CN106198468A - Electrochemiluminescence combination detection method in the case of a kind of single drop - Google Patents

Electrochemiluminescence combination detection method in the case of a kind of single drop Download PDF

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Publication number
CN106198468A
CN106198468A CN201610495191.2A CN201610495191A CN106198468A CN 106198468 A CN106198468 A CN 106198468A CN 201610495191 A CN201610495191 A CN 201610495191A CN 106198468 A CN106198468 A CN 106198468A
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electrode
detection
drop
fluorescence
single drop
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CN106198468B (en
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潘宏程
郑巨瑞
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Guilin University of Technology
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Guilin University of Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"

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  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention discloses electrochemiluminescence combination detection method in the case of a kind of single drop.Arranging a kind of detection device, including electrochemistry three-electrode system and fluorescent detection system, electrochemistry three-electrode system is formed with silver platinum combination electrode by rotating glass-carbon electrode;Fluorescent detection system is made up of optical detection darkroom and fluorescence detecting system, and optical detection darkroom is made up of optical encapsulant circle, example reaction room and base;Fluorescence detecting system is made up of excitation source, fiber spectrometer, SMA905 SMA905 optical fiber, data wire and computer;By sample list drop, applying voltage by electrochemistry three-electrode system, directly or indirectly produce fluorescent material, the irradiation at excitation source excites lower generation fluorescence, and fluorescence signal is finally transferred to computer disposal, obtains detecting the content of material.The inventive method utilizes single drop to replace traditional optical detection colorimetric pool, improves sensitivity and the accuracy of detection, and by the combination of two kinds of methods, is formed and have complementary advantages.

