CN215375213U - Device capable of rapidly and continuously modulating electrochemiluminescence light intensity information - Google Patents

Device capable of rapidly and continuously modulating electrochemiluminescence light intensity information Download PDF

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CN215375213U
CN215375213U CN202121803870.4U CN202121803870U CN215375213U CN 215375213 U CN215375213 U CN 215375213U CN 202121803870 U CN202121803870 U CN 202121803870U CN 215375213 U CN215375213 U CN 215375213U
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ecl
disc
optical filter
light intensity
filter
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邹桂征
申大忠
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Shandong University
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Shandong University
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Abstract

The utility model relates to a device capable of rapidly and continuously modulating electrochemiluminescence light intensity information, which comprises a fixed base fixedly provided with a direct current motor and an ECL cell bracket, wherein the direct current motor is connected with an optical filter turntable through a bearing, and optical filter groups with different central wavelengths are uniformly arranged along the circumference of the optical filter turntable. The switching speed of the optical filters of the optical filter set is 3-20 optical filters/second, and the number of the optical filters is 3-12. The device can be arranged in a cassette system of a conventional light intensity type ECL analyzer, and realizes rapid and continuous modulation of ECL radiation; under the assistance of a proper data analysis and processing system, the conventional light intensity type ECL analyzer can be assisted to have the performance of spectrum collection.

Description

Device capable of rapidly and continuously modulating electrochemiluminescence light intensity information
Technical Field
The utility model relates to a device for rapidly and continuously modulating electrochemiluminescence light intensity information, and belongs to the technical field of electrochemiluminescence detection.
Background
Electrochemiluminescence (ECL) is a chemical measurement technique that electrochemically produces an excited state of a substance (e.g., a fluorescent dye or a semiconductor nanomaterial) and emits light. ECL radiation is weak and unstable in intensity, and conventional ECL analyzers generally perform ECL analysis by directly collecting the total intensity of ECL radiation using a high-sensitivity Photomultiplier tube (PMT). Because a dispersion device is abandoned, the conventional light intensity type ECL analyzer can only use a means of modulating the ECL radiation intensity by a band-pass filter to draw the spectrum information of the ECL radiation by adopting a mode of multiple parallel measurements.
The method comprises the following specific steps:
placing a band-pass filter between a working electrode and a PMT, measuring the change curve of the ECL radiation intensity along with time in a certain waveband range, then replacing another band-pass filter with the center wavelength to measure the change curve of the ECL radiation intensity along with time in a second waveband range, and so on; by comprehensively using a plurality of band-pass filters, the change curve of the ECL radiation intensity along with time in different wave band ranges is obtained, and then the ECL spectrum is obtained. The related method needs to start the ECL test for many times to complete related modulation, and the ECL spectrum acquisition has the defects of low measurement speed, poor reproducibility and the like.
The conventional light intensity type ECL analyzer cannot realize multiple modulation of ECL radiation intensity in a mode of replacing a filter through one ECL test.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a device for rapidly and continuously modulating ECL light intensity information, i.e. an ECL light intensity modulation device. According to the utility model, the ECL light intensity modulation device is additionally arranged between the working electrode of the light intensity type ECL analyzer and the PMT, namely a mode of a rotating disk loaded with the light filter array is adopted, so that a series of light filters can be rapidly placed between the working electrode and the PMT, and the ECL spectrum can be rapidly and continuously modulated. The ECL light intensity modulation device can modulate an ECL light intensity-potential (or time) curve collected by the ECL analyzer into a series of small peaks, each small peak corresponds to ECL radiation of a plurality of specific wave bands in sequence, and the peak area or peak height of each small peak is in direct proportion to the ECL light intensity of the specific wave band; the influence of time difference is corrected through a data analysis program, an ECL light intensity-potential (or time) curve under a series of wave bands can be obtained, and high-sensitivity collection of an ECL spectrum is achieved. The utility model can realize the sensitive collection of the spectral information by one ECL test based on the conventional light intensity type ECL analyzer. In the utility model, the ECL light intensity modulation device can be directly installed in a cassette phase of a common light intensity type ECL analyzer, and the optical filter can be rapidly and continuously replaced without changing the original hardware configuration of the ECL analyzer.
