CN101059504B - Method of quantifying substrate - Google Patents
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- CN101059504B CN101059504B CN2007101018445A CN200710101844A CN101059504B CN 101059504 B CN101059504 B CN 101059504B CN 2007101018445 A CN2007101018445 A CN 2007101018445A CN 200710101844 A CN200710101844 A CN 200710101844A CN 101059504 B CN101059504 B CN 101059504B
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Abstract
A method of measuring a quantity of a substrate contained in sample liquid is provided. This method can reduce measurement errors caused by a biosensor. The biosensor includes at least a pair of electrodes on an insulating board and is inserted into a measuring device which includes a supporting section for supporting detachably the biosensor, plural connecting terminals to be coupled to the respective electrodes, and a driving power supply which applies a voltage to the respective electrodes via the connecting terminals. One of the electrodes of the biosensor is connected to the first and second connecting terminals of the measuring device only when the biosensor is inserted into the measuring device in a given direction, and has a structure such that the electrode becomes conductive between the first and second connecting terminals due to a voltage application by the driving power supply.
Description
The application is the original application (applying date: November 30 calendar year 2001; Application number: 01804349.6; Denomination of invention: biology sensor, biology sensor are with the quantivative approach of measurement mechanism and matrix) divide an application (the applying date: November 30 calendar year 2001; Application number: 200510003679.0, denomination of invention: biology sensor, biology sensor are with the quantivative approach of measurement mechanism and matrix) divide an application.
Technical field
The biology sensor that the present invention relates to quantitatively to be included in the matrix in the test liquid use measurement mechanism with this biology sensor, and a kind of quantivative approach that can reduce the biology sensor measuring error newly particularly is provided.
Background technology
Biology sensor be utilize biomaterials such as microorganism, enzyme, antibody, DNA, RNA molecular recognition can, with biomaterial as molecular recognition elements sensor that use, quantitative test test liquid mesostroma content.Promptly, utilize the reaction of generation when being familiar with biomaterial as purpose matrix, quantitative test is included in the matrix in the test liquid, for example, utilize the consumption, enzyme reaction, luminous etc. of the oxygen that the breathing of microorganism causes, quantitative test is included in the matrix in the test liquid.And the practicability of enzyme sensor develops rapidly, for example just is being used in medical treatment detection and food industry as glucose, lactic acid, cholesterol, amino acid with the enzyme sensor of biology sensor in various biology sensors.The electron reduction electric transmission body that this enzyme sensor is generated by the reaction that is included in matrix and enzyme etc. in the test liquid as a corpse or other object for laboratory examination and chemical testing, measurement mechanism by the also commercial weight of that electric transmission body of electrochemical detection, carry out the quantitative test of a corpse or other object for laboratory examination and chemical testing.
Various forms about this biology sensor have been proposed.Here, following explanation prior biological sensor biology sensor Z.Figure 16 (a) is the exploded perspective view of biology sensor Z, and Figure 16 (b) illustrates the pie graph of the electrode part on the front end that is formed on biology sensor Z.The quantivative approach of the matrix of test liquid in the biology sensor Z of this structure is described with reference to Figure 16 (b).
At first, biology sensor Z is inserted measurement mechanism, by this measurement mechanism apply certain voltage between to electrode 1103a and potential electrode 1103b, under such state, test liquid is supplied to the inlet 1106b on sample supply road.Attracted to the inside on sample supply road by the capillarity test liquid, through near its inlet 1106b to electrode 1103a, arrive potential electrode 1103b, begin to dissolve reagent layer 1105.At this moment, measurement mechanism detects and is created in the electric variation between electrode 1103a, potential electrode 1103b, the beginning paced work.Come the matrix content of quantitative sample liquid like this.
Specifically, oxidoreducing enzyme and the electronics receptor of taking on the reagent layer are dissolved in the test liquid, and carry out enzyme reaction between the matrix of test liquid, the electronics receptor is reduced.After reaction ends, with this electronics receptor electrochemical oxidation that is reduced, measure the substrate concentration the test liquid from the oxidation current value that at this moment obtains.
But prior biological sensor Z existence needs the problem of solution.Particularly during the electric variation in detecting reagent layer 1105, the such problem of measuring accuracy sensitivity of various factor affecting measurement mechanisms.
The 1st is the problem that causes because of misoperation of users.For example, hope to access can avoid because of 1. user in a single day test liquid is supplied to the sample supply road after, before measurement mechanism quantitatively is over; Further supply and supply with test liquid, 2. use the biology sensor of having used to attempt quantitative test again, 3. test liquid is supplied to wrong place, 4. the direction of biology sensor with mistake is inserted on the measurement mechanism, 5. can not test liquid be well lighted on the inlet on sample supply road; Since test liquid attached to around it, can not test liquid to be imported to the sample supply road medium, influences the method for these user's operating mistakes of measuring accuracy.The method that particularly can avoid the misoperation of users at advanced age.
The 2nd is the problem that the characteristic because of the measuring object thing causes.For example, under the situation with the concentration of glucose of biology sensor quantitative test from human intake's blood, the viscosity of blood influences measuring accuracy sometimes.Say that generally we know that hematocrit is arranged as the index of blood viscosity.Hematocrit is that red blood cell accounts for the volumetric ratio (%) in the blood.Say that generally moisture is not 50～60% in the human blood of anaemia, red blood cell accounts for 40～50%.Hematocrit descends when becoming renal anemia because of chronic renal failure, and situation about dropping to below 15% is also arranged.For the influence of carrying out suitable metacheirisis, suppressing the hematocrit of blood is necessary the concentration of glucose in the correct measurement blood, for example the diabetic just needs the concentration of glucose in the correct measurement blood.
The 3rd is the problem that the ambient temperature effect that relates to when measuring causes.Now, the biology sensor of popularizing arrives the portable degree of user with measurement mechanism miniaturization.Therefore, the situation of after the user moves within doors outside the room, testing immediately is inferior, and the temperature in measurement mechanism is unstable sometimes just begins before to measure.Oxidation current value, the measuring accuracy corresponding with substrate concentration because of the influence of temperature change of fierceness degenerate.Also have, the body temperature of user's self hand etc. is transmitted to measurement mechanism, and the temperature variation that causes because of body temperature also influences measuring accuracy.
As stated, the objective of the invention is: the good biology sensor of a kind of user's processing ease, measuring accuracy is provided, uses the quantitative analysis method and the measurement mechanism of biology sensor.
Summary of the invention
For solving above-mentioned problem the 1st form of the present invention is a kind of biology sensor; It is a kind ofly be inserted on the measurement mechanism, for quantitative test is included in the biology sensor of the matrix in the test liquid, measurement mechanism has following structure: a plurality of splicing ears that dress takes off freely the support sector that is supported in the biology sensor that has formed at least one pair of electrode on the insulated substrate, be electrically connected respectively with this electrode, apply the driving power of voltage respectively to this electrode through this splicing ear; Any one of the electrode of said biology sensor has following electrode structure: only when said biology sensor is inserted into the situation of support sector of measurement mechanism with the direction of regulation; The 1st splicing ear that possesses on the measurement mechanism just is connected with the 2nd splicing ear; And; Apply voltage by said driving power, make conducting between said the 1st splicing ear and the 2nd splicing ear.
On at least a portion of said insulated substrate, form conductive layer, said conductive layer by slit cut apart form said to electrode and potential electrode, also can further form detecting electrode as required.
Also have; The 2nd form of the present invention is that a kind of biology sensor is used measurement mechanism; It is to have a plurality of splicing ears of being electrically connected respectively with the support sector that supports freely in the biology sensor loading and unloading that formed at least one pair of electrode on the insulated substrate, with this electrode and on this electrode, apply the driving power of voltage respectively through this splicing ear, and quantitative test is included in the biology sensor of the matrix in the test liquid of supply on this biology sensor and uses measurement mechanism; Said measurement mechanism possesses to have only when said biology sensor and is inserted under the situation in the said support sector just any one the 1st splicing ear that is connected and the 2nd splicing ear in the electrode with biology sensor by prescribed direction; Apply voltage to the 1st splicing ear and the 2nd splicing ear respectively by said driving power, detect between said the 1st splicing ear, the 2nd splicing ear whether conducting.
Under the situation of conducting, said measurement mechanism can judge that said biology sensor is not inserted into the direction of regulation between detecting less than said the 1st splicing ear, the 2nd splicing ear.
Judging that said biology sensor is not inserted under the situation of prescribed direction, said measurement mechanism also can further possess the efferent of judged result to outside output.
Also have; The 3rd form of the present invention is a kind of stroma Quantitative method; It is a kind of biology sensor to be inserted into the stroma Quantitative method that quantitative test on the measurement mechanism is included in the matrix in this test liquid, biology sensor have at least a portion of insulated substrate, form the electrode part that comprises electrode, potential electrode and detecting electrode, with test liquid supply to this electrode part the sample supply road, with the reagent layer of the test liquid reaction of supplying with through this sample supply road; Measurement mechanism has the support sector of loading and unloading biological support sensor freely and is splicing ear and the driving power that applies voltage to this electrode part; Be inserted at said biology sensor under the situation of support sector of said measurement mechanism, saidly apply voltage respectively by said driving power to electrode and said potential electrode the 1st group, said potential electrode or to electrode and said detecting electrode the 2nd group.
On sample supply road, said biology sensor upper edge from the sample supply mouth to the flow direction of sample, form electrode, potential electrode and detecting electrode; Wherein detecting electrode is formed on downstream; Whether supplied with measuring the test liquid of necessary sufficient quantity by differentiating the threshold value that whether surpasses regulation from said the 1st group, the 2nd group electric current of exporting of said electrode part, differentiating.
Above surpassing under the situation of the threshold current of stipulating from said the 2nd group of electric current that comes after the threshold value of said regulation, in the elapsed time of regulation, can judge the test liquid deficiency from said the 1st group of next electric current.
Judging under the not enough situation of test liquid, also can be by measurement mechanism to its information of outside output.