Description

Electrochemistry-fluorescence combination detection method in the case of a kind of single drop
Technical field
The invention belongs to technical field of electrochemistry, particularly to electrochemistry in the case of one list drop-fluorescence combination detection Method.
Background technology
Electro chemical analysis has that method is easy, analyze that speed is fast, cost of equipment is cheap, facilitate implementation automatization and also have The advantages such as enrichment and separating power;And fluorescence analysis have highly sensitive, linear relationship good, sample requirement is few, can measure many Plant the advantages such as form sample.But we are undeniable, electro chemical analysis sensitivity is low, fluorescence analysis poor selectivity, colorimetric Pond is easy contaminated affects fluorescence signal detection etc..Along with the progress of science and technology, electrochemistry, fluorescence spectroscopy are at analytical chemistry Field is developed rapidly, and defines the analysis method shown unique characteristics.At life sciences, energy science, information science, environment Science and production practices activity widely play an important role.
Today, analytical chemistry worker is still constantly introducing and is utilizing modern science and technology improve existing method and build Vertical new analysis method, plays an active part in development and the utilization of multiple techniques simultaneously.
Electrochemiluminescence method is exactly to set up new analysis method based on electro chemical analysis and fluorimetry, electrification Learn and fluorescence spectroscopy differs from one another the most each weak point.Electrochemistry and optical bond are got up and usually can reach to take length Mend short effect, expand detection range, improve testing accuracy.Believe that the in the future analysis method utilization that combines will be analytical chemistry Development trend.
The colorimetric pool of necessary artificial optical interface in tradition photometric analysis, it is easily subject to sample and reagent contamination And because of optical interface on the absorption of light, scattering etc. caused on the impact measuring signal.
Summary of the invention
It is an object of the invention to provide electrochemistry-fluorescence combination detection method in the case of a kind of single drop.
Concretely comprise the following steps:
(1) arranging a kind of detection device, this device includes electrochemistry three-electrode system and fluorescent detection system, wherein electrochemistry three Electrode system is formed with silver platinum combination electrode by rotating glass-carbon electrode, and rotation glass-carbon electrode is working electrode, silver platinum combination electrode Being to be combined into combination electrode in filamentary silver and a platinum filament piece teflon rod of embedding, filamentary silver is reference electrode, and platinum filament is to electricity Pole, electrochemistry three-electrode system, for single drop is applied voltage, makes the detection material in single drop occur electroluminescent reaction to produce The product of fluorescent material or electroluminescent reaction produces hyperfluorescence material with other substance reactions;Fluorescent detection system is dark by optical detection Room and fluorescence detecting system composition, optical detection darkroom is made up of optical encapsulant circle, example reaction room and base, for fluoroscopic examination Build dark surrounds, it is to avoid other light disturbances;Fluorescence detecting system is by excitation source, fiber spectrometer, SMA905-SMA905 Optical fiber, data wire and computer composition, excite fluorescent material in single drop, detect, and process, record, show detection Result.
Described single drop be utilize micropipette rifle draw drop to be measured to rotate glass-carbon electrode and silver-colored platinum combination electrode it Between form single drop, using list drop as without optical window light pond, replace traditional colorimetric pool.
Described example reaction room and base are all bottomless optics camera bellows, and wherein example reaction room is the camera bellows having lid design, The circular hole that cap top center has a diameter of phi to be 9 mm, four sides are respectively arranged with an in/out mouth, can be equipped with SMA905 Fiber bench;Base as example reaction room base and silver platinum combination electrode bearing.
(2) in example reaction room, it is added drop-wise to sample list drop rotate between glass-carbon electrode and silver platinum combination electrode, logical Cross electrochemistry three-electrode system and apply voltage, the detection material in single drop occur electroluminescent reaction produce fluorescent material or electroluminescent instead The product answered produces hyperfluorescence material with other substance reactions, and then the irradiation at excitation source excites lower generation fluorescence, fluorescence Signal is sent in fiber spectrometer by SMA905-SMA905 optical fiber again, and the spectral signal of generation passes through data line transfer to meter Calculation machine, then by computer disposal, show, store, and then obtain detecting the content of material.
Device used by the inventive method uses the colorimetric pool that single drop replacement traditional optical is required, eliminates sample and examination The pollution in agent contrast color pond and because of optical interface on the absorption of light, scattering etc. caused on the impact measuring signal, significantly Improve sensitivity and the accuracy of detection;Meanwhile, electrochemical methods is combined by the present invention with fluorimetry, utilizes electrification Learning aid has enrichment and separating power, but also has the advantages such as stronger redox ability and fluorescence analysis has sensitivity The advantages such as high, linear relationship is good, by the combination of two kinds of methods, reach mutual supplement with each other's advantages, it is to avoid respective deficiency.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of detection device thereof in the embodiment of the present invention.
Labelling in figure: 1-rotates glass-carbon electrode;2-silver platinum combination electrode;3-optical encapsulant circle;4-example reaction room;At the bottom of 5- Seat;6-excitation source;7-fiber spectrometer;8-SMA905-SMA905 optical fiber;9-data wire;10-computer;WE-works electricity Pole;RE-reference electrode;CE-is to electrode.
Fig. 2 is the schematic diagram of the example reaction room of detection device thereof in the embodiment of the present invention.
Fig. 3 is the schematic diagram of the base of detection device thereof in the embodiment of the present invention.
Detailed description of the invention
Following example, detect as determinand with vitamin C (Vc).
Embodiment:
(1) arranging a kind of detection device, this device includes electrochemistry three-electrode system and fluorescent detection system, wherein electrochemistry three Electrode system is formed with silver platinum combination electrode 2 by rotating glass-carbon electrode 1, and rotating glass-carbon electrode 1 is working electrode WE, and silver platinum is combined Electrode 2 is to be combined into combination electrode in filamentary silver and a platinum filament piece teflon rod of embedding, and filamentary silver is reference electrode RE, platinum filament For to electrode CE, electrochemistry three-electrode system, for single drop is applied voltage, makes the detection material in single drop occur electroluminescent Reaction, the product of electroluminescent reaction produces hyperfluorescence material with other substance reactions;Fluorescent detection system by optical detection darkroom and Fluorescence detecting system forms, and optical detection darkroom is made up of optical encapsulant circle 3, example reaction room 4 and base 5, for fluoroscopic examination Build dark surrounds, it is to avoid other light disturbances;Fluorescence detecting system is by excitation source 6, fiber spectrometer 7, SMA905- SMA905 optical fiber 8, data wire 9 and computer 10 form, and fluorescent material in single drop are excited, are detected, and processes, remember Record, display testing result.
Described single drop is to utilize micropipette rifle to draw drop to be measured to rotating glass-carbon electrode 1 and silver platinum combination electrode 2 Between form single drop, using list drop as without optical window light pond, replace traditional colorimetric pool.
Described example reaction room 4 and base 5 are all bottomless optics camera bellows, and wherein example reaction room 4 is for there being the dark of lid design Case, the circular hole that cap top center has a diameter of phi to be 9 mm, four sides are respectively arranged with an in/out mouth, can be equipped with SMA905 fiber bench;Base 5 as example reaction room 4 base and silver platinum combination electrode 2 bearing.
(2) in example reaction room, be added drop-wise to Vc sample list drop to rotate glass-carbon electrode 1 and silver platinum combination electrode 2 it Between, applying voltage by electrochemistry three-electrode system, the Vc in single drop occurs electroluminescent oxidation reaction to produce DHVc, DHVc with adjacent Phenylenediamine (OPDA) reaction generates the quinoxaline (Quinoxalin, QNL) having fluorescence, and then the irradiation at excitation source 6 excites Lower generation fluorescence, fluorescence signal is sent in fiber spectrometer 7 by SMA905-SMA905 optical fiber 8 again, and the spectral signal of generation leads to Cross data wire 9 and be transferred to computer 10, then processed by computer 10, show, stored, and then obtain the content of Vc.
The concrete course of reaction of Vc is as follows:
In traditional method, Vc oxidation is general uses chemical reagent oxidation, such as: activated carbon and 2,6-sodium dichlorophenol indophenolate etc..And this enforcement Example uses electrochemical oxidation, oxidability by force and not chemical agent consumption, it is to avoid secondary pollution problem.

