TWI410624B - Method and apparatus for voltage providing of electrochemistry - Google Patents

Abstract

Method and apparatus for voltage providing of electrochemistry is disclosed, which the method is applicable to measurement of the consistency of a reactant. The method includes: First, provide an initial voltage to an electrochemistry reaction region, for detecting whether there is the reactant in the region or not. If there do have the reactant in the region, stop providing the initial voltage. Then provide a reset voltage signal to the region for resetting the electrochemistry reaction. Next, provide a reaction voltage to the region. After the reaction is done, a measurement voltage is then provided to the region for generating a measurement current. In which the measurement current can be processed for obtaining the consistency of the reactant.

Description

Electrochemical power supply method and device thereof

A power supply method and device thereof, in particular, a voltage supply method and device for electrochemical reaction.

With the development of biosensing technology, many biosensing devices combining biological characteristics and electronic technology have also been invented, such as blood glucose machines, blood fat machines, uric acid meters, or cholesterol measuring instruments, etc., which utilize active substances and The physical or chemical properties caused by the reaction of the substance to be tested are measured and converted to the amount of the substance to be tested for measurement purposes.

Depending on the measurement equipment and method, generally, the types of biosensing equipment include electrochemical biosensors, semiconductor ion sensors, fiber optic biosensors, piezoelectric crystal biosensors, and the like. The electrochemical biosensor converts the amount of the reactant to be tested by measuring the change in conductivity, voltage or current generated by the reaction of the reactant to be tested with a biologically active substance, an enzyme or an antibody.

However, because the pre-positioned active substances, enzymes, or antibodies are not stored before use, unintended chemical reactions may occur due to environmental light, heat, or moisture. Biosensing equipment measures the reactants to be tested. Unexpected chemical reactions will affect the correctness of the measured data and become the main source of error.

In addition to errors due to unintended impurity reactions prior to measurement, errors may also result in numerical measurements. For example, please refer to FIG. 1A, which is a schematic structural diagram of a conventional blood glucose test strip 40, in which a sample to be tested (in this embodiment, blood) is dropped from the inlet 41, because of the siphon phenomenon, The test body is gradually sucked into the siphon tank 42. The blood glucose test strip 40 has a reaction zone 43, an L-shaped electrode 45 and 47. When the sample to be tested is dropped from the inlet 41, the electrode 45 is first touched, and then the reaction zone 43 is gradually filled until the test zone 43 is continued. When the test object hits the electrode 47, it means that the sample to be tested has filled the reaction zone 43.

That is to say, the biosensor can supply a small voltage on the L-shaped electrodes 45, 47 first. Since the L-shaped electrodes 45, 47 are in a dry state at the beginning, the impedance measured by the biosensor is very high. high. When the sample to be tested is filled in the reaction zone 43 and is in contact with the L-shaped electrodes 45 and 47, the biosensor suddenly detects a significant drop in impedance, so that it is known that the sample to be tested is placed in the blood glucose test piece. 40, and has been filled with reaction zone 43. According to this method, the L-shaped electrodes 45 and 47 can be used to confirm the timing of the start of the electrochemical reaction to count the reaction time. However, in order to know the reaction initiation time point, it is necessary to use a specific electrode. The blood glucose test piece constructed, such as the electrodes 45 and 47 in this example, is a special L type, and has limitations in use.

Then, as shown in FIG. B, for the waveform of the supply voltage and the reaction current of the conventional biosensor, please refer to the first A diagram, and the reaction voltage 11 is when the biosensor determines the sample to be tested at the time point. The supply of t0 is started after the reaction zone 43 is filled to provide the energy required for the chemical reaction between the reactant to be tested in the sample to be tested and the active substance or enzyme in the reaction zone 43 to be chemically reacted. As the chemical reaction proceeds, a reaction current 21 is generated, and after a certain period of time, the reaction voltage 11 is stopped, and the reactant to be tested reacts with the enzyme or the active material, thereby generating a standing current of 23 . Next, the biosensor provides a measurement voltage 13 to generate a measurement current 27 for measurement (for example, measurement at time t1), and finally, according to the measured value of the measured current 27, it is obtained. Know the concentration of the reactant to be tested in the sample to be tested.