Surpass under the situation of threshold value of regulation from said the 2nd group of electric current that comes after surpassing the threshold value of said regulation from said the 1st group electric current that comes, in the elapsed time of regulation; For gauger's operation of additional services test liquid once again, measuring process is standby temporarily also.
On the sample supply road of this said biology sensor, from the sample supply mouth to the flow direction of sample, form electrode, potential electrode and detecting electrode; Wherein detecting electrode is in downstream; Meanwhile; On the more downstream of said detecting electrode, possess for impelling the exhausr port of test liquid circulation; When said the 1st group of situation of the threshold value that surpasses said regulation of elder generation also of the current ratio of coming, in the elapsed time of regulation, when said the 1st group of electric current that comes surpasses the threshold value of regulation, also can judge test liquid sucking by mistake from exhausr port from said the 2nd group.
Detecting after said the 1st group of electric current that comes surpass the threshold value of regulation,, also can revise and quantitative values by the corresponding matrix of the electric current of said electrode part detection according to the elapsed time that surpasses the threshold value of regulation from said the 2nd group of electric current that comes.
Said measurement mechanism further possesses the storage part that storage shows the detection data that the amount of the matrix that comprises in the electric current that detected by said biology sensor and the said test liquid is corresponding.
Also can be by quantitative values with reference to detection data, the decision of the said storage portion stores matrix corresponding with said detection electric current.
After test liquid is supplied with the sample supply road; With test liquid and reagent layer when certain hour is cultivated the quantitative matrix in back; After detecting the threshold value of said the 1st group of electric current that comes above regulation; According to elapsed time, also can change said incubation time from said the 2nd group of electric current that comes to the threshold value that surpasses regulation.
In said the 1st group, the 2nd group any one group, also can be at a distance from the place that applies of certain hour switched voltage.
The 4th form of the present invention is the quantivative approach of matrix; It has biology sensor, measures sample and measurement mechanism; Biology sensor has and measures the reagent layer of the matrix generation idiosyncrasy in the sample; Measurement mechanism is from obtaining the matrix amount that is included in the said measurement sample with the sample of the reagent of said reagent layer reaction; Said measurement mechanism possesses temperature survey portion and temperature correction data store, the temperature when temperature survey portion measures said measurement test liquid and said reagent layer and reacts, and temperature correction data store has because of several different measured value correction charts of temperature province; Select with the corresponding correction chart of temperature of said temperature survey portion measurement, calculate the modified value corresponding, revise with the measured value of said matrix.
Said biology sensor has the electrode part to electrode, potential electrode that comprises at least a portion that is formed on insulated substrate; And said measurement mechanism also can be used as and on said electrode part, applies voltage, detects from the measurement mechanism of the electric current of electrode output.
The 5th form of the present invention is the quantivative approach that is included in the matrix in the test liquid of supplying with biology sensor by the measurement mechanism measurement; Said measurement mechanism possesses the temperature survey portion of the temperature in the measurement mechanism; Temperature detection from the temperature that before said substrate measurement, obtains earlier and said matrix when quantitative goes out variation of temperature, judges whether carry out the measurement of said matrix according to this temperature variation.
The temperature variation of temperature that detection obtains before substrate measurement and the temperature when said substrate measurement surpasses when this temperature variation under the situation of the threshold value of stipulating, also can end the measurement of said matrix.
Temperature survey before the substrate measurement also can interrupted carrying out.
The 6th form of the present invention is to use biology sensor and measurement mechanism; Biology sensor has comprising the electrode part of electrode, potential electrode and the reagent layer that reacts with the test liquid of supplying with this electrode part at least a portion that is formed on insulated substrate; Measurement mechanism has the support sector of the loading and unloading said biology sensor of support freely and is splicing ear and the driving power to each electrode application voltage of this electrode part; It is on said electrode part, to be applied voltage, detected the electric current of exporting by this driving power; Quantitative test is included in the stroma Quantitative method of the matrix in this test liquid; Said measurement mechanism after being applied on the said electrode part during the said the 1st, stops to apply of said the 1st current potential applying the 1st current potential during the 1st on the electrode part of the said biology sensor of being supported by said support sector to said the 1st current potential during standby; After during the described standby; Applying the 2nd current potential during the 2nd on the said electrode part, coming quantitative matrix by the electric current of measuring output, said the 1st current potential is bigger than said the 2nd current potential.
The 7th form of the present invention by 2 pieces of substrates bonding, be formed in the sample supply road of taking test liquid between said substrate; The opening that on its sample supply road, will be located at said two substrates end is as inlet; Can said test liquid be imported such formation biology sensor; It is characterized in that: the end that constitutes the two substrates of said inlet is seen looking from the plane of said biology sensor, is positioned on the different each other positions.
Description of drawings
Fig. 1 is the figure that the bio-sensor system relevant with the present invention is shown.
Fig. 2 is the exploded perspective view of the biology sensor relevant with the present invention's the 1st embodiment.
Fig. 3 illustrates and combination with the identification part of relevant the having or not of the embodiment biology sensor that slit forms.
Fig. 4 be with the relevant biology sensor of embodiment and the structural drawing of measurement mechanism.
Biology sensor when Fig. 5 illustrates the matrix amount of quantitative sample liquid and the processing flow chart of measurement mechanism.
Biology sensor when Fig. 6 illustrates the matrix amount of quantitative sample liquid and the processing flow chart of measurement mechanism.
Biology sensor when Fig. 7 illustrates the matrix amount of quantitative sample liquid and the processing flow chart of measurement mechanism.
Fig. 8 illustrates the adjusted rate of the ratio that the matrix amount of measuring is revised and the figure of the relation of time delay.
Fig. 9 illustrates the sectional view that preliminary measurement is handled.
Figure 10 illustrates the graph of a relation of the viscosity of blood, the reaction time of reacting reagent layer and blood and measurement sensitivity.
Figure 11 is the figure that the existing method and the measurement result of the concentration of glucose (mg/dl) of this preliminary measurement processing are shown.
Figure 12 illustrates the example of slotted line data CA.
Figure 13 illustrates an example of temperature correction chart.
Figure 14 is the figure of relation that measurement temperature and the measured deviation of each substrate concentration are shown.
Figure 15 is the figure that is illustrated in the temperature variation in the measurement mechanism.
Figure 16 is the exploded perspective view that the prior biological sensor is shown.
Figure 17 illustrates the exploded perspective view and the sectional view of biology sensor in the present invention's the 2nd embodiment.
Figure 18 is the amplification plan view that illustrates with the sample supply road of biology sensor.
Figure 19 is exploded perspective view and the sectional view that illustrates with other example of biology sensor.
Figure 20 is the amplification plan view that illustrates with the sample supply road of biology sensor.
Figure 21 illustrates the key diagram that attracts test method with the blood of biology sensor.
Figure 22 illustrates the key diagram that attracts other example of test method with the blood of biology sensor.
The reference symbol complete list of accompanying drawing:
1-bio-sensor system, 2-support sector, 10-measurement mechanism, 11-display part, 12～17-connector, 18～22-switch; 23-current/voltage-converted circuit, 24-A/D change-over circuit, 25-CPU, 26-temperature survey portion, 27-switch, 28-temperature survey portion; 29-switch, 30-biology sensor, 30a-sample is lighted portion, 31-insulativity substrate, 32-insulativity substrate, 33-airport; 34-partition, 35-sample supply road, 36-reagent layer, 37-to electrode, 38-potential electrode, 39-detecting electrode; 40,41a～41h-slit, 42-identification part, 43,44-correction portion, 51-the 1 insulativity substrate, 52-potential electrode, 53-to electrode; 54-detecting electrode, 55-reagent layer, 56-partition, 57-sample supply road, 58-the 2 insulativity substrate, 59-airport; 60～62-leading part, 63a, 63b-intersection point, 64a, 64b-intersection point, 1101, the insulativity substrate, 1102a-to electrode is with lead-in wire; 1102b-potential electrode is used lead-in wire, 1103a-and to electrode, 1103b-potential electrode, 1104-photoresists, 1105-reagent layer; 1106-partition, 1106a-sample supply road, the inlet on 1106b-sample supply road, 1107-outer cover, 1107a-airport.
Embodiment
Below, with reference to description of drawings embodiment of the present invention.In addition, it only is an example that the embodiment that illustrates here mentions head, is not only to be defined in this embodiment.
(embodiment 1)
Below, the embodiment that present invention will be described in detail with reference to the accompanying.
Fig. 1 illustrates the bio-sensor system relevant with embodiment of the present invention 1.The measurement mechanism 10 that bio-sensor system 1 has biology sensor 30 and biology sensor 30 is installed freely, dismantled.Can quantitatively light the amount of lighting the matrix that the sample on the 30a of portion comprises at the sample that is arranged in biology sensor 30 leading sections by measurement mechanism 10.
In order to use the matrix content in this bio-sensor system 1 quantitative sample liquid; At first; After the user is inserted into biology sensor 30 on the measurement mechanism 10, by measurement mechanism 10 after apply certain voltage on the electrode of the biology sensor 30 stated, light on the 30a of portion under such state test liquid being supplied to sample.The inside that the test liquid of lighting is absorbed into biology sensor 30 begins to dissolve the reagent layer.Measurement mechanism 10 detections are created in biology sensor 30 interelectrode electric variations and begin to carry out paced work.
Here, the bio-sensor system 1 relevant with this embodiment be suitable for especially as the human body of test liquid blood, also have, have as matrix the glucose that is included in the blood, lactic acid, cholesterol amount quantitatively.The quantitative of the matrix that contains in the body fluid of human body is very important to specific physically different diagnosis and treatment.Particularly, need the concentration of glucose in the frequent assurance blood for the diabetic.
In addition, though in following explanation, with announce about be included in glucose in the blood of human body quantitatively,, when selecting suitable enzyme, the bio-sensor system of this embodiment also can be used in other matrix such as quantitative lactic acid, cholesterol.
