CN100451637C - Electrochemistry type sensor and its manufacturing method - Google Patents
Electrochemistry type sensor and its manufacturing method Download PDFInfo
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- CN100451637C CN100451637C CNB031029884A CN03102988A CN100451637C CN 100451637 C CN100451637 C CN 100451637C CN B031029884 A CNB031029884 A CN B031029884A CN 03102988 A CN03102988 A CN 03102988A CN 100451637 C CN100451637 C CN 100451637C
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Abstract
The present invention relates to an electrochemical sensor and a manufacturing method thereof. The manufacturing method comprises the steps: a device for injection moulding (a die) and an insulation base material are provided; the insulation base material is provided with a first groove and a first through hole; the insulation base material is conveyed into the device for injection moulding; a plastic conductive molding material is injected in the device for injection moulding in order that a first conductive strip is formed in the first groove; the first conductive strip is provided with a first output end and a corresponding second electrode end; the second electrode end is used as a first test electrode which is formed in the first through hole; a chemical reagent (a reagent) is provided and is arranged on the first test electrode so as to detect a fluid sample. The chemical reagent reacts with one ingredient of the fluid sample so as to generate a measuring signal; the measuring signal is output by the first test electrode.
Description
(1) technical field
The present invention is a kind of electrochemical transducer[sensor and manufacture method thereof.
(2) background technology
The principle of general 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 Fig. 1, 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 electrochemical measured 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, as 15 pairs of electrodes (Counter Electrode), 16 working electrodes (Working Electrode), 17 reference electrodes (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.
Except the difference of electrode number, different because of different electrode function (as the difference of counter electrode) and sensor chemistry reacted constituent with respect to working electrode, selecting for use of each electrode material can have very large variation.The general electrode material in laboratory is as follows, wherein to electrode 15 (CounterElectrode) material so long as the conduction material get final product, but conductive resistance is lower better,, graphite rod excellent or with carbon paste or the printed and formed conducting film electrode of elargol as copper rod, silver rod, nickel, certainly noble metals such as gold, platinum also can be used for when to utmost point electrode material, are the waste material cost.Wherein the material of reference electrode 17 (ReferenceElectrode) is the most frequently used is one silver medal/silver chloride modified electrode (Modified Electrode) 171, it is, respectively to republish one deck silver chloride or utilize electrolysis mode to plate one deck silver chloride on the printed conducting film electrode at silver rod or with carbon paste or elargol.
Wherein the electrode material of working electrode 16 (Working Electrode) select for use more complicated, it has two general orientation, the first kind is metal catalytic electrode (Metal-Catalyzed Electrode), its working electrode material of selecting for use can produce the chemical catalysis effect or analyte is had single selective analyte, these characteristics with catalytic action or single selective make measuring-signal that effect more stable or that detection signal more amplifies be arranged, its metal electrode material is generally as gold, platinum, palladium, noble metals such as rhodium (H2O2 has splendid catalytic action as rhodium rhodium electrode pair).Second class is for utilizing the vectorial modification working electrode of electron transfer (Electron-Transfer Mediator Modified Working Electrode), this electron transfer medium is generally a compound, the reagent that it is mixed by many chemical raw materials, this chemical reagent is solidified (immobilized) surface at working electrode, can produce electrochemical reaction with test analyte, and the electrical signals that produces after the electrochemical reaction is exported its measurement parameter via electrode, the purpose of this working electrode is only as the conduction function, and its electrode material needs and can not produce a self-chemical action and the interferometry accuracy with treating fluid measured 11 or chemical reagent 14.This electrode material that does not have that chemistry disturbs is an inactive, conductive material, is generally the electrode (as carbon film print electrode CarbonBase Screen Printing Electrode, graphite rod Graphite Bar) of inert metal Noble Metal (as metals such as gold, platinum, palladium palladium, rhodium rhodium) or carbon containing material.Because of carbon and inert metal can not chemically react at low temperatures, disturb so can not produce chemistry.
The present invention does not also lie in the electrode material problem that solves, but in the electrode material of using full-fledged various different demands, especially with carbon containing conductive material cheaply, produce a working area dimensionally stable, lower electrode resistance and do not have the working electrode that chemistry disturbs with method of the present invention and structure, can make the measuring-signal of electrochemical transducer[sensor more stabilize to its purpose.
Demonstrate a kind of basic framework of electrochemical transducer[sensor in Fig. 1, wherein electrode can be with two electric pole types or three electric pole types, and its circuit measuring structure is placed in the device of meter 18.Supply with a fixing magnitude of voltage E by meter 18 and export electrode 15 to through lead, 16,17 think the galvanochemistry operating voltage of fluid analysis thing 11 to be measured and chemical reagent 14, behind analysans and the reagent chemical reaction thus operating voltage produce a diffusion signal current i, the marking current i of this measurement and the concentration C of analyte (Concentration of the analyte) have the relation of a ratio, the galvanochemistry formula of i and C wherein, because of chemical action is reversible, will definitely contrary or irreversible difference, or chemical reagent is for maybe can not dissolve for solubilized, or because of electrode shape be dull and stereotyped, cylinder or its are the difference of a size less than the microelectrode (Micro-electrode) of 50 μ m, galvanochemistry formula such as Cottrell equation or Sampled-current voltammetry equation that it is suitable for, etc. variant, but be as follows comprehensively basically:
i(t)＝n.F.A.f(C).f(D).f(X).f(t)
I wherein: measure current value (Measure current)
N: electronics valence mumber (Number of transfer electrons)
F: Faraday constant (Faraday constant)
A: the surface area (Surface area of the working electrode) of making electrode
D: diffusion constant (Diffusion coefficient)
C: the concentration of test analyte (Concentration of the analyte)
X: the thickness of chemical reagent (Thickness of the reagent)
T: Measuring Time (Time from start measure)
Measuring current i and n, F, A is a linear proportional relation, but its with the concentration C of analyte or chemical reagent thickness X under various different situations, some is a linear relationship but some is a nonlinear relationship, so represent with funtcional relationship f (C), f (X).In addition most to measure electric currents be a unstable state value, and it is that the function of time t is represented with f (t).
In addition if the electrochemical measurement structure is two electric pole type circuit, the fixed voltage E that supplies with by meter 18 then, with the electrode operating voltage of reality be that V is unequal, wherein V can transmit pressure drop with signal and changes.
V＝E-I.R
V: actual electrode operating voltage
E: the fixed voltage value that meter provides
I: measure current value
R: the total resistance of electrode and guiding electrode line (LEAD)
I.R: the signal transfer overvoltage is fallen
Scientific principle data by above two formula are known, though chemical reaction is the principal element of decision sensor current measured value size, but except that the influence of chemical reaction, the stability that belongs to the total resistance R of the electrode worksheet area A of structure division of electrode and electrode all is the key factor of measuring-signal stay in grade when influencing sensor and producing in a large number.The coating thickness of chemical reagent is uniform and stable in addition also is a key element.
The electrode that pure inert metal made all has splendid effect in the worksheet area A of electrode and the total resistance R of electrode, but its cost height.And traditional screen painting conductive film type electrode at a low price is in this two shortcoming that will have to a certain degree.The present invention is in outer another solution cheaply of seeking out again of inert metal electrode material, and from how to improve chemistry disturbs and the total resistance R stable and the reduction electrode of the worksheet area of electrode sets about, to improve the shortcoming of traditional screen painting electrode.
General is breadboard general very expensive with electrode, thereby all can after repeatedly using, just abandon, but after whenever finishing once experiment, the electrode bar surface is polluted by determinand or chemical reagent, even electrode surface has been coated with one deck compound, it can't simple and easyly clean, and generally needs with lapping apparatus the removal of the pollution on the electric shock baton just can be used again.This process consumptive material is consuming time again.So the exploitation of deserted print electrode 20 (detail drawings 2) is arranged.This is deserted to print electrode 20, is with a screen printing technology one pasty state conductive paste to be printed as conducting film 20,22,222,23 and to print insulation course 223 etc. and moulding on the plastic cement insulating substrate 21 of a flat sheet.It has, and processing procedure is easy, shape is variable, and advantage such as cost is low, thereby is widely used.Because of its cost is low so use is once promptly abandoned, there is not the puzzlement of reusable pollution and cleaning.This deserted printing electrode because of cost is low, advantage such as shaped design is easy especially is widely used on the electrochemical sensor of medical treatment at home, as the detection test piece electrode of blood candy, uric acid, cholesterol.
As Taiwan patent announcement the 496th, 960,496,110,475,983,466,344,416,005,374,116,369, No. 411 etc., and United States Patent (USP) announces the 5th, 985,116,6,125,292,6,059,946,6,270,637,5,997,817,5,951,836,6,258,254,5,876,577,6,413,394,6,129,823,5,916,156,5,989,409,6,416,641,5,437,999,6,156,173,6,287,451,5,762,770,5,628,890,6,436, all be the deserted example that prints electrode in tens of patent specifications such as No. 256.
