CN102645428A - Electrochemiluminescence analysis and test system with easy-to-dismount additional functional mechanism - Google Patents

Abstract

The invention relates to an electrochemiluminescence analysis and test system with an easy-to-dismount additional functional mechanism, which belongs to the field of analysis and testing. A glassy carbon electrode in the system related to electrochemiluminescence analysis and testing can be easily polluted by adsorbed organic substances produced by electrolysis, the adsorbed pollution can lead to the rapid attenuation of the performance of the glassy carbon electrode, and the purpose of the scheme is to solve the problem. The structure of the system of the scheme comprises an electrolytic cell, a counter electrode, a reference electrode and the rod-shaped glassy carbon electrode, and the counter electrode, the reference electrode and the rod-shaped glassy carbon electrode are inserted in the electrolytic cell. The key points are as follows: the structure of the system also comprises a metal elastic clamp, the two jaws of the metal elastic clamp defines a shape which surrounds the electrode rod of the glassy carbon electrode, and at least one of the jaws is provided with an ultrasonic transducer. The scheme utilizes the electrode rod as an ultrasonic wave conduction medium of part of a path to conduct high-frequency ultrasonic waves nearby, and utilizes the high-frequency ultrasonic waves to clean the working face of the glassy carbon electrode in real time. Moreover, the metal elastic clamp and fittings thereof are easy to dismount.

Description

An electrochemiluminescence analysis and detection device with an additional functional mechanism that is easy to unload

technical field

The invention relates to an electrochemiluminescence analysis and detection device with an additional functional mechanism that is easy to unload, and belongs to the field of analysis and testing.

Background technique

Electrochemiluminescence, the technical meaning expressed by this term, is well known to those skilled in the field of analysis and testing.

In the practice of electrochemiluminescence analysis and detection, glassy carbon electrodes are often used as the working electrode in the electrolytic cell, which is based on its comprehensive advantages. However, the electrochemiluminescence analysis and detection device using glassy carbon electrodes is not flawless. , wherein, there is a common, well-known, and intractable problem, that is, the exposed electrode working surface of the glassy carbon electrode in the device is very susceptible to the adsorption pollution of organic substances produced by electrolysis, and the adsorption Contamination will lead to rapid attenuation of the performance of glassy carbon electrodes; therefore, how to effectively and instantly clean glassy carbon electrodes while performing electrochemiluminescence analysis and detection operations has become an urgent technical problem to be solved.

Contents of the invention

The problem to be solved by the present invention is to develop a novel electrochemiluminescence analysis and detection device capable of performing self-cleaning operation of electrodes in real time while performing electrochemiluminescence analysis and detection.

This case solves the above problems through the following scheme, which provides an electrochemiluminescence analysis and detection device with an additional functional mechanism that is easy to unload. Multiplier tube, the electrolytic cell is installed in the cartridge, and the working electrode, and the counter electrode, and the reference electrode, the counter electrode is a sheet-shaped, columnar or wire-shaped platinum electrode or gold electrode, so The reference electrode is an Ag/AgCl electrode or a calomel electrode, the working electrode is a glassy carbon electrode, and its outline of the glassy carbon electrode is rod-shaped, and the working ends of the working electrode, the counter electrode, and the reference electrode go deep into the The interior of an electrolytic cell, which is a concave cup-shaped vessel with a square, rectangular, round, or The two facing clamping arms tend to embrace each other, at least one of the clamping arms is equipped with an ultrasonic transducer, and the electrode rod of the rod-shaped glassy carbon electrode is located between the two clamping arms , the electrode rod of the rod-shaped glassy carbon electrode is perpendicular to the two clamping arms, and the two clamping arms are in the shape of embracing the electrode rod of the rod-shaped glassy carbon electrode.

The technical meaning of the term glassy carbon electrode is well known in the field of electrochemiluminescence analysis.

Generally, the glassy carbon electrodes selected in laboratories are mostly rod-shaped in profile.

The usual, commercially available, rod-shaped glassy carbon electrodes in the prior art, the details of their internal and external structures in the prior art, are well known to those working in the field of electrochemiluminescence .

The ultrasonic transducer is a device that converts high-frequency oscillating electrical signals into high-frequency mechanical oscillations. The technical meaning of the word ultrasonic transducer itself is well known in the field of ultrasonic technology.

