CN102645465B - Electrochemiluminescence analysis and detection device with interference-free precise self-cleaning mechanism - Google Patents
Electrochemiluminescence analysis and detection device with interference-free precise self-cleaning mechanism Download PDFInfo
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- CN102645465B CN102645465B CN201210141891.3A CN201210141891A CN102645465B CN 102645465 B CN102645465 B CN 102645465B CN 201210141891 A CN201210141891 A CN 201210141891A CN 102645465 B CN102645465 B CN 102645465B
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Abstract
The invention relates to an electrochemiluminescence analysis and detection device with an interference-free precise self-cleaning mechanism, belonging to the field of analysis and testing. How to realize the self-cleaning of a glass carbon electrode in a system on the premise that additional interference is not brought about is a problem which is needed to be solved urgently. The electrochemiluminescence analysis and detection device with the interference-free precise self-cleaning mechanism mainly aims at solving the problem. A micro ring piezoelectric element is coaxially installed at a position where the internal part of the glass carbon electrode in the system and the upper end surface of a cylindrical glass carbon electrode body are in contact with each other. At the same time, a pen-sleeve-shaped or test-tube-shaped ultrasonic energy absorber which is made of a microporous material is additionally arranged in the system. The closed end of the ultrasonic energy absorber is arranged in an electrolytic cell. The working end of a reference electrode goes deep into the cavity of the ultrasonic energy absorber. By adopting the technical scheme, the electrochemiluminescence analysis and detection device with the interference-free precise self-cleaning mechanism has the advantages that the structure is compact and the device has an instant electrode ultrasonic self-cleaning function; and besides, under the screening effect of the ultrasonic energy absorber, the reference electrode can be guaranteed not to be interfered and the potential of the reference electrode is kept stable. By adopting the structure, the electrochemiluminescence analysis and detection device with the interference-free precise self-cleaning mechanism has an electric and acoustic dual-excitation simulated chemiluminiscence analysis and detection function.
Description
Technical field
The present invention relates to a kind of Electrochemiluminescprocess process pick-up unit comprising noiseless precise and tiny self-cleaning mechanism, belong to analytical test field.
Background technology
Electrogenerated chemiluminescence, the art-recognized meanings expressed by this vocabulary, for the professional and technical personnel in analytical test field, is known.
Detect in practice at Electrochemiluminescprocess process, working electrode in involved electrolytic cell often selects glass-carbon electrode, this is considering based on its comprehensive advantage, but, the Electrochemiluminescprocess process pick-up unit employing glass-carbon electrode is not had no time, wherein, have one belong to general character, known and be intractable problem, that is exactly, its exposed electrode face of glass-carbon electrode in device is very easily subject to the adsorption fouling of the organic species that electrolysis produces, and described adsorption fouling can cause the rapid decay of glass-carbon electrode performance; Therefore, how carrying out while Electrochemiluminescprocess process detects operation, without additional interference ground, effectively, immediately cleaning glass-carbon electrode, just becoming a technical matters urgently to be resolved hurrily.
Summary of the invention
Problem to be solved by this invention is, researches and develops a kind ofly while carrying out Electrochemiluminescprocess process detection, can immediately carry out the novel Electrochemiluminescprocess process pick-up unit of the self-cleaning running of electrode, this self-cleaning function mode and should not introduce negative interference.