Secondly, with Fig. 2 the parts that constitute biology sensor 30 are described.Fig. 2 is the exploded perspective view of biology sensor 30.The 31st, the insulativity substrate of forming by poly terephthalic acid second two fat etc. (below, simply be called " substrate "), on the surface of substrate 31, form the conductive layer of forming by electrical conductivity property materials such as noble metals such as gold, palladium and carbon by grid print process, sputtering method.Conductive layer is formed on comprehensively going up of substrate 31 or at least a portion.The 32nd, central portion be provided with airport 33 the insulativity substrate, be clipped between substrate 32 and the substrate 31 partition 34 jaggy and substrate 31 integrated configurations.
On substrate 31, cutting apart conductive layer by a plurality of slits forms electrode 37, potential electrode 38 and detecting electrode 39.Detailed says, be formed on to the slightly circular-arc slit 40 on the electrode, be formed on substrate 31 lateral vertical directions on 41a, 41c and be formed on substrate 31 parallel directions on slit 41b, 41d, 41f and the slit 41e with V-shape shape conductive layer is cut apart formation to electrode 37, potential electrode 38 and detecting electrode 39.In addition, each electrode also can be formed at least a portion of substrate 31, also has, and being connected of measurement mechanism 10 and each electrode also can be lead.
On the covered substrate 31 of partition 34 configuration to electrode 37, potential electrode 38 and detecting electrode 39, form sample supply road 35 by the rectangle notch part of the leading edge central authorities that are located at partition 34.Also have, 30a is the inlet on sample supply road, and the test liquid of lighting at inlet 30a is attracted to (the arrow A R direction among Fig. 2) airport 33 that omits horizontal direction by capillarity.
The 36th, from what the notch part of partition 34 exposed electrode 37, potential electrode 38 and detecting electrode 39 are being applied the reagent layer that reagents such as containing enzyme, electronics receptor, amino acid and monoethylene glycol form.
Here, use as endonuclease capable: glucose oxidase, lactic acid ester oxidase, cholesterol oxidase, cholesterol esterase, uricase, ascorbic acid oxidase, bilirubin oxidase, GDH, propyl alcohol acid esters dehydrogenasa etc.
Preferably use the potassium ferricyanide as the electronics receptor, except that the potassium ferricyanide, can also use 1,4-benzoquinone and derivant thereof, azophenlyene paramethylaminophenol sulfate, methylenum careuleum, ferrocene and derivant thereof etc.
Under the situation of the bio-sensor system 1 relevant with this embodiment, be glucose oxidase for what measure that concentration of glucose in the blood of human body uses as the oxidoreducing enzyme of taking on reagent layer 36, what use as the electronics receptor is the potassium ferricyanide.
This oxidoreducing enzyme and electronics receptor are dissolved in the test liquid that is attracted on the sample supply road (under the situation at this embodiment; Be blood from the human intake), and test liquid in matrix glucose between carry out enzyme reaction, electronics receptor and be reduced and generate ferrocyanide (being the potassium ferricyanide under the situation at this embodiment).After reaction finishes, with this electronics receptor electrochemical oxidation that is reduced, the concentration of glucose from the current measurement test liquid that at this moment obtains.A series of like this reaction mainly is to carry out to the zone of detecting electrode 39 through slit 41e from slit 40, by can read the electric current of following electrochemical to change to electrode 37, potential electrode 38 and detecting electrode 39.
Also have, the 42nd, for the different identification part of discerning because of biology sensor 30 by measurement mechanism 10 of the different output characteristics of kind with the manufacturer.With the part that the identification part 42 of electrode 37, detecting electrode 39 is somebody's turn to do on, by forming the such slit 41g of Fig. 2, the combination of 41h, can discern difference because of the electric output characteristics of measurement mechanism 10.
Fig. 3 illustrates the combination of identification part 42 that has or not the biology sensor 30 of formation because of slit 41g, 41h.In Fig. 3, show 7 types combination as an example.
For example, Fig. 3 (a) is to be the identification part 42 of the biology sensor 30 under the quantitative object situation with cholesterol.In this case, slit 41g, 41h are not set.
Fig. 3 (b), (c), (d) are to be the identification part 42 of the biology sensor 30 under the quantitative object situation with lactic acid.In Fig. 3 (b), only on to electrode 37, be provided with slit 41h, formed correction portion 43.In Fig. 3 (c), only on detecting electrode 39, be provided with slit 41g, form correction portion 44.In Fig. 3 (d), on to electrode 37, detecting electrode 39, be respectively equipped with slit 41h, 41g, form correction portion 43,44.Further, Fig. 3 (e), (f), (g) are to be the identification part 42 of the biology sensor 30 under the measuring object situation with glucose.In Fig. 3 (e), only on detecting electrode 39, be provided with slit 41g, simultaneously, slit 41d only is formed into till the slit 41g.For this reason, correction portion 44 and potential electrode 38 integrated formation.In Fig. 3 (f), on the state of Fig. 3 (e), further form slit 41h and form correction portion 43.In Fig. 3 (g), till slit 41f only is formed into slit 41h on the state of Fig. 3 (f).Integrated for this reason formation correction portion 43,44 and potential electrode 38.
Like this, by the slot pattern of change identification part 42, can change area with the turning part of each electrode.Thus; Can be by the difference of the output characteristics (glucose, cholesterol, lactic acid concn) of measurement mechanism 10 identification biology sensors 30, because of manufacturer's foozle, be suitable for the measured value of obtaining that substrate concentration data measured, control program can be correct by switching.Because there is no need as existing method, the user uses input correction data such as correcting chip, can prevent the operating mistake that makes one nervous.In addition, the biology sensor with regard to 3 electrodes in this embodiment is illustrated, and number of electrodes is also can suitably change under the situation beyond 3, has at least pair of electrodes just passable.Also have, the formation figure of slit also can use the said figure in addition of Fig. 3.
Below, the structure of detailed description measurement mechanism 10.Fig. 4 illustrates the structure of biology sensor 30 (upward view) and measurement mechanism 10.Light a 30a on sample supply road 35, biology sensor 30 upper edge from sample and form electrode 37, potential electrode 38 and detecting electrode 39 to the sample flow direction, detecting electrode 39 is formed on the lower side.In addition, also can exchange configuration sequence to electrode 37, potential electrode 38.Also have, through slit 41c, 41e the distance of regulation is set between potential electrode 38 and detecting electrode 39, the test liquid of q.s can be differentiated really and absorbed to the situation that the electric current that is produced by the electric variation of following matrix changes whether.
Also have, in measurement mechanism 10, the 12,13,14,15,16, the 17th, the corresponding respectively connector that the identification part 42 of biology sensor 30 is divided into 6 regional A, B, C, D, E, F that connects.Zone A, B, C, D, E, F and slit 41d, f and slit 41g, the corresponding differentiation of h.A is corresponding with potential electrode 38 in the zone, and zone C is corresponding with detecting electrode 39, and area E is with corresponding to electrode 37.Area B and regional A are integrally formed, and region D, F be the correction portion 43,44 of corresponding diagram 3 respectively.Also have, 18,19,20,21,22 are provided in a side of each connector 13,14,15,16,17 and ground, and (being the meaning of deciding current potential, can not be to be necessary for 0 also.Identical in following instructions) between switch.In this ground, the voltage that is applied on each electrode can variablely be controlled.Each connector 13,14,15,16,17 and be connected in parallel, from connector 13～17, select necessary connector when measuring, to use by the control of the switch of each switch 18～22.
23 connect connectors 12, it is the current/voltage-converted circuit that flow through potential electrode 38 and other interelectrode electrorheological is changed into voltage output; 24 be connected, be the A/D change-over circuit that the magnitude of voltage from current/voltage-converted circuit 23 is converted to pulse with current/voltage-converted circuit 23; The switch of 25 each switch of control, be based on the CPU that calculates the matrix amount of test liquid from the pulse of A/D change-over circuit 24, the 11st, show the LCD (LCD: efferent) of the measured value of calculating by CPU.Also have, the 26, the 28th, the temperature survey portion of measuring the temperature in the measurement mechanism 10.One side of each temperature survey portion 26,28 is connected with ground, the opposing party is connected in parallel between connector 12 and the current/voltage-converted circuit 23 through switch 27,29.
In the measurement mechanism relevant 10 with this embodiment, use by will flow through each interelectrode current conversion of biology sensor 30 of current/voltage-converted circuit 23 to become magnitude of voltage (mV), detect each interelectrode change in current.In other words, magnitude of voltage becomes the index of size of current between each electrode of expression.
Below, with Fig. 5～Fig. 7 explanation when the matrix amount of the quantivative approach quantitative sample liquid of using the biology sensor 30 relevant with embodiment of the present invention, the work of biology sensor 30 and measurement mechanism 10.
At first, differentiated the whether certain support sector that is inserted into measurement mechanism 10 2 of biology sensor 30 (step S1).Whether specifically, differentiate biology sensor 30 by the switch (not shown) in the connector of Fig. 4 has inserted.(step S1 under the situation that biology sensor 30 has inserted; Yes), then carry out (potential electrode 38) conduction detection (step S2) between regional A, B.That kind as shown in Figure 3 is not provided with the slit that resembles slit 41h, the g an electrode insulation on potential electrode 38.Because regional A, B are connected with connector 12,13 respectively on potential electrode 38; When the conductive layer of biology sensor 30 with regular direction on the such direction (direction of regulation) in position biology sensor 30 is inserted under the situation measurement mechanism 10 in certainty conducting between regional AB.
So CS 18 makes it conducting, by confirming to have or not conducting can differentiate in the table of biology sensor 30 between regional AB.If between regional AB, can not detect is conducting (step S2; No), can think that biology sensor 30 is opposite insertions in the table, as differentiating the wrong measurement processing (step S3) that finishes in the table.Differentiate under the wrong situation detecting in the table, be preferably in the demonstration that makes mistake on the display part 11,, give a warning to the user from the alarm sound that gives a warning.Thus, just can avoid under the opposite state that inserts user error blood is lighted on biology sensor 30 easily with biology sensor 30 table.
