CN205719945U - A kind of can the detecting system of accurate acquisition electrogenerated chemiluminescence spectral information - Google Patents

Abstract

This utility model relate to a kind of can the detecting system of accurate acquisition electrogenerated chemiluminescence spectral information, process and control unit including electrochemical apparatus unit, ECL radiation generator unit, spectrum detection device unit and data.ECL radiation generator unit includes ECL pond and the working electrode being connected with electrochemical apparatus unit, reference electrode and to electrode；Spectrum detection device unit includes collecting object lens and CCD grating spectrograph；ECL radiation generator unit and collection object lens are arranged in magazine, and the light-emitting area of working electrode is just to collecting object lens, and gleanings mirror foci overlaps with CCD grating spectrograph entrance slit；Magazine is directly connected with the fixed plate of entrance slit, detecting system light path is hedged off from the outer world；CCD grating spectrograph and electrochemical apparatus unit are triggered by TTL signal and realize synchronous operation, and the electrochemical signals gathered and ECL spectral signal synchronization input data are processed and control unit.

Description

A detection system that can accurately collect electrochemiluminescence spectral information

technical field

The utility model relates to a detection system capable of accurately collecting electrochemiluminescence spectrum information, which belongs to the technical field of electrochemistry detection.

Background technique

Electrochemiluminescence (ECL) has the advantages of both electrochemiluminescence and chemiluminescence. It is an analytical technique that uses electrochemical methods to excite a certain substance and make it produce light radiation. ECL analysis technology does not require an excitation light source, has the characteristics of high signal-to-noise ratio, sensitive detection and simple equipment, and has been widely used in biochemical analysis, medical diagnosis and other fields. ECL radiation is usually weak and unstable, which makes it difficult to obtain its spectral information using conventional fluorescence spectrum acquisition devices or wavelength scanning acquisition methods. Therefore, ECL detection devices usually use photoelectric conversion with high sensitivity, fast time response and large acceptance area. Components (such as photomultiplier tubes, PMT) are used as detectors to efficiently collect the total intensity of ECL radiation by directly assembling the ECL reaction cell at the front end of the PMT in order to reduce light loss, improve signal-to-noise ratio and analysis sensitivity. At present, both the commercialized ECL analyzer and the ECL detection equipment assembled by each laboratory are simply combined by a chemiluminescence analyzer (or PMT and its power supply module) and an electrochemical instrument (Chem.Rev.2008 , 108, 2506). The E1ecsys series automatic electrochemiluminescence immunoassay analyzer produced by Roche (ROCHE) and the MPI series electrochemiluminescence detector produced by Xi'an Ruimai Analytical Instrument Co., Ltd. are typical representatives of the current research and development status of ECL analyzers. Among them, the E1ecsysl010 and Elecsys2010 automatic ECL immune analyzers based on the detection of the total intensity of ECL radiation of the ruthenium bipyridine system have been widely used in the detection of thyroid, hormones, myocardial injury, tumor markers, infectious diseases, anemia, and bone metabolism. Clinical diagnosis is widely used in large and medium-sized hospitals at home and abroad. The MPI-A capillary electrophoresis electrochemiluminescence detector and the MPI-E microfluidic chip electrochemiluminescence detector produced by Xi'an Ruimai Analytical Instrument Co., Ltd. are typical representatives of domestic commercial ECL analyzers. MPI-A and MPI-E ECL detectors can simultaneously display the total intensity signal of ECL radiation and the corresponding electrochemical signal, which is very helpful for the basic research of ECL.

Conventional ECL detection devices can only roughly draw the spectral information of ECL radiation by installing a filter between the ECL reaction cell and the PMT and performing multiple parallel measurements, and the reproducibility of the measurement results is poor. As a result, conventional ECL detection devices can only carry out simple qualitative analysis research, and cannot accurately and detailedly study the spectral properties and changing laws of ECL radiation, let alone carry out quantitative analysis research based on ECL spectral information, which greatly limits the application of ECL analysis in basic research and research. Applications in the field of diagnostics. In fact, due to the inability to accurately distinguish ECL radiation information from different signal sources in the form of spectral resolution, conventional ECL instruments (including E1ecsys series automatic electrochemiluminescence immunoassay analyzers) that rely on detecting the total intensity of ECL signals can only perform simple single Component Analysis.