Please refer to Fig. 2 and Fig. 3, it is a United States Patent (USP) the 5th, 985, the planimetric map of No. 116 embodiment and explosive view, it is the example of a deserted screen painting electrode, it is a test electrode of isolating mutually with a working electrode (Working Electrode) 22 of pasty state conductive paste printing moulding and to electrode (Counter Electrode) the 23rd, one first end 221 of this conducting film film 20 is a working electrode 22, be connected to i.e. one second end 222 of relative opposite side through conducting film film 20, with output terminal 222 as working electrode 22, be used to be connected to a meter 18 (be not shown in figure, it is as the meter 150 of Figure 15).Have an insulation course 223 as shown in Figure 3 on conducting film conducting film 20, be used for covering the zone except beyond electrode 22,23 areas and the output contact 222, the conducting film 20 and that insulation course 30 is used for beyond the isolated electrode treats that fluid measured contacts.One spacer (Spacer) 31 is arranged again on insulation course, treat the inflow of fluid measured, and utilize an overlayer 32 to form the measured zone of a capillary flow path for this.
As for the material of this pasty state conductive paste, be generally the conductive paste (Conductive Paste) that conductive metal powder (as gold, palladium, silver, copper, nickel etc.) or carbon containing conductive material (as carbon black, dag etc.) and solvent or ore oil or resin binder such as (Resin) be mixed into pasty state and republish on insulating trip.As adopt printing electrode of metal cream, has the low advantage of conduction impedance, but it can produce chemical interference effect if be used for working electrode most low price metal cream, and can't use, as ag material because of the material interference problem can't be applicable to blood candy concentration determination sheet working electrode (but silver electrode can be used for the reference electrode of blood candy concentration determination with to electrode).Like this thereby two selections are arranged, the one direction is for using noble metal film as gold, platinum, palladium, rhodium etc., another replaces with conductive carbon film at a low price for the overwhelming majority, carbon and noble metal none because of the caused chemical interference problem of material, but the noble metal cost is too expensive, and the carbonaceous conductive film can cause the error of measuring-signal because of the high caused conduct electricity pressure drop meeting of impedance, respectively is its shortcoming.
Also some screen painting electrode is for improving aforesaid two shortcomings separately, its stamp earlier one deck at a low price metal cream (as elargol) conducting film on a dull and stereotyped sheet to obtain low conduction impedance, then stamping one deck conductive carbon film on this metal powder conducting film again covers to obtain the not having chemistry interference, and have a dual effect (as the U.S. the 6th, the Example 1 described processing procedure of 458, No. 258 patents).But in the processing procedure of reality, carbon film is covered on this metal conductive film, and the pore that carbon film layer regular meeting has a little finished product still to leave a part does not cover metal conductive film fully, and this pore can cause this metal cream to produce chemistry with treating fluid measured directly to contact and disturb.Partly for solving this as the deserted disadvantage that prints electrode of above-mentioned half tone, and the structure of other different deserted electrodes of deriving, as United States Patent (USP) the 5th, 437, No. 999, promptly make a noble metal film with a kind of physical deposition method on insulating substrate, it is pasted on a soft or hard base material again and become a working electrode that is fit to chemical action, this method effect is fine but material cost and processing procedure cost are all very high.
As for No. the 496th, 110, Taiwan patent, it makes a Copper Foil (adding nickel plating) electrode with a print circuit plates making mode, plates the inert metal of one deck gold or platinum again on this copper foil electrode.Though it is that the deserted electrode of material has its advantage also to reduce a part of cost that this kind electroplated noble metal with one, but cost is still high.And the gold-plated mode of production on this printed circuit board (PCB), still have uneven coating when producing and cause remaining pore is arranged on the metal film, still the bad finished product of some ratio can produce the practice puzzlement that galvanochemistry is disturbed because of remaining pore makes copper film, though it can increase gold-plated thickness covering whole remaining pores, the gold-plated too thick cost that causes increase with the cost that uses pure conductive noble metal film much at one.
(3) summary of the invention
Therefore, the purpose of this invention is to provide a kind of electrochemical transducer[sensor and manufacture method thereof, the problem that galvanochemistry when solving electrochemical transducer[sensor and measure in mode is cheaply disturbed can reduce the resistance value of electrode again, and can significantly promote the degree of accuracy of the electrode area of test electrode, the repeatability accuracy (Reproducibility) of electrochemical transducer[sensor measuring-signal can significantly be promoted.
Manufacture method of the present invention is to comprise: a device for injection moulding is provided, one insulating substrate is provided, it has one first groove and one first perforation, this insulating substrate is sent in this device for injection moulding, the moulding material that injects plastic cement conduction is to this device for injection moulding, in this first groove, to form one first bus, and this first bus has one first output terminal and relative one second electrode tip, and with this second electrode tip is one first test electrode, this first test electrode promptly forms in this first perforation, and provide a chemical reagent (Reagent), it is arranged on this first test electrode, in order to detecting a fluid sample, this chemical reagent promptly with the composition reaction of this fluid sample, and then produce a measuring-signal, and through this first test electrode to export this measuring-signal.
The preferably, first test electrode of this method is exported this measuring-signal to one meter, and this plastic cement conductive material is the conducing composite material that is synthesized by the mixing of a carbon containing conductive material or a metal powder or two or more conductive materials and a resin base material, and this resin base material is a hot formed plastic cement resin (PlasticResin).
The preferably, this carbon containing conductive material of the plastic cement conductive material of this method is a carbon black (CarbonBlack), dag (Graphite Powder), carbon fiber (Carbon Fiber) or CNT (CarbonNanotube), this metal powder is a palladium, rhodium, gold etc., and this conductive carbon material has one 3～60% weight ratio of this plastic rubber substrate, and this metal powder has one 0.1～5% weight ratio of this plastic rubber substrate.
Certainly, this resin base material of the plastic cement conductive material of this method is to be an epoxy resin (epoxy), itself and this conductive carbon material or this metal powder stir and are one liquid and inject this first groove and this first perforation of this insulating substrate, and this first bus promptly forms one with this insulating substrate and closely connects.
The present invention also comprises a kind of structure of electrochemical transducer[sensor, be to be used to detect a fluid sample, it comprises an insulating substrate, it has one first groove and one first perforation, one first bus, be to be connected with this insulating substrate, so that this first bus is arranged in this first groove, and this first bus has one first output terminal and relative one second electrode tip, and with this second electrode tip is one first test electrode, this first test electrode promptly is arranged in this first perforation, and a chemical reagent, it is arranged on this first test electrode, in order to detect a composition of this fluid sample, and then produce a measuring-signal, and through this first test electrode to export this measuring-signal.
Certainly, this structure can also comprise an insulation course, and with so that this first bus obtains an insulation effect, and this first test electrode is the leading point for this first bus.
The preferably, first test electrode of this structure is to be a working electrode, and this structure also has one second bus, and this insulating substrate promptly is provided with one second groove and one second perforation, so that one second test electrode of this second bus and this second bus to be set respectively.This second test electrode can be pair of electrodes (Counter Electrode).
The preferably, this structure also have one the 3rd bus, and this insulating substrate promptly is provided with one the 3rd groove and one the 3rd perforation, so that one the 3rd test electrode of the 3rd bus and the 3rd bus to be set respectively, the 3rd test electrode can be a reference electrode (Reference Electrode).
The preferably, this insulating substrate has one and flows into recess, and for the inflow of this fluid sample, and this insulating substrate has fluid inlet, and this fluid intake, this inflow recess and this first perforation are formed in one.
Certainly, this structure can also comprise an overlayer, and this inflow recess of this insulating substrate is to have one to put recess, and for the complete storing of this chemical reagent, and this overlayer and this inflow recess form a measured zone.
Certainly, the overlayer of this structure can be a sheet, and it is that an electrode end face with this first test electrode forms a difference in height that one of this measured zone is measured the bottom surface, and the electrode end face puts recess with this and form one and synthesize the bottom surface, for the coating of this chemical reagent.
The preferably, the chemical reagent of this structure is to inject this storing recess with a certain amount of pattern, and forms a uniform thickness of this chemical reagent on this synthetic bottom surface.
The preferably, the storing recess of this structure has a recess thickness, and this recess thickness is this uniform thickness of this chemical reagent.
Certainly, the overlayer of this structure can have a printed conductive metal film (Conductive MetalFilm), and with this conducting film as the one test electrode.
Certainly, the overlayer of this structure is to weave cotton cloth or plastic net sheet material for one, presenting a mesh window, and has one 60～300 mesh numbers.
The preferably, the measured zone sidewall of this structure and overlayer inboard are to handle (Hydrophilic Coating) through a hydrophilic cover, adsorb fully and can not measure the dead angle because of air bubble cause in order to the measured region side walls of fluid.
The preferably, the test electrode of this structure need as with the solution polishing, with the powder polishing, with various programs such as pure water or deionized water ultrasonic cleansings, totally not have other foreign material of absorption to determine electrode surface through the pre-process of electrode.
The preferably again with distinct methods and program, modifies the modified electrode (Modified Electrode) that (Modify) becomes different special-purposes with this test electrode after the test electrode process pre-process of electrode of this structure.
The preferably will plate coating monochlor(in)ate silver (AgCl) layer with screen painting mode or electrolysis through the 3rd test electrode of this structure after the electrode pre-process, handle the back to form the silver-colored reference electrode of monochlor(in)ate through this electrode modification (Modified Electrode).
The preferably, first test electrode of this structure is coated with one deck chemical reagent (Reagent Matrix) through electrode pre-process and electrode modification (ModifiedElectrode) processing, to form a working electrode.Certainly, the chemical reagent of this structure is to produce an electrochemical reaction with this composition of this fluid sample, and transforms the measured value that this measuring-signal is an electrical parameter, and the measured value of this electrical parameter is relevant to a material concentration of this composition.