The structural technical meaning expressed by the term itself of the metal elastic clip is well known.

The technical meanings expressed by the metals and metal materials are well known.

The device of this case can certainly include a high-frequency oscillating electrical signal generator, and a high-frequency oscillating electrical signal transmission cable, one end of the high-frequency oscillating electrical signal transmission cable is connected to the ultrasonic transducer, and the high-frequency oscillating electrical signal transmission cable The other end of the high-frequency oscillating electrical signal generator is connected to the high-frequency oscillating electrical signal generator together with the ultrasonic transducer connected to it via the cable to form an ultrasonic emission mechanism, and the ultrasonic emission mechanism of the ultrasonic emission mechanism The power is between 1 milliwatt and 20 watts. Using lower power helps avoid damaging the electrodes and helps avoid interference with electrochemiluminescent detection.

The technical meaning expressed by the high-frequency oscillating electrical signal generator and the high-frequency oscillating electrical signal transmission cable is well known in the field of ultrasonic technology.

The structure of the device in this case can also include some accessories, such as: a weak light measuring instrument, which can be connected with the photomultiplier tube; and a recorder, which can be connected with the weak light measuring instrument. instrument connection.

The accessory is another example: an electrochemical workstation device, which can be connected to the working electrode, the auxiliary electrode and the reference electrode.

The accessories also include, for example: a fixed bracket for clamping the working electrode, the auxiliary electrode and the reference electrode; and the like.

The term expressions such as the weak light measuring instrument and the recorder and the electrochemical workstation device have well-known technical meanings in the field of instrumental analytical chemistry; the weak light measuring instrument and the recorder and the electrochemical workstation Devices and other markets are available for sale.

Ultrasonic cavitation is a very powerful effect. Low-frequency ultrasonic waves have a strong impact on the surface of the target workpiece. The cavitation effect of low-frequency ultrasonic waves is not suitable for the detection device as fine as this case; with the ultrasonic frequency The improvement of the cavitation effect on the target workpiece gradually weakens until it can be ignored; therefore, the preferred ultrasonic frequency suitable for the device in this case is not a random frequency.

As mentioned above, in order to avoid damage to the exposed electrode working surface of the glassy carbon electrode in the device by ultrasonic cavitation, and to avoid inducing sonoluminescence, the preferred frequency of the ultrasonic wave emitted by the ultrasonic emitting mechanism should be at least above 40KHz; The preferred frequency range of the ultrasonic waves emitted by the ultrasonic emitting mechanism is between 40KHz and 12MHz.

On a finer level, in order to avoid ultrasonic damage to the exposed electrode working surface of the glassy carbon electrode in the device, and to avoid inducing sonoluminescence more finely, the ultrasonic wave emitted by the ultrasonic emitting mechanism is further preferred. The frequency should be at least above 80KHz; the further preferred frequency range of the ultrasonic waves emitted by the ultrasonic emitting mechanism is between 80KHz and 12MHz.

Different electrolytic cell bottom liquids and different electrochemiluminescent detection and analysis objects have different sensitivities to ultrasonic waves of different powers and frequencies. Detect and analyze objects, gradually adjust and determine the required ultrasonic frequency and power.

As mentioned above, for different electrochemiluminescence analysis detection objects and electrolytic cell bottom liquid, the required ultrasonic frequency and power should be carefully adjusted and selected. However, if the previous work is not in place, when the selected ultrasonic frequency and power It is not appropriate enough to induce a certain intensity of sonoluminescence, and it is not enough to worry about. As long as the blank comparison value is deducted during the analysis and detection process, the device in this case is automatically converted into an electrode with instant self-cleaning. Functional electrochemiluminescence, sonochemiluminescence dual excitation joint analysis detection device.

The installation position of the ultrasonic transducer on the clamping arm may be on the inner side of the clamping arm facing the other clamping arm; in this case, the ultrasonic transducer is close to the rod The electrode rod of the glassy carbon electrode.

The installation position of the ultrasonic transducer on the clamping arm can of course also be on the outer side of the clamping arm away from the other clamping arm; in this case, the ultrasonic wave passes through the clamping arm Electrode rod delivery to the rod-shaped glassy carbon electrode.