If can detect between regional AB is conducting (step S2; Yes), whether differentiate the magnitude of voltage between regional A and zone C E, detect greater than 5 (mV) (step S4).By Switch Control make switch 19,21 become the conducting that kind simultaneously, by surveyed area A with regard magnitude of voltage between the zone C E of electric one as and differentiate and in step S1, insert whether the biology sensor 30 that detects is used.If biology sensor 30 is used, the reaction of the glucose in reagent layer 36 and the blood is carried out, and the magnitude of voltage of detection has the tendency that becomes big.
When differentiate the magnitude of voltage that detects between regional A and zone C E greater than the situation of 5 (mV) under (step S4; Yes), think used biology sensor 30 has been inserted, as using the wrong measurement processing (step S5) that finishes.Used under the wrong situation when detecting, be preferably in show on the display part 11 wrong, sounding from alarm gives a warning to the user.Thus, just can be easy to avoid under the state that will used biology sensor 30 inserts, user error blood is lighted on biology sensor 30.
Secondly, be lower than (step S4 under the situation of 5 (mV) when differentiating at the magnitude of voltage that detects between regional A and zone C E; No), by the slot pattern that is identified in biology sensor 30 identification parts 42 that insertion detected among the step S1, switch data and the program (step S6～10) that is fit to output characteristics by CPU25 according to this recognition result.Under the situation of this embodiment, in the example of Fig. 3, (f) (g) 3 types of slot pattern of Fig. 3 (e) are arranged on the blood glucose value sensor of measure glucose concentration.Specifically, at first, carry out the conduction detection (step S6) between regional AD.Switch transition controlled to make switch 20 conductings, differentiate it and be not the sensor used of lactic acid and cholesterol, whether be the biology sensor 30 corresponding with the blood glucose value sensor by carrying out conduction detection between regional A and region D.
If do not confirm conducting (step S6 between AD; No), differentiate the biology sensor 30 use as the blood glucose value sensor and do not have interchangeability, the warning tones that is shown, sent from alarm by the mistake of display part 11 gives a warning, finishes measurement processing (step S7) to the user.Thus, can avoid in advance user error quantitatively, its measurement result mistake letter is made concentration of glucose.
If confirmed in conducting between regional AD (step S6:Yes), just carried out conduction detection (step S8) between regional AF.Switch transition control makes switch 22 conductings, by the conduction detection of carrying out between regional A and regional F, can be identified in the biology sensor corresponding with the blood glucose value sensor 30, further can discern the difference because of the output characteristics of manufacturer.The user need not use correcting chip, change data and the program that manufacturer has considered output characteristics in advance automatically by CPU25.
Thus, not only improve operability, also can realize the high precision int of measuring accuracy.(step S8 under the situation that conduction detection is arranged between regional AF; Yes), the kind of biology sensor 30 is stored on the storer that does not show in the drawings (step S9) as the outcome record " I " of Fig. 3 (g).(step S8 under the situation that does not have conduction detection between regional AF; No), the kind of biology sensor 30 is stored (step 10) on the storer that does not show in the drawings as the outcome record " II " of Fig. 3 (e) or Fig. 3 (f).
After confirming the kind of biology sensor 30, whether differentiate the magnitude of voltage that between regional A and zone C E, detects greater than 5 (mV) (step S11) once more.Switch transition control makes switch 19,21 conductings simultaneously, by the electric current between surveyed area A and zone C E, differentiate before measurement mechanism 10 1 sides quantitatively are ready to complete, whether to have lighted test liquid by the user.Thus, the biology sensor of having used 30 is used in avoidance that not only can be certain, and can detect before measurement mechanism 10 1 sides quantitatively are ready to complete whether lighted test liquid by the user.
When differentiate the magnitude of voltage that detects between regional A and zone C E greater than the situation of 5 (mV) under (step 11; Yes), lighted test liquid before just the differentiation measurement is ready to complete, finished measurement processing (step 12) as lighting mistake.Light under the wrong situation when detecting, be preferably in show on the display part 11 wrong, sound, show that by LED (not shown) etc. gives a warning to the user from alarm.Thus, can avoid the influence that the misoperation because of the user brings measuring accuracy, the high precision that can keep measuring accuracy really.
Be lower than (step 11 under the situation of 5 (mV) when differentiating at the magnitude of voltage that detects between regional A and zone C E; No), differentiate quantitatively being ready to complete before and do not light test liquid, show etc. by LED the user is sent the notice (step 13) of quantitative preparation end by the user.Used under the wrong situation when detecting, preferably removed the LED demonstration, by the demonstration of display part 11, the alarm sound untill further notice user that alarm sends.The user who confirms these notices from the health of oneself gather blood as test liquid, will gather the blood that comes and light the sample that is inserted into the interior biology sensor 30 of measurement mechanism 10 and light in the portion.
Once more, light the 30a of portion from sample and pass to the sample supply road, confirm test liquid and differentiate the enough amounts (step S14～20) that whether attracted.In biology sensor 30, along sample supply road 35, light a 30a from sample and form electrode 37, potential electrode 38 and detecting electrode 39 towards the direction that sample flows, detecting electrode is formed on downstream one side.So, select whether any one group in 39 1 groups of electrode 37 and 38 1 groups of potential electrode, potential electrode 38 and the detecting electrodes by on each electrode of selected group, applying voltage, differentiated and supplied with measuring the test liquid of necessary q.s by certain cycle.As present; Does only the electric current by 39 of identification potential electrode 38 and detecting electrodes change, although be that test liquid has injected the sample supply road and measures and do not begin actually? Still the insufficient infusion (must measure fully measuring) because of test liquid have to measure? To specific be difficult.
Specifically, under situation to 38 1 groups of electrode 37 and potential electrode, with switch 19 break off, switch 21 conductings, make between regional AE and produce potential difference (PD).Also have, under situation, switch 19 conductings, switch 21 are broken off, make between regional AC and produce potential difference (PD) 39 1 groups of potential electrode 38 and detecting electrodes.Like this by CS 19,21 conductings respectively, disconnection, can select to change to electrode 37 and potential electrode 38 one group easily and still be potential electrode 38 and detecting electrode 39 one group.In addition; For convenience of description; In following explanation; To produce potential difference (PD) in that the situation that produces potential difference (PD) on 38 1 groups of electrode 37 and the potential electrode is called between regional AE, produce potential difference (PD) the situation that produces potential difference (PD) on potential electrode 38 and detecting electrode 39 one group is called between regional AC.
Further, as an example, under the situation of this embodiment, carry out the conversion and control between a sub-region AE, AC per 0.2 (second), applies 0.2V voltage respectively.Whether the magnitude of voltage that differentiation detects between regional AE, AC has reached 10 (mV) (threshold value of regulation).These numerical value can suitably change according to the kind of biology sensor.
The process flow diagram of getting back to Fig. 6 continues explanation.At first, between the regional AE that is positioned at upstream side position, sample supply road, produce the voltage of 0.2V, whether the magnitude of voltage of differentiating at regional AE measurements reaches (step S14) more than the 10mV.If the magnitude of voltage at regional AE measurements does not reach (step S14 more than the 10mV; No), just between the regional AC in downstream, produce the potential difference (PD) of 0.2V, whether the magnitude of voltage of differentiating at regional AE measurements has reached (step S15) more than the 10mV.
If the magnitude of voltage at regional AC measurements does not reach (step 15 more than the 10mV; No), differentiate in step S14 after producing potential difference (PD) between regional AE, whether to have passed through 3 minutes (step S16).Were it not for and reach 3 fens (step S16; No), repeat once more from the processing of step S14.If also do not reach 10mV (step S16 through 3 minutes magnitudes of voltage simultaneously between regional AE, between AC; Yes), measurement processing finishes.
Reach (step S14 under the situation of 10mV at the magnitude of voltage between determinating area AE; Yes), judge whether the magnitude of voltage between regional AC reaches 10mV (step S17).If the magnitude of voltage at regional AC measurements does not reach 10mV (step S17; No), judge after the magnitude of voltage between regional AE reaches 10mV, whether to have passed through 10 seconds (official hour) (step S18).Were it not for through 10 seconds, step S17,18 operation repeatedly, during through 10 seconds, (step S18 till the magnitude of voltage of regional AC measurements reaches 10mV; During the No) measurement processing becomes temporary transient holding state.In this case,, know that in order to promote the user test liquid is not enough and append enough test liquids because the not enough probability of the test liquid of lighting is high, be preferably on display part 11 grades show error message, sound gives a warning.Even still do not reach 10mV (step S18 through 10 seconds magnitudes of voltage at regional AC measurements; Yes), as the not enough measurement processing (step 19) that finishes of a corpse or other object for laboratory examination and chemical testing.
Here, the present inventor finds that through in 10 second time, supply the user under the situation of test liquid after the magnitude of voltage in step S14 between critical region AE reaches 10mV, final measuring accuracy degenerates.Detailed says, during being supplied by the user, owing to carry out enzyme reaction between the matrix of the test liquid formerly lighted and the enzyme in the reagent layer 36, goes back substance from measuring to have produced before the beginning.Then, the test liquid of supplying reaches between regional AC the back, when carrying out matrix quantitative, owing to receive the influence of going back substance that has produced, sees that in appearance magnitude of voltage has the tendency that becomes big.In other words, in step S14, the elapsed time when reaching 10mV along with the magnitude of voltage between determinating area AE strengthens, and is big to the influence change of measuring accuracy.
In order to remove because of supplying the measuring error that test liquid causes; In the measurement mechanism 10 of this embodiment; According to when the magnitude of voltage between determinating area AE reaches 10mV among step S14, beginning to judging that in step S17 the magnitude of voltage regional AC reaches the elapsed time (to call time delay in the following text) of 10mV, revises the matrix amount corresponding with the measured voltage value.
Fig. 8 shows the adjusted rate of the ratio that the matrix amount of having measured is revised and the sensitivity correction chart that concerns time delay.The longitudinal axis is an adjusted rate, and transverse axis is represented time delay.For example, be under 5 seconds the situation, the matrix amount of having measured to be carried out 10% low the correction when time delay, as a result of measuring 90% of matrix amount becomes revised matrix amount.Such sensitivity correction chart is stored in the storer (not shown) of measurement mechanism 10, reference when calculating final matrix amount.
