present application have found through a large number of experiments that the Co-MOFs has a flower shape with nanosheet stacking, and has an extremely high proportion of exposed catalytically active surface, and has unsaturated active sites, and thus, the Co-MOFs is suitable for use as a chemiluminescent material and for the detection of pyrogallol.
Based on the above findings, the present embodiment provides a MOFs material comprising a central atom and a ligand, wherein the central atom isCobalt element can be selected, and particularly, positive divalent cobalt ions can be selected. The organic ligand can be NH2·H2BDC。
The Co-MOFs provided by the embodiment can obviously enhance NaIO4-H2O2The chemiluminescence of the system is realized, and the enhanced chemiluminescence intensity is linearly related to the concentration of pyrogallic acid, so that the method can be used for detecting the concentration of the pyrogallic acid. Thus, the Co-MOFs provided by the examples may be referred to as chemiluminescence enhancers.
Example 2
This example provides a method for preparing the MOFs provided in example 1, specifically, an ultrasonic method is used to prepare NH with cobalt as a central atom2·H2BDC is the Co-MOFs of the ligand. The method specifically comprises the following steps.
2.1, 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of water are added to a reaction flask and mixed uniformly to obtain a mixed solvent.
2.2, 0.75mmol of 2-aminoterephthalic acid (NH)2·H2BDC) and 0.75mmol of divalent cobalt salt are dissolved in the solvent in sequence to obtain reaction solution. Wherein the divalent cobalt salt is CoCl2·6H2O。
2.3, to the reaction solution obtained in step 2.2, 0.8mL of triethylamine was added and mixed in a reaction flask and stirred rapidly for 5 min.
2.4, the reaction flask is reacted for 8 hours under ultrasound, and the temperature is kept unchanged. Wherein the frequency of the ultrasound is 80 kHz.
2.5, after the reaction is finished, centrifuging the reaction solution at 10000rpm for 5min, removing supernatant, washing and dispersing the residual precipitate with ethanol, centrifuging at 10000rpm for 5min, removing supernatant, repeating the washing twice, then adding proper distilled water to disperse the product into a culture dish, putting the culture dish into a refrigerator to freeze until the product is completely frozen, and finally freeze-drying for 24h to obtain the Co-MOFs.
4mg of Co-MOFs was dispersed in 1mL of water to obtain a Co-MOFs dispersion, which was used in the experiments in the following examples. Among them, the Co-MOFs dispersion may also be referred to as a chemiluminescence enhancing agent.
Next, the characteristic characterization of Co-MOFs provided in the present specification and the application of Co-MOFs in chemiluminescence are illustrated by specific examples.
Example 3, SEM, TEM characterization of Co-MOFs.
The morphology characterization of Co-MOF was observed by SEM and TEM and the results are shown in FIGS. 1 and 2, respectively. As can be seen from FIG. 1, the Co-MOFs are flower-like features formed by stacking sheet materials with a lateral dimension of several hundred nanometers. This feature is confirmed by the TEM image of fig. 2, and it can be seen from the transparency of the single-layer nanosheet that it has an ultra-thin feature.
Example 4, spectral characterization of Co-MOFs.
The XPS spectra shown in FIG. 3A, the characteristic signals of 781.6 and 797.6eV are assigned to Co2p3/2And Co2p1/2And satellite peaks associated with 786.4 and 802.7eV, respectively, reveal the formation of an inverted bond orbital between Co and O elements. As shown in FIG. 3B, the characteristic O1 s signal is at 531.8eV, and the fitting peaks at 531.6, 532.1 and 533.4eV can be assigned to Co-O, C-O and C ═ O, respectively, which confirms that Co is used as Co in Co-MOFs2+Is a connecting point and NH2·H2BDC coordinates.
