CN1811397A - Structure of electrochemical sensing test block and producing method thereof - Google Patents

Structure of electrochemical sensing test block and producing method thereof Download PDF

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CN1811397A
CN1811397A CN 200610009303 CN200610009303A CN1811397A CN 1811397 A CN1811397 A CN 1811397A CN 200610009303 CN200610009303 CN 200610009303 CN 200610009303 A CN200610009303 A CN 200610009303A CN 1811397 A CN1811397 A CN 1811397A
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electrode
metal
heat insulating
insulating lamella
hole
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CN100432660C (en
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黄椿木
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Abstract

The present invention relates to a disposable electrochemical sensing test block, its structure and preparation method. Said structure includes the following several portions: an insulating thin sheet which has at least a through hole and at least a conductive material said conductive material is placed in said through hole; a metal film which is used for covering said conductive material to synthesize an electrode, said electrode has an electrode action face and an electrode connecting face, said electrode action face can be used for producing electrode action; and at least a printing conductive strip which is mounted on said insulating thin sheet, and has a conductive strip connecting end and a signal output end, said conductive connecting end is electrically connected to the electrode connecting face, and said signal output end can be used for outputting a measuring signal produced by said electrode action.

Description

Structure of electrochemical sensing test block and preparation method thereof
The application be in the application number that on May 7th, 2003 submitted to be 03130909.7, denomination of invention divides an application for " structure of electrochemical sensing test block and preparation method thereof ".
(1) technical field
The present invention is the continuity of No. the 92100279th, the patent of preceding application.Should preceding patent be with the electrode of plastic cement conducing composite material with plastic rubber ejaculate molding mode moulding one sensing test piece, and the present invention continue this patent structure<but changed manufacture method, to make a kind of deserted sensing test piece with metal electrode (Metal Electrode).The present invention is the manufacture method and the structure thereof of the metal electrode (Metal Electrode) of especially a kind of sheet type test piece of a kind of electrochemical sensing test block (Electrochemical Sensor Strip) (Sheet Type Strip), it is applicable to the composition that certain analyte in the fluid measured is treated in test one, as the concentration of the blood sugar in the testing human blood, uric acid.
(2) background technology
Generally use noble metal can obtain the detection quality of a high stable and high repeatability as the electrode material of electrochemical sensor, be the known techniques of electrochemical field, but really need use the just surface area of electrode of noble metal characteristic on the sensor, the precious metal material of other areas is unnecessary, especially a deserted test piece is all waste in the noble metal beyond the electrode area.According to the metal electrode of purpose of the present invention for providing, it is except that can be applicable to not have the inert metal electrode of chemical interference demand, and it also can be used in various metal catalytic electrodes with direct catalysis<be not limited to inert metal 〉.Deserted electrode and the sensor made according to the present invention are applicable to the detection test piece (detecting test piece as blood sugar, uric acid, cholesterol etc.) of various electric chemical formula detecting electrode, biological sensor, fluid biochemical component sensor (becoming to grade to detect test piece as sewage, pesticide concentration, heavy metal), various house medical applications.
The principle of electrochemical sensor (Electrochemical Sensor), the biochemical component that has been applied to various fluids recent decades by maturation detects, and the equipment of the Electrochemical Detection in the control laboratory of a laboratory or specialty, because of different checking function demands can have different outfits.See also first figure, its basic framework that demonstrates an electrochemical detection device 10 is:
1. ccontaining one treats that one of fluid measured 11 takes up container 12, thinks that electrochemical one measures zone 13.
2. a chemical reagent (Reagent) 14 is used for and treats that an analyte of fluid measured 11 produces a chemical action, and produces the output signal of an electrical parameter, and the output valve of this electrical parameter is relevant with the biochemical component of this analyte for the treatment of fluid measured 11.For example treat that fluid measured 11 is people's blood, analyte is the concentration of blood candy, and then this chemical reagent 14 is essentially and can be a glucose oxidase and other compounds.
3. two to three test electrodes, be meant pair of electrodes (Counter Electrode) as label 15,16 is a working electrode (Working Electrode), 17 is a reference electrode (Reference Electrode), being used for the operating voltage that an electrochemical action is required is drawn by a meter 18 and is connected to chemical reaction container 12, and will treat this analyte this electrical parameter output signal electric current after an electrochemical action of fluid measured 11, draw and be connected to meter 18 and do a numerical analysis and demonstrations.
4. the galvanochemistry meter 18, and the operating voltage (or electric current) that provides this electrochemical action required is provided, and measure the output signal electric current (or voltage) of this electrical parameter after this electrochemical action, make a record with this numerical analysis and show test data.
Test electrode 15,16,17 wherein can only use two electrodes, and it is to electrode (CounterElectrode) and working electrode (Working Electrode).Maybe can use three electrodes, except that working electrode and to the electrode, another is reference electrode (Reference Electrode).Maybe can add the detecting electrode (Detecting Electrode) more than the 4th, because of the different adjustable different electrode numbers of electrochemical action demand.
Except the difference of electrode number, different because of different electrode function (as the difference of counter electrode) and sensor chemical reaction composition with respect to working electrode, each electrode material selected very large variation for use.The general electrode material in laboratory is as follows, wherein to electrode 15 (Counter Electrode) material so long as the conduction material get final product, but conductive resistance is low more good more,, graphite rod excellent as copper rod, silver rod, nickel or with carbon paste or the printed and formed conducting film electrode of elargol.Certainly noble metals such as gold, platinum also can be used for when to electrode material, are the material cost height.Wherein the material of reference electrode 17 (Reference Electrode) is the most frequently used is one silver medal/silver chloride correction electrode (Modified Electrode) 171, because of the galvanochemistry operating potential of silver chloride highly stable, thereby by widely with being reference electrode.
Wherein the electrode material of working electrode 16 (Working Electrode) select for use more complicated, it has two general orientation, the first kind is for utilizing the vectorial correction working electrode of electron transfer (Electron-TransferMediator Modified Working Electrode), and second class is metal catalytic electrode (Metal-Catalyzed Electrode).It solidifies (immobilized) one deck chemical reagent on the vectorial electrode of first kind electron transfer, in this chemical reagent, contain a kind of enzyme (Enzyme) as a glucose oxidase (Glucoseoxidase) and a redox reaction electron mediator (Redox Mediator), as one of the medium (Madiator) that is widely used in blood glucose test is time blood salt (potassium ferricyanide), enzyme and test analyte (or consume) a certain new chemical constitution (as producing H2O2) of deriving behind chemical reaction is utilized this electron mediator and H again 2O 2Oxidation-reduction process in the electronics that discharged and produce an electrical signals, and export its electrical measurement parameters via electrode, the purpose of this type of working electrode is only as the conduction function, do not have the chemical catalysis function, but it selects electrode material to produce a self-chemical action and to disturb the measurement accuracy with treating fluid measured 11 or chemical reagent 14 for use.
This electrode material that does not have the chemistry interference is necessary for an inactive, conductive material, be generally the electrode of inert metal noble metal (Noble Metal) (as metals such as gold, platinum, palladium, rhodiums) or carbon containing material, as carbon film print electrode (Carbon Base Screen Printing Electrode), graphite rod (Graphite Bar).Because of carbon and inert metal can not chemically react at low temperatures, disturb so can not produce chemistry.Because of noble metal cost height, so the working electrode of the correction working electrode of electron-like medium transfer thing (Electron-Transfer Mediator Modified WorkingElectrode) is generally all selected carbon electrode for use.