Actually, however, since the reaction is continued while the reaction voltage 11 is stopped and the standing reaction before the measurement voltage 13 starts to be supplied, a minute standing current 23 is generated. At this time, if a steeply rising measurement voltage 13 is supplied, the measurement current 27 has an unstable overcurrent 25 phenomenon, affecting the waveform of the measurement current 27 and the value of the measurement current 27 measured at the time point t1. Causes the measurement results to be incorrect. However, if the reaction result is not too much deviation, the measurement can be performed after the measurement current 27 is relatively stable, but this will inevitably prolong the measurement time and cause energy loss and reduce the measurement efficiency.

In view of this, the technical problem to be solved by the present invention is to improve the accuracy and efficiency of the measurement by removing the limitation of the electrode structure and reducing the measurement error of the biosensor by changing the power supply mode.

In order to achieve the above object, according to an aspect of the present invention, an electrochemical power supply device includes an electrochemical reaction region, a voltage supply unit, a current measuring unit, and a processing unit. The electrochemical reaction zone is a region for chemically reacting the reactant to be tested in the sample to be tested, and the voltage supply unit is for providing a reset voltage when the sample to be tested is placed in the electrochemical reaction zone. The signal is in the electrochemical reaction zone to eliminate impurity currents and other interfering currents, as well as provide reaction voltages and measurement voltages. The current measuring unit is coupled to the electrochemical reaction zone for measuring the current generated in the electrochemical reaction zone and transmitting it to the processing unit for calculating the concentration of the reactant to be tested.

It is worth mentioning that when the voltage supply unit supplies the measurement voltage for generating the measurement current, it is supplied in a gradually rising manner, so that the measurement current does not have an overcurrent phenomenon. In addition, the voltage supply unit provides an initial voltage in the electrochemical reaction zone before the sample to be tested is placed to detect whether the sample to be tested is placed.

According to another aspect of the present invention, an electrochemical power supply method is provided, comprising supplying an initial voltage to an electrochemical reaction zone to detect whether a sample to be tested is placed. It should be specially noted that the electrochemical reaction zone may be disposed on the bio-sensing test piece, and the test sample is gradually filled with the electrochemical reaction zone by the siphon principle after being dropped from the inlet of the test piece. When the sample to be tested is dropped, the impedance between the two power supply electrodes in the electrochemical reaction zone will suddenly drop, and the biosensor can detect whether the sample to be tested is instilled by detecting the impedance between the two electrodes. In the reaction zone.

When it is detected that the sample to be tested is placed in the electrochemical reaction zone, the initial voltage is stopped, and a waiting time is allowed to allow the test body to fill the electrochemical reaction zone, and then the reset voltage signal is supplied to the electrochemical The reaction zone is used to eliminate impurity currents and other disturbing currents, resetting the electrochemical reaction of the reactants to be tested, and recalculating the time of the chemical reaction. Wherein, the reset voltage signal may be in any form to remove the polarization phenomenon of the reactive ions, such as a reverse voltage pulse and the like.

Then, the reaction voltage is supplied, and the chemical reaction of the reactant to be tested with the enzyme, the antibody or the active material can be continued. After the reaction is completed, the measurement voltage is supplied to generate the measurement current. The magnitude of the measured current varies with the concentration of the reactant to be tested in the sample to be tested. Therefore, once the magnitude of the measured current is known, the concentration of the reactant to be tested can be known by conversion to obtain the desired Measurement results.

According to still another aspect of the present invention, there is provided an electrochemical power supply method, comprising: supplying an initial voltage to an electrochemical reaction zone to detect whether a sample to be tested is placed, and detecting an electrochemical reaction of the sample to be tested; When the zone is in place, the supply of the initial voltage is stopped. Then, the reaction voltage is supplied to electrochemically react the reactant to be tested in the sample to be tested with an enzyme, an active substance or an antibody, and after the reaction is completed, a gradually rising measuring voltage is supplied to the electrochemical reaction zone to generate a measurement. Current.