The technical scheme of the utility model is as follows:
the utility model provides a device that can quick and continuous modulation electrochemiluminescence light intensity information, is including the unable adjustment base that is provided with direct current motor and ECL pond support fixedly, direct current motor be connected with the light filter carousel through the bearing, evenly be provided with the filter group of different center wavelength along light filter carousel circumference.
According to the utility model, preferably, the optical filter turntable comprises an upper disc, a middle disc and a lower disc, wherein the middle disc is uniformly provided with round holes along the circumference, and each round hole is provided with an optical filter; the upper disc and the lower disc are also provided with holes which respectively correspond to the round holes of the middle disc; the upper disc and the lower disc fixedly clamp the middle disc together with the optical filter in the middle.
According to the utility model, the upper disc is used for fixing the optical filter, the middle disc is used for placing the optical filter, and the lower disc is used for fixing the optical filter and shading; preferably, the shape of the upper disc opening is circular, and the diameter of the opening is smaller than that of the middle disc opening; the shape of the lower plate opening is isosceles trapezoid, and the lower bottom of the isosceles trapezoid is located on the periphery of the lower plate. The filter turntable moves around the bearing in a circular manner to drive the filter set to move in a circular manner, and in order to ensure that the light transmission area of each filter is the largest and is as the same as the area of the lighting window as possible, the opening of the lower disc is in an isosceles trapezoid shape.
According to the utility model, preferably, the upper disc, the middle disc and the lower disc are all black PVC plastic wafers with the diameter of 90mm, the thickness of the black PVC plastic wafers is 2mm, 12 round holes with the diameter of 10mm are processed on the upper disc, and 12 round holes with the diameter of 13mm are processed on the middle disc; 12 isosceles trapezoid holes (6.2 mm at the inner edge, 8.1mm at the outer edge and 11mm in height) are processed on the base plate, and the center positions of the 12 groups of holes are the same in the three wafers; the upper, middle and lower three disks are fixed by 3 screws, wherein nuts are embedded in the wire exposing holes of the upper disk.
When the optical filter is used, the positions of round holes in the upper disc and the middle disc are aligned, the upper disc and the middle disc are bonded into a whole by tetrahydrofuran, 11 optical filters with different central wavelengths and the diameter of 12.7mm are placed in 12 round holes with the diameter of 13mm according to the number, and a black PVC plastic perforated circular sheet with the diameter of 12.7mm is additionally arranged in the other round hole; and covering a black PVC plastic wafer with isosceles trapezoid light holes, fixing the three PVC wafers and the optical filter by using bolts to form an optical filter turntable, and finally installing the optical filter turntable on a bearing.
According to the present invention, preferably, the shape of the optical filter with different central wavelengths in the optical filter set is circular;
preferably, the number of the filters is 3 or more, and more preferably 3 to 12.
According to the utility model, preferably, a lighting window and a closing gate are arranged between the filter set and the light gathering system, and the filter set, the ECL measuring cell, the filter set and the photomultiplier are positioned in the same light path. The gate can be closed and opened according to requirements, so that the electrochemical radiation light generated by the ECL measuring cell is blocked and opened to enter the light-gathering system.
According to the utility model, preferably, the lighting window is positioned at the bottom of the optical filter, is an isosceles trapezoid notch, the size of the isosceles trapezoid notch is smaller than the diameter of the optical filter, the projection of the lighting window and the fixed isosceles trapezoid notch positioned above the photomultiplier closing gate have a position which can be completely overlapped, and the lighting window formed by the overlapped area of the rotating isosceles trapezoid notch and the fixed isosceles trapezoid notch of the optical filter turntable ensures the separation of the measuring peaks between the optical filters.
In the utility model, the direct current motor can start the optical filter rotating disc to rotate, so that the band-pass optical filters with different central wave bands in the optical filter set are sequentially switched into the optical paths where the working electrode, the optical filters and the photomultiplier are positioned, and the ECL radiation is rapidly and continuously modulated.
According to the utility model, the ECL light intensity modulation device can be loaded into a common light intensity type ECL analyzer to form a high-sensitivity ECL spectrum acquisition device. The common light intensity type ECL analyzer can be an existing device and comprises an ECL analyzer host, a data acquisition and analysis system and a cassette system of the ECL analyzer;
the ECL analyzer is characterized in that an ECL measuring cell and a photomultiplier are arranged in a cassette system of the ECL analyzer, the ECL measuring cell is provided with a reference electrode, a working electrode and a counter electrode which are respectively connected with an ECL analyzer host, the working electrode and the photomultiplier are positioned in the same optical path, the photomultiplier is connected with the ECL analyzer host, and the ECL analyzer host is connected with a data acquisition and analysis system. Preferably, the ECL measuring cell is made of glass, the bottom is transparent, and the position of the working electrode is coaxial with the photomultiplier.
