CN107796801B - Method for constructing liquid-liquid interface electrochemical luminescence system - Google Patents

Method for constructing liquid-liquid interface electrochemical luminescence system Download PDF

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CN107796801B
CN107796801B CN201710801160.XA CN201710801160A CN107796801B CN 107796801 B CN107796801 B CN 107796801B CN 201710801160 A CN201710801160 A CN 201710801160A CN 107796801 B CN107796801 B CN 107796801B
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constructing
glassy carbon
liquid interface
carbon electrode
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CN107796801A (en
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卢小泉
蒲贵强
张东旭
王泽�
汪天胜
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Northwest Normal University
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    • 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
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    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N27/28—Electrolytic cell components
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Abstract

The invention discloses a method for constructing a novel liquid-liquid interface electrochemical luminescence system, which comprises tightly sleeving a polytetrafluoroethylene tube at the front end of a glassy carbon electrode, dropwise adding an organic solution containing a luminescent agent tetraphenylporphyrin and a coreactant tetrabutylammonium hexafluorophosphate into the polytetrafluoroethylene tube, and finally immersing the glassy carbon electrode into a water phase containing potassium chloride. The liquid-liquid interface electrochemical luminescence system is easy to construct, the using amount of the luminescent agent is very small, and the generated ECL signal has good stability and reproducibility; the ECL signal intensity of TPP in the system is about twice that of the ECL signal intensity of TPP in a pure organic phase, and the light-emitting efficiency is high; the system can separate the luminescent agent and the object to be detected by utilizing a liquid-liquid interface, so that mutual interference between the luminescent agent and the object to be detected is avoided; the detection of substances in the full pH environment can be realized; according to the polarity difference of the substances to be detected, the system can firstly extract and enrich the substances to be detected and then carry out quantitative detection, so that the system can improve the sensitivity and detection limit of substance detection.