The measuring voltage is supplied in a gradually rising manner, which can avoid the overshooting phenomenon of the measuring current and improve the correctness of the measurement result, and the converted current can be determined by the converted current to be tested. The concentration in the body.

Eliminate unintended impurity reactions and reset the start time of the electrochemical reaction by providing a reset voltage signal before providing the reaction voltage, and provide a gradually rising measurement voltage during measurement to avoid overcurrent of the measured current To reduce the measurement error and improve the accuracy and efficiency of the measurement.

The above summary and the following examples are intended to be illustrative of the invention and the embodiments of the invention.

Before the reaction of the reactants to be tested, the reset voltage signal is provided to eliminate the impurity reaction, thereby resetting the electrochemical reaction, and providing a gradually rising measurement voltage during the measurement to generate a stable measurement current to improve the measurement result. Correctness and efficiency.

Referring to the second figure, a block diagram of an embodiment of a biosensor includes a processing unit 31, a voltage supply unit 33, an electrochemical reaction zone 35, and a current measuring unit 37. The electrochemical reaction zone 35 is preliminarily provided with an active substance, an enzyme or an antibody for chemically reacting with a reactant to be tested. For example, if the biosensor is a blood glucose machine, the electrochemical reaction zone 35 is disposed at one end of the concentration test strip (in this embodiment, a blood glucose test strip) for the user to drip blood into the blood glucose concentration analysis. . The voltage supply unit 33 supplies the voltage required for the reaction or the voltage for measurement to the electrochemical reaction zone 35 through the two electrodes, and the current measuring unit 37 measures the current generated in the electrochemical reaction zone 35 through the electrodes. The value is sent to the processing unit 31 for conversion of the concentration of the reactant to be tested.

Referring to FIG. 3A, a schematic structural diagram of an embodiment of a blood glucose test strip 50 includes a inlet 51, a siphon tank 52, an electrochemical reaction zone 35, and electrodes 55 and 57, wherein the sample to be tested is a slave inlet. 51 is dropped and enters the electrochemical reaction zone 35 by the siphon principle of the siphon bath 52. Different from the conventional ones, the electrodes 55 and 57 in this embodiment are elongated and placed on both sides of the reaction zone, so that when the sample to be tested simultaneously contacts the electrodes 55 and 57, the blood glucose machine detects When the impedance suddenly drops, it is not determined whether the sample to be tested has "completely filled" the electrochemical reaction zone 35, and it can be confirmed that only the "subject to be tested" is placed in the electrochemical reaction zone 35.

Next, please refer to the third B diagram, which is a voltage and current waveform diagram of an embodiment of the electrochemical power supply method, please refer to the second diagram and the third A diagram. The method is applied to the measurement of the concentration of a reactant (such as glucose) to be tested in a sample to be tested (such as blood), and the reactant to be tested is chemically reacted with an active substance, an enzyme or an antibody previously placed in the electrochemical reaction zone 35. To cause changes in physical or chemical properties, such as changes in conductivity, voltage, or current, by measuring the amount of change (in this example, the amount of current is measured by current measuring unit 37), the reactants to be tested can be converted. The concentration in the sample to be tested.

As shown in the third diagram B, the time point tb is the time point at which the sample to be tested is dropped into the inlet 51 by the siphon principle, at which time an initial current 20 is suddenly generated in the electrochemical reaction zone 35. The voltage supply unit 33 stops the supply of the initial voltage 15 after the drop of the sample to be tested (that is, the time point t2 in the third B diagram). The initial voltage 15 is supplied through the electrodes 55 and 57, and can be used to detect whether the sample to be tested is placed in the electrochemical reaction zone 35. The detection principle is because the two electrodes 55 and 57 are dry at the beginning. The biosensor measures high impedance, so the initial voltage 15 is initially supplied to the two electrodes 55, 57 with little or no current. When the sample to be tested is placed in the electrochemical reaction zone 35 and simultaneously contacts the two electrodes 55 and 57, the biosensor suddenly measures the impedance drop between the two electrodes 55, 57, thereby It is judged that the sample to be tested is placed in the electrochemical reaction zone 35.