In recent years, the academic community has begun to try to collect ECL spectra by using CCD grating spectrometers or simply coupling charge-coupled devices (Charge-coupled Device, CCD) and monochromators (J.Am.Chem.Soc.2016, 138, 1947; J. Am. Chem. Soc. 2015, 137, 11266). However, due to the particularity of the ECL radiation generation method resulting in low incident luminous flux, poor coordination between the electrochemical equipment and the CCD grating spectrometer, stray light interference, and the noise signal of the instrument itself, the above-mentioned direct use of the CCD grating spectrometer to collect ECL The method of spectroscopy not only has low signal-to-noise ratio and poor sensitivity, it cannot accurately collect the spectrum of weak ECL radiation, but also has poor reproducibility, and cannot accurately compare the spectral changes of ECL radiation under different electrochemical states or experimental conditions. Therefore, the spectral ECL research based purely on the CCD grating spectrometer is also limited in the scope of simple qualitative analysis research.

Contents of the invention

Aiming at the deficiencies of the existing technology, the utility model adopts the method of building a closed optical path system, improving the efficiency of ECL radiation collection and using TTL signal to trigger the synchronous operation of electrochemical equipment and CCD grating spectrometer, and constructs a detection system that can accurately collect ECL spectral information This system not only has low background noise, but also has high analytical sensitivity. It can detect the spectral information of ultra-weak ECL radiation, and can accurately compare the spectral changes of ECL radiation under different electrochemical states or experimental conditions, and carry out quantitative analysis of spectral ECL. and multicomponent analysis studies.

The technical scheme of the utility model is as follows:

A detection system capable of accurately collecting ECL spectral information, including an electrochemical equipment unit, an ECL radiation generating device unit, a spectral detection device unit, and a data processing and control unit;

The ECL radiation generating device unit includes an ECL pool, the ECL pool is provided with a working electrode, a reference electrode and a counter electrode, and the working electrode, the reference electrode and the counter electrode are respectively connected to the electrochemical device unit;

Described spectral detection device unit comprises the collection objective lens and CCD grating spectrometer that are used to collect ECL radiation; Described CCD grating spectrometer is made up of CCD detector and grating spectrometer; The light-emitting surface of described working electrode faces described collection objective lens ;

The CCD grating spectrometer and the electrochemical equipment unit are respectively connected with the data processing and control unit, and the CCD grating spectrometer and the electrochemical equipment unit are connected through a TTL signal line. The CCD grating spectrometer and the electrochemical equipment unit are triggered by a TTL signal to realize synchronous operation, and the ECL spectral information collected by the CCD grating spectrometer and the electrochemical information collected by the electrochemical equipment unit are synchronously sent to the data processing and control unit to realize Accurate acquisition of ECL spectral information under different electrochemical states.

According to the present utility model, preferably, the ECL radiation generating device unit further includes an adjustable ECL cell support provided with a light-transmitting hole at the bottom, and the ECL cell is fixed on the adjustable ECL cell support. The adjustable ECL cell support can realize the adjustment of the geometric position of the ECL cell in three-dimensional space, ensuring that the ECL radiation generated at the bottom of the working electrode enters the CCD grating spectrometer to the greatest extent through the collecting objective lens.

According to the utility model, preferably, the bottom of the ECL pool is a transparent structure, further preferably, the ECL pool is a fully transparent structure;

Preferably, the ECL cell is provided with an electrode fixing device, and the working electrode, reference electrode and counter electrode are fixed on the electrode fixing device.

According to the present utility model, preferably, the detection system capable of accurately collecting ECL spectral information further includes a cassette, and the ECL radiation generating device unit and the collecting objective lens are arranged in the cassette;

Preferably, the cassette is provided with an electrode wire transfer port and an airway tube transfer port; on the premise of ensuring that the optical path is completely closed, it meets the needs of connecting the electrodes with the outside world and ventilating during the experiment.

According to the present invention, preferably, the ECL tank is further provided with an air guide tube, the air guide tube communicates with the inside of the ECL tank, and the air guide tube is connected to the outside of the cartridge through the air guide tube adapter. When detecting ECL spectral information, put quantum dot solution into the ECL pool, one end of the air guide tube is located below the liquid level in the ECL pool, and the other end can be connected to the gas supply device outside the cassette through the air guide tube adapter; Deoxygenate or oxygenate. Preferably, the surface of the air guide tube is provided with a scale mark, and the outlet of the air tube can be adjusted above the liquid level after the solution is ventilated, and the liquid level nitrogen (or some specific gas such as oxygen) atmosphere is maintained during the experiment.

According to the present invention, preferably, the working electrode, the reference electrode and the counter electrode are respectively connected to the electrochemical device unit through the electrode lead transfer interface.