Metal catalytic electrode (Metal-Catalyzed Electrode) as for second class, its working electrode material of selecting for use can directly produce electrochemical action with chemical reagent or analyte or derivatives thereof, and direct catalytic action is arranged or analyte is had the function of single selective, therefore do not need in chemical reagent, to add again electron transfer medium (Mediator).This has the electrode material of direct catalytic action, be generally the metal electrode that contains metal ingredient, the electrode of first kind can not be fit to any analyte so long as there is the conductive electrode of chemistry interference, but this type of has the electrode of direct catalytic action, the material that needs to have matching each other with analysans and chemical reagent just can have the catalysis function, so different analytes need be selected different metal electrode material for use, this type of electrode material is not limited to inert metal, its material such as copper, titanium, nickel, gold, platinum, palladium, rhodium ... on metal (as rhodium electrode to H 2O 2Splendid direct catalytic action is arranged).The electrode that above-mentioned Electrochemical Detection is used can be not limited to the inertia noble metal electrode and second class can be various metal electrodes with carbon-containing electrode or inert metal electrode in the first kind.
The used metal electrode of this two class is all high in two costs of its material of traditional method for making and processing procedure, especially the cost of inertia noble metal electrode is higher, though thereby its have quality stability preferably and still can't become the main flow that the medical treatment of deserted house detects examination.The electrochemical sensing device is in maximum use amount now, be deserted detection thin slices such as the blood sugar of house medical applications, uric acid, cholesterol, its most commodity belong to the aforementioned first kind for utilizing the vectorial correction working electrode of electron transfer (Electron-Transfer Mediator ModifiedWorking Electrode), therefore the class electrode can print electrode and obtains lower cost with carbon film, this type of representative instance is as being the 5th of the U.S., 985, No. 116 patents.
Be illustrated in figure 2 as United States Patent (USP) the 5th, 997, No. 817, the commercial prod of this patent is with two same sizes and lining<Coating all〉 bonding jumper 201 and 202 of one deck precious metal palladium is fixed on the heat insulating lamella 203 with the metal electrode as its sensor with glue, working electrode 204<Working Electrode of this sensor 〉, to electrode 205<Counter Electrode 〉, electrode lead wire 206 and 207<Lead 〉, signal output part 208 and 209<Output Terminal〉etc. complete in identical palladium metal bar moulding, the consumptive material of precious metal palladium is bigger, but its working electrode 204 that has only that really need use precious metal palladium material characteristic reaches electrode 205 these two segments, surplus person is as long as conduct electricity, and it need not use the characteristic of precious metal palladium.
Figure 3 shows that European EP1,098, No. 000 patent, it is the manufacture of another metal electrode, it is plastic rubber ejaculate molding one heat insulating lamella 301 in advance, have by recess<Recess on its heat insulating lamella〉with division island<Island the 306 electrode pattern<Pattern that surrounded 302 and electrode lead wire<Lead 303 and the position of output terminal 304 and 305, utilize precipitated metal method<Metallic Deposits〉with the evaporation of metal postprecipitation on the plastic cement heat insulating lamella, can be covered in the surface of full wafer heat insulating lamella because of the metal level of precipitation, need to process again the metal level that removes on the division island, only stay this metal electrode pattern, electrode lead wire and output terminal.The processing cost height of this method, and only suitable whole electrode materials are the situation with a kind of metal.
Cost of manufacture for the metal electrode that reduces deserted sensor test piece, to overcome the problem of waste precious metal material, just need a kind of structure and method for making of electrochemical sensing test block, except the shortcoming of the waste precious metal material of the previous metal electrode of effective solution, also can make variant metal electrode on the sensor can in variant coating bath, carry out a kind of a large amount of manufacturing in advance respectively and also can revise the modification level that (Modify) finish electrode in advance in a large number after be assembled to again on the heat insulating lamella, it can shorten one when having the worker of metal electrode sensing test piece.
(3) summary of the invention
Purpose of the present invention is the method for making and the structure of metal electrode that a deserted cheaply galvanochemistry test piece is provided, can be widely the use amount of noble metal is reduced and reduces cost.
Fundamental purpose of the present invention is to utilize being formed on the conduction material an of metallic film, with the use amount of the noble metal that reduces metal electrode.
Another object of the present invention is after making metal electrodes in advance in a large number and revising (Modify) this electrode, this metal electrode to be installed in the through hole of a heat insulating lamella again, makes the required time of this deserted sensing test piece significantly to shorten.
A further object of the present invention is to use a metal electrode to be installed in the through hole of heat insulating lamella, this via area is the action face of this electrode and amasss, when a large amount of production, can obtain a precise and stable electrode area, because of sensing tolerance side signal magnitude is directly proportional with electrode area, so the repeatability accuracy (Reproducibility) that the present invention can make the electrochemical sensing tolerance survey signal can significantly promote.
Another purpose of the present invention is the trip of utilization on one heat insulating lamella, fixes on this heat insulating lamella on a measuring instrument with the footpath row.
The present invention is structure of a kind of electrochemical sensing test block (Electrochemical Sensor Strip) and preparation method thereof, its structure comprises a heat insulating lamella, it has at least one through hole, at least one conduction material (Conductive Raw Material), it is installed in this through hole, one metallic film, cover on this conduction material with a synthetic electrode, and this electrode has an electrode acting surface and an electrode interface, to utilize this electrode acting surface to produce an electrode effect, and at least one printing conductive bar, it is installed on this heat insulating lamella, and have a bus cohesive end and a signal output part, and this bus cohesive end is electrically connected to this electrode interface, and this signal output part is then in order to export the measurement signal that this electrode effect produces.
The preferably, the conduction material of this sensing test piece is to be a metal, and synthesizes a metal electrode with this metallic film.
The preferably, this sensing test piece also comprises a kind of chemical reagent, it is arranged on this electrode acting surface, in order to detect certain analyte in the fluid sample, this chemical reagent promptly with the reaction of a composition of this fluid sample, and then produce a measurement signal, and through this signal output part to export this measurement signal.
Certainly, the electrode of this sensing test piece is to form an electrode area in this through hole, to transmit this measurement signal.
Through hole on preferably, the present invention can plastic cement ejecting devices, a press molding equipment or a computer drilling equipment are shaped this heat insulating lamella.
Preferably, the present invention insert this electrode in this through hole with a machinery processing apparatus after can be earlier finishing through hole on this heat insulating lamella with this plastic cement ejecting device again.
The preferably, the present invention can insert electrode in one plastic injecting mold in advance, the plastic material that reinjects in this plastic injecting mold with this heat insulating lamella that is shaped, its simultaneously with this electrode with " plastic cement penetrate encase " in this through hole.
Certainly, this sensing test piece also comprises an insulation course, in order to be covered on this printing conductive bar.
The preferably, the material of the metallic film of this sensing test piece is to be a gold, platinum, rhodium, palladium, ruthenium, iridium, silver, copper, nickel, titanium, chromium, iron or aluminium.
The preferably, the material of the conduction material of this sensing test piece is the plastic cement material of handling for a conducting metal, a carbon containing conductive material or a conduction lining.
Certainly, the metallic film of this sensing test piece can utilize a plating, an immersion plating, a precipitated metal or a spray metallic paint device to be covered on the conduction material, and this electroplanting device has taken up a plating bath, and this plating bath has a metallic ion, to form this metallic film.
Certainly, the conduction material of this sensing test piece can be circle, rectangle or annular, and has the thickness of 0.2~3.0mm, and the preferably is 0.5mm.
The preferably, the metallic film of this sensing test piece is to be a foil, and utilizes a bronze printing to belong to the cream device to be covered on this conduction material.