As described above, when it is detected that the object to be tested is placed in the electrochemical reaction zone 35, the voltage supply unit 33 stops supplying the initial voltage 15 (time point t2) and provides a waiting time (according to the average value of the experimental data) The test sample is indeed filled with the electrochemical reaction zone 35. Alternatively, the voltage supply unit 33 may additionally provide a blood measuring electrode in the lower region of the electrochemical reaction zone 35, measure the impedance between the blood measuring electrode and the electrode 55, or measure the impedance between the blood measuring electrode and the electrode 57. It is known whether the sample to be tested is filled in the electrochemical reaction zone 35. That is to say, when the sample to be tested is filled in the electrochemical reaction zone 35, the impedance between the blood measuring electrode and the electrode 55 or the impedance between the blood measuring electrode and the electrode 57 is lowered, and therefore, the impedance value is measured through the measurement. It is confirmed whether the sample to be tested is filled in the electrochemical reaction zone 35.

After the sample to be tested is filled in the electrochemical reaction zone, the voltage supply unit 33 provides a reset voltage signal 17 (which may be used to eliminate the polarization of the reactive ions in any form, such as a reverse voltage pulse, etc.) In the electrochemical reaction zone 35, the impurity reaction before the time point t2 at which the initial voltage 15 is stopped is removed, and the start time point of the chemical reaction is restarted. The reason for the impurity reaction is usually the active substance, enzyme or antibody, etc., due to factors such as environmental moisture or solar radiation, or chemical reactions caused by the incorporation of some impurities, which may cause some reaction charges to remain in the electrification. The reaction zone 35 is studied, and the residual charge causes deviations in the results of subsequent measurements, so it needs to be eliminated.

It is worth mentioning that by this waiting time, the sample to be tested is indeed filled with the electrochemical reaction zone 35, and a reset voltage signal 17 is provided to eliminate the impurity reaction to reset the electrochemical reaction, even if the conventional reaction is not used. The L-shaped electrode can also accurately set the starting time point of the electrochemical reaction, and thus the shape of the electrodes 55 and 57 is not limited, and can be designed into an arbitrary shape structure.

After the impurity reaction is eliminated, the voltage supply unit 33 supplies the reaction voltage 11' to the electrochemical reaction zone 35 to provide sufficient chemical reaction between the reactant to be tested and the active substance, enzyme or antibody in the sample to be tested. energy. At this time, since the chemical reaction starts, some ions and charges are generated, so that the reaction current 21' passes through the electrodes 55, 57 placed in the electrochemical reaction zone 35. Taking the measurement of blood glucose concentration as an example, the chemical reaction formula is as follows:

Glucose+GO/FAD→δ-Gluconolactone+GO/FADH ₂

GO/FADH ₂ +O ₂ →GO/FAD+H ₂ O ₂

H ₂ O ₂ → ₂ H ⁺ +O ₂ + ₂ e ^-

Among them, Glucose is glucose, which is the blood sugar to be tested. GO is a glucose oxidase that produces a series of chemical reactions with glucose that ultimately produce hydrogen ions and charges. The charges are received by the electrodes 55, 57 placed in the electrochemical reaction zone 35, and a current is formed, and because of the increasing number of hydrogen ions, the reaction voltage 11' applied to the electrochemical reaction zone 35 is generated. The current will also become higher and higher, so in combination with the above, the reaction current 21' will gradually increase as shown in the figure.