Fourier transform infrared spectroscopy (FT-IR) further verifies Co2+And NH2·H2Coordination between BDC, as shown in FIG. 4A, Co-MOFs with NH2·H2There is a clear difference between FT-IR for BDC, at NH2·H2the-OH of-COOH in BDC is 3000-2500 cm-1The region has a broad and weak absorption peak of stretching vibration, and the absorption peak in Co-MOFs disappears due to NH2·H2Deprotonation of BDC during which the ligand is reacted with Co2+Coordinated to form Co-MOFs. As shown in FIG. 4B, with NH2·H2Compared with BDC, in the formation process of Co-MOFs, the BDC is arranged at 708, 450 and 423cm of low wave band-1Three new peaks appear, which are due to the stretching vibration of Co-O. Furthermore, it is at 3087cm-1At H2Stretching vibration of O molecule shows that coordinated H exists in Co-MOFs2And (3) O molecules. At 1558 and 1381cm-1The region has two strong absorption peaks, which are (-COO) in the ligand-) asymmetrical, symmetrical stretching vibration absorption of functional groups at 3473, 3342cm-1Absorption peaks of the region ascribed to NH2·H2Amino (-NH) group in BDC2) Asymmetric, symmetric stretching vibration absorption peak of (1), and NH2·H2BDC is significantly weaker than these absorption peaks, further illustrating NH2·H2BDC coordination.
FIG. 5 is a fluorescence spectrum of Co-MOFs at an excitation wavelength of 240 nm-400nm, and it can be seen from FIG. 5 that the Co-MOFs can obtain the strongest emission fluorescence under the excitation condition of 370nm, and the wavelength is located at 425 nm. The excitation light and the emission light of the Co-MOFs have close wavelengths, the Stokes shift is small, and the optical property is stable. And, as shown in FIG. 6, the whole Co-MOFs-NaIO4-H2O2The uv-vis absorption spectrum of the system shows: NaIO4、H2O2、NaIO4-H2O2Mixture, Co-MOFs-NaIO4Mixture, and Co-MOFs-NaIO4-H2O2The mixture has no characteristic absorption peak, Co-MOFs has a strong absorption peak with obvious characteristic at 300nm-400nm, and H is added2O2Then, the absorbance of the absorption peak is reduced but the position range of the absorption peak is basically unchanged, which shows that Co-MOFs is used for H2O2Has a certain catalytic action. And compared with Co-MOFs, Co-MOFs-NaIO4In the system, the characteristic absorption peak of Co-MOFs at 300nm-400nm completely disappears, which further proves that the Co-MOFs not only serves as a catalyst in the system, but also participates in the reaction. In addition, there is no ultraviolet absorption by other substances, and thus it is understood that no other new substances may be generated in the light-emitting system.
Example 5 Co-MOFs-NaIO4-H2O2Construction of the chemiluminescent System
FIG. 7 shows the detection of NaIO in the case of whether Co-MOFs are added or not4-H2O2System and Co-MOFs-NaIO4-H2O2The chemiluminescence intensity of the system is examined to investigate the effect of Co-MOFs on NaIO4-H2O2Whether or not there is an enhancement in the chemiluminescence of the system can be seen in FIG. 7Out at NaIO4-H2O2The chemiluminescence intensity of the system is obviously enhanced after Co-MOFs is added into the system.
The experimental conditions were: 0.12 mol.L-1H2O2Is prepared from the mixture of 0.006 mol.L-1H2SO4Neutralized with 0.08 mol. L-1NaIO4Mixing with Co-MOFs solution to obtain Co-MOFs-NaIO4-H2O2And (4) preparing the system. Namely the Co-MOFs-NaIO obtained in the preparation4-H2O2In the system, H2SO4The concentration is 0.006 mol.L-1，NaIO4The concentration is 0.08 mol.L-1，H2O2The concentration is 0.12 mol.L-1. Wherein, each 2.1mL of Co-MOFs-NaIO4-H2O2The system contained 100. mu.L of Co-MOFs dispersion.
Using transient fluorescence spectrometer to perform fluorescence detection on Co-MOFs-NaIO4-H2O2The chemiluminescence spectrum of the system is detected, and the result shows that the strongest chemiluminescence peak of the system is positioned at about 470nm, and the luminescence range is 350nm-600 nm.
Example 6, Co-MOFs-NaIO4-H2O2Experimental condition optimization of chemiluminescence system
The primary test shows that the chemiluminescence intensity and H of the system2SO4Concentration, NaIO4Concentration, Co-MOFs concentration and H2O2The concentration shows a certain correlation, and NaIO is respectively considered in the experiment to obtain the best test condition4Concentration, H2O2Concentration and H2SO4Effect of concentration on chemiluminescence intensity.