According to the utility model, preferably, the CCD grating spectrometer is provided with an incident slit and an incident slit fixing plate, the cassette is provided with a C or F interface, and the collection objective lens is fixed on the cassette through the C or F interface Inside, the focal point of the collecting objective coincides with the entrance slit. The cassette can be directly connected to the incident slit fixing plate by means of screw fixing, and the connection between the cassette body and the incident slit fixing plate is provided with a C or F interface (preferably embedded C or F interface) for fixing the collecting objective lens and realizing ECL radiation The optical path connection between the generating device unit and the CCD grating spectrometer. When the working electrode generates ECL radiation, its light-emitting surface faces the collection objective lens, and the incident slit of the CCD grating spectrometer is located at the focal point of the collection objective lens, ensuring that the ECL radiation enters the CCD grating spectrometer with the maximum incident luminous flux. In short, the matching use of the collecting objective lens and the cassette can not only isolate the entire optical path from the outside world, effectively avoid the interference of stray light and dust, but also help to improve the incident light flux of the CCD grating spectrometer, improve the signal-to-noise ratio and the sensitivity of ECL spectral detection.

According to the utility model, preferably, the adjustable ECL pool bracket, the surface of the ECL pool, the electrode fixing device and the surface of the working electrode are all provided with scale marks and adjustable threads, which can accurately regulate the relative collection of the ECL pool and the working electrode. The geometrical position of the objective lens and the entrance slit. This design can not only ensure the maximum incident light flux through the precise adjustment of the geometric position, improve the efficiency of ECL radiation collection, but also help to ensure the reproducibility of the geometric position of the working electrode relative to the collection objective lens and the incident slit, thereby improving the quantitative analysis results reliability and reproducibility.

According to the utility model, the electrochemical equipment unit is capable of accepting the TTL signal triggering of the CCD detector to operate, or an electrochemical analyzer that can directly generate a TTL signal to trigger the synchronous operation of the CCD detector; it can ensure the use of TTL triggering The form realizes the coordinated operation of the electrochemical equipment unit and the spectral detection device unit.

According to the utility model, preferably, the ECL pool is provided with an anti-reflection film to reduce radiation loss.

According to the utility model, preferably, the cassette is made of stainless steel, the outer surface of the cassette is covered with insulating material, and the inner surface of the cassette is fixedly provided with a corrosion-resistant material. The dark box can not only effectively shield the interference of external electromagnetic radiation and stray light, but also ensure that the whole system can work normally without darkroom and dustproof experimental conditions.

According to the present invention, preferably, the CCD detector is a liquid nitrogen cooling type CCD detector, which can effectively reduce the background noise signal of the CCD detector and improve the signal-to-noise ratio and ECL spectral detection sensitivity.

According to the present invention, preferably, the data processing and control unit is a computer. The data processing and control unit is used to realize the synchronous operation of the ECL radiation generation device unit, the spectrum detection device unit and the electrochemical device unit and the accurate collection of spectral signals.

The beneficial effects of the utility model are as follows:

1. The utility model can accurately detect the spectral information of ECL radiation, compare the spectral changes of ECL radiation under different electrochemical states or experimental conditions, and carry out spectral ECL analysis and research.

2. The entire optical path system in the utility model can be isolated from the outside world, and ECL spectra can be collected in ordinary laboratories and under natural light conditions, without a special dust-removing darkroom.

3. The detection system in the utility model has a high signal-to-noise ratio and can accurately collect spectral information of ultra-weak ECL radiation.

4. The utility model can quantitatively detect the weak changes of ECL spectra under different experimental conditions, and carry out spectral ECL quantitative analysis research.

5. The utility model can identify the radiation signals of different ECL illuminants online, and carry out multi-component ECL analysis and research.

6. The utility model can detect the spectral information of various ultra-weak radiation including ECL in real time and dynamically within the spectral range of 300-900nm or wider, the wavelength accuracy is less than 1.0nm, and the exposure time is 1 millisecond to 1 hour It is controllable and can accurately measure the ECL signal intensity.

Description of drawings

FIG. 1 is a schematic diagram of the main structure of a detection system capable of accurately collecting ECL spectral information of the present invention.

Among them: 1. Electrochemical analyzer, 2. ECL cell, 3. CCD grating spectrometer, 4. Computer, 5. Cassette, 6. Working electrode, 7. Reference electrode, 8. Counter electrode, 9. Adjustable ECL cell Bracket, 10, collecting objective lens, 11, CCD detector, 12, grating spectrometer, 13, incident slit, 14, incident slit fixing plate, 15, C or F interface, 16, TTL signal line, 17, electrode wire transfer Interface, 18, airway tube transfer interface, 19, airway tube, 20, electrode fixing device.

detailed description

The utility model will be further described below through specific examples, but not limited thereto.