Referring to the third panel B, after the reaction voltage 11' is supplied for a certain period of time, the voltage supply unit 33 stops supplying the reaction voltage 11' after reacting the reactant to be tested with the enzyme, the active material or the antibody. On the other hand, when the supply of the reaction voltage 11' to the start of the supply of the measurement voltage 13' is stopped, there is still a so-called static reaction, so even if the voltage supply unit 33 does not supply a voltage, it still has a weak standing current 23 'produce.

When data is to be measured, the voltage supply unit 33 of the present invention provides a gradually rising measurement voltage 13' to the electrochemical reaction zone 35 to produce a measurement current 27'. Next, the current measuring unit 37 measures the value of the measured current 27' at the time point t3, since the magnitude of the measured current 27' is related to the amount of chemical reaction between the reactant to be tested and the enzyme, active substance or antibody ( Generally speaking, the higher the current, the higher the concentration, so the final concentration can be used to know the concentration of the reactants to be tested. It is worth mentioning that providing the measured voltage 13' in a gradual manner does not cause an unstable overshooting of the measuring current 27' as is conventionally known, thereby improving the accuracy and efficiency of data measurement.

Referring to the fourth figure, a flow chart of an embodiment of the electrochemical power supply method, please refer to the second figure and the third B figure. The method is applied to the measurement of a concentration of a reactant to be tested in a sample to be tested (for example, measuring the concentration of glucose in the blood), and the steps include: first, supplying an initial voltage 15 to the electrochemical reaction zone 35 (S401), wherein the method The initial voltage 15 can be used to detect whether a sample to be tested (such as blood) is placed in the electrochemical reaction zone 35 (such as the reaction zone of the blood glucose test strip). The detection method has been described above, and therefore will not be described again.

When it is detected that the test object is placed in the electrochemical reaction zone 35, the voltage supply unit 33 stops the supply of the initial voltage 15 (S403), and provides a waiting time for the test object to be surely filled with the electrochemical reaction. District 35. Next, the voltage supply unit 33 supplies a reset voltage signal 17 to the electrochemical reaction zone 35 (S405) to eliminate the charge remaining in the impurity reaction, resetting the chemical reaction in the electrochemical reaction zone 35, and allowing the reaction to start. Restart again. The voltage supply unit 33 then supplies the reaction voltage 11' to the electrochemical reaction zone 35 (S407) to provide the energy required for the reactant (e.g., glucose) to be chemically reacted with the active substance, enzyme or antibody.

After the reaction voltage 11' is stopped for a short period of time, the voltage supply unit 33 supplies the gradually rising measurement voltage 13' to the electrochemical reaction zone 35, generating a measurement current 27' (S409) for measurement. Finally, by measuring the magnitude of the measured current 27' and converting it, the concentration of the reactant (e.g., glucose) to be tested in the sample to be tested (e.g., blood) can be known. It is worth mentioning that the measurement voltage 13' is supplied in a gradually rising manner in order to avoid an unstable overcurrent phenomenon caused by the measurement current 27' and to increase the accuracy of the measurement result.

In summary, by resetting the voltage signal to eliminate the effect of the impurity reaction, and resetting the electrochemical reaction and restarting the chemical reaction, before the reaction between the reactant to be tested and the enzyme, active substance or antibody begins to react. The initial time allows the electrode shape configuration to be unrestricted. In addition, the measurement voltage is provided in a gradually rising manner when measuring data to avoid the phenomenon that the measurement current generates an unstable overcurrent, thereby reducing the error of the measurement result and improving the accuracy of the measurement data.

The above description of the embodiments of the present invention and the drawings are intended to be within the scope of the following claims, and any one skilled in the art of the present invention can easily Any changes or modifications may be covered by the patents defined in this case.