Certainly, the chemical reagent of this structure is to comprise enzyme (Enzyme), pH-value buffering agent (PHBuffer), interfacial agent (Surfactant, Surface Active Agent), redox reaction electron mediator (Redox Mediator), hydrophilic high molecular polymer (Hydrophilic PloymerCompound) etc. are formed compound.Its each chemical raw material can be mixed with different ratio gradation (or once) and gradation (or once) with its curing (immobilized, coated) on working electrode.
Certainly, the enzyme in the chemical reagent of this structure can have a glucose oxidase (GlucoseOxidase), thinks the whole blood (Whole Blood) of testing human, and this fluid analysis thing is the blood candy concentration in the human blood.
Certainly, the enzyme in the chemical reagent of this structure can have a urea oxidase, thinks the whole blood of testing human, and this fluid analysis thing is the uric acid concentration in the human blood.
Certainly, the enzyme of the chemical reagent of this structure in being can have a cholesterol oxidase, thinks the whole blood of testing human, and this fluid analysis thing is the cholesterol concentration in the human blood.
Certainly, the insulating substrate of this structure can have one first entrance side and relative one second pore side, is respectively as this fluid intake and form an air vent openings, and this air vent openings is beneficial to this fluid sample and makes a Capillary Flow.
The preferably, the insulating substrate of this structure is to have a projection of replacing, and replacing this overlayer, and utilizes this to replace projection and isolates this fluid sample and this tectal viscose.
Certainly, the insulation course of this structure is to be an insulation sheet or printing insulating gel, it is arranged at a bottom surface of this insulating substrate, and this first groove also is positioned on this bottom surface, and this insulating substrate has more the first printed conductive metal film, be positioned at an end face of this insulating substrate, think one second test electrode.
Certainly, this insulating substrate of this structure also has the second printed conductive metal film, is printed in an end face of this insulating substrate simultaneously with this first printed conductive metal film, thinks one the 3rd test electrode.And to be provided with the monochlor(in)ate silver layer in this electrode be monochlor(in)ate silver reference electrode to modify this third electrode.
Certainly, first perforation of this structure and this first test electrode can respectively have a perforation sectional area and an electrode sections is long-pending, and it is long-pending that this perforation sectional area promptly is same as this electrode sections, and this first perforation is a bottom surface that is positioned at this insulating substrate.
The preferably, the insulating substrate of this structure is to adopt a polyvinylchloride (polyvinyl chloride), polypropylene PP (Polypropylene), polycarbonate (Polycarbonate), poly terephthalic acid butenylidene ester PBT (Polybutylene Terephthalate), polyethylene terephtalate (Polyethylene Terephthalate), the inferior benzene PPO (Modified Polyphenlene Oxide) of polyoxygenated or acronitrile-butadiene-styrene resin ABS plastic resins such as (Acrylonitrile Butadiene Stytene).
The preferably, first bus of this structure is to be a moulding in advance, and imbeds this first bus in an insulating substrate shaped device, to form this insulating substrate.
Certainly, first bus of this structure and this insulating substrate are can the one-shot forming of a pair of material shoot mode.
Certainly, first bus of this structure is to utilize a viscose to be engaged on this insulating substrate.
Again on the other hand according to the present invention, a kind of structure of electrochemical transducer[sensor, be to be used to detect a fluid sample, it comprises an insulating substrate, it has one first dented space, one first electric installation, be located in this first dented space, this first electric installation tool, one first output terminal and relative one second electrode tip, and be one first test electrode with this second electrode tip, and a chemical reagent, it is arranged on this first test electrode, in order to detecting a composition of this fluid sample, and then produce a measuring-signal, and through this first test electrode to export this measuring-signal.
The preferably, first electric installation of this structure is to be one first bus, and this first dented space includes one first groove and one first perforation, and this first bus is set in this first groove, this first test electrode promptly is arranged in this first perforation.
The preferably, this of this structure first electric installation is to be one first conductive cushion block (Pad), first of conductive cushion block (Pad), working area with test electrode, and first dented space on this insulating substrate is one first perforation, this structure also has the guiding electric wire (Lead) that a metal conductive film (Conductive Metal Film) is thought this electrode, it is printed on the insulating substrate, one side of this printed conductive metal film also covers second linking mutually (back side that electrode face is long-pending) that is connected to this first conductive cushion block, and the opposite side of metal conductive film is thought first output terminal of this measuring-signal.This replaces the Lead section with the traditional printing method with low price metal conductive film (as elargol printing conductive film) method, impedance with the Lead section that reduces electrode, this metal conductive film can not have chemical interference problem with treating fluid measured to contact away from electrode face is long-pending, and itself and the long-pending nothing of electrode face are directly joined, though so it has printed and formed size instability, it can not influence the stability that plastic cement penetrates conductive electrode working area size fully.
If the present invention is with the resulting impedance of the electrode of this bus of carbon containing plastic cement conductive material injection molding, though lower tens of times than the electrode impedance of the electrode that is shaped with the carbon film printshop, it is still than the conduction impedance height with the printing conductive film (as elargol) of metal cream.Use because of elargol has chemical interference problem to be not suitable for working electrode, thus with the present invention with the working electrode of carbon containing plastic cement conductive material injection molding can obtain not have that chemistry disturbs, the advantage of stable working electrode size and low electrode resistance (carbon film with respect to the chemical interference of nothing does not print electrode).But do not disturb and the stable needs of problems of electrode size because reference electrode (Reference Electrode) all has chemistry with guide line (Lead) to electrode (CounterElectrode) and each electrode, thereby can use metal cream printing conductive film (as elargol) at a low price to hinder and make the measurement of sensor more stable to obtain lower conduction.This mixes the integration that plastic cement penetrates bus electrode and traditional printing metal cream conducting film, can get complementary effect, and that itself and this patent spirit desire to realize not having purposes such as working electrode that chemistry disturbs, low electrode resulting impedance and stable electrode face be long-pending with low cost is identical.
Certainly, first perforation of this structure more can have one and enlarge groove, to put an enlarged base of this first conductive cushion block.
Again according to the suitable technological layer of another kind, the structure of a kind of electrochemical transducer[sensor of the present invention, be to be used to detect a fluid sample, it comprises one first conducting element, it has one first test electrode, one insulating substrate, be to have one first dented space, to put this first conducting element, one first printed conductive metal film, itself and this insulating substrate joins, this first printed conductive metal film tool, one first output terminal and relative one second cohesive end, and be connected mutually with this first conducting element with this second cohesive end, and a chemical reagent, it is arranged on this first test electrode, in order to detect a composition of this fluid sample, and then produce a measuring-signal, and through this first test electrode to export this measuring-signal.
Certainly, the insulating substrate of this structure is to have one second dented space, and putting one second conducting element, and this structure has more one second printed conductive metal film, itself and this first printed conductive metal film is printed on this insulating substrate simultaneously, in order to be connected this second conducting element.
The preferably, this structure first dented space also links to each other with a sidepiece groove to form one " U " connected in star, to hold one " U " shape conducting element, and this structure also comprises an insulation course, be in order to covering this first printed conductive metal film, this insulation course also has one and flows into recess, for the inflow of this fluid sample, and this insulation course has a summary and is " ㄈ " shape opening, to form a measurement space.
The preferably, this structure also include one the 3rd printed conductive metal film, be to be printed in simultaneously on this insulating substrate with this first printed conductive metal film.
As technological layer from another kind of equity, the structure of a kind of electrochemical transducer[sensor of the present invention is used to detect a fluid sample, and it comprises: a conducting strip, it has one first output terminal and one second electrode tip, and is one first test electrode with this second electrode tip; One insulating substrate is to join with this conducting strip, and has an electrode perforation, to put this first test electrode; And a chemical reagent, it is arranged on this first test electrode, in order to detecting a composition of this fluid sample, and then produces a measuring-signal, and through this first test electrode to export this measuring-signal.
Certainly, first test electrode of this structure is can be positioned at one of this conducting strip to protrude on the position, to insert this electrode perforation of this insulating substrate.
Certainly, this structure can also comprise a modified electrode, is arranged on the one second printed conductive metal film, and becomes a reference electrode.
The present invention is via the explanation of above-mentioned conception, can observe the manufacture method and the structure thereof of the electrochemical transducer[sensor that is used, really can put an insulating substrate in device for injection moulding, have the characteristic of first bus (Conductive Strip) of formation in one first groove of this insulating substrate.
In order to be easy to explanation, the present invention must obtain one by following preferred embodiment and diagram and understand more.