This case is solved the problem by following scheme, the device that the program provides is a kind of Electrochemiluminescprocess process pick-up unit comprising noiseless precise and tiny self-cleaning mechanism, the structure of this device comprises electrolytic cell, and, be installed in below electrolytic cell or the photomultiplier of side, described electrolytic cell is installed within magazine, and, glass-carbon electrode, the binding post that this glass-carbon electrode contains column glass-carbon electrode body and is connected with this column glass-carbon electrode body, the material of binding post is metal material, that a part of binding post of this column glass-carbon electrode body and this column glass-carbon electrode body close is rolled in wherein by hollow edged electrode overcoat, the material of this hollow edged electrode overcoat is macromolecule electrically insulating material, and, to electrode, and, contrast electrode, described is sheet to electrode, column, cylindric or thread platinum electrode or gold electrode, described contrast electrode is Ag/AgCl electrode or mercurous chloride electrode, described glass-carbon electrode and the working end of electrode and contrast electrode is positioned to the inside of described electrolytic cell, this electrolytic cell is that its opening end profile is square, rectangle, the cup-shaped vessel of circular or oval indent, emphasis is, the structure of this device also comprises annular piezoelectric element, that end face of an end face of this annular piezoelectric element and the described binding post of connection of described column glass-carbon electrode body combines, connect the center hole of described binding post through this annular piezoelectric element of described column glass-carbon electrode body, the entity of this annular piezoelectric element is around described binding post, its position of the entity of this annular piezoelectric element is the position between described binding post and described hollow edged electrode overcoat, and, higher-order of oscillation electric signal transmission cable, one end of this higher-order of oscillation electric signal transmission cable is connected with this annular piezoelectric element through the pipeline of described hollow edged electrode jacket internal, and, ultrasonic energy absorber, this its profile of ultrasonic energy absorber is pen cap shape or test tube shape, the inside of electrolytic cell should be positioned in its one end closed of ultrasonic energy absorber in pen cap shape or test tube shape, the inside of this ultrasonic energy absorber is goed deep in its working end of described contrast electrode, this its material of ultrasonic energy absorber is micropore material, described micropore material is micropore ceramics, fine-celled foam glass, fine-celled foam aluminium, microporous silicon rubber, expanded microporous polytetra fluoroethylene-EPTEE or micropore Kynoar.
Described micropore ceramics, fine-celled foam glass, fine-celled foam aluminium, microporous silicon rubber, expanded microporous polytetra fluoroethylene-EPTEE and micropore Kynoar etc. poromerics, all have commercially available; Selected poromerics can be bought simply cut, punching, make required form.
Described working electrode one word, its art-recognized meanings, in Electrochemiluminescprocess process field, is known.
Described macromolecule electrically insulating material, its art-recognized meanings is known.
Traditional glass-carbon electrode on ordinary meaning, its CONSTRUCTED SPECIFICATION, for the professional in electrogenerated chemiluminescence field, is known.
Described annular piezoelectric element, the art-recognized meanings of this word itself is known at ultrasound wave professional skill field.The annular piezoelectric element of various, each size all has commercially available.
Miniature annular piezoelectric element also has commercially available certainly.
Only just comprise the joint detail of various piezoelectric element itself and the higher-order of oscillation electric signal transmission cable of annular piezoelectric element, for the professional of ultrasound wave professional skill field, be ripe, known technology, therefore not to repeat here.
This case device can also comprise higher-order of oscillation electric signal generator certainly, this higher-order of oscillation electric signal generator is connected with the other end of described higher-order of oscillation electric signal transmission cable, this higher-order of oscillation electric signal generator forms ultrasound emission mechanism together with the described annular piezoelectric element linked together with it via described higher-order of oscillation electric signal transmission cable, and the ultrasound emission power of this ultrasound emission mechanism is between 1 milliwatt and 10 watts.Adopt lower power, help avoid the described column glass-carbon electrode of damage particularly its exposed electrode face, and be conducive to avoiding interference electrochemiluminescdetection detection.
The art-recognized meanings of described higher-order of oscillation electric signal generator one word is known at ultrasound wave professional skill field.
Various higher-order of oscillation electric signal generator all has commercially available.
The structure of this case device, can also comprise some annexes, described annex such as: faint light measuring instrument, this faint light measuring instrument can be connected with described photomultiplier; And registering instrument, this registering instrument can be connected with described faint light measuring instrument.
Various faint light measuring instrument and various registering instrument all have commercially available.
Described annex is again such as: electrochemical operation station arrangement, and this electrochemical operation station arrangement can be connected with described working electrode and auxiliary electrode and contrast electrode.
This electrochemical workstation can certainly be the electrochemical workstation being integrated with faint light detection module and logging modle and data processing module.
Various electrochemical workstation all has commercially available.
Described annex is also such as: for clamping working electrode and to the electrode clamping of electrode and contrast electrode, fixed support; Etc..
Described faint light measuring instrument and the term such as described registering instrument and electrochemical operation station arrangement are expressed, and for instrumental analytical chemistry field, its art-recognized meanings is known.
Ultrasonic cavitation is the very strong effect of one, and low-frequency ultrasonic waves is comparatively strong to the surface impacts of objective workpiece, and the cavitation of this low-frequency ultrasonic waves is not too applicable to for the meticulous pick-up unit as this case; Along with the raising of ultrasonic frequency, cavitation weakens the damage of objective workpiece gradually until can ignore; Such as, the ultrasound wave of more than 100KHz may be used for the clean without wound of large scale integrated circuit; Again such as, the ultrasound wave of 1000KHz to 12000KHz may be used for human body without hindering health check-up, etc.; Therefore, the preferred ultrasonic frequency being suitable for this case device is not random frequency.
