An electrochemical sensor based on redundant electrodes and its attenuation compensation method

Abstract

The present invention relates to an electrochemical sensor based on redundant electrodes and an attenuation compensation method thereof. The sensor comprises an interface base and a probe portion, wherein the interface base is provided with three electrical connection terminals. The probe portion is provided with a primary electrode sensor and a redundant electrode sensor, wherein the redundant electrode sensor is located at the outer end of the probe portion. The primary electrode sensor and the redundant electrode sensor are both provided with a counter electrode, a working electrode, and a reference electrode, and the primary electrode sensor and the redundant electrode sensor share a counter electrode. The first terminal is connected to the counter electrode, the second terminal is connected to the working electrode, and the third terminal is connected to the reference electrode. The present invention achieves a very high similarity in characteristics between the primary electrode sensor and the redundant electrode sensor, utilizes the known characteristics of the redundant electrode sensor to predict the measurement results of the unknown primary electrode sensor, and calculates a relatively accurate correction value without the need for additional attenuation compensation. This method abandons traditional empirical compensation methods and attenuation curve fitting methods, thus avoiding the introduction of errors.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical sensors, and in particular to an electrochemical sensor based on redundant electrodes and an attenuation compensation method thereof. Background Art

[0002] Existing electrochemical sensors typically use three-electrode technology, adding a reference electrode to eliminate the effects of current fluctuations on the electrochemical reaction bias. Electrochemical sensors are used in many fields, particularly medicine, where high sensitivity and output accuracy are required. Failure to do so could result in medical accidents or even endanger the patient's life.

[0003] In the medical field, taking the measurement of human glucose concentration as an example, although the enzyme that mainly controls the sensitivity of the sensor will not decrease with the process of chemical reaction in theory, in actual applications, the enzyme that effectively participates in the chemical reaction is constantly decreasing, and the activity will gradually decrease with changes in the environment.

[0004] The traditional approach is to use empirical compensation values, or to fit a measured attenuation curve into a function formula, then compensate for the attenuated portion in actual use to obtain an output result that is as close to the true value as possible. This approach brings some problems, such as: the empirical compensation value is relatively fixed and does not reflect the subtle differences in signal output of each sensor; the measured attenuation curve is inherently nonlinear, and errors are continuously introduced in the process of empirical value-fitting-compensation regression, resulting in a certain difference between the final result and the actual result.

[0005] The above problems are worth solving. Summary of the Invention

[0006] In order to overcome the deficiencies of the existing technology, the present invention provides an electrochemical sensor based on redundant electrodes and an attenuation compensation method thereof.

[0007] The technical solution of the present invention is as follows:

[0008] An electrochemical sensor based on redundant electrodes includes an interface base and a probe portion, wherein the interface base is provided with three electrical connection terminals, including a first terminal, a second terminal, and a third terminal; the probe portion is provided with a primary electrode sensor and a redundant electrode sensor, wherein the redundant electrode sensor is located at the outer end of the probe portion; the primary electrode sensor and the redundant electrode sensor are both provided with a counter electrode, a working electrode, and a reference electrode, and the primary electrode sensor and the redundant electrode sensor share a counter electrode; the first terminal is connected to the counter electrode, the second terminal is connected to the working electrode, and the third terminal is connected to the reference electrode.

[0009] According to the present invention of the above aspect, the counter electrode is located on the back side of the probe portion.

[0010] The present invention according to the above aspect is characterized in that the counter electrode extends from the primary electrode sensor to the redundant electrode sensor.

[0011] The present invention according to the above scheme is characterized in that the working electrode includes the first working electrode of the original electrode sensor and the second working electrode of the redundant electrode sensor; the reference electrode includes the first reference electrode of the original electrode sensor and the second reference electrode of the redundant electrode sensor.

[0012] On the other hand, the present invention also provides an electrochemical sensor attenuation compensation method based on redundant electrodes, comprising the following steps:

[0013] S1. Calculate the current response formula of the redundant electrode sensor;

[0014] S2, removing the redundant electrode sensor to obtain the original electrode sensor;

[0015] S3, use the original electrode sensor to measure the current signal It, solution temperature T, and sensor working time t at a certain moment;

[0016] S4. Use the characteristics of the redundant electrode sensor to predict the results of the original electrode sensor.

