CN106198468B - Electrochemistry-fluorescence is combined detection method in the case of a kind of list drop - Google Patents

Electrochemistry-fluorescence is combined detection method in the case of a kind of list drop Download PDF

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Publication number
CN106198468B
CN106198468B CN201610495191.2A CN201610495191A CN106198468B CN 106198468 B CN106198468 B CN 106198468B CN 201610495191 A CN201610495191 A CN 201610495191A CN 106198468 B CN106198468 B CN 106198468B
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detection
electrode
fluorescence
electrochemistry
optical
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CN106198468A (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)
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  • 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)
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  • 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 electrochemistry-fluorescence in the case of a kind of single drop to be combined detection method.A kind of detection device, including electrochemistry three-electrode system and fluorescent detection system are set, and electrochemistry three-electrode system is made of rotation glass-carbon electrode and silver-colored platinum combination electrode;Fluorescent detection system is made of optical detection darkroom and fluorescence detecting system, and optical detection darkroom is made of optical encapsulant circle, example reaction room and pedestal;Fluorescence detecting system is made of excitation light source, fiber spectrometer, SMA905-SMA905 optical fiber, data line and computer;By sample list drop, voltage is applied by electrochemistry three-electrode system, directly or indirectly generates fluorescent material, generates fluorescence under the irradiation excitation of excitation light source, fluorescence signal is finally transferred to computer disposal, obtains the content of detection substance.The method of the present invention replaces traditional optical to detect colorimetric pool using single drop, improves the sensitivity and accuracy of detection, and by the combination of two methods, is formed and had complementary advantages.