(4) description of drawings
Fig. 1 is the schematic perspective view of the electrochemical detection device of prior art;
Fig. 2 is the deserted floor map that prints electrode of another prior art;
Fig. 3 is the deserted perspective exploded view that prints electrode of Fig. 2;
Fig. 4 is the solid of the preferred embodiment of unipolar manufacture method of electrochemical transducer[sensor of the present invention and structure thereof the synoptic diagram that pops;
Fig. 5 is the unipolar reverse side solid of the sensor of Fig. 4 synoptic diagram that pops;
Fig. 6 is that the sensor single electrode of Fig. 4 combines preceding schematic perspective view with a chemical reagent;
Fig. 7 is the schematic perspective view of electrochemical detection device that utilizes the sensor of Fig. 4;
Fig. 8 (a) ~ (b) is the three-dimensional positive combination and the synoptic diagram that pops of two utmost point formula electrochemical sensors of another preferred embodiment of the present invention;
Fig. 9 (a) is the schematic perspective view of positive exploded of the sensor of Fig. 8 (b); Fig. 9 (b) is the conductive section machine of electrode of Fig. 8 (b) sensor and the schematic perspective view of conductor thickness;
Figure 10 is the three-dimensional front of the three-pole electrochemical sensor of the another preferred embodiment of the present invention synoptic diagram that pops;
Figure 11 (a) ~ (c) is the three-dimensional front of the four pole type electrochemical sensor of a preferred embodiment more of the present invention, three-dimensional reverse side and the front synoptic diagram that pops;
Figure 12 (a) is the three-dimensional front of the three-pole electrochemical sensor of the another preferred embodiment of the present invention synoptic diagram that pops;
Figure 12 (b) is that the electrochemical sensor of Figure 12 (a) is placed in a three-dimensional diagrammatic cross-section that takes up in the container;
Figure 13 (a) is the three-dimensional front of the three-pole electrochemical sensor of a preferred embodiment more of the present invention synoptic diagram that pops;
Figure 13 (b) is the upright synoptic diagram of the front group of Figure 13 (a).
Figure 14 (a) is the three-dimensional front of the two plate electrochemical sensor of the another preferred embodiment of the present invention synoptic diagram that pops.
Figure 14 (b) is the three-dimensional front of the three-pole electrochemical sensor of the another preferred embodiment of the present invention synoptic diagram that pops.
Figure 15 be an electrochemical sensor test piece of the present invention be inserted into a known galvanochemistry meter solid combination synoptic diagram.
Figure 16 is the three-dimensional reverse side of the monopolar type electrochemical sensor of the another preferred embodiment of the present invention synoptic diagram that pops.
Figure 17 is the three-dimensional front of the electrochemical sensor of Figure 16 synoptic diagram that pops;
Figure 18 is the three-dimensional reverse side of two utmost point formula electrochemical sensors of a preferred embodiment more of the present invention synoptic diagram that pops; And
Figure 19 (a) ~ (d) is the synoptic diagram that three-dimensional reverse side combination, positive combination, positive exploded and the reverse side of the three-pole electrochemical sensor of a preferred embodiment more of the present invention pops;
Figure 20 (a) is that the three-dimensional front of the three-pole electrochemical sensor of another preferred embodiment of the present invention pops and makes up synoptic diagram (b): and
Figure 20 (c) is the three-dimensional front of the three-pole electrochemical sensor of a preferred embodiment more of the present invention synoptic diagram that pops.
(5) embodiment
See also Fig. 4 to 6, demonstrate a kind of manufacture method of electrochemical transducer[sensor, comprise: a device for injection moulding (mould is provided, not shown), one insulating substrate 40 is provided, it has first groove 50 (seeing Fig. 5 for details) and first perforation 41 that is positioned on insulating substrate one end that extend along the length direction of insulating substrate, insulating substrate 40 is sent into (mould) in this device for injection moulding, the moulding material that injects plastic cement conduction is to this device for injection moulding, in first groove 50, to form one first bus (Conductive Strip) 42, and first bus 42 has one first output terminal 43 and a guide wire lead 45 and one second relative electrode tip 44, and with second electrode tip 44 is one first test electrode 44, first test electrode 44 promptly forms in first perforation 41, and provide as shown in Figure 6 a chemical reagent 60, it is arranged on first test electrode 44, in order to detect a fluid sample, chemical reagent 60 promptly with the reaction of a composition of this fluid sample, and then produce a measuring-signal, and through first test electrode 44 to export this measuring-signal.
These measuring-signal to one meters of first test electrode 44 output of this method, and this plastic cement conductive material synthesized by a conductive carbon material or a metal powder and a resin base material, and this resin base material is a hot formed plastic cement resin (plastic resin).And this conductive carbon material of this plastic cement conductive material can be a carbon black (Carbon Black), graphite (Graphite Powder), carbon fiber (Carbon Fiber) or CNT (Carbon Nanotube), then can be palladium, rhodium, platinum, gold etc. as for this metal powder.And when using this conductive carbon material, can have one 3 ~ 60% weight ratio of this plastic rubber substrate.When using this metal powder, then can have one 0.1 ~ 5% weight ratio of this plastic rubber substrate, but and conductive carbon and any two or more uses that mix of metal powder.This resin base material of this plastic cement conductive material can be an epoxy resin (epoxy), itself and this conductive carbon material or this metal powder stir and are one liquid and inject first groove 50 of insulating substrate 40 and first perforation, 41, the first buss 42 and promptly form one with insulating substrate 40 and closely connect.
A kind of electrochemical transducer[sensor of the present invention, be used to detect a fluid sample, it comprises an insulating substrate 40, it has one first groove 50 and one first perforation 41, one first bus 42, be to be connected with insulating substrate 40, so that first bus 42 is arranged in first groove 50, and first bus 42 has one first output terminal 43 and a guide wire lead 45 and relative one second electrode tip 44, and with second electrode tip 44 is one first test electrode 44, first test electrode 44 promptly is arranged in first perforation 41, and a chemical reagent 60, it is arranged on first test electrode 44, in order to detect a composition of this fluid sample, and then produce a measuring-signal, and through first test electrode 44 to export this measuring-signal.
See also Fig. 8 (b), structure of the present invention can also comprise an insulation course 80, use so that first bus 81 obtains insulation effect, and first test electrode 82 is the electrode leading points 82 for first bus 81.First test electrode 82 of this structure is to be a working electrode 82, and also has one second bus 83, and insulating substrate 84 promptly is provided with one second groove 85 and one second perforation 86, so that one second test electrode 87 of second bus 83 and second bus 83 to be set respectively.Second test electrode 87 is a pair of electrodes 87.
See also Fig. 8 (b), this insulating substrate 84 has one and flows into recess 88, and for the inflow of this fluid sample, and insulating substrate 84 has fluid inlet 89, and fluid intake 89, inflow recess 88, first perforation 891 and second perforation 86 are formed in one.This structure can also comprise an overlayer 892, and the inflow recess 88 of insulating substrate 84 has a storing recess 894, and for the complete storing of chemical reagent 895, and overlayer 892 forms a measured zone 893 with inflow recess 88.Overlayer 892 can be a transparent or semitransparent sheet, it is that an electrode end face 91 with first test electrode 82 forms a difference in height Δ that one of this measured zone is measured bottom surface 90 (seeing Fig. 9 (a) for details), and electrode end face 91 forms a synthetic bottom surface 92 with putting recess 894, for the coating of chemical reagent 895.Chemical reagent 895 is to inject storing recess 894 with a certain amount of pattern after the furnishing liquid state, and forms a uniform thickness Δ of chemical reagent 895 on synthetic bottom surface 92.
See also Fig. 8 (b), demonstrate among the figure transparent window 896 is arranged on the overlayer 892 (or translucent window also can), observe this fluid sample in order to a user, and transparent window 896 is printed on a direction mark 898, to remind this user, insulating substrate 84 has two and replaces projection 897, replacing overlayer 892, and utilizes and replaces the viscose that projection 897 is isolated this fluid sample and overlayer 892.
See also Fig. 9 (a), this insulating substrate can have one first entrance side 93 and one second relative pore side 94, is respectively as fluid intake 89 and form an air vent openings 94, and air vent openings 94 is beneficial to this fluid sample and makes a Capillary Flow.
See also Figure 10, its structure also have one the 3rd bus 100, and insulating substrate 101 is provided with one the 3rd groove 102 and one the 3rd perforation 103, be a reference electrode (ReferenceElectrode) with one the 3rd test electrode, 104, the three test electrodes 104 that the 3rd bus 100 and the 3rd bus 100 are set respectively.
See also Figure 10, the overlayer 107 of this structure is to weave cotton cloth or plastic net sheet material for one, presenting a mesh window 109, and has 60 ~ 300 mesh numbers.Is to handle (hydrophilic coating) through hydrophilic cover and measure concave surface 108 one with this tectal bottom surface 1091.
See also Fig. 6, Fig. 7, Fig. 8 (b), Figure 10, Figure 11, Figure 12 (a) and Figure 13, first test electrode (working electrode) of this structure or second test electrode (to electrode) or the 3rd test electrode (reference electrode) can be through the pre-process of electrode, as with the solution polishing, with the powder polishing, with various programs such as pure water or deionized water ultrasonic cleansings, totally there are not other foreign material of absorption to determine electrode surface.
See also Fig. 6, Fig. 7, Fig. 8 (a), Fig. 8 (b) and Figure 10, Figure 11, Figure 12 (a) and Figure 13, first test electrode (working electrode) of this structure or the 3rd test electrode (reference electrode) are through after the pre-process of electrode, with distinct methods and program, this test electrode is modified the modified electrode (Modified Electrode) that (Modify) becomes different special-purposes again.As plating coating monochlor(in)ate silver (AgCl) layer with screen painting mode or electrolysis through the 3rd test electrode after the electrode pre-process, as Figure 10 105, Figure 12 (a) and Figure 12 (b) 126, visible the 3rd test electrode 71 is to be provided with one silver medal/silver chloride layer 72 among 138 and Fig. 7 of Figure 13, handle the back forming monochlor(in)ate silver reference electrode through this electrode modification (Modified Electrode), and label be 73 be pair of electrodes.