Ultrasonic transducers can also be installed on the two clamping arms; in this case, the ultrasonic transducers installed in different positions can work simultaneously or only individually; The ultrasonic transducers arranged in different positions can adopt the same ultrasonic frequency or different ultrasonic frequencies, for example, the ultrasonic transducer on one arm adopts a frequency of 1000KHz, and the other ultrasonic transducer on the arm The ultrasonic transducer on it takes a frequency of 8000KHz, and so on.

The embracing position of the two clamping arms on the electrode rod of the rod-shaped glassy carbon electrode can be any position on the electrode rod; of course, the preferred embracing position is on the upper half of the electrode rod The location close to the exposed terminal posts, as such, helps to avoid direct contact with the measurand solution in the cell.

In view of the chemical analysis laboratory environment of the actual work of the device in this case, it is sometimes important to consider the chemical corrosion resistance of the erodible elements in the device; in order to avoid the corrosion damage of the erodible elements in the device in this case, the further preferred scheme Yes, the metal elastic clip and the ultrasonic transducer installed on the clamping arm are all covered with a chemical corrosion-resistant protective layer. The material of the protective layer is polytetrafluoroethylene, and the thickness of the protective layer is between Between 0.01mm and 3.00mm.

As far as the PTFE coating engineering technology itself in the sense of general industrial technology is concerned, its coating technology is a mature and well-known technology.

The advantage of this case is that, using the device of this case, while performing electrochemiluminescence analysis and detection, the sound wave transmitted to the working end of the rod-shaped glassy carbon electrode via the rod body of the electrode rod of the rod-shaped glassy carbon electrode The solution in and around it transmits high-frequency, low-power ultrasonic waves, and uses the high-frequency, low-power ultrasonic waves to clean the exposed electrode working surface at the working end of the rod-shaped glassy carbon electrode in real time, in this way , immediately avoiding the adsorption pollution of the exposed electrode working surface by the organic impurities generated by the electrolytic redox reaction, so that the electrode working surface can always maintain a fresh state during the entire analysis and detection process, preventing the rod-shaped The rapid attenuation of the performance of the glassy carbon electrode; and, the additional functional mechanism in the device of this case, that is, the metal elastic clip on which the ultrasonic transducer is installed on the clamping arm, can be quickly removed and unloaded as required.

Based on the structural characteristics of the device in this case, the device in this case can also be converted into a double-electric and acoustic excitation-stimulated chemiluminescence analysis and detection device according to needs.

Description of drawings

Fig. 1 is a schematic diagram of an embodiment of the present case, which expresses a rough shape of the core structural part of the device.

In the figure, 1 is the counter electrode, which is also called the auxiliary electrode, 2 is the electrolytic cell, 3 is the auxiliary electrode, 4 is the rod-shaped glassy carbon electrode, 5 is the working end of the rod-shaped glassy carbon electrode, and 6 is the rod-shaped glassy carbon electrode The electrode rods of the electrodes, 7 and 13 are respectively two clamping arms located at different structural positions, 8 and 12 are two ultrasonic transducers respectively installed on the clamping arms 7 and 13, and 9 and 11 are respectively connected Two high-frequency oscillating electrical signal transmission cables of ultrasonic transducers 8 and 12, 10 is a terminal post of metal material, and 14 is a metal elastic clip equipped with ultrasonic transducers on its clamping arm.