As mentioned above, for avoiding ultrasonic cavitation to the damage of the exposed electrode face of this case glass-carbon electrode, and avoid bringing out sonoluminescence, the hyperacoustic preferred frequency that this ultrasound emission mechanism launches at least should at more than 40KHz; Its scope of hyperacoustic preferred frequency that this ultrasound emission mechanism launches is between 40KHz and 12MHz.
In more meticulous aspect, for avoiding the ultrasound injury of electrode face that this case glass-carbon electrode is exposed, and, avoid more subtly bringing out sonoluminescence, this ultrasound emission mechanism launch hyperacoustic further preferred frequency at least should at more than 80KHz; Hyperacoustic further preferred its scope of frequency that this ultrasound emission mechanism launches is between 80KHz and 12MHz.
Liquid at the bottom of different electrolytic cells and different electrochemiluminescdetection detection analytic targets, different to hyperacoustic susceptibility of different capacity and frequency, for avoiding ultrasound wave to the interference analyzed, according to liquid at the bottom of concrete electrolytic cell and concrete detection analytic target, progressively can adjust, determine required ultrasonic frequency and power.
As mentioned above, for liquid at the bottom of different Electrochemiluminescprocess process detected objects and electrolytic cell, should carefully adjust, ultrasonic frequency needed for selection and power, but, when previous work is not in place, when selected ultrasonic frequency and power are not enough appropriate, to such an extent as to induce the sonoluminescence of some strength, also be not enough worried, as long as deduct blank comparison value in analyte detection process, a kind of electrogenerated chemiluminescence with the instant self-cleaning function of electrode is automatically converted under this situation of this device of this case, electrochemiluminescence double excitation is excited chemiluminescence analysis pick-up unit.
This ultrasonic energy absorber of this case is for containing the integrated interference of ultrasound wave to contrast electrode, and the current potential maintaining contrast electrode is stablized.
The poromerics in any aperture has certain absorbing high-frequency to shake the function of ripple; The preferred value of this its micropore size of micropore material of this case is less than 1.0 millimeters.
The described ultrasonic energy absorber of any wall thickness all has that certain ultrasound wave is cleared up, absorption function; This case is somebody's turn to do in pen cap shape or the preferred value of its wall thickness of ultrasonic energy absorber of test tube shape is between 0.3 centimetre and 3.0 centimetres.
Only with regard to poromerics to the absorption of higher-order of oscillation wave energy, clear up function and principle, for the professional of field of acoustics, be known.
Annular piezoelectric element miniature involved by this case, be integrated in the inside of described glass-carbon electrode precise and tinyly, and, higher-order of oscillation electric signal transmission cable is also through the internal pipeline that described hollow edged electrode overcoat holds and is connected with described micro loop piezoelectric element, for avoiding its electromagnetic wave leakage of higher-order of oscillation electric signal transmission cable to the interference of other circuit of neighbour, this structure of this case is preferred scheme further, is the surface clad silk screen screen layer at this higher-order of oscillation electric signal transmission cable.
The advantage of this case is, this case device can while carrying out Electrochemiluminescprocess process detection, utilize the ultrasound emission being positioned at endface position on the upside of column glass-carbon electrode body, through the short distance internal delivery of column glass-carbon electrode body, act on exposed electrode face and the periphery solution thereof of glass-carbon electrode, the settle accounts immediately realized for described electrode face operates, in this way, immediately the organic impurities of electrolysis oxidation-reduction reaction generation is avoided to the adsorption fouling of described electrode face, make described electrode face can remain its pure and fresh state in whole described analyte detection process, prevent the rapid decay of electrode performance.Based on the structural form of this device of this case, hyperacoustic settle accounts immediately effect can be played to greatest extent, meanwhile, this also means and with minimum power, the interference of minimum ultrasound wave, can realize the maximized settle accounts immediately effect for described electrode face.Further, its structure of the glass-carbon electrode containing adventitious sound excitation mechanism in this case device is very compact.