And first test electrode of this structure is coated with one deck chemical reagent (Reagent Matrix) through electrode pre-process and electrode modification (ModifiedElectrode) processing, to form a working electrode, as working electrode 44 at Fig. 7,124 etc. of the chemical reagent 895 of Fig. 8 (b), the chemical reagent 106 of Figure 10 and Figure 12 (a) and Figure 12 (b).This chemical reagent is to produce an electrochemical reaction with this composition of this fluid sample, and transforms the measured value that this measuring-signal is an electrical parameter, and the measured value of this electrical parameter is relevant to a material concentration of this composition.The chemical reagent of this modification working electrode can comprise enzyme (Enzyme such as Glucose Oxidase, enzyme catalysts such as Uricase), pH-value buffering agent (PHBuffer such as Citrate buffer), interfacial agent (Surfactant, the FC-170C of Surface Active Agent such as 3M), redox reaction electron mediator (Redox Mediator such as Ferricyanide), hydrophilic high molecular polymers (Hydrophilic Ploymer Compound is as the mixing of Polyethylene Oxide or Carboxymethyl Cellulose etc.) etc. are formed compound.Its each chemical raw material can be mixed with different ratio gradation (or once) and gradation (or once) with its curing (immobilized, coated) on working electrode.
Enzyme in the chemical reagent of this structure can have a glucose oxidase (Glucose Oxidase), thinks the whole blood (Whole Blood) of testing human, and this fluid analysis thing is blood candy (Glucose) concentration in the human blood.
Enzyme in the chemical reagent of this structure can have a urea oxidase (Uricase), thinks the whole blood of testing human, and this fluid analysis thing is uric acid (Uric Acid) concentration in the human blood.
The enzyme of the chemical reagent of this structure in being can have a cholesterol oxidase (CholesterolEsterase and Cholesterol Oxidase), think the whole blood of testing human, this fluid analysis thing is cholesterol (Cholesterol) concentration in the human blood.
See also Figure 11, overlayer 110 is to have a printed conductive metal film 111 via printing, conductive metal film 111 can be printed as two isolate conductive films and think a reference electrode 112 and pair of electrodes 114, and join with insulating substrate 116,118 at one pore and a flow detecting electrode 115 are positioned at second perforation 117 jointly, and this convection current pore 118, inflow recess 1193 and fluid intake 1192 form the capillary convection passage of fluids.1121,1131,1141,1151 is the output terminal of each test electrode, and another " ㄈ " type opening 1191 is thought the position of printed conductive metal membrane electrode output terminal 1121,1141.The 4th electrode 115 is the flow detection electrode of a fluid, when fluid is flowed into 115 beginnings of the 4th electrode at last and finishes filling through flowing into recess 1193, working electrode 113 by fluid intake 1192, if fluid no show the 4th electrode 115, then meter (consulting the meter 150 of Figure 15) can detect the 4th electrode 115 and not learn that through fluid communication fluid does not fill up with other electrodes.
See also Figure 12 (a); last layer insulation glue-line 121 is also printed at the back side of the insulating substrate 120 of this structure; so that the part of bus except that electrode area and electrode output formed an insulation protection effect, can directly immerse in the solution to be measured in order to whole sensor.The visible chemical agent 124 on a working electrode 123 that takes up in the container 127 of Figure 12 (b), the silver chloride modified electrode 126 on the reference electrode 125, and to electrode in 122 position, whole sensor can directly immerse in the solution to be measured.This chemical reagent can produce an electrochemical reaction with this composition of this fluid sample, and transforms the measured value that this measuring-signal is an electrical parameter, and the measured value of this electrical parameter is relevant to a material concentration of this composition.
See also Figure 13 (a), another embodiment of one three-pole electrode is shown, shown 133 is a netted window, it is placed in a netted window and puts in the recess 132, this storing recess has a working electrode 134, pair of electrodes 135, a reference electrode 131, a chemical reagent 137, monochlor(in)ate silver layer 138 etc. simultaneously, also have an overlayer 136 to place netted window top, surrounded a measured zone should put recess.Know that by Figure 13 (b) this overlayer 136 has an opening and thinks fluid inlet, this fluid can directly be splashed into by netted window, this netted window 133 is to handle (hydrophilic coating) through a hydrophilic cover with this storing recess 132, is full of whole measured zone easily fully in order to fluid.
The insulating substrate 40 of Fig. 4 is to adopt a polyvinylchloride (polyvinyl chloride), polypropylene PP (Polypropylene), polycarbonate (Polycarbonate), poly terephthalic acid butenylidene ester PBT (Polybutylene Terephthalate), polyethylene terephtalate (Polyethylene Terephthalate), inferior benzene PPO (Modified PolyphenleneOxide) of polyoxygenated or acronitrile-butadiene-styrene resin ABS plastic resins such as (Acrylonitrile Butadiene Stytene).
Again according to the enforceable technical scheme of another kind, the structure of a kind of electrochemical transducer[sensor of the present invention, be used to detect a fluid sample, it comprises an insulating substrate 40, it has one first dented space (as first groove 50 and one first perforation 41), one first electric installation (as first bus 42), be located in first dented space 50, first electric installation 42 has one first output terminal 43 and one second relative electrode tip 44, and with second electrode tip 44 is one first test electrode 44, an and chemical reagent 60, it is arranged on first test electrode 44, in order to detecting a composition of this fluid sample, and then produce a measuring-signal, and through first test electrode 44 to export this measuring-signal.
As shown in Figure 4, this first electric installation is to be one first bus 42, and this first dented space includes one first groove 50 and one first perforation 41, and first bus, 42, the first test electrodes 44 are set in first groove 50 promptly are arranged in first perforation 41.See also Figure 16 and Figure 17, this first electric installation is to change one first conductive cushion block (Pad) 160 into, and this first dented space is one first perforation 161, first of this first conductive cushion block 160 is electrode face long-pending 177, this structure also has one first printed conductive metal film 162 with the printing of metal cream and is printed on second an of insulating substrate, and it is connected to receive this measuring-signal mutually with one first electrode output 164.First perforation 161 can also have one and enlarge groove 165, to put an enlarged base 176 of first conductive cushion block 160.Though this printed conductive metal film 162 of present embodiment is the output terminal of first test electrode (working electrode), but it directly links to each other with effective working area 177 nothings of working electrode, so metal cream printing conductive film does not have the misgivings that chemistry disturbs with treating fluid measured to contact, any instability of its printed dimensions can not influence working electrode area 177 yet, so all have no adverse effects on the detection signal measuring stability, and its resistance value and improving that can reduce this guide wire lead45 of this first bus 42 (please refer to Fig. 4) is measured stable.First test electrode 951 of Fig. 9 (b) is with plastic cement carbon containing conducing composite material ejection formation, it can be reduced to below 300 Ω by electrode area 951 to the all-in resistance of electrode output 953, it has reduced tens of times than the resistance value that carbon film prints electrode, but it is still than the high several times of low price metal cream printing conductive film (can be lower than 10 Ω as the elargol impedance).The embodiment of Figure 16 of the present invention has the present invention and contains the stable working electrode optkmal characteristics (carbon film that disturbs with respect to same nothing chemistry prints electrode) of the one nothing chemistry interference of carbonaceous conductive composite wood ejection formation, low electrode impedance and area size with the low price plastic cement, but other electrodes beyond working electrode and all available low price metal of the guide wire Lead cream printing conductive film of each electrode are realized, so that advantage is brought into play separately.Please refer to Figure 14 (a) is the plastic cement ejaculation conductive electrode of one or two electric pole type and the compound embodiment that metal cream prints electrode, first bus (Conductive Strip) 143 is with the moulding of plastic cement conductive material, electrode face long-pending 147 moulding in first perforation 146 can obtain one and be lower than 0.6% error with interior stabilized electrodes area, and 145 its demand events of not having chemistry interference and electrode area dimensionally stable can be printed one first printed conductive metal film 145 on insulating substrate 141 by metal cream to electrode (Counter Electrode), improve the measurement accuracy of electrochemical sensor to obtain lower electrode impedance.Figure 14 (b) is the compound embodiment of another three electric pole type, one second printed conductive metal film, 149 electrodes and the first printed conductive metal film are printed on the insulating substrate simultaneously to form a reference electrode, and monochlor(in)ate modified by silver layer 148 is in order to be modified to monochlor(in)ate silver reference electrode with 149.Embodiment of the invention Figure 18, Figure 19, Figure 20 all are the extensions again that a plastic cement penetrates the compound embodiment spirit of a conductive electrode and a printed conductive metal membrane electrode.
According to the suitable technological layer of another kind, see also Figure 18 again, a kind of electrochemical transducer[sensor of the present invention is used to detect a fluid sample, and it comprises: one first conducting element 180, and it has one first test electrode 181; One insulating substrate 182 has one first dented space 183, to put first conducting element 180; One first printed conductive metal film 184, itself and insulating substrate 182 join, first printed conductive metal film 184 tools, one first output terminal 185 and the one second relative cohesive end 186, and be connected mutually with first conducting element 180 with second cohesive end 186; And a chemical reagent 187, it is arranged on first test electrode 181, in order to detecting a composition of this fluid sample, and then produces a measuring-signal, and through first test electrode 181 to export this measuring-signal.