According to the utility model, the optical filter turntable is provided with an optical filter group consisting of more than three optical filters with different central wavelengths, and a positioning hole for not placing the optical filters; the switching speed of the optical filter is 3-20 optical filters/second, the optical filter penetrates through a measuring light area between the working electrode and the photomultiplier in the rotating process, and an ECL light intensity-potential (or time) curve is modulated into a series of small peaks.
According to the utility model, preferably, the optical filter switching adopts a mode of adopting an optical filter rotating disc, the optical filter rotating disc is driven by a direct current motor, the rotating speed of the motor is controlled by adjusting the working voltage (0.5-7V), the speed change range is 10-150 rpm, and the working voltage of the direct current motor is supplied by an external direct current stabilized power supply. When ECL radiation passes through the positioning round hole without the optical filter, the light intensity of the ECL radiation is 2-3 times of the maximum peak light intensity after passing through the optical filter (regulated and controlled by the diameter of the opening of the black PVC plastic wafer), and the ECL radiation becomes the strongest peak in 12 modulated light intensity peaks in the same circle to be used as a positioning peak, so that the central wavelength of the optical filter corresponding to other 11 light intensity peaks in the same circle is determined.
According to the present invention, it is preferable that the central wavelength (λ) of each filter is calculated by measuring the transmittance-wavelength curve of the selected filter using a spectrophotometeri) Transmittance-wavelength integral area (A)i) For ECL spectrometry and calibration.
According to the utility model, when the data processing and display interface of the original photoelectrochemical workstation is used, an ECL light intensity-potential (or time) curve consisting of a series of small peaks can be observed, from which the approximate profile of the ECL spectrum can be seen. After scanning is finished, introducing the measured ECL light intensity-potential (or time) curve into data analysis software, and after the time difference correction of the optical filter pass band width and the optical filter wheel disc is carried out, obtaining the ECL spectrum of the measured system and the change curve of the ECL spectrum along with the scanning potential or the scanning time; analyzing the measured ECL light intensity-potential (or time) curve by a matched data analysis method to obtain an ECL spectrum;
the utility model has not been described in detail, but is in accordance with the state of the art.
The utility model has the following beneficial effects:
1. the ECL light intensity modulation device is compatible with a cassette system of a conventional light intensity ECL instrument, can realize the rapid and continuous modulation of ECL light intensity information under the condition of not changing other hardware facilities of the instrument, and can recover the original shape and the function of the ECL instrument by removing the ECL light intensity modulation device.
2. The detection system is a photomultiplier, and the light filter has a large light transmission area and is suitable for light intensity modulation of an ultra-weak ECL system.
3. The switching speed of the optical filter of the ECL light intensity modulation device can reach 10-20 pieces/second or even higher, and the ECL light intensity modulation device can be used as a light splitting element.
Drawings
Fig. 1 is a schematic structural diagram of a main body of an ECL light intensity modulation device in embodiment 1 of the present invention.
Fig. 2 is a schematic structural view of the filter carousel and the filter set in the ECL light enhancement device according to embodiment 1 of the present invention. Wherein: a is an upper disc used for fixing the optical filter; b is a middle disc for placing the optical filter; and c is a lower disc used for fixing the optical filter and shading.
Fig. 3 is a schematic diagram of an ECL spectrum acquisition device based on an ECL light intensity modulation device in embodiment 2 of the present invention.
Wherein: the ECL analyzer comprises an ECL analyzer host, 2, a data acquisition and analysis system, 3, a cassette system of the ECL analyzer, 4, a photomultiplier, 5, a light gathering system, 6, a shutter, 7, a light filter rotating disc, 8, a light collecting window, 9, a light filter set, 10, a bearing, 11, a fixed base, 12, a direct current motor, 13, an ECL measuring cell, 14, a reference electrode, 15, a working electrode and 16, a counter electrode.
FIG. 4 is a graph of anodic ECL light intensity versus time raw curves of ruthenium-pyridine measured based on rapid and continuous modulation of ECL light intensity in inventive test example 1. Wherein the inset is the resolved ECL spectrum with a potential scan rate of 50 mV/s.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to describe only some, but not all, embodiments of the utility model. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms "comprises," "comprising," or any other variation thereof, in the embodiments are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but also other elements not expressly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device that comprises the element.
