CN108489970B - Electrochemical luminescence reagent prepared from macrocyclic compound and application thereof - Google Patents
Electrochemical luminescence reagent prepared from macrocyclic compound and application thereof Download PDFInfo
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- CN108489970B CN108489970B CN201810305957.5A CN201810305957A CN108489970B CN 108489970 B CN108489970 B CN 108489970B CN 201810305957 A CN201810305957 A CN 201810305957A CN 108489970 B CN108489970 B CN 108489970B
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Abstract
The electrochemical luminescence reagent prepared from the macrocyclic compound is simple to operate and short in time consumption, can detect fused ring aromatic hydrocarbons (naphthalene, pyrene, anthracene, phenanthrene, perylene and 9.10-benzophenanthrene triphenylene) by using the electrochemical luminescence reagent, is different from the conventional method for detecting fused ring aromatic hydrocarbons by using a chromatography, has a cavity structure, is different from common electrochemical luminescence substances (such as luminol, terpyridyl ruthenium and the like), develops a new electrochemical luminescence substance, and provides a new development direction for research and application of macrocyclic subject and object chemical compounds and electrochemical luminescence.
Description
Technical Field
The invention relates to the field of electrochemical luminescence, in particular to an electrochemical luminescence reagent prepared from a macrocyclic compound and application thereof.
Background
Electrochemiluminescence (ECL), also called Electrochemiluminescence, is a product of combining chemiluminescence and an electrochemical method, and refers to a luminescence phenomenon generated by generating some special substances through an electrochemical method and then further reacting among the electric substances or among the electric substances and other substances; in addition to the advantages of chemiluminescence analysis, such as high sensitivity, wide linear range, and simple device, the electrochemiluminescence analysis method can overcome the disadvantages of chemiluminescence analysis, such as difficulty in storing or instability of chemiluminescence reagents under specific conditions, difficulty in realizing time and space control, difficulty in reusing chemiluminescence reagents, and relatively poor reproducibility due to non-uniform solution mixing.
Polycyclic Aromatic Hydrocarbons (PAHs) are a subset of polycyclic aromatic compounds, organic compounds that are ubiquitous in the environment. Fused ring aromatic hydrocarbons are formed when organic matter, primarily from human activities such as fossil fuel combustion, biomass combustion, cooking and smoking, is incompletely combusted. They are known to have oncogenic and reproductive toxicities and to cause cardiovascular disease in animal studies. At present, the fused ring aromatic hydrocarbon is generally detected by chromatography, but the sample preparation is difficult, the time consumption is long, and the analysis cost is high.
Disclosure of Invention
The invention aims to provide an electrochemiluminescence reagent prepared from a macrocyclic compound and application thereof. The reagent is simple to operate and short in time consumption, and can be used for detecting fused ring aromatic hydrocarbons (naphthalene, pyrene, anthracene, phenanthrene, perylene and 9.10-benzophenanthrene triphenylene). At the same time, a new electrochemical luminescence substance has been developed.
The technical scheme of the invention is as follows: an electrochemiluminescent reagent prepared from a macrocyclic compound having the formula: c60H60N12O6The structural formula is as follows:
the electrochemiluminescence reagent is prepared by the following steps: with Al2O3Polishing the glassy carbon electrode with the polishing powder, cleaning, airing, and modifying the macrocyclic compound on the electrode to obtain the electrode.
In the electrochemiluminescence reagent prepared from the macrocyclic compound, the electrochemiluminescence reagent is prepared by: taking 3-7 μ l of 1 × 10-5And (3) coating the macrocyclic compound solution of mol/l on the cleaned glassy carbon electrode, after the solvent is volatilized, coating the macrocyclic compound solution of 3-7 mu l on the cleaned glassy carbon electrode, and repeating for 10 times to obtain the compound.
In the electrochemiluminescence reagent prepared from the macrocyclic compound, the fused ring aromatic hydrocarbon is detected.
In the electrochemiluminescence reagent prepared from the macrocyclic compound, the fused ring aromatic hydrocarbon is naphthalene, pyrene, anthracene, phenanthrene, perylene or 9, 10-benzophenanthrene triphenylene.
The application of the electrochemiluminescence reagent prepared from the macrocyclic compound for detecting the fused ring aromatic hydrocarbon specifically comprises the following steps:
is prepared from acetonitrileIs prepared to have a concentration of 1.0 × 10-15mol/L-1.0×10-5A p-fused ring aromatic hydrocarbon solution of mol/L;
secondly, stirring the electrochemical luminescence reagent and the para-fused ring aromatic hydrocarbon solution in the first step at normal temperature for 20-30min, and drying to obtain a standby electrode;
and thirdly, measuring the electrode to be used in the step II in an electrochemical luminescence tester, wherein the detection parameters of the electrochemical luminescence tester are as follows: the potential range is 0-1.6V, and the scanning speed is 50 mv/s.