Description

Method for constructing liquid-liquid interface electrochemical luminescence system
Technical Field
The invention belongs to the technical field of construction of an electrochemical luminescence system, and particularly relates to a construction method of a liquid-liquid interface electrochemical luminescence system.
Background
In the case of electrochemiluminescence systems, the customary luminophores are hydrophobic. Although these luminescent agents have strong and stable electrochemical luminescence signals in organic solutions, the organic phase is not favorable for practical detection application of electrochemical luminescence systems and pollutes the environment. If these poorly water-soluble luminescent agents are used in aqueous-phase electrochemiluminescence systems, their luminous efficiency is particularly low, which is also disadvantageous for practical detection applications. Although the water solubility and the luminous efficiency of the luminescent agent can be improved by some chemical modifications and chemical modifications, the process is extremely complicated, and the stability and the reproducibility are poor.
Disclosure of Invention
The invention aims to solve the problems and provides a method for constructing a liquid-liquid interface electrochemiluminescence system, which is easy to construct, has less luminescent agent dosage and good reproducibility and can generate strong and stable electrochemiluminescence signals.
The purpose of the invention is realized by the following technical scheme:
a method for constructing a liquid-liquid interface electrochemical luminescence system comprises the steps of tightly sleeving a polytetrafluoroethylene tube at the front end of a glassy carbon electrode, dropwise adding an organic solution containing a luminescent agent tetraphenylporphyrin and a coreactant tetrabutylammonium hexafluorophosphate into the polytetrafluoroethylene tube, and finally immersing the glassy carbon electrode into a water phase containing potassium chloride.
Further, the method specifically comprises the following steps:
(1) drying the glassy carbon electrode after treatment, and tightly sleeving a polytetrafluoroethylene tube at the front end of the glassy carbon electrode;
(2) dissolving tetraphenylporphyrin serving as a luminescent agent and tetrabutylammonium hexafluorophosphate serving as a coreactant in 1, 2-dichloromethane to obtain luminescent liquid;
(3) and (3) dripping the luminescent liquid obtained in the step (2) into the polytetrafluoroethylene tube obtained in the step (1), then immersing the glassy carbon electrode into a water phase containing potassium chloride, and immersing a platinum wire and an Ag/AgCl electrode serving as a counter electrode and a reference electrode into the water phase respectively.
Furthermore, in the step (1), the glassy carbon electrode is treated by the following method: sequentially using 0.3 μm and 0.05 μm Al2O3Polishing the slurry, and then sequentially washing with secondary distilled water and ethanol;
the drying temperature is 80 ℃;
the polytetrafluoroethylene tube is a transparent tube, the volume is 100uL, and the inner diameter of the tube is 3 mm.
Furthermore, in the step (2), the concentration of the luminescent agent tetraphenylporphyrin in the luminescent liquid is 10-4And the concentration of the co-reactant tetrabutylammonium hexafluorophosphate is 0.3 mol/L.
Further, in the step (3), the concentration of potassium chloride in the aqueous phase containing potassium chloride is 0.1 mol/L.
Furthermore, the potential scanning rate of the system constructed by the method is 0.3 V.S-1The potential window is-2.2- + 1.1V.
The invention has the following beneficial effects:
(1) the liquid-liquid interface electrochemical luminescence system is easy to construct, the using amount of the luminescent agent is very small, and the generated ECL signal has good stability and reproducibility;
(2) the ECL signal intensity of TPP in the system is about twice that of the ECL signal intensity of TPP in a pure organic phase, and the light-emitting efficiency is high;
(3) the system can separate the luminescent agent and the object to be detected by utilizing a liquid-liquid interface, so that mutual interference between the luminescent agent and the object to be detected is avoided;
(4) the detection of substances in the full pH environment can be realized;
(5) according to the polarity difference of the substances to be detected, the system can firstly extract and enrich the substances to be detected and then carry out quantitative detection, so that the system can improve the sensitivity and detection limit of substance detection.
Drawings
FIG. 1 is a schematic diagram of a liquid-liquid interface electrochemiluminescence system;
FIG. 2(a) shows TPP (10)-4mol/L) and TBAPF6(0.3mol/L) CV diagrams in the separate organic phase (dotted line) and liquid-liquid interface electrochemiluminescence system (solid line), respectively, and FIG. 2(b) shows the ECL signal intensity-time diagram corresponding to FIG. 2 (a);
FIG. 3(a), FIG. 3(b), and FIG. 3(c) show TBAPF6The concentration, the sweep rate and the potential window condition of the sample;
FIG. 4 is a stability test of a liquid-liquid interface electrochemiluminescence system in the first 300s, and the relative standard deviation is 1.44%;
FIG. 5(a) is a graph showing ECL intensity versus time in a liquid-liquid interface electrochemiluminescence system when an aqueous phase is acidic, neutral, and basic, respectively, and FIG. 5(b) is a graph showing an ultraviolet-visible absorption spectrum of an organic phase corresponding to FIG. 5 (a).