Also have; In biology sensor shown in Figure 2 30; Prolong with slit 41b to the direction of slit 41c and be connected such formation fully if will be formed on slit 41f on the substrate 31, might detect the positional fault of lighting of lighting on airport 33 that kind of test liquid mistake electrode 37.In the flow process of Fig. 6, not between regional AE but reach (step S15 under the situation more than the 10mV at magnitude of voltage between regional AC earlier when judging; Yes), in judging during thereafter 0.2 second between regional AE magnitude of voltage whether reached (step S20) more than the 10mV.When not reaching under the situation more than the 10mV, judge that test liquid is lighted on the position of mistake, end measurement processing (step 50) at magnitude of voltage between regional AE.
As normal, light and light test liquid on the 30a of portion at sample and be attracted along sample supply road 35 to airport 33 orders and soak into to electrode 37, potential electrode 38, detecting electrode 39.But under the situation that only change of the magnitude of voltage between regional AC is big, the probability of on airport 33, lighting test liquid of user error becomes big.In this case, differentiate correct implementation measurements be difficult, force the end measurement processing as lighting positional fault.Thus, can remove really because of misoperation of users and cause measuring error.
Also have, reach (step S17 under the situation of 10mV at the magnitude of voltage between determinating area AC; Yes) or the magnitude of voltage between determinating area AE reach (step 20 under the situation of 10mV; Yes), test liquid only detects the value of q.s, when beginning to the preliminary treatment of quantitative matrix by the timer of measurement mechanism 10 (among the figure for illustrating) start time count (step S21).
Once more, carry out conduction detection (step S22) between regional AF.Switch transition control makes switch 22 conductings carry out the conduction detection between regional A and regional F.(step S22 under the situation that detects conducting between regional AF; Yes), whether be stored in (step S23) in the storer in step S9, judgement as the outcome record " I " of the kind of biology sensor 30.(step S23 under biology sensor 30 kind outcome record " I " quilt situation about writing down; Yes), the kind of differentiating biology sensor 30 is Fig. 3 (g), and the magnitude of voltage that will under the electronics receptor electrochemical oxidation situation that is reduced, obtain is as slotted line data, setting measurement line F7 (step S24) for the concentration of glucose the particular sample liquid.
On the other hand, (step S23 under the situation of event memory record " II "; No), the kind of differentiating biology sensor 30 is Fig. 3 (e), and setting measurement line F5 is as slotted line data (step S25).There is not (step S22 under the situation of regional AE conduction detection; No), the kind of differentiating biology sensor 30 is Fig. 3 (f), and setting measurement line F6 is as slotted line data (step S26).
Like this, can discern the difference of biology sensor 30 output characteristics automatically, select to be provided with the slotted line data of the characteristic that is fit to it automatically according to the slit of biology sensor 30 identification parts 42.The user need not use correcting chip, switches the slotted line data that manufacturer considers in advance automatically by CPU25.Thus, can avoid the mistake of using wrong data to cause because of the user and measure, can keep the high precision int of measuring accuracy.
In step S24～S26 behind the setting measurement line, the beginning preliminary measurement is handled (step S27～S29).At first, with Fig. 9 this preliminary measurement processing is described.Fig. 9 illustrates the sectional view that preliminary measurement is handled in this embodiment.
In the sectional view of Fig. 9, begin in this preliminary treatment of moment t0.Specifically, it illustrates the moment by the timer (not shown) time numeration beginning of measurement mechanism 10.In the sectional view of this preliminary treatment by forming between 3 continuing phases, for example, by forming during the 2nd current potential during the standby during the 1st current potential from moment t0 to t1, from moment t1 to t2, from moment t2 to t3.
On during the 1st current potential, on regional A, C and E, apply current potential V1 in order to carry out enzyme reaction, the increase of the magnitude of voltage exponential function that the ferrocyanide electrochemical oxidation of generation obtains down.Secondly, during standby, the current potential V1 that during the 1st current potential, applies is set at zero.During this period, ferrocyanide is not by electrochemical oxidation, and the amount of proceeding enzyme reaction, ferrocyanide continues to accumulate down.And on during the 2nd current potential, current potential V2 is applied on regional A, C and the E, because the ferrocyanide of during standby, accumulating oxidized electronics quantitative change of emitting simultaneously is many, shows high response value at moment t2.The magnitude of voltage of the high response value that shows is in time through reducing, final moment t3 measured be stable magnitude of voltage i3.In this preliminary measurement is handled, in measurement mechanism 10 by CS 19,21 conductings simultaneously, to electrode 37, detecting electrode 39 are applied current potential as one.
Here, hope to shorten Measuring Time as the specification of the biology sensor that requires in recent years.The present inventor finds that carrying out with biology sensor under the situation of high speed substrate measurement, the viscosity of test liquid has very big influence to measuring accuracy.Particularly, when the blood of human body being done under the situation of test liquid, under the situation of viscosity high (Hct is high: below be called high viscosity) blood, it is low to measure sensitivity, under the situation of viscosity low (Hct is low: below be called low viscosity) blood, measures highly sensitive.This phenomenon is to be produced by the dissolution velocity of reacting reagent layer and blood, and is fast owing in high viscosity blood, dissolving slowly, in low viscosity blood, dissolving, and influences the measurement sensitivity with biology sensor.
Figure 10 illustrates the relation of the viscosity of blood, the reaction time of reacting reagent layer and blood and measurement sensitivity.The data of Figure 10 are measured with current measuring methods.So-called existing method be deserve on only during the 2nd current potential in Fig. 9 during in apply current potential, measure the method for its magnitude of voltage.Can understand that from Figure 10 the reaction time shortens, because of the difference of viscosity (being Hct under the situation of blood) big more to the influence of measuring sensitivity.Particularly, the reaction time during 5 seconds degree low viscosity blood and high viscosity blood to measuring the very big difference of sensitivity generation.
Therefore, in current measuring methods, the significant tendency of change is arranged because of the viscosity measuring error of blood.
So during the 1st current potential that this preliminary measurement is handled, current potential V1 is enforceable to consume by applying for reagent layer 36 and the resultant of reaction that produces at the dissolving initial stage.During the 1st current potential because low viscosity blood is faster than high viscosity blood enzyme reaction velocity, in the more resultant of reaction of generation, have more resultant of reaction to be consumed.But the long time adds current potential, and resultant of reaction consumption is too much, and the responsiveness of the magnitude of voltage that might during the 2nd current potential, detect degenerates.Therefore, the length t1-t0 during effective the 1st current potential can be 3～13 seconds, preferably is made as 2～10 seconds owing to apply the further rising application time of voltage.Also have, as current potential V1 0.1V～0.8V preferably.
Once more, carry out enzyme reaction once more in stand-by time, the used up product that comes from low viscosity blood also recovers rapidly during the 1st current potential, accumulates almost with the product of measuring with high viscosity blood.But no matter the length of stand-by time is that the long or too short final influence to measuring sensitivity is different.
Under the too short situation of stand-by time, low excessively at the response value of moment t3 measured voltage value i3, it is big that measuring error becomes.Also have, under the long situation of stand-by time, might further enlarge in the difference of the enzyme reaction rate in low viscosity blood and the high viscosity blood.Therefore, the difference by the enzyme reaction rate that does not make low viscosity blood and high viscosity blood enlarges such length that decides stand-by time.Therefore, though the length t2 of stand-by time-t1 can be made as 1～10 second, preferably be made as 2～10 seconds.
During the 2nd current potential, magnitude of voltage is unstable when just beginning to apply the moment t2 of current potential V2, for stable voltage must the elapsed time.Further, there is no need to apply with the 1st current potential during the current potential of same degree, preferably apply than the low current potential of current potential V1 during the 1st current potential.So long as can make the abundant low voltage of potassium ferricyanide oxidation just passable.Therefore, the length t3-t2 during the 2nd current potential is preferably 2～10 seconds.Also have, as current potential V2 0.05～0.6V preferably.Magnitude of voltage i3 between the final regional A, C and the E that read in moment t3, the amount of the matrix (glucose) from the magnitude of voltage i3 calculating test liquid that reads.
In addition; Such time set is the biology sensor with the noble metal electrode of palladium etc.; Reagent prescription be not only glucose oxidase perhaps/and the GDH and the potassium ferricyanide, using the biology sensor that comprises amino acid and monoethylene glycol is specially suitable to quantitative measurment.It is suitable also having comprising the organic acid situation.
Also have; After test liquid is supplied with sample supply road 35; The reaction of test liquid and reagent layer 36 is carried out matrix when quantitative behind certain hour; According to surpassing threshold value (more than the 10mV) back to surpassing elapsed time of the threshold value of stipulating (10mV) at the magnitude of voltage of regional AC measurements, also can change incubation time at step S17 from detecting at step S14 at the magnitude of voltage of regional AE measurements.
It is 25%, 45%, 65% blood that Figure 11 illustrates with hematocrit (following Hct), the measurement result of the concentration of glucose of handling with existing method and this preliminary measurement (mg/dl).R among Figure 11 is the measurement result with this preliminary treatment, and other is that the existing method reaction time of use is 15 seconds, the 30 seconds measurement results under the situation.In addition, the length during the 1st current potential is that 6 seconds, current potential V1 are that the length of 0.5V, stand-by time is that length during 6 seconds, the 2nd current potential is that 3 seconds, current potential V2 are 0.2V in this preliminary treatment.Under situation about measuring as benchmark with Hct45%, concentration of glucose 100mg/dl; If the words of the high viscosity blood of the low viscosity blood of Hct25%, Hct65%; Measurement result can produce big deviation; The low more response value deviation of the viscosity of blood is high more, and the high more response value deviation of the viscosity of blood is low more.
Further, short more deviation is big more the reaction time.Produce the deviation of high by 10% (the low viscosity blood of Hct25%), low 10% (the low viscosity blood of Hct65%) under the situation in 15 seconds reaction time.Under the situation in 30 seconds reaction time, produce the deviation of high by 5% (the low viscosity blood of Hct25%), low 5% (the high viscosity blood of Hct65%).In this preliminary treatment, produce the deviation of high by 3% (the low viscosity blood of Hct25%), low 3% (the high viscosity blood of Hct65%).For the measurement result in 15 seconds reaction time, although total reaction time equate, can lower deviation by Hct.