In the embodiment, 150 line gratings with blaze wavelengths of 500nm and 800nm, Acton standard SP-2150 spectrometer and PYLON-400BRX liquid nitrogen cooling type CCD detector are used to form a CCD grating spectrometer.

The reason for choosing a 150-line grating is that the ECL radiation belongs to the molecular spectrum with a very wide band, and there is no need for high spectral resolution accuracy. The combination of two gratings with blaze wavelengths of 500nm and 800nm can better realize the spectrum collection of ECL in the visible and near-infrared regions. The reason for choosing the Acton standard SP-2150 spectrometer is that the focal length of this spectrometer is 150 mm, which is the spectrometer with the shortest focal length and the largest luminous flux among similar instruments, which can effectively reduce light loss. The reason for choosing PYLON-400BRX liquid nitrogen cooling CCD detector is that this type of detector can realize sensitive collection of ultra-weak signals with wavelengths in the range of 300-1000nm under ultra-low temperature conditions.

The electrochemical analyzer used in the examples is VersaSTAT 3 type electrochemical analyzer.

Example 1

A detection system capable of accurately collecting ECL spectral information, including an electrochemical equipment unit, an ECL radiation generating device unit, a spectral detection device unit, and a data processing and control unit;

Described ECL radiation generating device unit comprises ECL cell 2, and described ECL cell 2 is provided with working electrode 6, reference electrode 7 and counter electrode 8, and described working electrode 6, reference electrode 7 and counter electrode 8 respectively connected with the electrochemical equipment unit;

Described spectral detecting device unit comprises the collecting objective lens 10 and CCD grating spectrometer 3 that are used to collect ECL radiation; Described CCD grating spectrometer 3 is made up of CCD detector 11 and grating spectrometer 12; The light-emitting surface of described working electrode 6 Facing the collection objective lens 10;

The CCD grating spectrometer 3 and the electrochemical equipment unit are respectively connected to the data processing and control unit, and the CCD grating spectrometer 3 and the electrochemical equipment unit are linked through a TTL signal line 16 .

The electrochemical equipment unit described in this embodiment is an electrochemical analyzer 1 that can be triggered by the TTL signal of the CCD detector 11 to run; the data processing and control unit is a computer 4 .

The bottom of the ECL pool 2 described in this embodiment is a transparent structure.

Example 2

As described in Example 1, the difference is:

The detection system that can accurately collect ECL spectral information also includes a cassette 5, the ECL radiation generating device unit and the collection objective lens 10 are arranged in the cassette 5; the CCD grating spectrometer 3 is provided with an incident slit 13 and an incident slit Slit fixing plate 14, described cassette 5 is provided with embedded C or F interface 15, and described collecting objective lens 10 is fixed in cassette 5 through C or F interface 15, makes the focal point of collecting objective lens 10 coincide with incident slit 13 ;

The cassette 5 is provided with an electrode wire transfer port 17 and an airway tube transfer port 18;

The ECL pool 2 is also provided with an air duct 19, the air duct 19 is connected to the inside of the ECL pool 2, and the air duct 19 is connected to the outside of the cartridge 5 through the air duct adapter 18;

The working electrode 6 , reference electrode 7 and counter electrode 8 are respectively connected to the electrochemical device unit through the electrode lead transfer interface 17 .

In this embodiment, the cassette 5 is directly connected to the incident slit fixing plate 14 by means of screw fixing, and a C or F interface 15 is provided at the connecting part of the box body of the cassette 5 and the incident slit fixing plate 14 for fixing the collection objective lens 10 to realize ECL. The optical path between the radiation generating device unit and the CCD grating spectrometer 3 is connected. When the working electrode 6 produces ECL radiation, its light-emitting surface faces the collection objective lens 10, and the incident slit 13 of the CCD grating spectrometer 3 is located on the focal point of the collection objective lens 10 to ensure that the ECL radiation enters with the maximum incident luminous flux. CCD grating spectrometer3.

Example 3

As described in Example 2, the difference is:

The ECL radiation generating device unit also includes an adjustable ECL pool support 9 provided with a light-transmitting hole at the bottom, and the ECL pool 2 is fixed on the adjustable ECL pool support 9 .

For the ECL cell support 9, reference may be made to the electrochemiluminescence reaction cell spatial position control device for spectrum collection disclosed in Chinese patent document CN 204807438U.