Description

Electrochemistry-fluorescence is combined detection method in the case of a kind of list drop
Technical field
The invention belongs to electrochemical technology field, in particular to electrochemistry-fluorescence combination detection in the case of a kind of single drop Method.
Background technique
Electrochemical analysis has that method is easy, analysis speed is fast, cost of equipment is cheap, is easy to implement automation and also The advantages that enrichment and separation ability;And fluorescence analysis is with high sensitivity, linear relationship is good, sample requirement is few, can measure more The advantages that kind form sample.But we are undeniable to be, electrochemical analysis sensitivity is low, fluorescence analysis poor selectivity, colorimetric Pool capacity vulnerable to pollution influences fluorescence signal detection etc..With the progress of science and technology, electrochemistry, fluorescence spectroscopy are in analytical chemistry Field is rapidly developed, and forms the analysis method to show unique characteristics.In life science, energy science, information science, environment It plays an important role in scientific and extensive production practices activity.
Today, analytical chemistry worker still in constantly introduction and improve existing method using modern science and technology and build New analysis method is found, while playing an active part in the development and utilization of joint technology.
Electrochemiluminescence method is exactly that new analysis method is established based on electrochemical analysis and fluorescence analysis, electrification It learns and both fluorescence spectroscopies also each shortcoming with their own characteristics.Electrochemistry and optical bond are got up usually to can achieve and take length Short effect is mended, detection range is expanded, improves testing accuracy.It is believed that it will be analytical chemistry that analysis method in future, which combines utilization, Development trend.
The colorimetric pool of necessary artificial optical interface in traditional photometric analysis is easy by sample and reagent contamination And because optical interface is to the influence to measuring signal caused by absorption, scattering of light etc..
Summary of the invention
The object of the present invention is to provide electrochemistry-fluorescence in the case of a kind of single drop to be combined detection method.
Specific steps are as follows:
(1) a kind of detection device is set, which includes electrochemistry three-electrode system and fluorescent detection system, wherein electrification It learns three-electrode system to be made of rotation glass-carbon electrode and silver-colored platinum combination electrode, rotation glass-carbon electrode is working electrode, and silver-colored platinum is compound Electrode is that filamentary silver and platinum filament are embedded in a teflon rod to be combined into combination electrode, and filamentary silver is reference electrode, and platinum filament is To electrode, electrochemistry three-electrode system is used to apply voltage to single drop, makes the detection substance in single drop that electroluminescent reaction occur The product and other substance reactions for generating fluorescent material or electroluminescent reaction generate hyperfluorescence substance;Fluorescent detection system is examined by optics Darkroom and fluorescence detecting system composition are surveyed, optical detection darkroom is made of optical encapsulant circle, example reaction room and pedestal, is fluorescence Dark surrounds is built in detection, avoids other light disturbances;Fluorescence detecting system is by excitation light source, fiber spectrometer, SMA905- SMA905 optical fiber, data line and computer composition, excite fluorescent material in single drop, are detected, and handle, record, show Show testing result.
The list drop be drawn using micropipette rifle prepare liquid drip to rotation glass-carbon electrode and silver-colored platinum combination electrode it Between form single drop and replace traditional colorimetric pool using single drop as no optical window light pond.
The example reaction room and pedestal are bottomless optics camera bellows, and wherein example reaction room is the camera bellows for having lid to design, It is the circular hole of 9 mm that, which there is a diameter of phi at cap top center, and respectively there are an in/out mouth in four sides, can be equipped with SMA905 Fiber bench;Pedestal is as the pedestal of example reaction room and the support of silver-colored platinum combination electrode.
(2) in example reaction room, sample list drop is added drop-wise between rotation glass-carbon electrode and silver-colored platinum combination electrode, is led to It crosses electrochemistry three-electrode system and applies voltage, the detection substance in single drop occurs electroluminescent reaction and generates fluorescent material or electroluminescent anti- The product and other substance reactions answered generate hyperfluorescence substance, then generate fluorescence, fluorescence under the irradiation excitation of excitation light source Signal is transmitted in fiber spectrometer by SMA905-SMA905 optical fiber again, and the spectral signal of generation is transferred to meter by data line Calculation machine, then by computer disposal, display, storage, and then obtain the content of detection substance.
Device used in the method for the present invention replaces colorimetric pool necessary to traditional optical using single drop, eliminates sample and examination The pollution in agent contrastive colours pond and because optical interface is to the influence to measuring signal caused by absorption, scattering of light etc., significantly Improve the sensitivity and accuracy of detection;Meanwhile the present invention combines electrochemical methods with fluorescence analysis, utilizes electrification Learning aid has enrichment and separation ability, but also has many advantages, such as that stronger redox ability and fluorescence analysis have sensitivity High, the advantages that linear relationship is good, by the combination of two methods, mutual supplement with each other's advantages is reached, avoids respective deficiency.
Detailed description of the invention
Fig. 1 is the schematic diagram of detection device thereof in the embodiment of the present invention.
Marked in the figure: 1- rotates glass-carbon electrode;2- silver platinum combination electrode;3- optical encapsulant circle;4- example reaction room;The bottom 5- Seat;6- excitation light source;7- fiber spectrometer;8-SMA905-SMA905 optical fiber;9- data line;10- computer;WE- work 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 pedestal of detection device thereof in the embodiment of the present invention.
Specific embodiment
Following embodiment for determinand, is detected with vitamin C (Vc).
Embodiment:
(1) a kind of detection device is set, which includes electrochemistry three-electrode system and fluorescent detection system, wherein electrification It learns three-electrode system to be made of rotation glass-carbon electrode 1 and silver-colored platinum combination electrode 2, rotation glass-carbon electrode 1 is working electrode WE, silver-colored platinum Combination electrode 2 is that filamentary silver and platinum filament are embedded in a teflon rod to be combined into combination electrode, and filamentary silver is reference electrode RE, Platinum filament is to electrode CE, and electrochemistry three-electrode system is used to apply voltage to single drop, and the detection substance in single drop occurs Electroluminescent reaction, the product of electroluminescent reaction and other substance reactions generate hyperfluorescence substance;Fluorescent detection system is dark by optical detection Room and fluorescence detecting system composition, optical detection darkroom are made of optical encapsulant circle 3, example reaction room 4 and pedestal 5, are fluorescence Dark surrounds is built in detection, avoids other light disturbances;Fluorescence detecting system is by excitation light source 6, fiber spectrometer 7, SMA905- SMA905 optical fiber 8, data line 9 and computer 10 form, and are excited, are detected to fluorescent material in single drop, and handled, remember Record, display testing result.
The list drop is to draw prepare liquid using micropipette rifle to drip to rotation glass-carbon electrode 1 and silver-colored platinum combination electrode 2 Between form single drop and replace traditional colorimetric pool using single drop as no optical window light pond.
The example reaction room 4 and pedestal 5 are bottomless optics camera bellows, and wherein example reaction room 4 is to have to cover the dark of design Case, it is the circular hole of 9 mm that, which there is a diameter of phi at cap top center, and respectively there are an in/out mouth in four sides, can be equipped with SMA905 fiber bench;Pedestal 5 is as the pedestal of example reaction room 4 and the support of silver-colored platinum combination electrode 2.
(2) in example reaction room, by Vc sample list drop be added drop-wise to rotation glass-carbon electrode 1 and silver-colored platinum combination electrode 2 it Between, voltage is applied by electrochemistry three-electrode system, the Vc in single drop occurs electroluminescent oxidation reaction and generates DHVc, DHVc and neighbour Phenylenediamine (OPDA) reaction generates the quinoxaline (Quinoxalin, QNL) for having fluorescence, then excites in the irradiation of excitation light source 6 Lower generation fluorescence, fluorescence signal are transmitted in fiber spectrometer 7 by SMA905-SMA905 optical fiber 8 again, and the spectral signal of generation is logical It crosses data line 9 and is transferred to computer 10, then handled by computer 10, display, storage, and then obtain the content of Vc.
The specific reaction process of Vc is as follows:
Vc oxidation is generally aoxidized using chemical reagent in conventional method, such as: active carbon and 2,6- sodium dichlorophenol indophenolate etc..And this Embodiment is using electrochemical oxidation, and oxidability is strong and not chemical agent consumption, avoids secondary pollution problem.