The above description of the disclosed embodiments: to enable any person skilled in the art to make or use the utility model. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the utility model. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The embodiment is based on an MPI-E type electrochemical luminescence detector produced by Siemens analysis instruments, Inc., ECL signal modulation is implemented in a mode that an ECL light intensity modulation device is loaded into a cassette system of the ECL analyzer, and the modulation signal is processed by a data analysis program on the basis to realize the collection of ECL spectrum. After the ECL light intensity modulation device is removed, the instrument can restore the original appearance and the original functions.
Example 1
As shown in fig. 1, an ECL light intensity modulation apparatus includes a fixed base 11 fixedly provided with a dc motor 12 and an ECL cell holder, the dc motor 12 is connected to an optical filter turntable 7 through a bearing 10, and optical filter sets 9 with different central wavelengths are uniformly arranged along the circumference of the optical filter turntable 7;
as shown in fig. 2, the optical filter turntable 7 includes an upper disc, a middle disc and a lower disc, the middle disc is uniformly provided with circular holes along the circumference, and each circular hole is provided with an optical filter; the upper disc and the lower disc are also provided with holes which respectively correspond to the round holes of the middle disc; the upper disc and the lower disc fixedly clamp the middle disc and the optical filter in the middle;
the upper disc is used for fixing the optical filter, the middle disc is used for placing the optical filter, and the lower disc is used for fixing the optical filter and shading light; the upper disc, the middle disc and the lower disc are all black PVC plastic wafers with the diameter of 90mm, the thickness of the black PVC plastic wafers is 2mm, 12 round holes with the diameter of 10mm are processed on the upper disc, and 12 round holes with the diameter of 13mm are processed on the middle disc; 12 isosceles trapezoid holes (6.2 mm at the inner edge, 8.1mm at the outer edge and 11mm in height) are processed on the base plate, and the center positions of the 12 groups of holes are the same in the three wafers; the upper, middle and lower three disks are fixed by 3 screws, wherein nuts are embedded in the wire exposing holes of the upper disk.
When the optical filter is used, the positions of round holes in the upper disc and the middle disc are aligned, the upper disc and the middle disc are bonded into a whole by tetrahydrofuran, 11 optical filters with different central wavelengths and the diameter of 12.7mm are placed in 12 round holes with the diameter of 13mm according to the number, and a black PVC plastic perforated circular sheet with the diameter of 12.7mm is additionally arranged in the other round hole; and covering a black PVC plastic wafer with isosceles trapezoid light holes, fixing the three PVC wafers and the optical filter by using bolts to form an optical filter turntable, and finally installing the optical filter turntable on a bearing.
Example 2
As shown in fig. 3, based on the MPI-E electrochemiluminescence detector, the ECL light intensity modulation device in the embodiment 1 of the apparatus forms a device capable of realizing spectrum collection by rapidly and continuously modulating ECL intensity, which includes: the system comprises an MPI-E type ECL analyzer host 1, a data acquisition and analysis system 2 and an MPI-E type ECL analyzer cassette system 3;
an ECL light intensity modulation device, an ECL measuring cell 13 and a photomultiplier tube 4 are arranged in a cassette system 3 of the ECL analyzer, the ECL measuring cell 13 is arranged on an ECL cell bracket of the ECL light intensity modulation device, the ECL measuring cell 13 is provided with a reference electrode 14, a working electrode 15 and a counter electrode 16 which are respectively connected with an ECL analyzer host 1, the working electrode 15, a filter set 9 and the photomultiplier tube 4 are positioned in the same light path, the photomultiplier tube 4 is connected with the ECL analyzer host 1, and the ECL analyzer host 1 is connected with a data acquisition and analysis system 2;
the ECL measuring cell 13 is made of glass, has good bottom light transmission, is arranged on the ECL cell bracket, and the position of the working electrode 15 and the photomultiplier tube 4 are in a coaxial position.