See according to the enforceable viewpoint of another kind, a kind of electrochemical sensing test block of the present invention, it comprises a heat insulating lamella, and it has at least one through hole, at least one conduction material, it is installed in this through hole, and a metallic film, cover on this conduction material with a synthetic electrode, and this electrode has an electrode acting surface and a signal output part, to utilize this electrode acting surface to produce an electrode effect, this signal output part is then in order to export the measurement signal that this electrode effect produces.
The preferably, this sensing test piece also comprises a web, it is installed on this heat insulating lamella, and this sheet metal has an electrode convergence hole, to be connected a riveted joint salient point of this electrode.
From the another one angle, a kind of electrochemical sensing test block of the present invention, it comprises a heat insulating lamella, it has at least one recess, at least one metal electrode, it is installed in this recess, and this metal electrode has an electrode acting surface and a signal output part, to utilize this electrode acting surface to produce an electrode effect, this signal output part is then in order to export the measurement signal that this electrode effect produces.
Certainly, this sensing test piece can also comprise a bus, and this bus is to be formed in one with this metal electrode, in this recess that places this heat insulating lamella.
Certainly, this sensing test piece can also comprise a modification level, and it solidifies on this metal electrode, revises electrode to form one.
The preferably, this thin slice is the metal electrode that includes a pair of electrodes and a working electrode, it is arranged at respectively in two through holes of this heat insulating lamella, produces this electrode effect.
The preferably, this thin slice is the metal electrode that includes pair of electrodes, a working electrode and a reference electrode, it is arranged at respectively in three through holes of this heat insulating lamella, produces this electrode effect.
Certainly, the working electrode of this sensing test piece has one " U " tee section, on one " U " shape recess that is installed in this heat insulating lamella.
Certainly, this sensing test piece can comprise a pair of electrodes and a working electrode, and this is formed one to print electrode on this heat insulating lamella to print a conductive paste to electrode, and this working electrode then is installed in the metal electrode in this through hole on this heat insulating lamella.
Certainly, this sensing test piece comprises pair of electrodes, a reference electrode and a working electrode, and this all is that printing one conductive paste formed one prints electrode on this heat insulating lamella to electrode and this reference electrode, and this working electrode then is installed in the metal electrode in this through hole on this heat insulating lamella.
Certainly, this sensing test piece can also comprise a metallic film, and this metallic film and this metal electrode are formed in one.
As viewpoint according to Another application, a kind of electrochemical sensing test block of the present invention, it comprises a heat insulating lamella, it has at least one through hole, at least one metal electrode, it is installed in this through hole, and this metal electrode has an electrode acting surface and an electrode interface, to utilize this electrode acting surface to produce an electrode effect, and at least one printing conductive bar, it is installed on this heat insulating lamella, and has a bus cohesive end and a signal output part, this bus cohesive end is electrically connected to this electrode interface, and this signal output part is then in order to export the measurement signal that this electrode effect produces.
The preferably, the metal electrode of this sensing test piece is to be a copper electrode.
If from another suitable aspect, a kind of electrochemical sensing test block of the present invention, it comprises a heat insulating lamella, it has at least one through hole, and at least one metal electrode, it is installed in this through hole, and this metal electrode has an electrode acting surface and a signal output part, to utilize this electrode acting surface to produce an electrode effect, this signal output part is then in order to export the measurement signal that this electrode effect produces.
The preferably, this sensing test piece also comprises a bus, and this bus is to be formed in one with this metal electrode, in a recess that places this heat insulating lamella.
Certainly, this sensing test piece comprises pair of electrodes, a reference electrode, a working electrode, first-class body examination examination recess and an overlayer, and this all is formed one to print electrode on this overlayer to print a conductive paste to electrode and this reference electrode, and this working electrode then is installed in the metal electrode in this through hole on this heat insulating lamella.
Certainly, the heat insulating lamella of this sensing test piece can have three through holes, and holding three electrodes, and this heat insulating lamella has a trip, and to put this thin slice on a measuring instrument, this trip promptly is fixed in the draw-in groove of this measuring instrument.
The preferably, respectively this electrode of this sensing test piece has a signal output contact, is connected point with a signal that connects this measuring instrument.
From another one technology kenel, the manufacture method of a kind of electrochemical sensing test block of the present invention, it comprises the steps: to provide a heat insulating lamella, it has at least two recesses, preparation one conduction material group, and it has at least one first and one second conduction material, at least revise and finish this first conduction material, revise electrode to form one, and put this corrections electrode and this second conduction material in this two recess, with this deserted chemical sensing test piece of formation.
The preferably, this sensing test piece also comprises a galvanizing process, is to form a metallic film in this first conduction material, to obtain this correction electrode.
The preferably, this sensing test piece also comprises the program curing of a chemical reagent, to obtain an enzyme electrode.
The preferably, this sensing test piece also comprises a print routine, in order to printing at least one bus forming at least one signal output part, and is electrically connected this signal output part that outputs signal to of this electrode.
The present invention is the manufacture method and the structure of a deserted detection thin sheet of metal electrode, and it comprises the inert metal electrode of the nothing chemistry interference that is applicable to that first kind electron transfer media correction electrode is used and second metalloid catalysis electrode (being not limited to inert metal).The patented invention of deserted sensor with metal electrode is very many, and its major requirement is for can obtain preferable quality stability.The invention provides a kind of method for making and structure of metal electrode cheaply, it not only can be applicable to not have the inert metal electrode of chemical interference demand, or have various metal catalytic electrodes of direct catalysis, more because of metal electrode cost of manufacture of the present invention is extremely low, so it can be fit to reference electrode simultaneously and to the making of electrode.
Electrode structure of the present invention in addition, it is long-pending to obtain a point-device electrode face, the present invention is directly proportional because of the measurement electric current of electrochemical sensing device and electrode face are long-pending, so can make the repeatability accuracy (Reproducibility) of electrochemical sensing tolerance survey signal significantly promote.
The present invention is via the explanation of above-mentioned conception, can observe the structure and the method for making of the electrochemical sensing test block that is used, really can utilize being formed on the conduction material of a metallic film, use amount with the noble metal that reduces metal electrode, and have in the through hole that is installed in heat insulating lamella that uses a metal electrode, make this deserted sensing test piece characteristic of required time significantly to shorten.
In order to be easy to explanation, the present invention can obtain one by following preferred embodiment and diagram and more clearly understand.