Insulating substrate 182 can have one second dented space 188, to put one second conducting element 189, and this structure also has one second printed conductive metal film 1891, and itself and the first printed conductive metal film 184 are printed on the insulating substrate 182 simultaneously, in order to be connected second conducting element.First dented space 183 of Figure 18 is first dented space 190 that can make the pattern shown in Figure 19 (D) into again, this first dented space 190 also links to each other with a sidepiece groove 191, one first " U " type conducting element 1901 is placed in this first dented space 190 and this sidepiece groove 191 simultaneously and forms close-fitting, first side 1903 of this first " U " type conducting element places in first dented space 190 and forms one first test electrode 1903, one first printed conductive metal film 193 is printed on the insulating substrate 199, first cohesive end 193 is connected mutually, to export the measuring-signal of this first test electrode 1903 with a conducting element interface 1904 of second side of this first " U " type conducting element 1901.And also comprise an insulation course 192, in order to cover the first printed conductive metal film 193 and this conducting element interface 1904, " design of type conducting element can be printed in the same one side of insulating substrate top electrode with one second and one the 3rd printed conductive metal film 19,198 to this U simultaneously in order to this first printed conductive metal film 193.Insulation course 192 also has one and flows into recess 194, and for the inflow of this fluid sample, and insulation course 192 has one and be " ㄈ " shape opening 195, to form a measurement space 196 (seeing Figure 19 (a) for details).This structure also includes one second and one the 3rd printed conductive metal film 197,198, be to be printed in simultaneously on the insulating substrate 199 with the first printed conductive metal film 193, can see an overlayer 1991 from Figure 19 (b) and be positioned on the insulation course 192, Figure 19 (c) demonstrates a modified electrode 1992 and is positioned at the second printed conductive metal film, 197 tops.
As technological layer from another kind of equity, see also Figure 20 (a), a kind of electrochemical transducer[sensor of the present invention, be used to detect a fluid sample, it comprises: a plastic cement penetrates conducting strip 200, it has one first output terminal 201 and one second electrode tip 202, and is one first test electrode 202 with second electrode tip 202; One insulating substrate 203 is to join with conducting strip 200, and has an electrode perforation 204, to put first test electrode 202; And a chemical reagent 205, it is arranged on first test electrode 202, in order to detecting a composition of this fluid sample, and then produces a measuring-signal, and through first test electrode 202 to export this measuring-signal.
As technological layer from another kind of equity, see also Figure 20 (C), a kind of electrochemical transducer[sensor of the present invention, be used to detect a fluid sample, it comprises: with a smooth conductive base 2001 of a plastic cement conducing composite material moulding, it has one first output terminal 2011 and one second electrode tip 2021, and is one first test electrode 2021 with second electrode tip 2021; One first insulation course 2031, be to join with this smooth conductive base 2001, and this first insulation course 2031 has an electrode perforation 2041 to form a depression electrode area 2041 of first test electrode 2021, and form one with this electrode perforation and put storing place that recess 2041 is thought a chemical reagent 2051, this chemical reagent is in order to detect a composition of this fluid sample, and then produce a measuring-signal, and reach this first output terminal 2011 to export this measuring-signal through first test electrode 2021.Certainly, the structure of this moment can also comprise monochlor(in)ate silver layer 2061, is arranged on the one second printed conductive metal film 2071, and becomes monochlor(in)ate silver reference electrode.
The fundamental purpose of embodiment bus (Conductive Strip) serve as the manufacture method when obtaining to help extra quality plastic cement ejaculation before the inventive embodiments of this Figure 20 replaced with conducting strip (Conductive Sheet), in plastic cement ejaculation process, need plastic rubber material is injected the film cave of plastic mould and thinks that with pressurize plastic rubber material is fully full in whole finished product, its air that former die cavity Central Plains need be had is extruded and is thought that plastic rubber material injects die cavity easily, the bus of preceding embodiment is insulated base material three bread, only surplus one side need be stayed the feeding mouth that penetrates into plastic cement again, air is wrapped and is difficult for extruding and does not cause the plastic rubber material that penetrates finished product full and cause finished product to lack material and bad in injection molding like this, the conducting strip of present embodiment all can contact with die steel at the four sides with insulating substrate, and the steel membrane sidewall can be easy to make a steel membrane venthole so that air is drawn die cavity.
Please refer to Figure 15, it is a known portable galvanochemistry meter 150, be used to insert of the present invention one electrochemical sensor test piece 841 (as Fig. 8, Figure 10, Figure 11, Figure 13 and Figure 18 to Figure 20 of the embodiment of the invention) to a draw-in groove 153 of this dosimeter, treat that fluid measured is introduced in the sensor by fluid intake 89 after a Measuring Time, this meter can show the biochemical component numerical value of fluid analysis thing to be measured.
After the comprehensive said structure explanation, the spy replenishes following practice data declaration again, can get advantage of the present invention more than you know.The influence factor that is depicted as the conduction resistance of plastic rubber ejaculate molding electrode of the present invention as Fig. 9 (b) is the synoptic diagram of conductor width (W) and conductor thickness (t), the conductor thickness t1 of the long-pending A of the conductive cross-section of the bus that the present invention finished (ConductiveStrip) can be by 0.2-3mm design arbitrarily according to need, electrically conductive film (Conductive Film) thickness of itself and traditional printing electrode only for number μ m to tens of μ m (as print electrode 20 print thickness of Fig. 2 deserted), both differ hundreds of times by thickness thickness, compare if reach the same carbon containing material low price material (not having chemical the interference) of using with same conductor length and width, the present invention can make Conductor Impedance reduce greatly.By formula of impedance:
Conduction impedance R=ρ .L/A=ρ .L/ (W.t)
ρ wherein: resistance is number L: conductor length A: cross-sectional area of conductor is long-pending
A=conductor width (W). conductor thickness (t)
Certainly the screen painting mode can select the thickness of half tone or thickness that the mesh number increases conducting film to reduce impedance, but work as the print film elevated thickness to more than the certain limit, conductive paste causes the long-pending instability of electrode face to external diffusion easily because of too thick when printing, it is even more serious that unstable higher than conduction resistance influence is measured in the unstable and influence of working area, so the conducting film of screen painting formula electrode can't thicken arbitrarily.
The invention process is for example shown in Fig. 9 (b), a thickness t 1 that accounts for the plastic cement conducing composite material shaping of 30% ratio with Carbon is that 0.6mm and width W are the bus of 1.5mm, if its electrode impedance value is with areal survey, one is that 20-50 Ω (measures with avometer Multimeter by electrode surface area 951 to the actual test value of the resistance at its electrode back side 952, influence measured resistance value and change because of the contact area of the prod of avometer and electrode varies in size) by 20-50 Ω, by the electrode back side 952 to the actual test value of resistance of the Lead section of the 30mm length of output terminal 953 is 100-220 Ω, and its sum total electricity group is lower than 300 Ω.The resistance value that prints electrode with respect to the conductive carbon film of traditional carbon back (Carbon Base) is one to improve greatly by number K Ω to ten K Ω, this can be by reference United States Patent (USP) the 5th, 985, the technology contents of the claim 2 of No. 116 patents is done relatively, it is its patent required value that its electrode impedance value with the printing conductive carbon film is not higher than 10K Ω, with the embodiment of the invention tens of times difference is arranged, it serves to show that the present invention can obtain the impedance improvement of the electrode of suitable effect with low price carbon back (CarbonBase) material.
As the long-pending size of working electrode surface as described in the preceding electrochemical measurement current formula with to measure output signal linearly proportional, so the long-pending size of working electrode surface influence stablizing of electrochemical measurement.Its electrode surface area of the embodiment of the invention is determined by the perforation area, the punching block size that the plastic cement punching block is held its mould top electrode of back successfully is can not changing of fixing, adopt multimode cave plastic mould can once penetrate the multi-disc electrode for increasing productivity effect, the scale error of multimode cave plastic mould is controlled at below 0.3% error is the general technology of plastic cement punching block, plastic cement penetrates the variability that washing shrinkage is arranged in addition, the variability of its washing shrinkage is present in different penetrate batch, the plastic cement washing shrinkage is different because of unlike material, PC for example, ABS, the total washing shrinkage of the plastic cement of the material of high-dimensional stabilities such as PBT is less than 0.5%, and its variability is the difference of total washing shrinkage between difference production is criticized, as a collection of shrink of behind the plastic rubber ejaculate molding certain example be 0.45% another batch be 0.38% then therebetween difference be 0.07%, difference between general washing shrinkage can not be higher than 0.3% (fixedly selecting same plastic cement material for use), then the size total error with plastic cement ejaculation electrode is the difference that plastic cement punching block scale error adds the plastic cement washing shrinkage, and then the present invention can reach electrode worksheet area scale error in 0.6%.
And selecting for use of traditional screen painting electrode mode half tone generally has dual mode, and one is soft silk version, and another is hard steel version.The order number and the thickness of control silk version, or the thickness of control steel version all can change the print film thickness of conducting film, and the strength that puts on half tone when more changing printing also can change print film thickness.The silk quality half tone in general multimode cave, the compact dimensions of its half tone film and error are big than the steel version, and the pellicle of soft silk version can peel off and reaming gradually in printing, conducting film can be to external diffusion before the printing back is done admittedly, conducting film is healed thick diffusion more greatly, so in the undersized electrode area of printing (as each electrode area of blood sugar test test piece during less than 2mm * 2mm), its printing error circle is a normal specifications in 5-10%, it is possible being controlled at below 5%, but its management and control needs strict, and check frequently can cause the reduction of production efficiency and cost increases.Though the half tone dimensionally stable of steel format, invar version printing position are complete to reveal emptyly, though printing conductive cream thickness is very thick can reduce resistance for it, the too thick conductive paste that makes can be big to external diffusion, and electrode area is bigger than the silk version because of the scale error that diffusion causes.Except that traditional screen painting mode, also can thick film technology (Thick Film) come the shaped electrode area, its electrode size is stable, but the very thin thickness of the conducting film of thick film production makes the carbon film electrodes conductive resistance very high to ten number K Ω.