Another important component in this case structure, i.e. the ultrasonic energy absorber in pen cap shape or test tube shape of micropore material, it exists, and can contain the integrated interference of ultrasound wave to contrast electrode, and the current potential maintaining contrast electrode is stablized; Thus, both realized the self-cleaning running of glass-carbon electrode, do not brought additional interference again.
In addition, in view of the design feature of this case device, by the ultrasonic power of enhancing deliberately and the ultrasonic frequency being intended to bring out electrochemiluminescence of deliberately choosing simultaneously, this device of this case brings out the chemiluminogenic object of electrogenerated chemiluminescence harmony while also can serving deliberately, and in this way, carry out electricity deliberately, sound double excitation is excited chemiluminescent analytical and detecting work; And, if carry out electricity deliberately, sound double excitation be excited chemiluminescence analysis testing, so, the special construction of the glass-carbon electrode in this case device, the stimulated luminescence of electricity, sound double excitation can be made to concentrate to be resulted from a zonule, so, the photomultiplier that convenience of window size is limited is fully picked up light signal.
Accompanying drawing explanation
Fig. 1 is this case embodiment schematic diagram, the rough form of expressed the is core structure portion profile of this device.
In figure, 1 is contrast electrode, 2 is electrolytic cells, 3 is its profiles is the ultrasonic energy absorber of pen cap shape or test tube shape, 4 is working ends of glass-carbon electrode, 5 is end window type photomultipliers, 6 is the stitch holding window type photomultiplier, 7 is those exposed end faces not wrapped of column glass-carbon electrode body, 8 is annular piezoelectric elements, 9 is column glass-carbon electrode bodies, 10 is to electrode, this to electrode also known as auxiliary electrode, 11 is hollow edged electrode overcoats of the glass-carbon electrode be exposed outside, 12 is higher-order of oscillation electric signal transmission cables, 13 is binding posts of this case glass-carbon electrode.
Embodiment
In this case embodiment that Fig. 1 shows, the structure of this device comprises electrolytic cell 2, and, be installed in the photomultiplier 5 below electrolytic cell 2, this photomultiplier 5 is end window type photomultipliers, this photomultiplier 5 also can change into and use side window type photomultiplier, the installation position of this photomultiplier 5 is not limited in the below of electrolytic cell 2, installation position also can be changed into the side of electrolytic cell 2 by this photomultiplier 5, described electrolytic cell 2 is installed within magazine, magazine is not drawn in legend, and, glass-carbon electrode, the binding post 13 that this glass-carbon electrode contains column glass-carbon electrode body 9 and is connected with this column glass-carbon electrode body 9, the material of binding post 13 is metal materials, that a part of binding post 13 of this column glass-carbon electrode body 9 and this column glass-carbon electrode body 9 close is rolled in wherein by hollow edged electrode overcoat 11, the material of this hollow edged electrode overcoat 11 is macromolecule electrically insulating materials, and, to electrode 10, and, contrast electrode 1, described is sheets to electrode 10, column, cylindric or thread platinum electrode or gold electrode, described contrast electrode 1 is Ag/AgCl electrode or mercurous chloride electrode, described glass-carbon electrode and the working end of electrode 10 and contrast electrode 1 is positioned to the inside of described electrolytic cell 2, this electrolytic cell 2 is that its opening end profile is square, rectangle, the cup-shaped vessel of circular or oval indent, emphasis is, the structure of this device also comprises annular piezoelectric element 8, that end face of an end face of this annular piezoelectric element 8 and the described binding post 13 of connection of described column glass-carbon electrode body 9 combines, connect the center hole of described binding post 13 through this annular piezoelectric element 8 of described column glass-carbon electrode body 9, the entity of this annular piezoelectric element 8 is around described binding post 13, its position of the entity of this annular piezoelectric element 8 is the position between described binding post 13 and described hollow edged electrode overcoat 11, and, higher-order of oscillation electric signal transmission cable 12, one end of this higher-order of oscillation electric signal transmission cable 12 is connected with this annular piezoelectric element 8 through the pipeline of described hollow edged electrode overcoat 11 inside, and, ultrasonic energy absorber 3, this its profile of ultrasonic energy absorber 3 is pen cap shape or test tube shape, the inside of electrolytic cell 2 should be positioned in its one end closed of ultrasonic energy absorber 3 in pen cap shape or test tube shape, the inside of this ultrasonic energy absorber 3 is goed deep in described its working end of contrast electrode 1, this its material of ultrasonic energy absorber 3 is micropore material, described micropore material is micropore ceramics, fine-celled foam glass, fine-celled foam aluminium, microporous silicon rubber, expanded microporous polytetra fluoroethylene-EPTEE or micropore Kynoar.