(4) description of drawings
Fig. 1 is the schematic perspective view of the electrochemical detection device of prior art;
Fig. 2 is that the solid of the deserted metal electrode sensor of another prior art is decomposed front schematic view;
Fig. 3 is the schematic perspective view of another prior art with the deserted metal electrode sensor of precipitated metal manufactured;
Fig. 4 (a)-(d) is the three-dimensional front schematic view of the preferred embodiment of the unipolar structure of electric chemical formula thin slice sensor of the present invention, three-dimensional schematic rear view, the three-dimensional schematic perspective view that decomposes front schematic view and a conduction material coating one metallic film;
Fig. 5 (a)-(b) is the three-dimensional front schematic view and the three-dimensional front schematic view of decomposing of another preferred embodiment of the unipolar structure of electric chemical formula thin slice sensor of the present invention;
Fig. 6 (a)-(c) is the three-dimensional front schematic view of another preferred embodiment of the unipolar structure of electric chemical formula thin slice sensor of the present invention, three-dimensional schematic rear view and the three-dimensional schematic rear view that decomposes;
Fig. 7 (a)-(b) is the solid of another preferred embodiment of the unipolar structure of electric chemical formula thin slice sensor of the present invention front schematic view and the solid schematic rear view that pops that pops;
Fig. 8 (a)-(b) is the structural upright front schematic view and the three-dimensional front decomposing schematic representation of of the present invention one unipolar correction electrode;
Fig. 9 is the three-dimensional front schematic view of the application example behind combination single electrode of the present invention and the correction electrode;
Figure 10 (a)-(b) is the three-dimensional front schematic view and the three-dimensional front decomposing schematic representation of another preferred embodiment of the structure of electric chemical formula thin slice sensor bipolar electrode of the present invention;
Figure 11 (a)-(b) is the three-dimensional front schematic view and the three-dimensional front decomposing schematic representation of another preferred embodiment of the three electrode structure of electric chemical formula thin slice sensor of the present invention;
Figure 12 is the three-dimensional front schematic view of the application example of a slice three electrode detection thin slices of the present invention;
Figure 13 (a)-(d) is the schematic perspective view of a metallic film in three-dimensional front schematic view, three-dimensional schematic rear view, three-dimensional front decomposing schematic representation and the conduction material correction of a preferred embodiment of the thin slice sensor with capillary channel (be applicable to detect micro fluid sample) of the present invention;
Figure 14 detects the three-dimensional front schematic view of the application example of thin slice and measuring instrument combination for the present invention;
Figure 15 (a)-(c) is three-dimensional front schematic view, three-dimensional front decomposing schematic representation and the three-dimensional back side decomposing schematic representation of another preferred embodiment of another three electrode structure of electric chemical formula thin slice sensor of the present invention;
Figure 16 (a)-(c) is three-dimensional front schematic view, three-dimensional front decomposing schematic representation and the three-dimensional back side decomposing schematic representation of another preferred embodiment of another three electrode structure of electric chemical formula thin slice sensor of the present invention;
Figure 17 (a)-(b) is the three-dimensional schematic rear view and the three-dimensional front decomposing schematic representation of a preferred embodiment of the thin slice sensor with capillary channel (be applicable to detect micro fluid sample) of the present invention; And
Figure 18 (a)-(d) is the three-dimensional front schematic view that the three-dimensional front schematic view of another preferred embodiment of thin slice sensor of the present invention, three-dimensional front decomposing schematic representation, three-dimensional schematic rear view and the embodiment of the invention are connected to the combination of a measuring instrument.
(5) embodiment
See also Fig. 4 (a)-(c), be to detect thin slice for a single electrode, demonstrate the structure of a kind of electrochemical sensing test block of the present invention, it comprises a heat insulating lamella 40 (also can be described as an insulating substrate), it has at least one through hole 402, at least one conduction material 403, it is installed in the through hole 402, one metallic film 404, cover on the conduction material 403 with a synthetic electrode 411, and electrode 411 has an electrode acting surface 409 and an electrode interface 408, in order to produce the electrode effect usefulness of an electrode (promptly as) with electrode acting surface 409, and at least one printing conductive bar 410, it is installed on the heat insulating lamella 401, and have a bus cohesive end 405 and a signal output part 406, and bus cohesive end 405 is electrically connected to electrode interface 408, and signal output part 406 is then in order to export the measurement signal that this electrode effect produces.
The conduction material 403 of this sensing test piece can be a kind of metal, and synthesizes metal electrodes 411 with metallic film 404.This sensing test piece also comprises a kind of chemical reagent 414, it is arranged on the electrode acting surface 409 of metal electrode 411 to form an enzyme electrode 413, in order to detect certain analyte in the fluid sample, chemical reagent 414 promptly with the reaction of a composition of this fluid sample, and then produce a measurement signal, and through signal output part 406 to export this measurement signal.The electrode 411 of this sensing test piece can form an electrode area 412 in through hole 402, to transmit this measurement signal.That is heat insulating lamella 401 has a through hole 402 at least, one metallic film 404 is covered on the conduction material 403 and synthesizes a metal electrode 411, put metal electrode 411 and in through hole 402, form close-fitting, the side that through hole 402 tightly encases metal electrode 411 makes it expose an electrode acting surface 409 and connects face 408 with electrode, produces an electrode effect to utilize this electrode acting surface 409.
And print a bus 410 on heat insulating lamella 401, and have a bus cohesive end 405 and a signal output part 406, bus cohesive end 405 is electrically connected to electrode interface 408, and signal output part 406 is then in order to export the measurement signal that this electrode effect produces.The signal output part 406 of printing conductive bar 410 is only exposed at the back side that one insulation course 407 is coated on heat insulating lamella 40, and it is used to isolate treats that fluid measured contacts with any conducting position beyond the electrode acting surface 409, in order to avoid influence accuracy in detection.
The final electrode material of present embodiment is this metallic film 404, its material can be gold, platinum, rhodium, palladium, ruthenium, silver, copper, nickel, titanium, aluminium, iron, etc.Selecting for use of material 403 of conduction need be beneficial to metallic film 404 and can be closely as one, the plastic cement material that its material can be any conducting metal or any carbon containing conductive material or handles through the conduction lining.
The method that metallic film 404 is coated on the conduction material can be plating, immersion plating, precipitated metal method, spray metallic paint etc.Conduction material 403 can first receiving through-hole after coated metal film 404 again, conduction material 403 also can first coated metal film 404 after again in the receiving through-hole 402.The best flow process of present embodiment plates behind the noble metal film 404 in the receiving through-hole 402 in the mode of a large amount of plating (also be about to many conduction materials 403 be placed in same coating bath interior) for conduct electricity material 403 earlier again.The material of conduction material 403 is to be copper or its alloy, and as brass, oxygen-free copper, bronze, phosphor-copper, foreign copper-nickel alloy, beryllium copper, this copper metal is easy to each electrode shape of moulding, and it is suitable to electroplate correction metallic film 404 on the supervisor to have electric conductivity again.The material of conduction material 403 can be carbon containing plastic cement conducing composite material, and this contains the shape of carbonaceous conductive material 403 with the moulding of plastic rubber ejaculate molding mode, and this carbon containing plastic cement conducing composite material has electric conductivity and is suitable for electroplating this metallic film of correction on the supervisor.
" plastic cement plating " has been a kind of very ripe prior art at present, it is the shape of this non-conductive plastic cement material 403 of mode moulding of plastic cement material ejection formation generally, one deck conductive layer that is covered again on the plastic cement material can carry out the plating of metal film 404, generally can plate desired upper strata metallic film 404 again after as bottom plating one deck nickel on the former plastic cement material earlier.The printing conductive cream material of printing conductive bar 410 can be the conducting resinl of arbitrary or its mixing of a kind of carbon containing, silver, copper, nickel, aluminium, gold, stainless steel.The material of heat insulating lamella 401 can adopt a kind of polyvinylchloride (polyvinyl chloride), polypropylene PP (polypropylene), polycarbonate (polycarbonate), poly terephthalic acid butenylidene ester PBT (polybutylene Terephthalate), polyethylene terephtalate (polyethyleneTerephthalate), inferior benzene PPO (modified polyphenlene oxide) of polyoxygenated or acrylonitrilebutadienestryrene resin/ABS plastic resins such as (acrylonitrile butadiene stytene).The thickness of heat insulating lamella 401 can be 0.2mm-3.0mm.Conduction material 403 can be circle, rectangle or annular, the few 0.00mm-0.15mm of the thickness of the comparable heat insulating lamella 401 of its thickness.The metallic film 404 that is covered in electrode 411 can be gold, and the metallic film 404 that is covered in 411 electrodes can change silver into, and behind treated one deck silver chloride layer to form one silver medal/silver chloride reference electrode.And the metallic film 404 that is covered in electrode 411 also can be platinum, or the metallic film 404 that is covered in electrode 411 can be rhodium metal.The metallic film 404 that is covered in electrode 411 can be palladium metal, and the metallic film 404 that is covered in electrode 411 can be the ruthenium metal.Certainly, the metallic film 404 that the conduction material 403 of electrode 411 can be copper metal and this covering also is the copper metal, and meaning is that this electrode 411 is a fine copper metal electrode.