Example 4

As described in Example 3, the difference is:

The ECL pool 2 is a fully transparent structure;

The adjustable ECL cell support 9, the surface of the ECL cell 2, the electrode fixing device 20 and the surface of the working electrode 6 are all provided with scale marks and adjustable threads, which can precisely regulate the ECL cell 2 and the working electrode 6 relative to the collecting objective lens 10. and the geometric position of the incident slit 13.

Example 5

As described in Example 2, the difference is:

Described ECL pool 2 is provided with anti-reflection film, to reduce radiation loss;

The cassette 5 is made of stainless steel, the outer surface of the cassette 5 is covered with insulating material, and the inner surface of the cassette 5 is fixed with a corrosion-resistant material.

The principle of the utility model system:

As shown in Figure 1, the solution containing the ECL substance and its co-reactant is loaded into the ECL cell 2, and the electrochemical analyzer 1 can generate ECL radiation on the surface of the working electrode 6 when the electrochemical analyzer 1 is started, and at the same time trigger the CCD grating spectrometer through the TTL signal 3 start synchronously, the ECL radiation is effectively collected into the CCD grating spectrometer 3 through the collecting objective lens 10 and the incident slit 13, the ECL spectral information collected by the CCD grating spectrometer 3 and the electrochemical information collected by the electrochemical analyzer 1 are then It is independently and synchronously input into the computer 4, and after the data processing is completed in the computer 4, the ECL spectrum information under different electrochemical states can be obtained and output, and the online detection of the ECL spectrum can be realized.

Rotating the grating G in the monochromator can change the central wavelength, so that the entire spectral band moves accordingly, so as to obtain ECL spectra in different wavelength ranges.

Claims (10)

1. A detection system that can accurately collect ECL spectral information is characterized in that the detection system includes an electrochemical equipment unit, an ECL radiation generating device unit, a spectrum detection device unit and a data processing and control unit; The ECL radiation generating device unit includes an ECL pool, the ECL pool is provided with a working electrode, a reference electrode and a counter electrode, and the working electrode, the reference electrode and the counter electrode are respectively connected to the electrochemical device unit; Described spectral detection device unit comprises the collection objective lens and CCD grating spectrometer that are used to collect ECL radiation; Described CCD grating spectrometer is made up of CCD detector and grating spectrometer; The light-emitting surface of described working electrode faces described collection objective lens ; The CCD grating spectrometer and the electrochemical equipment unit are respectively connected with the data processing and control unit, and the CCD grating spectrometer and the electrochemical equipment unit are connected through a TTL signal line. 2. the detection system that can accurately collect ECL spectral information according to claim 1, is characterized in that, described ECL radiation generating device unit also comprises the adjustable ECL pool support that is provided with light-transmitting hole at the bottom, and ECL pool is fixed On adjustable ECL cell holder. 3. the detection system that can accurately collect ECL spectral information according to claim 1, is characterized in that, described ECL pool is provided with electrode fixing device, and described working electrode, reference electrode and counter electrode are fixed on electrode fixing device. on the device. 4. the detection system that can accurately collect ECL spectral information according to claim 1, is characterized in that, the described detection system that can accurately collect ECL spectral information also comprises cassette, and described ECL radiation generating device unit and collecting objective lens are arranged in the cassette. 5 . The detection system capable of accurately collecting ECL spectral information according to claim 4 , wherein the cassette is provided with an electrode wire transfer port and an airway tube transfer port. 6 . 6. The detection system capable of accurately collecting ECL spectral information according to claim 5, wherein the ECL pool is also provided with an airway, the airway is connected to the inside of the ECL pool, and the airway is connected to the airway through the airway adapter. Cassette exterior. 7. the detection system that can accurately collect ECL spectral information according to claim 4, is characterized in that, described CCD grating spectrometer is provided with incident slit and incident slit fixed plate, and described cassette is provided with C or F interface, the collection objective lens is fixed in the cassette through the C or F interface, and the focal point of the collection objective lens coincides with the incident slit. 8. the detection system that can accurately collect ECL spectral information according to claim 2, is characterized in that, described adjustable ECL pool support, ECL pool surface, electrode fixture and working electrode surface are all provided with scale mark and can Adjustment thread. 9. The detection system capable of accurately collecting ECL spectral information according to claim 1, characterized in that, said electrochemical device unit operates for being able to accept the TTL signal trigger of a CCD detector, or can directly generate a TTL signal An electrochemical analyzer that triggers the simultaneous operation of the CCD detector. 10. The detection system capable of accurately collecting ECL spectral information according to claim 1, wherein the data processing and control unit is a computer.