Detailed ways

In the embodiment of this case shown in Figure 1, the structure of the device includes an electrolytic cell 2, and a photomultiplier tube installed below or on the side of the electrolytic cell, which is not shown in the legend, and the electrolytic cell 2 is Installed in the cassette, the cassette is not shown in the legend, the structure of the cassette is known, and the working electrode 4, the working electrode is a glassy carbon electrode, and the counter electrode 1, and the reference electrode 3, The counter electrode 1 is a sheet-like, columnar or wire-like platinum electrode or gold electrode, the reference electrode 3 is an Ag/AgCl electrode or a calomel electrode, and the working electrode 4 is a glassy carbon electrode as described above. The outline of the glassy carbon electrode 4 is It is rod-shaped, and the working ends of the working electrode 4, the counter electrode 1 and the reference electrode 3 go deep into the inside of the electrolytic cell 2. In the illustration, the electrolytic cell 2 is a concave cup-shaped vessel whose open end outline is circular, However, the electrolytic cell 2 can also be a concave cup-shaped vessel whose open end profile presents other shapes, such as a concave cup-shaped vessel whose open end profile presents other shapes, for example, its open end profile is Square, rectangular, oval concave cup-shaped vessel, the key point is that the structure of the device includes a metal elastic clip 14, and the metal elastic clip 14 has two opposite clamping arms tending to embrace, the two The opposite clamping arms are respectively clamping arm 7 and clamping arm 13. In the illustration, ultrasonic transducers are all installed on clamping arm 7 and clamping arm 13, and the ultrasonic transducer installed on clamping arm 7 The transducer is an ultrasonic transducer 8, and the ultrasonic transducer installed on the clamping arm 13 is an ultrasonic transducer 12, and the electrode rod 6 of the rod-shaped glassy carbon electrode 4 is located between the clamping arm 7 and the clamping arm 13. Between the positions, the electrode rod 6 of the rod-shaped glassy carbon electrode 4 is perpendicular to the clamping arm 7 and the clamping arm 13 at the same time, and the two clamping arms, namely the clamping arm 7 and the clamping arm 13, present a rod-shaped glassy carbon The form of the electrode rod 6 of the electrode 4.

In this legend, the high-frequency oscillating electrical signal generator connected to the ultrasonic transducers 8, 12 via the cables 9, 11 is not shown; the photomultiplier tube and the weak light measuring instrument connected to the photomultiplier tube are not shown; And, the recorder connected with the weak light measuring instrument is not drawn; the legend also does not draw the electrochemical workstation device connected to the counter electrode 1 and the rod-shaped glassy carbon electrode 4 and the reference electrode 3 via cables; in the legend Fixing brackets for holding the individual electrodes, etc. are also not depicted.

As mentioned above, the ultrasonic transducers 8 and 12 in the illustration can be connected to the high-frequency oscillating electrical signal generator via the cables 9 and 11, including the high-frequency oscillating electrical signal generator and the ultrasonic transducer connected to it via the cables 9 and 11. Transducer 8,12 constitutes ultrasonic emission mechanism, and its preferred range of the ultrasonic emission total power of this ultrasonic emission mechanism is between 1 milliwatt and 20 watts; Its preferred range of the frequency of the ultrasonic emission of this ultrasonic emission mechanism is in Between 40KHz and 12MHz; a further preferred range of the frequency of the ultrasonic waves emitted by the ultrasonic emitting mechanism is between 80KHz and 12MHz. Any value within the above-mentioned preferred value range is the operating parameter value allowed to be selected by the device in this case; of course, the actual selected specific operating parameter value should be carefully selected according to the specific conditions of the specific analysis object system.

Ultrasonic transducer, the technical meaning of this word is well known.

Various types of ultrasonic transducers are commercially available.

As shown in the illustration, the installation position of the ultrasonic transducer on the clamping arm can be on the inner side of the clamping arm facing the other clamping arm; in this case, the ultrasonic transducer is close to the rod-shaped The electrode shaft of the glassy carbon electrode.

The installation position of the ultrasonic transducer on the clamping arm can of course also be on the outer side of the clamping arm away from the other clamping arm; in this case, the ultrasonic wave passes through the clamping arm Electrode rod delivery to the rod-shaped glassy carbon electrode. This structural morphology is not represented in the legend.

In this illustration, ultrasonic transducers are installed on the two clamping arms; in this case, the ultrasonic transducers installed in different positions can work at the same time, or only work individually; and, The ultrasonic transducers respectively installed in different positions can adopt the same ultrasonic frequency or different ultrasonic frequencies. For example, the ultrasonic transducer on one arm adopts a frequency of 1000KHz, and the other The ultrasonic transducer on the arm adopts a frequency of 8000KHz, etc.

Of course, generally speaking, it is sufficient to only install an ultrasonic transducer on one of the clamping arms.