Through hole 402 on the heat insulating lamella 401 can pass through a plastic cement ejecting device, a press molding equipment or a computer drilling equipment and be shaped on heat insulating lamella 401.As adopting the mode that electrode 411 is placed through hole 402, can be earlier with this plastic cement ejecting device, this press molding equipment or this computer drilling equipment shaping through hole 402 after on the heat insulating lamella 401, insert electrode 411 in this through hole with a machinery processing apparatus again and form close-fitting.In addition, can make in advance electrode to be inserted in the plastic injecting mold in " plastic cement penetrate encase " mode, the plastic material that reinjects, and encases this electrode in this through hole with this heat insulating lamella that is shaped simultaneously in this plastic injecting mold.
See also Fig. 5 (a)-(b), be to detect thin slice for a single electrode, one heat insulating lamella 501 has a through hole 502 at least, one conduction material 503 is placed in the through hole 502 and forms close-fitting, one metallic film 504 is covered on the end face 509 of conduction material 503 and synthesizes a metal electrode (this moment conduction material 503 be a kind of metal or carbon containing plastic cement conducing composite material), this metal electrode has an electrode acting surface 504 and electrode interface 508, in order to producing an electrode effect with electrode acting surface 504, and print a bus 510 on heat insulating lamella 501, and have a bus cohesive end 505 and a signal output part 506, bus cohesive end 505 is electrically connected to electrode interface 508, signal output part 506 is then in order to export the measurement signal that this electrode effect produces, label 507 expressions one insulation course.The method of conduction on the material 503 that be coated on of metallic film 504 can be plating, immersion plating, precipitated metal method, spray metallic paint or bronze printing and belongs to cream etc.
As according to the enforceable viewpoint of another kind, printing conductive bar 410 among Fig. 4 is can be substituted, see also Fig. 6 (a)-(c), be to detect thin slice for a single electrode, the embodiment of Fig. 6 replaces the type metal bar 410 of Fig. 4 embodiment with a web 606, this web 606 has a signal output part 608 and a bus convergence hole 607, this conduction cylindrical void 607 is electrically connected to one on the metal electrode 603 riveted joint salient point 604 exporting the measurement signal of this electrode, and label 605 is meant the electrode acting surface.Electrode is a pure nickel metal electrode, and this electrode can also be a pure iron metal electrode.
If from the another one angle, conduction material 403 among Fig. 4 can change a kind of conduction material of simple metal into, to form a metal electrode, and has a recess to contain through hole and metal conductive strips, see also Fig. 7 (a)-(b), be to detect thin slice for a single electrode, the embodiment of Fig. 7 replaces the web 606 and metal electrode 603 of Fig. 6 embodiment with integrated bonding jumper 703, bonding jumper 703 has an electrode face 704, electrode lead wire 705 and signal output part 706 (this sheet metal 703 can a plastic cement conductive material emission forming device or the metal stamping device with electrode face 704, electrode lead wire 705 and signal output part 706 are integrally formed and get, be different with the mode of the printing conductive bar 410 of Fig. 4), heat insulating lamella 701 has a through hole 702 and a recess 707 (recess) to put sheet metal 703 and to form close-fitting.And the program of covering layer of metal film (on the figure and do not show) on bonding jumper 703, can just insert in the through hole 702 of heat insulating lamella 701 after on bonding jumper 703 in covering earlier this metallic film, cover this metallic film again after also can earlier bonding jumper 703 being inserted the through hole 702 of heat insulating lamella 701.
See also Fig. 8 (a)-(b), it is synoptic diagram for a correction electrode, according to the metal electrode that Fig. 4 to Fig. 7 finished, appropriate selects for use conduction material and metallic film material applicable to working electrode (Working Electrode) or to electrode (Counter Electrode), and in electrochemical sensor is used, can on electrode 802, solidify a modification level (Modified Layer) 801 through specific production process, so that pure electrode 802 is revised the correction electrode (Modified Electrode) that (Modify) becomes special-purpose.For example: electrochemical action or the mode of printing of metal electrode 802 through being immersed in Klorvess Liquid that will be coated with the silver metal film makes silver layer and chlorine produce chemical bond and form one silver medal/silver chloride reference electrode (Ag/AgClReference Electrode).
Or solidify that ((immobilized, coated) one deck chemical reagent (Reagent) 414 is on the metal electrode 411 of Fig. 4, chemical reagent 414 comprises the compound that an enzyme catalyst (Enzyme), a pH-value buffering agent (PH Buffer), an interfacial agent (Surfactant/Surface Active Agent), a redox reaction electron mediator (Redox Mediator), a hydrophilic high molecular polymer (Hydrophilic Ploymer Compound) etc. mix, to form an enzyme electrode (EnzymeElectrode) 413.
Chemical reagent 414 on the enzyme electrode 413 in order to one treat that certain analyte in the fluid measured produces chemical reaction and produces an electrical signals, via electrode 411 these electrical measurement signal to electrochemical analysis instrument 18 (seeing Fig. 9 for details) of output, to calculate the concentration of this analyte.Contain a redox reaction electron mediator (Redox Mediator) in the chemical reagent (Reagent) 414 of enzyme electrode 413 as above, it is the vectorial correction working electrode of an electron transfer (Electron-Transfer Mediator ModifiedWorking Electrode).Aforesaid enzyme electrode 413, if with this redox reaction electron mediator (Redox Mediator) reject in the chemical reagent (Reagent) 414, and the selection one metal film electrode material of matching, to can be used as a metal catalytic electrode (Metal-CatalyzedElectrode), for example a platinum metal catalytic electrode.
Aforesaid enzyme electrode 413, enzyme in the chemical reagent 414 can have a glucose oxidase (Glucose Oxidase), think the whole blood (Whole Blood) of test one human body, and obtain the analysis result to this fluid sample, this analysis result is the blood candy concentration in this human blood.Aforesaid enzyme electrode 413, the enzyme in the chemical reagent 414 can change into has a urea oxidase, thinks the whole blood of test one human body, and analyzes the uric acid concentration in this human blood.Aforesaid enzyme electrode 413, the enzyme in the chemical reagent 414 can have a cholesterol oxidase, thinks the whole blood of test one human body, and analyzes the cholesterol concentration in this human blood.
See also Fig. 9, be in conjunction with three deserted test sheets of the present invention to replace the application example of Fig. 1 traditional electrode, the conduction material of each electrode can be arbitrary conductive material through revising the layer of metal film separately to form a special electrodes, as a gold film to electrode (Counter Electrode) 409, a reference electrode (Ag/AgClReference Electrode) that one silver medal film reference electrode 802 and one silver medal/silver chloride (Ag/AgCl) modification level 801 are formed and a platinum thin film electrode are modified to one and contain three deserted test sheets such as enzyme working electrode (Enzyme Electrode) 413 of chemical reagent layer 414 to replace the application example of Fig. 1 traditional electrode.