[0017] The present invention according to the above scheme is characterized in that the current response formula of the redundant electrode sensor in step S1 is Ic=F1(C)*F2(T)*F3(t), where C is the solution concentration, T is the solution temperature, and t is the working time of the sensor.

[0018] Furthermore, in step S1, the redundant electrode sensors are tested and fitted to obtain the specific forms and parameters of F1(C), F2(T), and F3(t), including:

[0019] Concentration function F1(C) = k*C+b, where k and b are constants;

[0020] Temperature function F2(T)=a2*T 2 +a1*T+a0, where a0, a1, and a2 are constants;

[0021] The time function formula F3(t)=log(a4) / log(t), where a4 is a constant, is obtained by fitting after measurement.

[0022] The present invention according to the above solution is characterized in that step S4 includes:

[0023] S401. Substitute the parameters measured in step S3 into the formula It=F1(C)*F2(T)*F3(t)

[0024] Substitute the known quantities It, F2(T), and F3(t) into the formula It=F1(C)*F2(T)*F3(t);

[0025] S402, inversely calculate the glucose concentration of the solution where the original electrode sensor is located

[0026] By inferring F1(C), we can obtain the solution concentration C where the original electrode sensor is located.

[0027] The present invention according to the above scheme has the following beneficial effects:

[0028] The present invention manufactures primary electrode sensors and redundant electrode sensors on the same substrate, and the two share a counter electrode, thereby ensuring a high degree of similarity between the redundant electrode and the primary electrode. The present invention first obtains the characteristics of the redundant electrode sensor, including mastering its time attenuation performance, and then uses the known characteristics of the redundant electrode sensor to predict the measurement results of the unknown primary electrode sensor, thereby calculating and obtaining more accurate results without the need for additional attenuation compensation. This abandons traditional empirical compensation methods and attenuation curve fitting methods, avoids the introduction of errors, and produces more accurate results. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a front structural schematic diagram of the present invention;

[0030] Figure 2 It is a schematic diagram of the back structure of the present invention;

[0031] Figure 3 Flow chart of the method of the present invention.

[0032] In the figure, 1, interface base; 11, first terminal; 12, second terminal; 13, third terminal;

[0033] 2. Probe portion; 21. Counter electrode; 221. First working electrode; 222. Second working electrode; 231. First reference electrode; 232. Second reference electrode. DETAILED DESCRIPTION

[0034] In order to better understand the purpose, technical solutions and technical effects of the present invention, the present invention is further explained below with reference to the accompanying drawings and embodiments. It is also stated that the embodiments described below are only used to illustrate the present invention and are not intended to limit the present invention.

[0035] It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it may be directly on the other element or there may be an intermediate element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be an intermediate element.

[0036] The directions or positions indicated by terms such as "up", "down", "left", "right", "front", "back", "vertical", "horizontal", "top", "bottom", "inside" and "outside" are based on the directions or positions shown in the accompanying drawings and are only for the convenience of description and should not be understood as limiting the present technical solution.

[0037] like Figure 1 and Figure 2 As shown, an electrochemical sensor based on redundant electrodes includes an interface base 1 and a probe portion 2. The interface base 1 has three electrical connection terminals for powering the sensor and outputting signals, specifically a first terminal 11, a second terminal 12, and a third terminal 13. For example, the second terminal 12 is used for power supply, while the first terminal 11 and the third terminal 13 are used for signal output. The probe portion 2 is distributed with a counter electrode 21, a working electrode, and a reference electrode for electrochemical reactions. The first terminal 11 is connected to the counter electrode 21, the second terminal 12 is connected to the working electrode, and the third terminal 13 is connected to the reference electrode. The connection method is to connect the terminals to the electrodes via printed circuits.

[0038] The probe part 2 of the present invention is provided with an original electrode sensor and a redundant electrode sensor. The redundant electrode sensor is located at the outer end of the probe part 2, so that the redundant electrode sensor at the outer end can be easily removed during operation.

[0039] Both the original electrode sensor and the redundant electrode sensor are provided with a counter electrode 21, a working electrode and a reference electrode, and the original electrode sensor and the redundant electrode sensor share one counter electrode 21; the working electrode includes a first working electrode 221 of the original electrode sensor and a second working electrode 222 of the redundant electrode sensor; the reference electrode includes a first reference electrode 231 of the original electrode sensor and a second reference electrode 232 of the redundant electrode sensor.