Fix 0.1 mol. L-1H2O2The addition volume of (2) is 1mL, 0.1 mol. L-1NaIO4The addition volume of (2 mg. multidot.mL) of (1)-1Co-MOFs was added in a volume of 100. mu.L, H2SO4The concentration is observed in the range of 0.002-0.009 mol.L-1. In addition, H is2SO4At a concentration of acidified H2O2The concentration of the above componentsIs the concentration prior to mixing.
Fixed 0.006 mol. L-1H2SO4Acidified 0.1 mol. L-1H2O2The addition volume of (2 mg. multidot.mL) of (1)-1Co-MOFs was added in a volume of 100. mu.L, NaIO4The concentration is observed in the range of 0.01-0.20 mol.L-1. The concentrations of the respective components are those before mixing.
Fixed 0.006 mol. L-1H2SO4Acidified 0.1 mol. L-1H2O2The addition volume of (2) is 1mL, 0.08 mol.L- 1NaIO4The volume of addition of (1 mL) and the range of investigation of the concentration of the Co-MOFs dispersion was 1 mg/mL-1-10mg·mL-1. The concentrations of the respective components are those before mixing.
Fixed H2SO4Has a concentration of 0.006 mol. L-1、0.08mol·L-1NaIO4The addition volume of (2) is 1mL, 4 mg. mL-1Co-MOFs was added in a volume of 100. mu.L, H2O2The concentration is observed in the range of 0.01-0.20 mol.L-1. The concentrations of the respective components are those before mixing.
And examining the chemiluminescence intensity under different conditions, thereby determining the optimal experimental conditions. Acidification is a necessary condition for the system to produce chemiluminescence. In this example, the value of H2SO4As acidification H2O2Thus, first on H2SO4The concentration is optimized.
As shown in FIG. 9, when other conditions are fixed, H is2SO4The concentration is 0.006 mol.L-1The chemiluminescence signal obtained is strongest.
As shown in FIG. 10, when other conditions are fixed, NaIO is used4The concentration is 0.08 mol.L-1The chemiluminescence signal obtained is strongest.
As shown in FIG. 11, when other conditions were fixed, the concentration of the dispersion in Co-MOFs was 4 mg/mL-1The chemiluminescence signal obtained is strongest. Co-MOFs fractionWhen the concentration of the dispersion is too high, luminescence is quenched, and when the concentration of the dispersion is too low, a luminescence signal is weak.
As shown in FIG. 12, when other conditions are fixed, H is2O2The concentration is 0.12 mol.L-1The chemiluminescence signal obtained is strongest. H2O2When the concentration is too high, luminescence is quenched, and when the concentration is too low, a luminescence signal is weak.
Therefore, the optimal conditions for this experiment are: 0.12 mol. L-1H2O2Prepared at 0.006 mol.L-1H2SO4Middle, 0.08 mol. L-1NaIO4、4mg·mL-1The amount of Co-MOFs dispersion added was 100. mu.L. 1mL of H2SO4Acidified H2O2Adding to 100. mu.L Co-MOFs and 1mL NaIO4The optimal chemiluminescence intensity can be obtained in the mixed solution.
Example 7 preparation of Standard Curve for detecting pyrogallic acid
On the basis of the optimal experimental condition exploration, the method is used for measuring the low-concentration pyrogallic acid which has a linear correlation with the chemiluminescence intensity. The experimental conditions were: 1mL of 0.12 mol. L-1H2O2Prepared at 0.006 mol.L-1H2SO4、1mL 0.001mol·L-1NaIO4And 100. mu.L of 4 mg. multidot.mL-1When Co-MOFs is used, the pyrogallic acid concentration is 1X 10-7mol·L-1-1×10-3mol·L-1And (5) establishing a standard curve in the range and performing linear fitting.
As shown in FIG. 13, the chemiluminescent signal was gradually increased and showed good linearity as the pyrogallic acid concentration was increased (wherein, the pyrogallic acid concentration was 1X 10)-7mol·L-1-1×10-3mol·L-1In the range, y is 176.8x +0.695, R2＝0.9995)。
The chemiluminescence reinforcing agent provided by the specification can linearly reinforce Co-MOFs-NaIO added with pyrogallic acid4-H2O2The chemiluminescence intensity of the system. The detection sensitivity of the gallic acid can reach 1 × 10- 7mol·L-1. Therefore, the Co-MOFs-NaIO established by the present embodiment4-H2O2The system can be used for detecting pyrogallic acid based on a chemiluminescence method.