As viewpoint according to Another application, recess 707 among Fig. 7 can have only through hole instead and not contain metal conductive strips, see also Figure 10 (a)-(b), be embodiment for a slice two electrode detection thin slices, the embodiment of Figure 10 is for having the through hole 1002 of a rectangle and the through hole 1003 of an annular on a heat insulating lamella 1001, one annular is placed in through hole 1003 respectively to electrode (Counter Electrode) metal electrode 1006 and a rectangle working electrode (Working Electrode) metal electrode 1004, in 1002 to form close-fitting, two bus cohesive ends 1007 place the below of heat insulating lamella, this two bus respectively have a signal output part 1008 and with metal electrode 1004,1006 have electrical connection, think this measurement signal of this electrode effect of output; One chemical reagent 1005 solidifies on working electrode 1004, in order to one treat that certain analyte in the fluid measured produces chemical reaction and produces an electrical signals, via electrode 1004,1006 and bus 1107 and output terminal 1008, export this electrical measurement signal to electro-chemical test instrument 18.
See also Figure 11 (a)-(b), be embodiment for the present invention's three electrode detection thin slices, on a heat insulating lamella 1101, have three through holes 1102, pair of electrodes (Counter Electrode) 1105, one working electrode (Working Electrode), 1103 and one reference electrode (Reference Electrode) 1104 is placed in respectively in the through hole 1102 to form close-fitting, three buss 1108 place the below of heat insulating lamella 1101, its respectively have a signal output part 1109 and with each metal electrode 1103,1104,1105 have electrical connection, think this measurement signal of this electrode effect of output, monochlor(in)ate silver modification level 1107 places on the reference electrode 1104, become monochlor(in)ate silver reference electrode (Ag/AgCl Reference Electrode) to revise electrode 1104, one chemical reagent 1106 solidifies on working electrode 1103, in order to one treat that certain analyte in the fluid measured produces chemical reaction and produces an electrical signals, via electrode 1103 and bus output terminal 1109, export this electrical measurement signal to electro-chemical test instrument 18.
Seeing also Figure 12, is the application example for a slice three electrode detection thin slices of the present invention, and deserted three electrode detection thin slices that use Figure 11 embodiment to finish make use-case with the traditional electrode that replaces Fig. 1.
See also Figure 13 (a)-(c), it is the application example that has three electrode detection thin slices of capillary flow path for a slice of the present invention, embodiment in Fig. 4 to Figure 12, it is fit to a large amount of fluid sample in the test, the detection thin slice (only using the blood volume of number μ 1 as the deserted blood sugar test thin slice of the blood of testing human) that is used for small amount of fluid, generally on the electrode detection thin slice, has a structure, be used for absorption and treat fluid measured in a small amount, and being covered with fully on whole electrodes of making, if being arranged, partial electrode do not treated that fluid measured covers, and then can cause the detection mistake.This adsorption structure generally has capillary channel inlet 1308, one capillary flow path 1314 and a capillary convection pore 1309, and capillary channel logical 1314 also is that one of this fluid measures the zone usually.
Treat fluid measured when this and run into capillary channel inlet 1308 that capillary channel 1314 utilizes a kind of capillarity can adsorb this fluid automatically promptly to stop automatically can not inhaling again after being covered with this measurement zone.The embodiment of Figure 13 to Figure 18 is all and is applicable to the detection thin slice embodiment that detects small amount of fluid, Figure 13 one is used to detect the embodiment of deserted three electrode detection thin slices of small amount of fluid, one heat insulating lamella 1301 has a Fluid Volume on it and surveys recess 1314 (being capillary flow path 1314), the bottom surface that fluid measures recess 1314 has chemical reagent storing recess 1306, be used to put a chemical reagent 1307 and make it produce the coating of a uniform thickness, the bottom surface of putting recess 1306 in reagent 1307 has three through holes 1302, and through hole 1302 is used to put a working electrode 1303, a pair of electrodes 1305 and a reference electrode 1304.
Three electrodes 1303,1304,1305 form close-fitting in three through holes 1302, each electrode 1303,1304, the 1305th, after covering a metallic film 1315 separately, (see Figure 13 (d) for details) by a conduction material 1313, each forms a metal electrode 1303,1304,1305, each electrode 1303,1304,1305 respectively have an electrode acting surface and an electrode interface, to utilize this electrode acting surface to produce an electrode effect, three buss 1311 are placed in the bottom surface of heat insulating lamella 1301, and each bus 1311 respectively has a bus cohesive end and each signal output part 1312, respectively the cohesive end of this bus 1311 each have with this electrode interface and to be electrically connected, think and utilize signal output part 1312 outputs one electrode measurement signal; Fluid measures to have fluid inlet 1308 and one capillary convection pore 1309, one overlayers 1310 and places top that fluid measures recess 1314 to form the adsorption structure of a complete capillarity on the recess 1314.Have two in the top of heat insulating lamella 1301 and replace projection 1316,1317, replacing overlayer 1310, and utilize and replace projection 1316,1317 to isolate the viscose on this fluid sample and the overlayer 1310.
This chemical reagent 1307 is placed in three electrodes 1303,1304,1305 end face is used for treating that with this certain analyte of fluid measured produces chemical action and produces an electrical signals, this electrical signals size has a proportionate relationship with the concentration of this analyte, via electrode 1303,1304,1305 these electrical signals of output are to signal output part 1312 and be connected to instrument 18, in order to calculate the parameter of this analyte, the conduction material 1315 of each electrode 1303,1304,1305 can be arbitrary conductive material.And the metallic film 1315 that is covered in working electrode 1303 can be gold.The metallic film 1315 that is covered in reference electrode 1304 can be silver, and behind treated one deck silver chloride layer to form one silver medal/silver chloride reference electrode.Be covered in this metallic film 1315 and can be platinum electrode 1305.
The metallic film 1315 that is covered in this working electrode 1303 can change a rhodium metal into, the metallic film 1315 that is covered in this working electrode 1303 can be palladium metal, the metallic film 1315 that is covered in this working electrode 1303 can be the ruthenium metal, the conduction material 1313 of working electrode 1303 can be the copper metal, and the metallic film 1315 of this covering also can be the copper metal, and meaning is that the metallic film 1315 that this electrode can be former material of a bronze medal and covering is integral with each other moulding.
See also Figure 14, be to be the detection thin slice embodiment of Figure 13 to Figure 17 of the present invention and the applied in any combination of a galvanochemistry instrument, one galvanochemistry measuring instrument, 1401 tools one insert mouth 1402, insert mouth 1402 and be used to introduce a sheet type Electrochemical Detection thin slice 1301, this treats that fluid measured is sucked in the thin slices by capillary channel inlet 1308.Measuring instrument 1401 is used to provide the required operating voltage of an electrochemical action to each electrode, and receives the measurement signal by electrode output, shows an information as calculated behind the measurement signal.
See also Figure 15 (a)-(c), it is the application example that has three electrode detection thin slices of capillary flow path for another sheet of the present invention, present embodiment is used for working electrode 1505 in conjunction with the metal electrode of spirit of the present invention, the working electrode performance of utilizing the metallic film of this metal electrode to obtain, the present invention forms working electrode 1506 and can obtain a point-device active area in through hole 1503 in addition, improves the quality repeatability of sensor widely.And in to electrode 1515 and reference electrode 1512, its electrode material and electrode active area do not need the accurate demand as working electrode 1505, so can produce to reduce cost with traditional printing electrode mode electrode 1515 and reference electrode 1512.