Claims (1)

1. electrochemistry-fluorescence combination detection method in the case of a single drop, it is characterised in that concretely comprise the following steps:
(1) arranging a kind of detection device, this device includes electrochemistry three-electrode system and fluorescent detection system, wherein electrochemistry three Electrode system is formed with silver platinum combination electrode by rotating glass-carbon electrode, and rotation glass-carbon electrode is working electrode, silver platinum combination electrode Being to be combined into combination electrode in filamentary silver and a platinum filament piece teflon rod of embedding, filamentary silver is reference electrode, and platinum filament is to electricity Pole, electrochemistry three-electrode system, for single drop is applied voltage, makes the detection material in single drop occur electroluminescent reaction to produce The product of fluorescent material or electroluminescent reaction produces hyperfluorescence material with other substance reactions;Fluorescent detection system is dark by optical detection Room and fluorescence detecting system composition, optical detection darkroom is made up of optical encapsulant circle, example reaction room and base, for fluoroscopic examination Build dark surrounds, it is to avoid other light disturbances;Fluorescence detecting system is by excitation source, fiber spectrometer, SMA905-SMA905 Optical fiber, data wire and computer composition, excite fluorescent material in single drop, detect, and process, record, show detection Result;
Described single drop is to utilize micropipette rifle to draw drop to be measured to rotating shape between glass-carbon electrode and silver platinum combination electrode Become single drop, using list drop as without optical window light pond, replace traditional colorimetric pool;
Described example reaction room and base are all bottomless optics camera bellows, and wherein example reaction room is the camera bellows having lid design, lid The circular hole that top center has a diameter of phi to be 9 mm, four sides are respectively arranged with an in/out mouth, can be equipped with SMA905 optical fiber Seat;Base as example reaction room base and silver platinum combination electrode bearing;
(2) in example reaction room, it is added drop-wise to sample list drop rotate between glass-carbon electrode and silver platinum combination electrode, by electricity Chemistry three-electrode system applies voltage, and the detection material in single drop occurs electroluminescent reaction to produce fluorescent material or electroluminescent reaction Product produces hyperfluorescence material with other substance reactions, and then the irradiation at excitation source excites lower generation fluorescence, fluorescence signal Be sent in fiber spectrometer by SMA905-SMA905 optical fiber again, the spectral signal of generation by data line transfer to computer, Again by computer disposal, show, store, and then obtain detecting the content of material.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106906132A (en) * 2017-03-21 2017-06-30 广东顺德工业设计研究院(广东顺德创新设计研究院) Digital polymerase chain reaction optical detection apparatus and method
CN107764857A (en) * 2017-01-10 2018-03-06 广西民族大学 A kind of micro- calorimeter and fluorescence in situ spectrum on line combined system
CN117214260A (en) * 2023-09-15 2023-12-12 西南大学 Thin layer flow type electrochemiluminescence imaging analysis instrument

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CN2209331Y (en) * 1994-07-07 1995-10-04 李兆林 Dark box for zinc protoporphyrin blood fluorescent metering device
CN1678896A (en) * 2002-08-26 2005-10-05 独立行政法人科学技术振兴机构 Droplet operation device
US20080090244A1 (en) * 2002-12-20 2008-04-17 Caliper Life Sciences, Inc. Methods of detecting low copy nucleic acids
CN201016979Y (en) * 2007-01-30 2008-02-06 中山大学 Non-contact conductive and fluorescence detecting apparatus of micro total analysis system
CN102604074A (en) * 2012-02-28 2012-07-25 吉林大学 Electroactive fluorescent polymer, preparation method and use for detecting oxidizing or reducing substance

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107764857A (en) * 2017-01-10 2018-03-06 广西民族大学 A kind of micro- calorimeter and fluorescence in situ spectrum on line combined system
CN106906132A (en) * 2017-03-21 2017-06-30 广东顺德工业设计研究院(广东顺德创新设计研究院) Digital polymerase chain reaction optical detection apparatus and method
CN106906132B (en) * 2017-03-21 2018-06-29 广东顺德工业设计研究院(广东顺德创新设计研究院) Digital polymerase chain reaction optical detection apparatus and method
CN117214260A (en) * 2023-09-15 2023-12-12 西南大学 Thin layer flow type electrochemiluminescence imaging analysis instrument

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