Described micropore ceramics, fine-celled foam glass, fine-celled foam aluminium, microporous silicon rubber, expanded microporous polytetra fluoroethylene-EPTEE and micropore Kynoar etc. poromerics, all have commercially available; Selected poromerics can be bought simply cut, punching, make required form.
Annular piezoelectric element 8 in legend can be connected with higher-order of oscillation electric signal generator via higher-order of oscillation electric signal transmission cable 12, comprise this higher-order of oscillation electric signal generator and form ultrasound emission mechanism via the annular piezoelectric element 8 that higher-order of oscillation electric signal transmission cable 12 links together with it, its preferable range of ultrasound emission power of this ultrasound emission mechanism is between 1 milliwatt and 10 watts; Its preferable range of hyperacoustic frequency that this ultrasound emission mechanism launches is between 40KHz and 12MHz; The further preferred scope of hyperacoustic frequency that this ultrasound emission mechanism launches is between 80KHz and 12MHz.Arbitrary value within above-mentioned preferred value scope is all the operational parameter value that this case device allows to select; Certainly, the concrete operations parameter value of actual selection will do careful selection according to the concrete condition of concrete analysis object system.
Contrast electrode 1 comes with Ultrasonic Radiation source is completely isolated by the ultrasonic energy absorber 3 in this case structure, and contain that ultrasound wave is to the integrated interference of contrast electrode 1 thus, the current potential maintaining contrast electrode 1 is stablized.
The poromerics in any aperture has certain absorption to shake the function of ripple; Required poromerics can be selected according to used ultrasonic frequency and power.
The preferred value of this its micropore size of micropore material of this case is less than 1.0 millimeters.
The described ultrasonic energy absorber 3 of any wall thickness all has that certain ultrasound wave is cleared up, absorption function; This case is somebody's turn to do in pen cap shape or the preferred value of its wall thickness of ultrasonic energy absorber 3 of test tube shape is between 0.3 centimetre and 3.0 centimetres.
Only with regard to poromerics to the absorption of higher-order of oscillation wave energy, clear up function and principle, for the professional of field of acoustics, be known.
Annular piezoelectric element 8 miniature involved by this case, be integrated in the inside of described glass-carbon electrode precise and tinyly, and, higher-order of oscillation electric signal transmission cable 12 is also through the internal pipeline that described hollow edged electrode overcoat 11 holds and is connected with described micro loop piezoelectric element 8, for avoiding its electromagnetic wave leakage of higher-order of oscillation electric signal transmission cable 12 to the interference of other circuit of neighbour, this structure of this case is preferred scheme further, is the surface clad silk screen screen layer at this higher-order of oscillation electric signal transmission cable 12.
In this legend, do not draw higher-order of oscillation electric signal generator; The faint light measuring instrument be connected with photomultiplier is not drawn yet; Further, the registering instrument be connected with this faint light measuring instrument is not drawn; This legend does not draw the electrochemical operation station arrangement with each Electrode connection yet; The electrode clamping for clamping each electrode, fixed support is not drawn in this legend yet, etc.
The embodiment of this case device is not limited to this case figure legends.