In view of the chemical analysis laboratory environment of the actual work of the device in this case, the consideration of chemical corrosion resistance is sometimes important; in order to avoid corrosion damage to the erodible components involved in the device in this case, a further preferred solution is that the metal elastic clip 14 And the ultrasonic transducer installed on its described clamping arm is all covered with the protection layer of anti-chemical corrosion, and its material of this protection layer is polytetrafluoroethylene, and its range of the preferred thickness of this protection layer is between 0.01 millimeter and between 3.00 mm. The PTFE protective layer with a thickness between 0.01 mm and 3.00 mm is a protective layer with an appropriate thickness. The thicker and thinner points are just different in corrosion resistance. Any specified thickness within this range is reasonable. The implementation value of the protective layer thickness.

As far as the PTFE coating engineering technology itself in the sense of general industrial technology is concerned, its coating technology is a mature and well-known technology.

The additional functional mechanism in the device of this case, that is, the metal elastic clip 14 on which the ultrasonic transducer is installed on the clamping arm, can be quickly removed and unloaded as required.

The specific implementation of the device in this case is not limited to the illustrations in the drawings of this case.

Claims (9)

1. the additional functional mechanism Electrochemiluminescprocess process pick-up unit that is easy to unload, the structure of this device comprises electrolytic cell, and; Be installed in the photomultiplier of electrolytic cell below or side, said electrolytic cell is installed within the magazine, and; Working electrode, and, to electrode; And, contrast electrode, said is sheet, column or thread platinum electrode or gold electrode to electrode; Said contrast electrode is Ag/AgCl electrode or mercurous chloride electrode, and said working electrode is a glass-carbon electrode, and its profile of this glass-carbon electrode is shaft-like; Said working electrode and the working end of electrode and contrast electrode goed deep into the inside of said electrolytic cell, this electrolytic cell are that its opening end profile is square, the cup-shaped vessel of rectangle, circle or oval-shaped indent, it is characterized in that; The structure of this device comprises a metal elastic force folder; These metal elastic force anchor clamps have two clamping limbs in opposite directions that are tending towards filling the span of a man's arms, and are equiped with ultrasonic transducer on the clamping limb at least therein, the position of the electrode stem of said shaft-like glass-carbon electrode between said two clamping limbs; The electrode stem of said shaft-like glass-carbon electrode is vertical each other with said two clamping limbs, and said two clamping limbs present the form of the electrode stem of the shaft-like glass-carbon electrode of filling the span of a man's arms.

2. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload; It is characterized in that; The structure of this device comprises higher-order of oscillation electric signal generator, and, higher-order of oscillation electric signal transmission cable; One end of this higher-order of oscillation electric signal transmission cable is connected with said ultrasonic transducer; The other end of this higher-order of oscillation electric signal transmission cable is connected with this higher-order of oscillation electric signal generator, and this higher-order of oscillation electric signal generator constitutes ultrasound emission mechanism together with the said ultrasonic transducer that links together with it via said cable, and the ultrasound emission power of this ultrasound emission mechanism is between between 1 milliwatt and 20 watts.

3. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 2 mechanism is easy to unload is characterized in that the frequency of this institute of ultrasound emission mechanism ultrasonic waves transmitted is between 40KHz and 12MHz.

4. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 3 mechanism is easy to unload is characterized in that the frequency of this institute of ultrasound emission mechanism ultrasonic waves transmitted is between 80KHz and 12MHz.

5. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload; It is characterized in that the installation position of said ultrasonic transducer on said clamping limb is the medial surface position towards another clamping limb at said clamping limb.

6. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload; It is characterized in that the installation position of said ultrasonic transducer on said clamping limb is the lateral surface position that deviates from another clamping limb at said clamping limb.

7. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload is characterized in that, on two said clamping limbs, all is equiped with ultrasonic transducer.

8. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload; It is characterized in that; The fill the span of a man's arms position of said two clamping limbs on the electrode stem of said shaft-like glass-carbon electrode is the position near exposed binding post at the upper half of this electrode stem.

9. the Electrochemiluminescprocess process pick-up unit that additional functional according to claim 1 mechanism is easy to unload; It is characterized in that; Said metal elastic force folder and the ultrasonic transducer of on its said clamping limb, installing all are coated with the protective seam of resist chemical; Its material of this protective seam is a teflon, and the thickness of this protective seam is between 0.01 millimeter and 3.00 millimeters.

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