Moreover, turn back to Fig. 7 and continue to explain measurement processing.The beginning preliminary measurement is handled, as the current potential 0.5V (step S27) that between regional A, C and E, applied for 6 seconds during the 1st current potential.And after ending during the 1st current potential, become 6 seconds holding state, cancelling the current potential (step S28) between them during this period.After ending during the standby, as the current potential 0.2V (step S29) that between regional A, C and E, applied for 3 seconds during the 2nd current potential, through reading magnitude of voltage i3 (step S30) at that time after 3 seconds.
After step S30 reads magnitude of voltage i3, be configured in temperature survey portion 26 and its switch 27 and temperature survey portion 28 and switch 29 on the measurement mechanism 10 by control, implement the temperature survey in the measurement mechanism 10.Specifically, make switch 27 conductings measure temperature (step S31) by temperature survey portion.Then, CS 27 disconnections, switch 29 conductings are measured temperature (step S32) by temperature survey portion 28.
2 temperature measurement result relatively measuring respectively in temperature survey portion 26, temperature survey portion 28, whether the difference of judging it is in the threshold value of stipulating (step S33).Difference is under the situation in threshold range, has fault to finish measurement processing (step S33 as in the temperature survey portion 26,28 any one; No).The a plurality of temperature survey portion of temperature survey portion 26,28 is set in measurement mechanism 10, relatively their measurement result can be correctly, easy detection failure.Thus, can avoid the measuring error that produces because of irregular temperature survey.Thermometric timer begins after step S30 reads magnitude of voltage immediately, also can handle beginning at step S21 preliminary measurement and regularly implement temperature survey.
(step S33 under the situation of difference in the threshold range of regulation of 2 temperature measurement result; Yes), temperature measurement result temporarily is stored in the storer (not shown).At this moment, select in the temperature survey portion 26,28 any one storage can, the mean values of store 2 measurement temperature also can.And, can be specific necessary with reference to slotted line (step S34) at step S30 measured voltage value i3.With reference to the slotted line of setting at step S24,25,26, under the situation of the biology sensor corresponding 30 with step S24 reference measure line F7 (step S35).Reference measure line F5 (step S36) under the situation of equally, corresponding biology sensor 30 with step S25.Also has reference measure line F6 (step S37) under the situation of the biology sensor 37 corresponding with step S26.
Figure 12 is illustrated in the example of the slotted line data CA of step S34,35,36 measurements.On slotted line CA, be defined as the output characteristics F1～F7 of biology sensor 30 in step S30 measured voltage value and the concentration (mg/dl) that is included in the matrix in the test liquid.For example, the measured voltage value is under the situation of 25 (mV), if the biology sensor corresponding with slotted line F5 is stored in the storer as the concentration of matrix with 14 (mg/dl).
The concentration basis of the matrix of then, in step S35, S36 or S37, extracting out is revised (step S38) with the corresponding adjusted rate of obtaining at step S14, S17 time delay that is stored in the storer.Specifically, revise with following formula (1).
D1=(substrate concentration that is drawn out of) * { (100-sensitivity adjusted rate)/100}
Here, D1 representes revised substrate concentration.Thus, can remove the measuring error of supplying test liquid work generation because of the user.
Then, according to the temperature of in step S31～S33, measuring, revise concentration (step S39) in the corrected matrix of step S38.Specifically, read out in the temperature (following, measurement temperature) that is stored among the step S33 in the storer, with reference to temperature correction chart decision shown in Figure 13 temperature adjusted rate to substrate concentration D1.
Figure 13 illustrates an example of temperature correction chart.As an example, T10 shows at the temperature correction chart of measuring under 10 ℃ of the temperature in Figure 13.Below, same T15 is illustrated in and measures 15 ℃ of temperature correction charts down of temperature, and T20 is illustrated in the temperature correction chart under 20 ℃ of the measurement temperature.In each temperature correction chart, substrate concentration D1 and the relation of temperature adjusted rate in the test liquid have been stipulated.The temperature adjusted rate will be that 25 ℃ substrate concentration is made as benchmark in temperature, and the ratio of revising corresponding substrate concentration is shown.Specifically, carry out the temperature correction according to following formula (2).
D2＝D1×(100—Co)/100
Here, D2 is the revised substrate concentration of temperature, and D1 is the substrate concentration of in step 38, calculating, and Co is the specific temperature adjusted rate of reference temperature(TR) correction chart.
Also have, inventors of the present invention also find to measure the combined effect measuring accuracy of temperature and substrate concentration from experiment.Bright specifically below influence to measuring accuracy.Measurement temperature when Figure 14 illustrates with concentration of glucose as substrate concentration, under each concentration of glucose and the relation of measured deviation (bias).What the measured deviation in Figure 14 showed is to measure 25 ℃ of concentration of glucose of measuring down of temperature with measuring the ratio that variation of temperature changes.Figure 14 (a) is illustrated in the measured deviation and the relation of measuring temperature under the situation of 25 ℃ of following concentration of glucose 50mg/dl.Below, same Figure 14 (b) is to be to be to be to be measured deviation and the relation of measuring temperature under the situation of 25 ℃ of following concentration of glucose 550mg/dl at 25 ℃ of following concentration of glucose 420mg/dl, Figure 14 (f) at 25 ℃ of following concentration of glucose 300mg/dl, Figure 14 (e) at 25 ℃ of following concentration of glucose 200mg/dl, Figure 14 (d) at 25 ℃ of following concentration of glucose 100mg/dl, Figure 14 (c).
2 tendencies are clear and definite below these experimental datas.At first, the 1st in the relation of identical concentration of glucose, big more from 25 ℃ of big more measured deviations of difference of measuring temperature of reference temperature.Detailed says, measures temperature and becomes big to negative direction more than the low more measured deviation of reference temperature, and the high measurement deviation is big to the positive dirction change more more than reference temperature to measure temperature.Even the 2nd to make concentration of glucose become big, concentration of glucose be the border with the situation of 300mg/dl, measured deviation focuses on this.Specifically, for example, in Figure 14 (a), the measured deviation under 40 ℃ is 28%, is 50% in Figure 14 (c), is 60% in Figure 14 (d), is the passing of about 50% that kind in Figure 14 (f).Measuring temperature is that the low temperature zone of 10 ℃ of that kind also has same tendency.
So such tendency also is reflected on the temperature survey table shown in Figure 13.Specifically; Consideration is in the relation of same concentration of glucose; This telogenesis is to have considered from 25 ℃ of bigger these facts of the big more measured deviation of difference of measuring temperature of reference temperature; Even concentration of glucose is big, concentration of glucose is that the boundary survey deviation focuses on this true table with the situation of 300mg/dl.Revising than only revising measuring accuracy according to the measurement temperature according to combination, the reference temperature(TR) correction chart of measuring temperature and substrate concentration has tremendously and improves.
In addition, in the serviceability temperature scope of biology sensor 30 (in this embodiment be 10 ℃～40 ℃ as an example), also can have with 1 ℃ be the temperature correction chart of unit, also can use temperature width (the for example 5 ℃) regulation of regulation.Under the situation of the measurement temperature in set point of temperature width centre position, use the temperature correction chart of the detected measurement temperature of clamping at detecting position, can calculate the temperature adjusted rate by a linear interpolation.
Turn back to the process flow diagram of Fig. 7, implemented on the revised substrate concentration D2 of such temperature outputs to measurement mechanism 10 as final substrate concentration the display part 11 (step S40).Like this, because be that the viscosity of test liquid of influence or Hct of having considered the time of supplying, measure temperature, having measured the combination of temperature and substrate concentration is carried out the quantitative of matrix amount, comparing measuring accuracy with existing method can be significantly improved.
Also have,, can also use following method in order further to suppress the measuring error of Yin Wendu.
Do not insert at biology sensor 30 and continue under the state of measurement mechanism 10 to implement temperature survey in advance, accumulate the temperature of this measurement in advance.After inserting biology sensor 30, measurement temperature of measuring at step S31～S32 and the temperature of in advance accumulating compare and get final product.When the temperature of accumulating in advance with under situation about existing between the measurement temperature that step S31～S32 measures, can bring the temperature variation of influence degree, compulsory end measurement processing to measuring error as existing than big difference.
The portable biometric sensing system of this embodiment that kind can run into the various temperature variation because of external environment condition for the ease of carrying.For example, there is temperature, the user of user's hand within doors the situation of outside the room, entering to follow the situation of the fierce variation of environment temperature.On the one hand environment temperature is fierce changes, in the reasonable time of in measurement mechanism 10, the needs for the equilibrium temperature variation.
For example, Figure 15 illustrates the temperature variation in the measurement mechanism 10.In figure shown in Figure 15, show measurement mechanism 10 and move to the situation of 25 ℃ of temperature and move to the temperature variation in measurement mechanism 10 under 25 ℃ the situation from 40 ℃ of temperature from 10 ℃ of temperature.Can understand 10 ℃～40 ℃ in case need 30 minutes under the temperature stabilization that produces from Figure 15.Temperature variation carry out the temperature correction midway the time, the situation of temperature correction that can not be correct will take place.
So,, be necessary the enforceable termination measurement processing of temperature variation that can influence the measuring error degree as existing when the temperature of accumulating in advance with under the situation that difference is big between the measurement temperature that step S31～S32 measures.Thus, can further improve the precision of the temperature correction in the measurement mechanism 10.In addition, the temperature of biology sensor 30 under the state that does not insert measurement mechanism 10 measured in advance, can carry out implementation that also can be continuous with official hour (for example, the 5 minutes) cycle.Also have, judge the degree of temperature variation, under the big situation of temperature variation, can not implement measurement processing even the user wants to implement measurement processing.
(embodiment 2)
Below, explain and the relevant biology sensor of the present invention's the 2nd embodiment.In addition, do bright specifically with regard to the enzyme sensor of the use enzyme of the molecular recognition elements of the predetermined substance generation idiosyncrasy in conduct and the test liquid here.