Claims (1)

1. electrochemistry-fluorescence is combined detection method in the case of a kind of list drop, it is characterised in that specific steps are as follows:
(1) a kind of detection device is set, which includes electrochemistry three-electrode system and fluorescent detection system, wherein electrochemistry three Electrode system is made of rotation glass-carbon electrode and silver-colored platinum combination electrode, and rotation glass-carbon electrode is working electrode, silver-colored platinum combination electrode It is that filamentary silver and platinum filament are embedded in a teflon rod to be combined into combination electrode, filamentary silver is reference electrode, and platinum filament is to electricity Pole, electrochemistry three-electrode system are used to apply voltage to single drop, make the detection substance in single drop that electroluminescent reaction occur and generate Fluorescent material or the product of electroluminescent reaction and other substance reactions generate hyperfluorescence substance;Fluorescent detection system is dark by optical detection Room and fluorescence detecting system composition, optical detection darkroom are made of optical encapsulant circle, example reaction room and pedestal, are fluorescence detection Dark surrounds is built, other light disturbances are avoided;Fluorescence detecting system is by excitation light source, fiber spectrometer, SMA905-SMA905 Optical fiber, data line and computer composition, excite fluorescent material in single drop, are detected, and handle, record, showing detection As a result;
The list drop is to draw prepare liquid using micropipette rifle to drip to shape between rotation glass-carbon electrode and silver-colored platinum combination electrode Traditional colorimetric pool is replaced using single drop as no optical window light pond at single drop;
The example reaction room and pedestal are bottomless optics camera bellows, and wherein example reaction room is the camera bellows for having lid to design, lid It is the circular hole of 9 mm that top center, which has a diameter of phi, and respectively there are an in/out mouth in four sides, can be equipped with SMA905 optical fiber Seat;Pedestal is as the pedestal of example reaction room and the support of silver-colored platinum combination electrode;
(2) in example reaction room, sample list drop is added drop-wise between rotation glass-carbon electrode and silver-colored platinum combination electrode, electricity is passed through Chemical three-electrode system applies voltage, and electroluminescent reaction generation fluorescent material or electroluminescent reaction occur for the detection substance in single drop Product and other substance reactions generate hyperfluorescence substance, then generate fluorescence, fluorescence signal under the irradiation excitation of excitation light source It being transmitted in fiber spectrometer by SMA905-SMA905 optical fiber again, the spectral signal of generation is transferred to computer by data line, Again by computer disposal, display, storage, and then obtain the content of detection substance.
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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
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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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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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
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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