Example 8 Co-MOFs enhancement of NaIO4-H2O2Principle of chemiluminescence of system
In acidic NaIO4-H2O2In the system, the catalytic action of Co-MOFs is beneficial to the generation of free radicals. In the system H2O2HO is first generated by the reaction formula (1)2 -Then, OH and O are further formed2 -And HO2(equations (2) and (3)). Unstable. O2 -Can initiate chain reaction of active oxygen to generate active oxygen free radical1O2(reactions (4) and (5)). Furthermore, Co (II) may be reacted with H2O2The reaction produces Co (III) and. OH (reaction (6)). Thus, Co-MOFs can catalyze H as a catalyst2O2Decompose to produce more free radicals,. O2 -And OH form a higher energy1O2And (a)1O2)2And is one of the luminophores of the system (equation (8)).
H2O2+OH-→HO2 -+H2O (1)
H2O2+HO2 -→·OH+·O2 -+H2O (2)
·OH+H2O2→HO2·+H2O (3)
·O2 -+·OH→1O2+OH- (4)
HO2·+HO2·→1O2+H2O2 (5)
H2O2+Co2+→·OH+Co3+ (6)
Figure BDA0003388796570000121
(1O2)2 *→2O2+hv λem＝470 nm (8)
(1O2)2The Chemiluminescence Resonance Energy Transfer (CRET) effect between the Co-MOFs and the electron-hole recombination annihilation of free radicals and the Co-MOFs enhances the Co-MOFs-NaIO4-H2O2Chemiluminescence of the system. First, IO4 -Reaction with dissolved oxygen to form O2 -(reaction formula (9)) and further (1O2)2(reaction formula (10)). Excited state of (due to the CRET effect)1O2)2Transfer of its energy to Co-MOFs generates Co-MOFs (equation (11)), resulting in strong chemiluminescence. Injection of H during detection2O2The reactions (12) and (13) may be initiated. IO (input/output)4 -And oxidizing radicals OH as electron acceptors for Co-MOFs, and reducing O in the Co-MOFs by injecting holes (reaction formulae (14) and (15))2 -It is possible to act as an electron donor (formula (16)). When electron-hole recombination occurs inside Co-MOFs to cause energy to be released in a light radiation mode, Co-MOF-NaIO is generated4-H2O2Chemiluminescence phenomenon of the system (reaction formulae (17) and (18)).
IO4 -+O2+H2O→2·O2 -+IO3 -+2H+ (9)
2·O2 -+2·O2 -+2H+→(1O2)2*+H2O2 (10)
(1O2)2*+Co-MOFs→Co-MOFs*+2O2 (11)
IO4 -+H2O2→·O2 -+IO3+H2O (12)
·O2 -+H2O2+H+→·OH+H2O+O2 (13)
·OH+Co-MOFs+H+→Co-MOFs·++H2O (14)
IO4 -+Co-MOFs→Co-MOFs·++IO3 -+H2O (15)
·O2 -+Co-MOFs→Co-MOFs·-+O2 (16)
Co-MOFs·++Co-MOFs·-→Co-MOFs*+Co-MOFs (17)
Co-MOFs*→Co-MOFs+hv (18)
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 (10)

1. Can strengthen NaIO4-H2O2The chemiluminescence reinforcing agent of the system chemiluminescence intensity is characterized in that the chemiluminescence reinforcing agent is as follows: the metal-organic framework (MOFs) material is formed by assembling positive divalent cobalt element serving as a central atom and 2-aminoterephthalic acid serving as an organic ligand.
2. The chemiluminescent enhancer of claim 1,
in the chemiluminescence reinforcing agent, the molar ratio of the divalent cobalt element to the 2-amino terephthalic acid is 1:1-1: 3;
the chemiluminescence reinforcing agent is in a flower-shaped structure stacked by nanosheets.