In addition, no matter be the conducting film electrode of screen painting or thick film technology moulding, the effective working area of its real electrode is not that a size by the electrode area that prints determines separately, because of electrode area needs to link to each other with the guide line (Lead) of extraction electrode to output terminal, need stamp a layer insulating in addition to cover guide line, not all standing and guide line area under residual also is effective working area of electrode entirely of guide line, as Fig. 2 and Fig. 3 is United States Patent (USP) the 5th, 985, No. 116 situation, the working electrode area 221 of printing needs be drawn by guide line 20 and is connected to output contact 222, real working electrode area can't be determined by 221 areas separately, need to determine jointly by insulation course 223 printing positions again, because of the half tone scale error of insulation course, the diffusion of glue etc. all can change the real effectively working electrode area 22 of electrode after printing dislocation between insulation course and conductive layer or the insulation course printing.
Learn the conducting film electrode of screen painting or thick film technology moulding by last narration, the factor of the real effectively working area of decision working electrode is too many, and every factor fundamental error is big again, and with respect to the present invention in the ballast of working electrode area not only merely but also make a variation for a short time, both have very big difference.Because of the real effectively linear proportional relation of working area of the measuring-signal of electrochemical sensor size and electrode, it serves to show that the accuracy that the present invention goes up the measurement repeatability of electrochemical sensor in working electrode area stable has very big contribution.
The embodiment of the invention with the bus electrode total resistance value of low price carbon containing plastic cement conducing composite material injection molding less than 300 Ω, it does not have impedance (number K Ω to ten number K Ω) that carbon film that chemistry disturbs prints electrode and has reduced tens of times than being all, but it is still than still big a lot of with the electrode impedance of the printed conductive metal membrane electrode of metal cream (as elargol) at a low price (can less than 10 Ω).Total electrode resistance of the embodiment of the invention is less than 300 Ω, its almost high-fall guiding line segment at the plastic cement bus, this can add one program again with the traditional electrode mode of printing, (as the back side 164 of the electrode worksheet area of Figure 16) is to printing between output terminal one conducting film of metal cream (as elargol) at a low price at the back side of working electrode, then total resistance can be reduced to below 50 Ω, and metal cream conducting film can not contact the interference of event nothing chemistry with treating fluid measured at the long-pending back side of electrode face.
In addition test electrode beyond the working electrode such as reference electrode (Reference Electrode) with to electrode (Counter Electrode), it does not have chemical interference problem (working electrode just has chemical interference problem), and the print electrode instability of size of the measurement electric current so need not worry that its electrode area size can't influence sensor, so reference electrode, can be shaped obtaining penetrating the lower impedance of electrode with low price metal cream printing conductive film to the guide wire of electrode and each electrode than plastic cement, and only that working electrode is stable with the working area of asking for working electrode with the plastic cement carbon containing conducing composite material bus that is shaped, not having chemistry disturbs and electrode resistance value advantages such as (littler tens of times than traditional printing carbon film electrodes).This integrates with carbon containing conducing composite material plastic rubber ejaculate molding one working electrode, and with printing the be shaped guide wire of other electrodes and each electrode of conductive metal film at a low price, so that advantage is brought into play and also is the characteristics of the embodiment of the invention separately.
Manufacture method of the present invention comprises provides a device for injection moulding (mould), and an insulating substrate is provided, and injects the moulding material of plastic cement conduction, and a chemical reagent etc. is provided.Manufacture method and structure thereof by electrochemical transducer[sensor provided by the present invention, can obtain the surface area of the extremely low working electrode of a scale error of this electrochemical sensor, because the size that working electrode surface is long-pending and the linear proportional relation of measurement signal value of sensor are so the present invention can improve the repeatability degree of stability (Reproducibility) of electrochemical transducer[sensor measuring-signal greatly.
Again because of the bus (Conductive Strip) of the present invention by the mode shaped electrode of plastic cement ejaculation, the thickness of its bus sectional area can be designed according to need by the 0.2-3mm size, this thickness be traditional printing conducting film (Conductive Film) formula electrode with printing technology can not reach, it is tens of to hundred times that both thickness differ, thereby electrode resistance of the present invention than the electrode resistance of printing-type conductive carbon film (Carbon Conductive Film) little tens of times (if same be the conductive material of working electrode) with carbon material cheaply because avoid the chemistry of working electrode to disturb, this low electrode resistance has reduced sensor and has fallen because of measuring the transfer overvoltage that electric current produced, and has improved accuracy of measurement.
The present invention is electrode and the insulating substrate with plastic cement shoot mode shaping sensor, penetrating program in identical plastic cement can be with needed other mechanism's once-forming of sensor, as fluid intake to be measured, fluid capillary flow path groove, capillary convection pore, chemical reagent are put multiple structure once-formings such as recess, not only can reduce element assembling number to reduce cost, more can reduce the assembly error of multicomponent.
The present invention also combines the advantage separately that the plastic cement conduction penetrates electrode and traditional printing conductive metal film (Metal ConductiveFilm) electrode, the method that the plastic cement conduction is penetrated electrode is used to be shaped working electrode (WorkingElectrode) to obtain stable electrode area and not have chemical the interference, and with tradition printed conductive metal film (as the elargol) reference electrode (Reference Electrode) that is used to be shaped at a low price, to the guide wire of electrode (CounterElectrode) and each electrode etc. to obtain penetrating the lower resistance value of bus, to bring into play both advantages separately than plastic cement.
The electrode and the sensor of the electric chemical formula of making according to the present invention are applicable to the application of various electric chemical formula detecting electrode, fluid biochemical component sensor (as sewage, the test piece of pesticide concentration composition detection), biology sensor, various deserted detection test piece aspects such as (detecting test piece as blood sugar, uric acid).
In sum, the present invention really can be in the mode of a novelty, by putting an insulating substrate in device for injection moulding, to form first bus in one first groove of this insulating substrate, and can utilize first perforation of this insulating substrate, to form a working electrode of this first bus.And in this device for injection moulding of injection of the moulding material of employed plastic cement conduction, obtaining this first bus and this a plastic rubber substrate close-fitting effect to each other, and extremely suitable industrial production.
Claims (17)
1. the manufacture method of an electrochemical transducer[sensor is characterized in that, comprises:
A device for injection moulding is provided;
A kind of insulating substrate is provided, and it has first groove and first perforation that is positioned on insulating substrate one end that extend along the length direction of insulating substrate, and this first groove and the connection of this first perforation item;
This insulating substrate is sent in this device for injection moulding;
The moulding material that injects a kind of plastic cement conduction is to this device for injection moulding, in this first groove, to form one first bus, and this first bus has one first output terminal and one second relative electrode tip, and with this second electrode tip is one first test electrode, and this first test electrode promptly forms in this first perforation; And
A kind of chemical reagent is provided, and it is arranged on this first test electrode, in order to detecting a kind of fluid sample, this chemical reagent promptly with the composition reaction of this fluid sample, and then produce a measuring-signal, and through this first test electrode to export this measuring-signal.
2. the method for claim 1, it is characterized in that, this first test electrode is exported this measuring-signal to one meter, and this plastic cement conductive material is synthesized with a kind of conductive carbon material or a kind of metal powder respectively by a kind of resin base material, this resin base material is a kind of hot formed plastic cement resin or a kind of epoxy resin, and this conductive carbon material of this plastic cement conductive material is a carbon black, graphite, carbon fiber or CNT, this metal powder is a gold, platinum, palladium or rhodium, and this conductive carbon material has 3～60% weight ratio of this resin base material, and this metal powder has 0.1～5% weight ratio of this resin base material, wherein this epoxy resin and this conductive carbon material or this metal powder stir this first groove and this first perforation that is a liquid state and injects this insulating substrate, and this first bus promptly forms one with this insulating substrate and closely connects.
3. an electrochemical transducer[sensor is used to detect a fluid sample, it is characterized in that, comprises:
A kind of insulating substrate, it has first groove and first perforation that is positioned on insulating substrate one end that extend along the length direction of insulating substrate, and this first groove is connected with this first perforation;
One first bus, be to be connected with this insulating substrate, so that this first bus is arranged in this first groove, and this first bus has one first output terminal and one second relative electrode tip, and with this second electrode tip is one first test electrode, and this first test electrode promptly is arranged in this first perforation; And
A kind of chemical reagent, it is arranged on this first test electrode, in order to detecting this fluid sample composition, and then produces a measuring-signal, and through this first test electrode to export this measuring-signal.
4. electrochemical transducer[sensor as claimed in claim 3, it is characterized in that, also comprise an insulation course, use so that this first bus obtains insulation effect, and this first test electrode is a leading point for this first bus, and this first test electrode is to be a working electrode; And this electrochemical transducer[sensor also has one second bus, and this insulating substrate is provided with one second groove and one second perforation, so that one second test electrode of this second bus and this second bus to be set respectively, wherein, second test electrode is a pair of electrodes.