Detailed Description
In order to further highlight the objects, technical solutions and advantages of the present invention, the present invention is further described with reference to the following examples, but the present invention is not limited to the scope of the examples.
Example 1
A method for constructing a liquid-liquid interface electrochemical luminescence system comprises the following specific steps:
(1) the glassy carbon electrode was successively coated with 0.3 μm and 0.05 μm Al2O3The slurry was polished and then sequentially washed with redistilled water and ethanol.
(2) The surface of the glassy carbon electrode was thoroughly dried with a hot air gun (temperature set at 80 ℃), and then a transparent polytetrafluoroethylene tube having a volume of 200uL and diameters at both ends of 5mm and 3mm, respectively, was tightly fitted over the front end of the glassy carbon electrode.
(3) The luminescent agent Tetraphenylporphyrin (TPP) and the coreactant tetrabutylammonium hexafluorophosphate (TBAPF)6) Dissolving in organic phase 1, 2-dichloromethane with TPP concentration of 10-4mol/L, TBAPF6The concentration of the fluorescent powder is 0.3mol/L, the front end of the modified electrode faces upwards, and then a liquid transfer device is used for dropping the luminescent liquid into the transparent polytetrafluoroethylene tube.
(4) The glassy carbon electrode containing the luminescent liquid was immersed with the tip thereof facing downward in an aqueous solution containing 0.1mol/L potassium chloride, the volume of the aqueous solution being 8 mL.
(5) The platinum wire and the Ag/AgCl electrode are respectively used as a counter electrode and a reference electrode to be immersed into the water phase. After the system was constructed, detection was carried out using an MPI-A type capillary electrophoresis-electrochemiluminescence analyzer (purchased from Seaanrei analytical instruments, Ltd.) (the photomultiplier bias was set at 700V).
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A method for constructing a liquid-liquid interface electrochemical luminescence system is characterized in that a polytetrafluoroethylene tube is tightly sleeved at the front end of a glassy carbon electrode, an organic solution containing a luminescent agent tetraphenylporphyrin and a coreactant tetrabutylammonium hexafluorophosphate is dripped into the polytetrafluoroethylene tube, and finally the glassy carbon electrode is immersed into a water phase containing potassium chloride.
2. The method for constructing a liquid-liquid interface electrochemiluminescence system according to claim 1, specifically comprising the steps of:
(1) drying the glassy carbon electrode after treatment, and tightly sleeving a polytetrafluoroethylene tube at the front end of the glassy carbon electrode;
(2) dissolving tetraphenylporphyrin serving as a luminescent agent and tetrabutylammonium hexafluorophosphate serving as a coreactant in 1, 2-dichloromethane to obtain luminescent liquid;
(3) and (3) dripping the luminescent liquid obtained in the step (2) into the polytetrafluoroethylene tube obtained in the step (1), then immersing the glassy carbon electrode into a water phase containing potassium chloride, and immersing a platinum wire and an Ag/AgCl electrode serving as a counter electrode and a reference electrode into the water phase respectively.
3. The method for constructing the liquid-liquid interface electrochemiluminescence system according to claim 2, wherein in the step (1), the glassy carbon electrode is treated by: with 0.3 μm and 0.05 μm Al in sequence2O3Polishing the slurry, and then sequentially washing with secondary distilled water and ethanol;
the drying temperature is 80 ℃;
the polytetrafluoroethylene tube is a transparent tube, the volume is 100 mu L, and the inner diameter of the tube is 3 mm.
4. The method for constructing a liquid-liquid interface electrochemiluminescence system according to claim 2, wherein in the step (2), the concentration of tetraphenylporphyrin as a luminescent agent in the luminescent liquid is 10-4And the concentration of the co-reactant tetrabutylammonium hexafluorophosphate is 0.3 mol/L.
5. The method for constructing a liquid-liquid interface electrochemiluminescence system according to claim 2, wherein in the step (3), the concentration of potassium chloride in the aqueous phase containing potassium chloride is 0.1 mol/L.
6. The method for constructing a liquid-liquid interface electrochemiluminescence system according to claim 1 or 2, wherein a potential scanning rate of the system constructed by the method is 0.3V-S-1The potential window is-2.2- + 1.1V.
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CN109030433A (en) * 2018-06-13 2018-12-18 西北师范大学 The preparation and its application in detection hydrogen peroxide and glucose of porphyrin compound fluorescent molecule
CN111239110B (en) * 2020-02-10 2022-07-22 西北师范大学 Construction method of porphyrin derivative with aggregation-induced emission performance applied to electrochemiluminescence system
CN112179960B (en) * 2020-08-20 2023-04-07 西北师范大学 Construction method of aqueous phase electrochemical luminescence system based on pentaphenyl pyrrole

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CN104330553A (en) * 2014-11-20 2015-02-04 扬州大学 Unmarked chemiluminescent immunosensor and immunoassay method thereof

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Investigation of Oxalate Oxidation and Electrogenerated Chemiluminescence across the Liquid-Liquid Interface;Bard 等;《The Journal of Physical Chemistry》;20010810;第105卷(第37期);第8951-8962页 *

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