3. A chemiluminescence enhancing reagent for detecting pyrogallic acid, which is prepared from the chemiluminescence enhancing agent according to claim 1 or 2 and water, wherein 1-10mg of the chemiluminescence enhancing agent is matched with 1mL of water; the chemiluminescence enhancing reagent is used for enhancing NaIO4-H2O2The chemiluminescence intensity of the system.
4. The chemiluminescence enhancing reagent according to claim 3, wherein 4mg of the chemiluminescence enhancing agent is collocated per 1mL of water.
5. A method of preparing a chemiluminescent enhancer of claim 1 or claim 2 comprises the steps of:
step (1), preparing a reaction solution, and dissolving 2-amino terephthalic acid and a divalent cobalt salt in a solvent in sequence to obtain the reaction solution; wherein the solvent is a mixed solution of N, N-Dimethylformamide (DMF), ethanol and water; in the reaction solution, the mole ratio of the divalent cobalt salt to the 2-amino terephthalic acid is (1:1) - (1: 3);
step (2), adding triethylamine into the reaction solution, mixing, and oscillating to obtain a first mixed solution;
step (3), transferring the first mixed solution into a reaction bottle for ultrasonic treatment; and after the ultrasonic treatment is finished, centrifuging and removing supernatant, washing the precipitate with ethanol, dispersing the precipitate into water, and freeze-drying to obtain the chemiluminescence reinforcing agent.
6. The method of claim 5,
in the step (1), 32mL of N, N-dimethylformamide, 2mL of ethanol and 2mL of water are uniformly mixed to obtain the solvent; dissolving 0.75mmol of 2-amino terephthalic acid and 0.75mmol of divalent cobalt salt in the solvent in sequence to obtain a reaction solution;
in the step (2), 0.8mL of triethylamine is added into the reaction solution, and the mixture is rapidly oscillated for 5min to obtain the first mixed solution;
in the step (3), the first mixed solution is subjected to ultrasonic treatment at room temperature, wherein the frequency of the ultrasonic treatment is 80kHz, and the time is 8 h; then, centrifuging the first mixed solution for 5min at 10000rpm, washing the centrifuged precipitate with ethanol, dispersing the precipitate into water, freezing the precipitate until the precipitate is completely frozen, and freeze-drying the frozen precipitate to obtain the chemiluminescence reinforcing agent;
wherein the divalent cobalt salt is CoCl2·6H2O。
7. Use of the chemiluminescence enhancing reagent according to claim 3 or 4 for detecting pyrogallic acid.
8. Use according to claim 7, wherein the use is the chemiluminescence enhancing agent in combination with NaIO4And H2O2The application in detecting pyrogallic acid; wherein the chemiluminescence enhancing reagent is used for enhancing NaIO4-H2O2The chemiluminescence intensity of the system.
9. A pyrogallic acid detection method is characterized in that the detection limit of pyrogallic acid detected by the method is equal to or less than 1.0 x 10-7mol·L-1；
The method comprises the following steps:
(1) preparing a solution to be detected;
(2) adding the chemiluminescence enhancing reagent according to claim 3 or 4 to a solution to be detected to obtain a first mixed solution;
(3) adding H into the first mixed solution obtained in the step (2)2O2H of (A) to (B)2SO4Dissolving to obtain a second mixed solution, wherein H in the second mixed solution2O2The final concentration is 0.12 mol.L-1，H2SO4The final concentration is 0.006 mol.L-1And every 1200 mul of the second mixed solution contains 100 mul of the chemiluminescence enhancing reagent;
(4) detecting the luminous intensity of the second mixed solution;
(5) and determining the pyrogallic acid concentration in the solution to be detected according to the luminous intensity and the standard curve.
10. The pyrogallic acid detection kit is characterized in that the detection limit of the kit for detecting the pyrogallic acid is equal to or less than 1.0 x 10-7mol·L-1；
The kit comprises:
the chemiluminescent enhancer of claim 1 or claim 2;
alternatively, the first and second electrodes may be,
the chemiluminescent enhancing reagent of claim 3 or claim 4.
CN202111462517.9A 2021-12-02 2021-12-02 Chemiluminescence reinforcing agent, preparation method thereof and application thereof in detection of pyrogallic acid Pending CN114163995A (en)

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