5. electrochemical transducer[sensor as claimed in claim 4, it is characterized in that, also has one the 3rd bus, and this insulating substrate is provided with one the 3rd groove and one the 3rd perforation, so that one the 3rd test electrode of the 3rd bus and the 3rd bus to be set respectively, the 3rd test electrode is one with reference to the utmost point.
6. electrochemical transducer[sensor as claimed in claim 4 is characterized in that:
Have a netted window on the insulating substrate and put recess, to put a netted window, the bottom of this storing recess or sidepiece are equipped with this test electrode and this chemical reagent, to form a measured zone of fluid;
This electrochemical transducer[sensor also has an overlayer to place this netted window top and to join with this insulating substrate, and this overlayer has an opening and thinks the place that splashes into that treats fluid measured to expose a part of netted window;
This netted window is a kind of weaving cotton cloth or plastic net sheet material, so that this window presents mesh, and has 60～300 mesh numbers; And/or
This netted window and this storing recess are to handle through hydrophilic cover, are full of whole measured zone easily fully in order to fluid.
7. electrochemical transducer[sensor as claimed in claim 4, it is characterized in that this insulating substrate has one and flows into recess, for the inflow of this fluid sample, and this insulating substrate has a fluid intake, and this fluid intake, this inflow recess and this first perforation are formed in one.
8. electrochemical transducer[sensor as claimed in claim 7 is characterized in that, by being seated in insulating substrate upper caldding layer and fluid intake and this inflow recess forms capillary flow path and measured zone.
9. electrochemical transducer[sensor as claimed in claim 8, it is characterized in that, this inflow recess of this insulating substrate has one and puts recess, complete storing for this chemical reagent, and one of this measured zone to measure the bottom surface be that an electrode end face with this first test electrode forms a difference in height, and electrode end face and this are put recess and are formed a synthetic bottom surface, coating for this chemical reagent, and this chemical reagent is to inject this storing recess with a kind of quantitative pattern, and forms the uniform thickness of this chemical reagent on this synthetic bottom surface.
10. electrochemical transducer[sensor as claimed in claim 8 is characterized in that:
This insulating substrate has one and replaces projection, replacing this overlayer, and utilizes this to replace projection and isolates, and makes this fluid sample be avoided this tectal viscose of contact;
This overlayer is to be a kind of sheet or a kind of transparent or semitransparent material or a kind of weaving cotton cloth, this overlayer of this sheet and have one deck printed conductive metal film wherein, and with this conductive metal film as second or the 3rd test electrode;
This electrochemical transducer[sensor also has one the 4th test electrode, treats the flow of fluid measured in order to detection, and makes the 4th test electrode become a flow detection electrode;
This overlayer of this transparent or semitransparent material has an opaque paint part, the flow situation of observing this fluid sample in order to the user, and this overlayer is printed on a direction mark, to remind this user that it is a fluid intake place;
This is weaved cotton cloth or this overlayer of plastic net sheet material presents mesh, and has 60～300 mesh numbers;
This measured zone and overlayer medial surface are to handle through hydrophilic cover, are full of whole measured zone easily fully in order to fluid; And/or
This insulating substrate has one first entrance side and one second relative pore side, is respectively as this fluid intake and form an air vent openings, and this air vent openings is beneficial to this fluid sample and makes capillary flow.
11. electrochemical transducer[sensor as claimed in claim 10 is characterized in that this sheet is a kind of plastic net sheet material.
12. electrochemical transducer[sensor as claimed in claim 10 is characterized in that:
This first test electrode, second test electrode and the 3rd test electrode can be through the pre-process of electrode, this pre-process comprises solution polishing, powder polishing, pure water ultrasonic cleansing or deionized water ultrasonic cleansing program, and is clean to determine the not having electrode surface that adsorbs other foreign material;
This first test electrode or the 3rd test electrode are also through modifying operation, to form the modified electrode of special-purpose;
The 3rd test electrode so that a silver/silver chloride layer to be set, finishing this modification operation, and forms a silver chloride reference electrode with screen painting or metallide;
This first test electrode also is provided with one deck chemical reagent through modifying operation, to form a working electrode;
The chemical reagent of this electrochemical transducer[sensor comprises the compound that enzyme catalyst, pH-value buffering agent, interfacial agent, redox reaction electron mediator, hydrophilic high molecular polymer etc. mix;
Enzyme in the chemical reagent of this electrochemical transducer[sensor has glucose oxidase, thinks the whole blood of testing human, and obtains the analysis result to this fluid sample, and this analysis result is the blood candy concentration in this human blood;
Enzyme in the chemical reagent of this electrochemical transducer[sensor has the urea oxidase, thinks the whole blood of testing human, and analyzes the uric acid concentration in this human blood; And/or
Enzyme in the chemical reagent of this electrochemical transducer[sensor has cholesterol oxidase, thinks the whole blood of testing human, and analyzes the cholesterol concentration in this human blood.
13. electrochemical transducer[sensor as claimed in claim 3 is characterized in that:
This first perforation and this first test electrode respectively have a perforation sectional area and an electrode sections is long-pending, and this perforation sectional area is to be same as this electrode sections to amass, and this first perforation is the bottom surface that is positioned at this insulating substrate;
This first bus places the bottom surface of this insulating substrate, and this first bus via first perforation to form this first test electrode, this first test electrode promptly is positioned at the end face of this insulating substrate, and the end face of this insulating substrate also has one deck first printed conductive metal film, to form one second test electrode, and the end face of this insulating substrate also has one deck second printed conductive metal film, forming one the 3rd test electrode, and this second printed conductive metal film of the end face of this insulating substrate can be thought a silver chloride reference electrode through the electrode face finish of silver chloride;
This chemical reagent is that this composition with this fluid sample produces electrochemical reaction, and transforms the measured value that this measuring-signal is an electrical parameter, and the measured value of this electrical parameter is relevant to a kind of material concentration of this composition;
This insulating substrate is to adopt a kind of plastic resin, comprises Polyvinylchloride, polypropylene, polycarbonate, poly terephthalic acid butenylidene ester, polyethylene terephthalate, the inferior benzene of polyoxygenated or acronitrile-butadiene-styrene resin; And/or
This first bus has a guide wire and connects this first output terminal and this second electrode tip, and this electrode has the bus thickness of 0.3mm-3mm, and this guide wire has the bus thickness of 0.2mm-2.8mm.
14. electrochemical transducer[sensor as claimed in claim 13 is characterized in that this insulating substrate is to be moulding in advance, and imbed this insulating substrate in one first sliver shaped device, to form this first bus.
15. electrochemical transducer[sensor as claimed in claim 13 is characterized in that this first bus is to be moulding in advance, and imbed this first bus in an insulating substrate shaped device, to form this insulating substrate.
16. electrochemical transducer[sensor as claimed in claim 13 is characterized in that this first bus and this insulating substrate are with the one-shot forming of two material shoot mode.
17. electrochemical transducer[sensor as claimed in claim 13 is characterized in that this first bus is to utilize viscose to be engaged on this insulating substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031029884A CN100451637C (en) | 2003-01-24 | 2003-01-24 | Electrochemistry type sensor and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031029884A CN100451637C (en) | 2003-01-24 | 2003-01-24 | Electrochemistry type sensor and its manufacturing method |
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| CN1519561A CN1519561A (en) | 2004-08-11 |
| CN100451637C true CN100451637C (en) | 2009-01-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1860432B1 (en) * | 2006-05-24 | 2017-12-13 | Bionime GmbH | A method for operating a measuring meter and a measuring meter |
| US20110082356A1 (en) * | 2009-10-01 | 2011-04-07 | Medtronic Minimed, Inc. | Analyte sensor apparatuses having interference rejection membranes and methods for making and using them |
| US20140190839A1 (en) * | 2012-08-06 | 2014-07-10 | Google Inc. | Contact lenses having two-electrode electrochemical sensors |
| TWI550272B (en) * | 2014-04-02 | 2016-09-21 | The Method and Structure of Biological Test Specimen | |
| CN105277597B (en) * | 2014-07-17 | 2017-09-15 | 光宏精密股份有限公司 | Electrochemical sensing test piece electric-conductor method to set up |
| CN105259221B (en) * | 2014-07-17 | 2017-09-22 | 光宏精密股份有限公司 | The electric-conductor method to set up of electrochemical sensing test piece |
| CN105021689B (en) * | 2015-07-30 | 2017-08-11 | 华南农业大学 | A kind of environmental hormone detection means and detection method |
| CN105963073A (en) * | 2016-04-22 | 2016-09-28 | 济南圣泉集团股份有限公司 | Microcurrent band-aid |
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| US5437999A (en) * | 1994-02-22 | 1995-08-01 | Boehringer Mannheim Corporation | Electrochemical sensor |
| US5985116A (en) * | 1996-12-24 | 1999-11-16 | Matsushita Electric Industrial Co., Ltd. | Biosensor |
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| US5437999A (en) * | 1994-02-22 | 1995-08-01 | Boehringer Mannheim Corporation | Electrochemical sensor |
| US5985116A (en) * | 1996-12-24 | 1999-11-16 | Matsushita Electric Industrial Co., Ltd. | Biosensor |
| CN1243951A (en) * | 1998-06-11 | 2000-02-09 | 松下电器产业株式会社 | Biological sensor |
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