11, 11’. . . Reaction voltage

13, 13’. . . Measuring voltage

15. . . Initial voltage

17. . . Reset voltage signal

20. . . Initial current

21, 21’. . . Reaction current

23, 23’. . . Standing current

25. . . Overcurrent

27, 27’. . . Measuring current

31. . . Processing unit

33‧‧‧Voltage supply unit

35‧‧‧Electrochemical reaction zone

37‧‧‧ Current measuring unit

40, 50‧ ‧ blood glucose test strips

41, 51‧‧ ‧ entrance

42, 52‧‧‧ siphon slot

43‧‧‧Reaction zone

45, 47, 55, 57‧‧‧ electrodes

Tb, t0, t1, t2, t3‧‧‧ time point

S401~S409‧‧‧ Flowchart Step Description

The first A picture is a schematic diagram of the structure of a conventional blood glucose test piece;

The first B picture is a voltage and current waveform diagram of a conventional electrochemical power supply method;

The second figure is a block diagram of an embodiment of the biosensor of the present invention;

The third A is a schematic structural view of an embodiment of the blood glucose test strip of the present invention;

3B is a voltage and current waveform diagram of an embodiment of the electrochemical power supply method of the present invention;

The fourth figure is a flow chart of an embodiment of the electrochemical power supply method of the present invention.

S401～S409. . . Flow chart step description

Claims (12)

An electrochemical power supply method includes: supplying an initial voltage to an electrochemical reaction zone to detect whether a sample to be tested is placed in the electrochemical reaction zone, wherein the electrochemical reaction zone is pre-positioned for An active substance, an enzyme or an antibody which is chemically reacted with one side of the sample to be tested; when the sample to be tested is placed in the electrochemical reaction zone, the supply of the initial voltage to the electrochemical reaction zone is stopped; And resetting the voltage signal in the electrochemical reaction zone to reset the starting time point of the electrochemical reaction; supplying a reaction voltage to the electrochemical reaction zone to electrify the reactant to be tested in the sample to be tested Learning the reaction; and supplying a gradual rise in one of the measured voltages in the electrochemical reaction zone to produce a measured current. The electrochemical power supply method of claim 1, further comprising: providing a waiting time for the sample to be tested to fill the electrochemical reaction zone before the step of supplying the reset voltage signal. The electrochemical power supply method of claim 1, wherein the reaction voltage provides energy sufficient to electrochemically react the reactant to be tested. The electrochemical power supply method of claim 1, wherein the current amount of the measured current is used to convert the concentration of the reactant to be tested in the sample to be tested. The electrochemical power supply method according to claim 1, wherein the electrochemical reaction zone is disposed on a concentration test piece. The electrochemical power supply method according to claim 5, wherein the concentration test piece is a blood glucose test piece. An electrochemical power supply device comprising: an electrochemical reaction zone, wherein a chemical reaction zone of a sample to be tested is chemically reacted, wherein the electrochemical reaction zone is pre-positioned for use with the test An active substance, an enzyme or an antibody for chemically reacting the side reactant; a voltage supply unit coupled to the electrochemical reaction zone, supplying an initial voltage to the electrochemical reaction zone, and being subjected to the test After the body is placed in the electrochemical reaction zone, the initial voltage is stopped, and a reset voltage signal is provided in the electrochemical reaction zone to reset the starting time of the electrochemical reaction, and a reaction voltage is provided to the electrochemical a reaction zone, and finally a gradually increasing voltage; a current measuring unit coupled to the electrochemical reaction zone for measuring a current generated in the electrochemical reaction zone; and a processing unit coupled to the voltage The supply unit and the current measuring unit perform an operation of the concentration of the reactant to be tested according to the measurement result of the current measuring unit. The electrochemical power supply device of claim 7, wherein the voltage supply unit further comprises a blood measuring electrode disposed in the electrochemical reaction zone to detect whether the sample to be tested is full of the electrochemical In the reaction zone. The electrochemical power supply device of claim 8, wherein the current measuring unit measures the value of the measured current and transmits the value of the measured current to the processing unit. The electrochemical power supply device of claim 9, wherein the processing unit converts the reactant to be tested according to the value of the measured current. The concentration content in the sample to be tested. The electrochemical power supply device of claim 7, wherein the electrochemical reaction zone is disposed on a concentration test strip. The electrochemical power supply device of claim 11, wherein the concentration test piece is a blood glucose test piece.