This embodiment is the problem that produces because of misoperation of users; Particularly; Bright specifically can avoiding owing to can not well test liquid be lighted on the inlet on sample supply road; Test liquid can not import to test liquid and wait the embodiment that influences the such user's operating mistake of measuring accuracy in the sample supply road attached to around it.
In Figure 16 structure perhaps shown in Figure 2; Because porch on the sample supply road of supplying with test liquid; The end that the insulativity substrate on formation sample supply road and the plane of shell are looked has same shape at same position, and the angle of supplying with test liquid is little, also has; It is inferior that one side (not forming the face of electrode) at the back side of insulativity substrate of mistake is adhered to the situation of test liquid; When thinking to supply with test liquid again, can not well supply with test liquid attached to the test liquid generation trouble at the back side is feasible, bring out the problem wrong, measuring error of measuring.
Below, just can be correctly and the biology sensor that is easy to supply with test liquid do bright specifically.
Figure 17 (a) is the exploded perspective view of the biology sensor relevant with this embodiment 2, and Figure 17 (b) is along the length direction of the biology sensor sectional view at the central cutout on sample supply road.In Figure 17, on the 1st insulativity substrate 51, form the potential electrode 52 formed by electrical conductivity property material, to electrode 53 and detecting electrode 54.The detecting electrode 54 here not only has the function as the electrode that detects corpse or other object for laboratory examination and chemical testing quantity not sufficient, also can be as reference electrode or to the part of electrode.
In Figure 17, show configuration at the 1st the above each electrode of insulativity substrate, these electrodes not only can be configured on the insulativity substrate 51, also can cut apart and be configured on the 2nd insulativity substrate 58 that becomes the shell of subtend substrate.
Here as the material that is fit to said the 1st insulativity substrate 51 and the 2nd insulativity substrate 58 parylene's second two fat, polycarbonate, polyimide etc. are arranged.
Also have, can enumerate the noble metal of gold, platinum, palladium etc., monomer materials such as carbon, the perhaps compound substance of carbon paste, noble metal paste etc. as the electrical conductivity property material that constitutes each electrode.Under the former situation, with can on the 1st insulativity substrate 51 or the 2nd insulativity substrate 58, forming conductive layer easily with grid print process etc. under sputter vaporization method etc., the latter's the situation.
In the formation of each electrode, comprehensively or after forming said conductive layer on the part of the 1st insulativity substrate 51 or the 2nd insulativity substrate 58, slit is set, can cuts apart the formation electrode with laser etc. with described sputter vaporization method, grid print process etc.Also have, with the galley, the mask that have been pre-formed electrode pattern, with grid print process, sputter vaporization method etc. also can be same the formation electrode.
On the electrode that forms like this, form the reagent layer 55 that contains enzyme, electronics reception and registration body and hydrophilic macromolecule.Here use as endonuclease capable: glucose oxidase, lactic acid ester oxidase, cholesterol oxidase, cholesterol esterase, uricase, ascorbic acid oxidase, bilirubin oxidase, GDH, propyl alcohol acid esters dehydrogenasa etc., pass on body to remove the enough 1,4-benzoquinone of potassium ferricyanide external enwergy and derivant, azophenlyene paramethylaminophenol sulfate, methylenum careuleum, ferrocene and derivant thereof etc. as electronics.
Also have, can use as hydrophilic macromolecule: amino acids, sulfonated polystyrene, gelatin and derivant thereof, acrylic acid and derivant thereof, methacrylic acid and salt thereof, starch and derivant thereof, maleic anhydride and salt thereof, Ago-Gel and the derivant thereof of CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, ethyl cellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polylysine etc.
Then, said the 1st insulativity substrate 51 and the 2nd insulativity substrate 58 are fitted with the partition 56 with slit-shaped incised notch portion 57 each other, form the sample supply road 57 of supplying with test liquid.
Here; With the prior biological sensor very big be not both porch on sample supply road 57; Form the 1st insulativity substrate 51 and the 2nd insulativity substrate 58 on sample supply road 57, the plane is looked the end of seeing it and is positioned at mutual diverse location that kind, the applying of can staggering.In other words, though the 1st insulativity substrate 51 is identical with near the 2nd insulativity substrate 58 shape inlet on sample supply road 57, can the 2nd insulativity substrate 58 and partition 56 is outstanding to Way in facing to the 1st insulativity substrate 51.
Thus, also can correctly and be easy to attract test liquid even supply with the angle insufficient (even little) of test liquid.Further, also have the effect that prevents to adhere to test liquid, suppose adhering on the back side of substrate under the situation of test liquid,, also can supply with test liquid smoothly by supplying with test liquid once more to the back side of the 1st insulativity substrate 51.
In order to obtain such effect; Misfitting of the end seen looked on said the 1st insulativity substrate 51 and the 2nd insulativity substrate 58 planes; In other words, in the centre line L on sample supply road 57 shown in Figure 180 and between the point of crossing 63a of near the point of crossing 64a of the 1st insulativity substrate 51 the inlet on sample supply road 57 and the 2nd insulativity substrate 58, hope it more than the 0.1mm, more suitably is 0.25mm～1.0mm apart from S1.
In addition, under the situation of S1 less than 0.1mm, distance is insufficient, under the little situation of the angle that attracts test liquid, equally with the prior biological sensor can not well supply with test liquid.
Also have, that kind shown in figure 19 even the 1st insulativity substrate 51 and the 2nd insulativity substrate 58 are being under the difform situation near the inlet on sample supply road 57, also can obtain and said same effect.
Even under these circumstances; The misfitting of end of said the 1st insulativity substrate 51 seen and the 2nd insulativity substrate 58 looked on the plane; In other words; The centre line L on sample supply road 57 shown in Figure 20 and between the intersection point 63b of near the intersection point 64b of the 1st insulativity substrate 51 the porch on sample supply road 57 and the 2nd insulativity substrate 58, hope it is more than the 0.1mm apart from S2 more suitably is 0.25mm～1.0mm.
In addition, in the structure of said Figure 17～Figure 20, in order rapidly test liquid to be supplied with the sample supply road 57 of slit-shaped, the height on sample supply road, the thickness of partition 56 hopes it is the scope of 0.05～0.3mm in other words.
Here, as the material of suitable partition 56, can enumerate: polyethylene terephthalate, polycarbonate, polyimide, polybutylene terephthalate, polyamide, PVC, two Vingon, polyimide, nylon.
Also have, also can the 2nd insulativity substrate 58 and partition 56 integrated formation backs and 51 applyings of the 1st insulativity substrate be formed sample supply road 57.
Here, said reagent layer 55 on being configured in electrode comprehensively or a part goes up, so long as do not make in the scope of mis-behave of biology sensor, even any places that are configured in the sample supply road 57 of supplying with test liquid can.
Also have, supply with by the capillarity realization,, air is escaped to biology sensor air outside hole 59 in order to realize the smooth supply of test liquid by the test liquid that such sample supply road 57 is formed to biology sensor.Airport 59 is that the circular polygon of rectangle can.
Here, the configuration of airport 59 is as long as be arranged on Anywhere can in the sample supply road 57 in the scope that does not hinder test liquid to supply with.
Also have, on the inner face on said sample supply road 57, implement hydrophilicity-imparting treatment, can be rapider and correct test liquid is imported in the sample supply road 57.
As the method for launching interfacial agent on oriented the 1st insulativity substrate 51 of the method for such hydrophiling or the 2nd insulativity substrate 58 self, its surface, perhaps side blasting treatment, electrodischarge machining, non-glare treated, rough surface processing, electroless plating etc. make the method for baseplate material surface roughening etc.
In by such biology sensor that forms; The current value that the reaction of special component in the test liquid and the reagent layer 55 that comprises enzyme etc. obtains is through potential electrode 52, to the leading part separately 60,61,62 of electrode 53, detecting electrode 54, and the measurement mechanism that connects to not shown outside reads.
In current measurement; Except that the described three electrode modes of forming by potential electrode 52, to electrode 53, detecting electrode 54 of this embodiment; Only also have the two electrode modes of forming by potential electrode 52, to electrode 53; Though for the effect that realizes obtaining in the present invention adopt the sort of mode can, can access more accurate measurement with 3 electrode modes.
(concrete example 1)
On the 1st insulativity substrate of forming by poly terephthalic acid second two fat; By the sputter vaporization method after the surface of said insulativity substrate forms the thick palladium membranes of about 8nm on comprehensively; On the part of said film, slit is set with the YAG laser instrument, with dividing electrodes become potential electrode, to electrode and detecting electrode.On it, drip round shape to comprise that enzyme, electronics pass on the WS of body, hydrophilic macromolecule, cover with said potential electrode be the part to electrode and detecting electrode at center, make its drying, form the reagent layer.Further; From forming of it by poly terephthalic acid second two fat partition that form, that have notch; It and the 2nd insulativity substrate (shell) same that be made up of poly terephthalic acid second two fat, that have airport are fitted, become blood and conduct sample supply capillaceous road.
In addition; In order to confirm effect of the present invention; Here made the blood glucose value survey sensor of totally 6 kinds, misfit (S) that the end of seeing is looked on the plane of their said insulativity substrate and said partition and shell is respectively S=0 (existing sensors), 0.1,0.25,0.5,1.0,2.0mm.
Also have,, on the surface of shell (medial surface on sample supply road), used to have applied interfacial agent here in order to supply with blood to the sample supply road more rapidly.
The angle that Figure 21 is illustrated in the blood glucose value survey sensor of such formation by blood supply is to confirm the experimental technique of the blood absorption characteristic of sensor, and (table 1) illustrates its experimental result.
The definition of symbol in the table; A zero common resorption draws
△ supplies with 2～3 resorptions and draws
* do not attract
Can know that from (table 1) in the existing sensors of S=0mm, (0～30 degree) do not attract blood, supplies with action for good attraction needs several under the little situation of blood supply angle.This possibly be because supplying with under the little situation of angle; When with blood supply sample supply road, blood at first attached to the back side of insulativity substrate; Even think that once more with blood supply sample supply road, it also is attracted to blood one side attached to this insulativity substrate back.