Have an electrode acting surface through hole 1503 and an electrode interface through hole 1504 and this two through hole on one heat insulating lamella 1501 and 1502 link to each other forming one " U " shape recess 1502 in the bottom; One " U " shape electrode slice 1505 (promptly having one " U " tee section) is placed in this " U " shape recess 1502 and forms close-fitting, have an electrode acting surface 1506 and an electrode interface 1507 on " U " shape electrode slice 1505, in order to producing a working electrode effect with electrode acting surface 1506, one first printing conductive bar 1508 is printed on the heat insulating lamella 1501 and is covered on the electrode interface 1507, the first printing conductive bar 1508 has a bus cohesive end 1509 and a working electrode output terminal 1510, bus cohesive end 1509 is electrically connected with electrode interface 1507, to export this electrode measurement signal to working electrode output terminal 1510.
One second printing conductive bar 1514 and one the 3rd printing conductive bar 1511 and the first printing conductive bar 1508 are printed in heat insulating lamella 1501 simultaneously, the second printing conductive bar 1514 has pair of electrodes output terminal 1516 and one second electrode tip 1515 is thought pair of electrodes 1515, the 3rd printing conductive bar 1511 has a reference electrode output terminal 1513 and a third electrode end 1512, it is as a reference electrode 1512, and reference electrode 1512 has become monochlor(in)ate silver reference electrode after the correction of one silver medal/silver chloride modification level 1518; One insulation course 1519 has one " C " shape opening 1520 and is covered in three buss 1508,1511, the top that has a capillary convection pore 1522 on electrode acting surface 1506 and electrode output 1510, one overlayers 1521 and be covered in " C " shape opening 1520 is only exposed to form a complete capillary adsorption structure in 1514 top.The utilization of this structure is somebody's turn to do " U " shape recess 1502 and is somebody's turn to do cooperating of " U " shape electrode slice 1505, can make be connected this working electrode this first printing conductive bar 1508 can with this second and third printing conductive bar 1511,1514 with the same one side that once is printed on the heat insulating lamella, thereby can save the one-step print program.
One chemical reagent 1517 is placed in the end face of working electrode 1505, is used for treating that with this certain analyte of fluid measured produces chemical action and produces an electrical signals, and exports these electrical signals to signal output part 1510 via electrode 1505.The material of three printing conductive bars 1508,1511,1514 can be a carbon containing conductive paste or a silver paste, and label 1523 is expression one fluid inlets.
If from another suitable aspect, printing conductive bar 1006 among Figure 10 can be made into integrated bus or be cancelled no, see also Figure 16 (a)-(c), it is the application example that has three electrode detection thin slices of capillary flow path for another sheet of the present invention, the three electrode electrode effect end of present embodiment, electrode lead wire and electrode output are all integrated conducting strip, one heat insulating lamella 1601 has one first 1602 and 1 second 1603, have one first recess 1604 and a through hole 1605 (seeing Figure 16 (c) for details) on second 1603, through hole 1605 communicates with this first 1602; Integrated one first bus 1606 is placed in first recess 1604 and forms close-fitting, first bus 1606 has one first electrode output 1608 and one first electrode tip 1607, produces the function of a working electrode 1607 to utilize first electrode tip 1607.
On first 1602 of heat insulating lamella 1601, have one second recess 1611 and one the 3rd recess 1610 again, integrated one second bus 1616 is placed in second recess 1611 and forms close-fitting, have a secondary signal output terminal 1618 and one second electrode tip 1617 on second bus 1616, in order to do utilizing second electrode tip 1617 to produce pair of electrodes 1617, and integrated one the 3rd bus 1612 is placed in the 3rd recess 1610 and form close-fitting, have one the 3rd signal output part 1614 and a third electrode end 1613 on the 3rd bus 1612, to utilize third electrode end 1613 to produce the function of a reference electrode 1613, reference electrode 1613 has become monochlor(in)ate silver reference electrode after the correction of one silver medal/silver chloride modification level 1615, one insulation course 1619 has one " C " shape opening 1620 and is covered in two buss 1614, electrode acting surface 1607 and electrode output 1608 are only exposed in 1618 top.
Have a capillary convection pore 1622 on one overlayer 1621 and be covered in the top of " C " shape opening 1620, to form a complete capillary adsorption structure, one chemical reagent 1609 is placed in the end face of working electrode 1607, be used for producing chemical action and producing an electrical signals with certain analyte for the treatment of fluid measured, and via these electrical signals of electrode 1607 output to signal output part 1608, and label 1623 is expression one fluid inlets.
See also Figure 17 (a)-(b), it is the application example that has three electrode detection thin slices of capillary flow path for another sheet of the present invention, the embodiment of the invention is the modification of Figure 16 embodiment, this Figure 16 will be printed on the heat insulating lamella 1601 in traditional printing electrode mode electrode 1617 and reference electrode 1613, wherein reference electrode 1613 need be through the makeover process of one silver medal/silver chloride, because of reference electrode 1613 and working electrode 1607 equally all are attached on the same heat insulating lamella 1601, and be afraid of in the makeover process of carrying out this silver/silver chloride, can pollute working electrode 1607, so present embodiment will change into electrode 1617 and reference electrode 1613 and being printed on the overlayer 1716, when making the makeover process of this silver/silver chloride, this overlayer 1716 separates with the heat insulating lamella 1701 that depends on working electrode 1707, so working electrode 1707 can not made the makeover process of this silver/silver chloride and can pollute.
One heat insulating lamella 1701 has a Fluid Volume on it and surveys recess 1702, the bottom surface that fluid measures recess 1702 has chemical reagent storing recess 1703, be used to put a chemical reagent 1708, the bottom surface of putting recess 1703 in reagent has a through hole 1704, through hole is used to put one first electrode 1707, first electrode 1707 forms close-fitting in through hole 1704, first electrode 1707 is to form a metal electrode 1707 after covering a metallic film by a conduction material, first electrode 1707 has one first electrode acting surface and one first electrode interface, with the effect that utilizes the first electrode acting surface to produce a working electrode 1707, one first bus 1718 is placed in the bottom surface of heat insulating lamella 1701, and first bus 1718 has a bus cohesive end 1719 and a signal output part 1720.
The cohesive end 1719 of first bus 1718 has with this first electrode interface and is electrically connected, think and utilize signal output part 1720 outputs one working electrode measurement signal, fluid measures to have a fluid and goes into 1705 and one capillary convection pore, 1706, one overlayers 1716 and place top that fluid measures recess 1702 to form the adsorption structure of a complete capillarity on the recess 1702.Printing one second bus 1709 and one the 3rd bus 1713 on the overlayer 1716, the second printing conductive bar 1709 has pair of electrodes output terminal 1711 and one second electrode tip 1710 is thought pair of electrodes 1710, the 3rd printing conductive bar 1713 has a reference electrode output terminal 1715 and a third electrode end 1714 is thought a reference electrode 1714, reference electrode 1714 is after the correction of one silver medal/silver chloride modification level 1712, to synthesize monochlor(in)ate silver reference electrode.
One chemical reagent 1708 is placed in the end face of working electrode 1707, be used for treating that with this certain analyte of fluid measured produces chemical action and produces an electrical signals, and via these electrical signals of electrode 1707 output to signal output part 1720, and label 1717 is expression one " C " shape openings.