The ECL spectrum device also comprises a light-condensing system 5, wherein the light-condensing system 5 is positioned between the filter set 9 and the photomultiplier tube 4 and is used for condensing ECL radiation generated by the working electrode 15 into the photomultiplier tube 4 to the maximum extent;
a light collecting window 8 and a closing gate 6 are also arranged between the filter set 9 and the light condensing system 5, and are positioned in the same light path with the ECL measuring cell 13, the filter set 9, the light condensing system 5 and the photomultiplier tube 4. The gate 6 can be closed and opened as required to block and open the electrochemical radiation light generated by the ECL measuring cell 13 into the light-focusing system 5.
When the device is used for collecting the dynamic electrochemiluminescence spectrum with high sensitivity, a reaction solution is added into the ECL measuring cell 13, the light intensity type ECL analyzer is started, and ECL radiation is generated on the surface of the working electrode 15; synchronously starting the direct current motor 12, driving the optical filter group 9 to rotate by the optical filter turntable 7, so that the ECL radiation generated by the working electrode 15 periodically passes through the band-pass optical filters with different central wave bands in the optical filter group 9 to obtain a modulated ECL light intensity-potential curve or an ECL light intensity-time curve;
the obtained ECL light intensity-potential curve or ECL light intensity-time curve is processed by using a data analysis method, when the data processing and interface display of the original photoelectrochemical workstation are adopted, the ECL light intensity-potential (or time) curve formed by a series of small peaks can be observed, and the approximate outline of the ECL spectrum can be seen. After scanning is finished, the measured ECL light intensity-potential (or time) curve is introduced into data analysis software, and after the pass band width of the optical filter and the time difference of the optical filter wheel disc are corrected, the ECL spectrum of the measured system can be obtained.
Test example 1
And (3) measuring the electrochemical luminescence spectrum of the ruthenium bipyridyl. 20 microliter of a mixed solution of 0.025mg/mL ruthenium pyridine and 0.7 percent chitosan is dripped on the surface of the glassy carbon electrode, and the infrared lamp is used for baking. Taking a certain volume of phosphate buffer solution (pH 7) as a supporting electrolyte solution in an ECL measuring cell 13, adding 100mmol/L triethanolamine, placing a glassy carbon working electrode, an Ag/AgCl reference electrode and a Pt wire counter electrode, connecting with an ECL analyzer host 1, starting potential scanning, wherein the cyclic scanning potential range is 0-1.5V, the potential scanning speed of the test is 50mV/s, and the obtained result is shown in figure 4. When the rotation speed of the filter rotating disk 7 is set to 80rpm, the scanning period of the spectrum measurement is 0.75s, because the light-collecting area of the light-splitting device of the utility model is large, and the spectrum of the electrochemical luminescence system can be measured by using a high-sensitivity PMT detector and only one measurement period. In the electrochemical luminescence, different measurement periods correspond to different electrochemical conditions, so that after the ECL light enhancement device is added, the change information of the ECL spectrum along with the scanning potential or the scanning time can be obtained by using a common electrochemical luminometer.

Claims (5)

1. The device is characterized by comprising a fixed base fixedly provided with a direct current motor and an ECL cell bracket, wherein the direct current motor is connected with an optical filter turntable through a bearing, and optical filter groups with different central wavelengths are uniformly arranged along the circumference of the optical filter turntable.
2. The device of claim 1, wherein the filters of the set of filters having different center wavelengths are circular in shape.
3. The device of claim 1, wherein the number of filters with different center wavelengths in the filter set is 3-12.
4. The device of claim 1, wherein the filter carousel comprises an upper disk, a middle disk and a lower disk, the middle disk has circular holes uniformly arranged along a circumference, and each circular hole is provided with a filter; the upper disc and the lower disc are also provided with holes which respectively correspond to the round holes of the middle disc; the upper disc and the lower disc fixedly clamp the middle disc together with the optical filter in the middle.
5. The device capable of rapidly and continuously modulating the electrochemiluminescence light intensity information according to claim 4, wherein the upper disc, the middle disc and the lower disc are all wafers with the diameter of 90mm and the thickness of 2mm, the upper disc is provided with 12 circular holes with the diameter of 10mm, and the middle disc is provided with 12 circular holes with the diameter of 13 mm; 12 isosceles trapezoid holes are arranged in the lower disc, and the inner edge of each isosceles trapezoid is 6.2mm, the outer edge of each isosceles trapezoid is 8.1mm, and the height of each isosceles trapezoid is 11 mm.
CN202121803870.4U 2021-08-04 2021-08-04 Device capable of rapidly and continuously modulating electrochemiluminescence light intensity information Active CN215375213U (en)

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