In the application of the electrochemiluminescence reagent prepared from the macrocyclic compound, the macrocyclic compound is mainly prepared from 1-3 parts by weight of 2-hydroxybenzimidazole, 0.1-0.5 part by weight of tetrabutylammonium bromide, 40-60 parts by volume of toluene, 10-30 parts by volume of 40% sodium hydroxide solution and 1-3 parts by volume of methyl iodide, and the electrochemiluminescence reagent is prepared by the following steps:
(1) mixing 2-hydroxybenzimidazole, tetrabutylammonium bromide, toluene, 40% sodium hydroxide solution and methyl iodide, and heating at 60-80 deg.C for 19 hr to obtain product A;
(2) mixing the product A, hydrochloric acid solution and pure formic acid to obtain a product B;
(3) adding 30-50% formaldehyde solution into product B, and stirring to obtain product C;
(4) stirring product C at room temperature for 4-6 hr to obtain white precipitate and product D;
(5) and (5) performing suction filtration on the product D, washing with methanol and dichloromethane in sequence, and drying to obtain a white solid.
In the application of the electrochemiluminescence reagent prepared from the macrocyclic compound, in the step (2), the concentration of the hydrochloric acid solution is 4-8mol/L, and 10-15ml of hydrochloric acid solution and 3-6ml of pure formic acid are added to every 300mg of 2-hydroxybenzimidazole.
In the application of the electrochemiluminescence reagent prepared from the macrocyclic compound, in the step (3), the addition amount of the 30-50% formaldehyde solution is calculated by the molar ratio of the product A to the formaldehyde being 1: 10-12.
In the application of the electrochemiluminescence reagent prepared from the macrocyclic compound, the macrocyclic compound is mainly prepared from 2 parts by weight of 2-hydroxybenzimidazole, 0.24 part by weight of tetrabutylammonium bromide, 50 parts by volume of toluene, 20 parts by volume of 40% sodium hydroxide solution and 2 parts by volume of methyl iodide.
Compared with the prior art, the electrochemiluminescence reagent prepared by the macrocyclic compound provided by the invention is simple to operate and short in time consumption, can be used for detecting fused ring aromatic hydrocarbons (naphthalene, pyrene, anthracene, phenanthrene, perylene and 9.10-triphenylene), is different from the conventional method for detecting fused ring aromatic hydrocarbons, has a cavity structure, is different from common electrochemiluminescence substances (such as luminol and terpyridyl ruthenium) at the same time, develops a new electrochemiluminescence substance, and provides a new development direction for research and application of macrocyclic subject and object chemical compounds and electrochemiluminescence.
Description of the drawings:
FIG. 1(a) is a cyclic voltammogram of a macrocyclic compound, and FIG. 1(b) is an electrochemiluminescence thereof;
FIG. 2(a) is an electrochemiluminescence diagram of a guest 9, 10-triphenylene modified with a guest; (b) the ECL intensity is plotted against the negative log of guest 9.10-triphenylene concentration.
The invention is further described with reference to the following examples and the accompanying drawings.
Detailed Description
A macrocyclic compound of the formula C60H60N12O6The structural formula is as follows:
example 1
A macrocyclic compound of the formula C60H60N12O6The structural formula is as follows:
the synthesis method of the macrocyclic compound comprises the following steps:
(1) heating 2-hydroxybenzimidazole (2g, 0.015mol), tetrabutylammonium bromide (0.24g, 0.75mmol), toluene 50mL, 40% sodium hydroxide solution 20mL and methyl iodide (2mL, 0.032mol) at 60-80 deg.C for 19 hr to obtain product A;
(2) mixing the product A, hydrochloric acid solution and formic acid to obtain product B;
(3) adding 40% formaldehyde solution into the product B, and stirring to obtain product C;
(4) stirring product C at room temperature for 5 hr to obtain white precipitate and product D;
(5) and (5) performing suction filtration on the product D, washing with methanol and dichloromethane in sequence, and drying to obtain a white solid.
The concentration of the hydrochloric acid solution is 6mol/L, and 10ml of hydrochloric acid solution and 5ml of pure formic acid are added into every 300mg of 2-hydroxybenzimidazole; the addition amount of the 40% formaldehyde solution is calculated according to the molar ratio of the A product to the formaldehyde being 1: 11.
The electrochemiluminescence reagent prepared by the macrocyclic compound specifically comprises:
(1) with Al2O3Polishing glassy carbon electrode with polishing powder, cleaning, air drying, and collecting 5ul of glass carbon electrode with concentration of 1.0 × 10-5Coating the macrocyclic compound solution of mol/l on a cleaned glassy carbon electrode, taking 5ul of the macrocyclic compound solution after the solvent is volatilized, airing, and repeating for 10 times to obtain a modified glassy carbon electrode;
(2) a conventional three-electrode system is adopted, a platinum wire is used as a counter electrode, a glassy carbon electrode (GCE, phi is 3mm) is used as a working electrode, Ag/AgCl is used as a reference electrode, a buffer solution is a mixed solution of 0.1mol/l 4-hydroxyethyl piperazine ethanesulfonic acid and 0.1mol/l sodium hydroxide in a volume ratio of 1:1, and the pH value is 12.0;
(3) as a result, as shown in FIG. 1, it was observed that an oxidation peak occurred at +1.1v, accompanied by an electrochemiluminescence phenomenon.