In contrast; In sensor of the present invention; Even under the situation of the shortest S=0.1mm of distance, though need to supply with for several times action under the little situation of angle and not have situation about not attracting fully when supplying with, if more than the S=0.25mm, can both be easy to attract blood in any angle.
Also have; Figure 22 is illustrated in use and adheres in the scope of its about 5mm of front end under the situation of substrate of blood to the back side of insulativity substrate in advance for the back side that hinders blood and be attracted to the 1st insulativity substrate; In order to confirm that blood because of the sensor of the supply angle of blood attracts the experimental technique of characteristic, (table 2) illustrates its experimental result.
The definition of symbol in the table; A zero common resorption draws
△ supplies with for 2～3 times and attracts
* do not attract
Can know from (table 2); In the existing sensors of S=0mm; In the blood supply angle is can not attract blood under the situation beyond 90 degree; And under the situation with sensor of the present invention, though under the little situation of the blood supply angle when S=0.1mm the situation that can not attract is arranged, if no matter can both be easy to attract blood when S=0.25mm is above in any attraction angle.
Like this, adopt this embodiment, with the 1st insulativity substrate 51 that forms the sample supply road and the 2nd insulativity substrate 58 look from the plane end of seeing is positioned at different positions each other, applyings of staggering, so just can be correctly and easy attraction test liquid.
Also have; In this embodiment 2; Enumerating enzyme sensor as biology sensor is that example is described; The present invention also can be equally applicable to utilize the biology sensor of antibody, microorganism, DNA, RNA etc. for the molecular recognition elements of the predetermined substance generation idiosyncrasy in conduct and the test liquid beyond dezymotizing.
As said, adopt this embodiment; By with 2 pieces baseplate-laminating, between said substrate, form the sample supply road of taking test liquid, on this sample supply road; With the opening that is arranged on said two substrates end as inlet; Said test liquid is imported such biology sensor that constitutes, and the end of two substrates that constitutes said inlet is in the overlooking of said biology sensor, because be positioned at different each other positions or different shapes; Even supply with the angle insufficient (even little) of test liquid, also can access the correct and easy effect that attracts test liquid.Further, also have and to prevent the effect of test liquid,, also can supply with the effect that test liquid is supplied with test liquid smoothly once more even under the situation of test liquid attached to the back side of substrate attached to the back side of the 1st insulativity substrate 51.
The possibility of utilizing on the industry
Adopt the present invention the good biology sensor of user easier operation, measuring accuracy can be provided easily, with the quantivative approach and the measurement mechanism of biology sensor.
Claims (4)
1. the quantivative approach of a matrix comprises following operation:
Biology sensor preparatory process, biology sensor have insulated substrate, are formed on comprising the electrode part of electrode, potential electrode and the reagent layer that reacts with the test liquid of supplying with on said electrode part at least a portion on the said insulated substrate;
Measurement mechanism preparatory process, this measurement mechanism have that the support sector of said biology sensor is supported in loading and unloading freely and on each electrode of said electrode part, applying the splicing ear and the driving power of voltage;
On the said electrode part that is supported in the said biology sensor in the said support sector, supplied with under the state of said test liquid, to electrode and said potential electrode, during the 1st, applied the operation of the 1st current potential through said;
During the said the 1st after applying said the 1st current potential on the said electrode part, stop to apply the operation of said the 1st current potential in the time during standby;
After during the said standby, once more saidly during the 2nd, apply the 2nd current potential on to electrode and said potential electrode, by the said matrix in the quantitative said test liquid of electric current of measuring output, said the 1st current potential is than the bigger operation of said the 2nd current potential.
2. quantivative approach according to claim 1 is characterized in that:
During the said standby more than or equal to 2 seconds smaller or equal to 10 seconds.
3. quantivative approach according to claim 2 is characterized in that:
Said the 1st current potential more than or equal to 0.1V smaller or equal to 0.8V, and during the said the 1st more than or equal to 2 seconds smaller or equal to 10 seconds.
4. quantivative approach according to claim 3 is characterized in that:
Said the 2nd current potential more than or equal to 0.05V smaller or equal to 0.6V, and during the said the 2nd more than or equal to 2 seconds smaller or equal to 10 seconds.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000364225A JP4639465B2 (en) | 2000-11-30 | 2000-11-30 | Biosensor |
| JP2000-364225 | 2000-11-30 | ||
| JP2000364225 | 2000-11-30 | ||
| JP2001357144A JP2003156469A (en) | 2001-11-22 | 2001-11-22 | Biosensor, measuring device for biosensor and quantitative determination method of substrate |
| JP2001357144 | 2001-11-22 | ||
| JP2001-357144 | 2001-11-22 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018043496A Division CN100510732C (en) | 2000-11-30 | 2001-11-30 | Biosensor and measuring instrument for biosensor |
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| Publication Number | Publication Date |
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| CN101059504A CN101059504A (en) | 2007-10-24 |
| CN101059504B true CN101059504B (en) | 2012-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101018445A Expired - Lifetime CN101059504B (en) | 2000-11-30 | 2001-11-30 | Method of quantifying substrate |
| CN 200710101843 Expired - Lifetime CN101059503B (en) | 2000-11-30 | 2001-11-30 | Biosensor |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200710101843 Expired - Lifetime CN101059503B (en) | 2000-11-30 | 2001-11-30 | Biosensor |
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| JP (1) | JP4639465B2 (en) |
| CN (2) | CN101059504B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10397018A5 (en) * | 2002-07-02 | 2015-05-28 | Panasonic Healthcare Holdings Co., Ltd. | Biosensor, biosensor chip and biosensor device |
| JP4009683B2 (en) | 2002-09-26 | 2007-11-21 | アークレイ株式会社 | Method for manufacturing analytical tool |
| US6939450B2 (en) * | 2002-10-08 | 2005-09-06 | Abbott Laboratories | Device having a flow channel |
| JP3910148B2 (en) * | 2003-03-14 | 2007-04-25 | アークレイ株式会社 | Analysis tool with exhaust port |
| JP4501793B2 (en) | 2005-06-24 | 2010-07-14 | パナソニック株式会社 | Biosensor |
| US8721851B2 (en) | 2008-11-28 | 2014-05-13 | Panasonic Healthcare Co., Ltd. | Sensor chip, biosensor system, method for measuring temperature of biological sample, method for measuring temperature of blood sample, and method for measuring concentration of analyte in blood sample |
| CN113092562B (en) * | 2009-04-17 | 2024-03-29 | 环球生物医疗感测仪私人有限公司 | Electrochemical on-board control detection |
| JP4840521B2 (en) * | 2010-04-27 | 2011-12-21 | パナソニック株式会社 | Biosensor, biosensor measuring apparatus, and substrate quantification method |
| JP4840520B2 (en) * | 2010-04-27 | 2011-12-21 | パナソニック株式会社 | Biosensor, biosensor measuring apparatus, and substrate quantification method |
| JP5818275B2 (en) * | 2011-03-29 | 2015-11-18 | 株式会社テクノメデイカ | Biosensor |
| JP6149470B2 (en) * | 2013-04-04 | 2017-06-21 | 大日本印刷株式会社 | Biosensor |
| JP6191203B2 (en) * | 2013-04-04 | 2017-09-06 | 大日本印刷株式会社 | Biosensor electrode and biosensor |
| US20180353111A1 (en) * | 2017-06-09 | 2018-12-13 | Covidien Lp | Systems and methods for driving optical sensors |
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| US5352351A (en) * | 1993-06-08 | 1994-10-04 | Boehringer Mannheim Corporation | Biosensing meter with fail/safe procedures to prevent erroneous indications |
| WO1994029704A2 (en) * | 1993-06-08 | 1994-12-22 | Boehringer Mannheim Corporation | Biosensing meter with ambient temperature estimation method and system |
| US5653863A (en) * | 1995-05-05 | 1997-08-05 | Bayer Corporation | Method for reducing bias in amperometric sensors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0658338B2 (en) * | 1988-05-18 | 1994-08-03 | 松下電器産業株式会社 | Biosensor |
| JPH0816664B2 (en) * | 1989-04-18 | 1996-02-21 | 松下電器産業株式会社 | Biosensor and manufacturing method thereof |
| US5798031A (en) * | 1997-05-12 | 1998-08-25 | Bayer Corporation | Electrochemical biosensor |
| JPH11304748A (en) * | 1998-04-23 | 1999-11-05 | Omron Corp | Biosensor |
| JP3874321B2 (en) * | 1998-06-11 | 2007-01-31 | 松下電器産業株式会社 | Biosensor |
| JP4352109B2 (en) * | 1999-01-29 | 2009-10-28 | アークレイ株式会社 | Biosensor |
| US6814843B1 (en) * | 2000-11-01 | 2004-11-09 | Roche Diagnostics Corporation | Biosensor |
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2000
- 2000-11-30 JP JP2000364225A patent/JP4639465B2/en not_active Expired - Lifetime
-
2001
- 2001-11-30 CN CN2007101018445A patent/CN101059504B/en not_active Expired - Lifetime
- 2001-11-30 CN CN 200710101843 patent/CN101059503B/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352351A (en) * | 1993-06-08 | 1994-10-04 | Boehringer Mannheim Corporation | Biosensing meter with fail/safe procedures to prevent erroneous indications |
| WO1994029704A2 (en) * | 1993-06-08 | 1994-12-22 | Boehringer Mannheim Corporation | Biosensing meter with ambient temperature estimation method and system |
| US5653863A (en) * | 1995-05-05 | 1997-08-05 | Bayer Corporation | Method for reducing bias in amperometric sensors |
Non-Patent Citations (2)
| Title |
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| JP特开平11-304748A 1999.11.05 |
| JP特开平5-215712A 1993.08.24 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101059503B (en) | 2013-02-13 |
| CN101059504A (en) | 2007-10-24 |
| JP2002168821A (en) | 2002-06-14 |
| JP4639465B2 (en) | 2011-02-23 |
| CN101059503A (en) | 2007-10-24 |
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