See also Figure 18 (a)-(c), it is application example for another sheet three electrode detection thin slices of the present invention, present embodiment directly utilizes the back side of metal electrode to be signal output part, the input that this metal signal output terminal is connected directly to measuring instrument is connected end points, one heat insulating lamella 1801 (being insulating substrate) has a Fluid Volume on it and surveys recess 1802, the bottom surface that fluid measures recess 1802 has three through holes 1803,1804 and 1805, three electrodes 1808,1809 and 1810 are placed in three through holes 1803,1804, in 1805 and form close-fitting, each electrode 1808,1809,1810 have an electrode signal output face 1813 and electrode acting surface 1811, and in order to producing an electrode function with electrode acting surface 1811, a chemical reagent 1814 is placed in the top of electrode acting surface 1811.
This treats the foreign material of fluid measured with protection chemical reagent 1814 and filtering in the top that one shape sheet 1815 places chemical reagent 1814; one overlayer 1816 is covered on shape sheet 1815 and the heat insulating lamella 1801, and overlayer 1816 has an opening 1817 and thinks the input port that this treats fluid measured.Respectively have a card article 1806 and 1807 (being trip) in the both sides of heat insulating lamella 1801, card article 1806,1807 is used for thin slice 1801 with the embodiment of the invention to be slipped into and inserts draw-in grooves 1821 as two of the measuring instrument 1820 of Figure 18 (d) and form positioning function.The signal output contact 1813 that thin slice 1801 inserts draw-in groove 1821 back sensing test pieces 1801 directly contacts with the input signal linking point 1822 of measuring instrument 1820, can finish the signal transmission, and need not use bus 1006, wherein label 1818 is represented a thin slice bottom surface.
If use as working electrode (WorkingElectrode), it is applicable to " the vectorial correction working electrode of first kind electron transfer (electron-transfer mediator modified working electrode) " and " the metal catalytic electrode of second class (metal-catalyzed electrode) " according to the metal electrode of the made deserted sensor of the present invention.In first kind metal electrode so long as do not have the inert metal (noble Metal) that chemistry disturbs and get final product, which kind of noble metal electrode it does not limit (as gold, platinum, palladium, rhodium etc. all can), the present invention uses a noble metal film 404 to be coated on the conduction material 403 with a synthetic metal electrode 411 in the framework of this type of electrode, and insert this metal electrode 411 in a through hole 402 of a heat insulating lamella 401, it can reduce the use amount of noble metal, the making man-hour of reduction metal electrode, and can make sensor obtain one to stablize accurate electrode area and obtained the detection repeatability (Reproducibility) of quality.As for the metal catalytic electrode that is suitable for second class, its working electrode material of selecting for use need be participated in electrochemical catalysis effect (not needing to add again electron transfer medium in chemical reagent) directly, its material needs to have chemical matching with chemical reagent and test analyte, adapt to the different chemical framework and need use different metal materials, it can be various metal electrodes and is not limited to the inertia precious metal material, and for example copper electrode can be used as and detects H 2O 2Working electrode (Working Electrode).When the material of the metal electrode that uses is inexpensive, structure of the present invention can directly be selected this conduction material 403 and these metal electrode 411 required identical materials for use, can save the program of this metal film 404 of lining, use structure of the present invention and method this moment and still can reduce the making man-hour of metal electrode, and can make sensor acquisition one stablize accurate electrode area and obtained the detection repeatability of quality, it is compared with the method structure of the deserted metal electrode of prior art on the structure of electrode and processing procedure and still obtains very large improvement.
If from another one technology kenel Figure 13, the manufacture method of a kind of electrochemical sensing test block of the present invention, it comprises the steps to provide a heat insulating lamella 1301, it has at least two recesses (through hole) 1302, preparation one conduction material group, it has at least one first and one second conduction material (being the former material of electrode 1313), at least revise and finish this first conduction material, revise electrode 1315 (1315 can be and electroplate a last platinum thin film with as a working electrode to form one, electroplate last one silver medal/silver chloride layer with as a reference electrode), and put to revise electrode 1315 and this second conduction material in two recesses 1302, to form this deserted chemical sensing test piece.This sensing test piece also comprises a galvanizing process, is to form a metallic film in this first conduction material, to obtain this correction electrode 1315.This sensing test piece also comprises the program curing of a chemical reagent, to obtain an enzyme electrode.
The present invention designs structure of the present invention and manufacture method according to the principle of not wasting precious metal material.The present invention uses the conduction material 403 of a low price (as the column type shot copper, its diameter 1.5mm, thickness 0.5mm) is beneficial to electroplate one deck inertia noble metal film (as electroplating platinum, the thick 0.025-5 μ of plated film m) forms a noble metal electrode 411, electrode 411 is inserted in the through hole 402 of a heat insulating lamella 401 and form close-fitting, electrode 411 is insulated only exposes an electrode acting surface 409 and an electrode interface 408 after thin slice 401 encases, in order to producing an electrode effect with electrode acting surface 409, and republish a bus 410 and be connected interface 408 in electrode 411, with guide wire 410 and output terminal 406 as electrode 411.The precious metal material that this structure is used is an electroplated film disk layer 404, only limit the use of the electrode area 412 in through hole 402 again, can reduce to the use amount of noble metal minimum like this, and after it can once electroplate millions of electrodes 411, machining is inserted in the through hole 402 of heat insulating lamella 401 again, so can reduce the material and the processing procedure cost of this noble metal electrode in a large number.
Electrode 411 of the present invention places the through hole 402 of heat insulating lamella 401 to form close-fitting in addition, heat insulating lamella 401 tightly encases the side of electrode 411 and only exposes an electrode acting surface 409 and an electrode interface 408, printing conductive bar 410 is connected guide wire 410 and the output terminal 406 of thinking electrode 411 in the interface 408 of electrode 411 again, it directly contacts with electrode acting surface 409 nothings, the area of electrode acting surface 409 fully independently and by through hole 402 areas is determined, and can obtain a point-device electrode area 412, because of the measurement electric current of electrochemical sensing device is directly proportional with electrode area 412, so the repeatability accuracy (Reproducibility) that the present invention can make the electrochemical sensing tolerance survey signal significantly promotes.
The present invention can use the electrode through hole 402 on the plastic cement shoot mode shaping sensor heat insulating lamella 401, penetrating program in identical plastic cement can be with needed other mechanism's once-forming of sensor, as with fluid intake 1308 to be measured, fluid capillary flow path groove 1314, capillary convection pore 1309, the storing recess 1306 of chemical reagent 1307 is replaced multiple structure once-formings such as projection 1316, not only can reduce element assembling number to reduce cost, more can reduce the assembly error of multicomponent.
In sum, the present invention really can be in a brand-new mode, by utilize a metallic film be formed at one the conduction material on, use amount with the noble metal that reduces metal electrode, and in the through hole that is installed in heat insulating lamella of the metal electrode that is used, can significantly shorten and make the required time of this deserted sensing test piece, and extremely be fit to industrial production.

Claims (2)

1. the manufacture method of an electrochemical sensing test block is characterized in that, comprises the steps:
One heat insulating lamella is provided, and it has at least two recesses;
Preparation one conduction material group, it has at least one first and one second conduction material;
At least revise and finish this first conduction material, revise electrode to form one; And
Put this correction electrode and this second conduction material in this two recess, to form this deserted chemical sensing test piece.
2. the method for claim 1 is characterized in that, also comprises:
One galvanizing process is used to revise this first conduction material to form a metallic film, to obtain this correction electrode;
With a print routine, in order to printing at least one bus forming at least one signal output part, and be electrically connected this signal output part that outputs signal to of this electrode; And/or
One chemical reagent program curing is used to revise this electrode to obtain an enzyme electrode.
CNB2006100093035A 2003-05-07 2003-05-07 Structure of electrochemical sensing test block and producing method thereof Expired - Lifetime CN100432660C (en)

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