Example 2:
(1) preparation of 1.0X 10 with acetonitrile-5mol/l、1.0×10-6mol/l…1.0×10-14mol/l、1.0×10- 15A solution of each of the above-mentioned fused ring aromatic hydrocarbons in an equal concentration of mol/l;
(2) stirring the glassy carbon electrode modified with the macrocyclic compound and the fused ring aromatic hydrocarbons in the step (1) at normal temperature for 25min, and airing for later use;
(3) measuring the electrode to be used in the step (2) in an electrochemical luminescence tester;
(4) the data for the completion of the assay is plotted and the results are shown in FIG. 2, where FIG. 2(b) shows that the 9.10-triphenylene guest is not completely quenched for the electrochemiluminescence of the macrocyclic compound and all other guests are completely quenched.
Claims (5)
1. The application of the electrochemical luminescence reagent prepared by the macrocyclic compound is characterized in that: the macrocyclic compound has the formula: c60H60N12O6The structural formula is as follows:
the electrochemiluminescence reagent is prepared by the following steps: with Al2O3Polishing the glassy carbon electrode by using polishing powder, cleaning, airing, and modifying the macrocyclic compound on the electrode to obtain the electrode; the electrochemiluminescence reagent is prepared by the following steps: taking 3-7 μ l of 1 × 10-5Coating the macrocyclic compound solution of mol/l on a cleaned glassy carbon electrode, after the solvent is volatilized, coating the macrocyclic compound solution of 3-7 mu l on the cleaned glassy carbon electrode, and repeating for 10 times to obtain the compound solution; the application of the electrochemiluminescence reagent prepared by the macrocyclic compound is to detect fused ring aromatic hydrocarbon; the fused ring aromatic hydrocarbon is naphthalene, pyrene, anthracene, phenanthrene, perylene or 9, 10-benzophenanthrene triphenylene; the method for detecting the fused ring aromatic hydrocarbon specifically comprises the following steps:
prepared with acetonitrile in the concentration of 1.0X 10-15mol/L-1.0×10-5A p-fused ring aromatic hydrocarbon solution of mol/L;
secondly, stirring the electrochemical luminescence reagent and the para-fused ring aromatic hydrocarbon solution in the first step at normal temperature for 20-30min, and drying to obtain a standby electrode;
and thirdly, measuring the electrode to be used in the step II in an electrochemical luminescence tester, wherein the detection parameters of the electrochemical luminescence tester are as follows: the potential range is 0-1.6V, and the scanning speed is 50 mv/s.
2. Use of an electrochemiluminescent reagent prepared from a macrocyclic compound according to claim 1, wherein: the macrocyclic compound is mainly prepared from 1-3 parts of 2-hydroxybenzimidazole, 0.1-0.5 part of tetrabutylammonium bromide, 40-60 parts of toluene, 10-30 parts of 40% sodium hydroxide solution and 1-3 parts of methyl iodide by weight part according to the following steps:
(1) mixing 2-hydroxybenzimidazole, tetrabutylammonium bromide, toluene, 40% sodium hydroxide solution and methyl iodide, and heating at 60-80 deg.C for 19 hr to obtain product A;
(2) mixing the product A, hydrochloric acid solution and pure formic acid to obtain a product B;
(3) adding 30-50% formaldehyde solution into product B, and stirring to obtain product C;
(4) stirring product C at room temperature for 4-6 hr to obtain white precipitate and product D;
(5) and (5) performing suction filtration on the product D, washing with methanol and dichloromethane in sequence, and drying to obtain a white solid.
3. Use of an electrochemiluminescent reagent prepared from a macrocyclic compound according to claim 2, wherein: in the step (2), the concentration of the hydrochloric acid solution is 4-8mol/L, and 10-15ml of hydrochloric acid solution and 3-6ml of pure formic acid are added into every 300mg of 2-hydroxybenzimidazole.
4. Use of an electrochemiluminescent reagent prepared from a macrocyclic compound according to claim 2, wherein: in the step (3), the adding amount of the 30-50% formaldehyde solution is calculated by taking the molar ratio of the product A to the formaldehyde as 1: 10-12.
5. Use of an electrochemiluminescent reagent prepared from a macrocyclic compound according to claim 2, wherein: the macrocyclic compound is mainly prepared from 2 parts by weight of 2-hydroxybenzimidazole, 0.24 part by weight of tetrabutylammonium bromide, 50 parts by volume of toluene, 20 parts by volume of 40% sodium hydroxide solution and 2 parts by volume of methyl iodide.
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