Claims (4)
1. comprise the Electrochemiluminescprocess process pick-up unit of noiseless precise and tiny self-cleaning mechanism, the structure of this device comprises electrolytic cell, and, be installed in below electrolytic cell or the photomultiplier of side, described electrolytic cell is installed within magazine, and, glass-carbon electrode, the binding post that this glass-carbon electrode contains column glass-carbon electrode body and is connected with this column glass-carbon electrode body, the material of binding post is metal material, that a part of binding post of this column glass-carbon electrode body and this column glass-carbon electrode body close is rolled in wherein by hollow edged electrode overcoat, the material of this hollow edged electrode overcoat is macromolecule electrically insulating material, and, to electrode, and, contrast electrode, described is sheet to electrode, column, cylindric or thread platinum electrode or gold electrode, described contrast electrode is Ag/AgCl electrode or mercurous chloride electrode, described glass-carbon electrode and the working end of electrode and contrast electrode is positioned to the inside of described electrolytic cell, this electrolytic cell is that its opening end profile is square, rectangle, the cup-shaped vessel of circular or oval indent, it is characterized in that, the structure of this device also comprises annular piezoelectric element, that end face of an end face of this annular piezoelectric element and the described binding post of connection of described column glass-carbon electrode body combines, connect the center hole of described binding post through this annular piezoelectric element of described column glass-carbon electrode body, the entity of this annular piezoelectric element is around described binding post, its position of the entity of this annular piezoelectric element is the position between described binding post and described hollow edged electrode overcoat, and, higher-order of oscillation electric signal transmission cable, one end of this higher-order of oscillation electric signal transmission cable is connected with this annular piezoelectric element through the pipeline of described hollow edged electrode jacket internal, and, ultrasonic energy absorber, this its profile of ultrasonic energy absorber is pen cap shape or test tube shape, the inside of electrolytic cell should be positioned in its one end closed of ultrasonic energy absorber in pen cap shape or test tube shape, the inside of this ultrasonic energy absorber is goed deep in its working end of described contrast electrode, this its material of ultrasonic energy absorber is micropore material, described micropore material is micropore ceramics, fine-celled foam glass, fine-celled foam aluminium, microporous silicon rubber, expanded microporous polytetra fluoroethylene-EPTEE or micropore Kynoar, and, higher-order of oscillation electric signal generator, this higher-order of oscillation electric signal generator is connected with the other end of described higher-order of oscillation electric signal transmission cable, this higher-order of oscillation electric signal generator forms ultrasound emission mechanism together with the described annular piezoelectric element linked together with it via described higher-order of oscillation electric signal transmission cable, the ultrasound emission power of this ultrasound emission mechanism is between 1 milliwatt and 10 watts, hyperacoustic frequency that this ultrasound emission mechanism launches is between 80KHz and 12MHz.
2. the Electrochemiluminescprocess process pick-up unit comprising noiseless precise and tiny self-cleaning mechanism according to claim 1, is characterized in that, this its micropore size of micropore material is less than 1.0 millimeters.
3. the Electrochemiluminescprocess process pick-up unit comprising noiseless precise and tiny self-cleaning mechanism according to claim 1, is characterized in that, should be that its wall thickness of ultrasonic energy absorber of pen cap shape or test tube shape is between 0.3 centimetre and 3.0 centimetres.
4. the Electrochemiluminescprocess process pick-up unit comprising noiseless precise and tiny self-cleaning mechanism according to claim 1, it is characterized in that, this its Surface coating of higher-order of oscillation electric signal transmission cable has wire gauze screen layer, this wire gauze screen layer, for containing its electromagnetic wave leakage, prevents it to the interference of other circuit of neighbour.
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| CN201210141891.3A CN102645465B (en) | 2012-04-23 | 2012-04-23 | Electrochemiluminescence analysis and detection device with interference-free precise self-cleaning mechanism |
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| CN102645465B true CN102645465B (en) | 2015-04-08 |
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| CN113433116B (en) * | 2021-06-25 | 2022-12-20 | 中国科学院长春应用化学研究所 | Stainless steel ultrasonic sheet chemiluminescence solution detection device and application method thereof |
| CN114689662B (en) * | 2022-05-31 | 2022-09-02 | 山东省科学院海洋仪器仪表研究所 | Self-cleaning electrode type conductivity sensor |
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| WO2006007533A1 (en) * | 2004-07-01 | 2006-01-19 | Tracedetect, Inc. | Method for ultrasonic cleaning of a working electrode in electrochemical cell useful for automated trace metals measurement |
| CN101162199A (en) * | 2007-11-19 | 2008-04-16 | 福州大学 | Heat controlled electric pole electrogenerated chemiluminescence testing apparatus and testing-pool preparation method |
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|---|---|---|---|---|
| US3680841A (en) * | 1969-10-23 | 1972-08-01 | Yokogawa Electric Works Ltd | Liquid characteristic measuring instrument |
| JPS5431717B2 (en) * | 1971-10-21 | 1979-10-09 | ||
| US4033830A (en) * | 1976-03-17 | 1977-07-05 | The Foxboro Company | On-line amperometric analysis system and method incorporating automatic flow compensation |
| GB1581291A (en) * | 1976-12-09 | 1980-12-10 | Kkf Corp | Sensor device |
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| CN101162199A (en) * | 2007-11-19 | 2008-04-16 | 福州大学 | Heat controlled electric pole electrogenerated chemiluminescence testing apparatus and testing-pool preparation method |
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