[0040] In terms of electrical connection, the first terminal 11 is connected to the common counter electrode 21 , the second terminal 12 is connected to the first working electrode 221 and the second working electrode 222 , and the third terminal 13 is connected to the first reference electrode 231 and the second reference electrode 232 .

[0041] In summary, the counter electrode 21, the first working electrode 221 and the first reference electrode 231 constitute the primary electrode sensor of the upper half of the probe part 2, and the counter electrode 21, the second working electrode 222 and the second reference electrode 232 constitute the redundant electrode sensor of the lower half of the probe part 2.

[0042] In the present invention, the counter electrode 21 is located on the back of the probe portion 2, while the two sets of working electrodes and the reference electrode are located on the front of the probe portion 2. Compared to traditional electrochemical sensors, the counter electrode 21 is longer, extending from the primary electrode sensor to the redundant electrode sensor. Because the primary and redundant electrode sensors are fabricated on the same substrate, their characteristics are highly similar.

[0043] like Figure 3 As shown, the present invention also provides an electrochemical sensor attenuation compensation method based on redundant electrodes, using the electrochemical sensor of the above solution, comprising the following steps:

[0044] S1. Calculate the current response formula of the redundant electrode sensor;

[0045] S2, removing the redundant electrode sensor to obtain the original electrode sensor;

[0046] S3, use the original electrode sensor to measure the current signal It, solution temperature T, and sensor working time t at a certain moment;

[0047] S4. Use the characteristics of the redundant electrode sensor to predict the results of the original electrode sensor.

[0048] In this embodiment, the current response formula of the redundant electrode sensor in step S1 is Ic=F1(C)*F2(T)*F3(t), where C is the solution concentration, T is the solution temperature, and t is the operating time of the sensor. Specifically, the specific forms and parameters of F1(C), F2(T), and F3(t) are obtained by testing and fitting the redundant electrode sensors, including:

[0049] Concentration function F1(C) = k*C+b, where k and b are constants;

[0050] Temperature function F2(T)=a2*T 2 +a1*T+a0, where a0, a1, and a2 are constants;

[0051] The time function formula F3(t)=log(a4) / log(t), where a4 is a constant, is obtained by fitting after measurement.

[0052] In this embodiment, step S4 includes:

[0053] S401. Substitute the parameters measured in step S3 into the formula It=F1(C)*F2(T)*F3(t)

[0054] Due to the high similarity between the original electrode and the redundant electrode, the current response formula of the redundant electrode sensor can be used to express the current formula of the original electrode sensor, so It = F1(C) * F2(T) * F3(t) is obtained, and the known quantities It, F2(T) and F3(t) are substituted into the formula It = F1(C) * F2(T) * F3(t);

[0055] S402, inversely calculate the glucose concentration of the solution where the original electrode sensor is located

[0056] By inferring F1(C), we can obtain the solution concentration C where the original electrode sensor is located.

[0057] The technical features of the above embodiments can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0058] The above embodiments merely illustrate several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. An electrochemical sensor based on redundant electrodes, characterized in that: It includes an interface base and a probe part, wherein the interface base is provided with three electrical connection terminals, including a first terminal, a second terminal and a third terminal; The probe portion is provided with a primary electrode sensor and a redundant electrode sensor, and the redundant electrode sensor is located at the outer end of the probe portion; the primary electrode sensor and the redundant electrode sensor are both provided with a counter electrode, a working electrode and a reference electrode, and the primary electrode sensor and the redundant electrode sensor share a counter electrode; The first terminal is connected to the counter electrode, the second terminal is connected to the working electrode, and the third terminal is connected to the reference electrode.

2. The electrochemical sensor based on redundant electrodes according to claim 1, characterized in that The counter electrode is located on the back side of the probe portion.

3. The electrochemical sensor based on redundant electrodes according to claim 1, characterized in that The counter electrode extends from the primary electrode sensor to the redundant electrode sensor.

4. The electrochemical sensor based on redundant electrodes according to claim 1, characterized in that The working electrodes include a first working electrode of the primary electrode sensor and a second working electrode of the redundant electrode sensor; the reference electrodes include a first reference electrode of the primary electrode sensor and a second reference electrode of the redundant electrode sensor.

5. A method for attenuation compensation of an electrochemical sensor based on redundant electrodes according to any one of claims 1 to 4, comprising the following steps: S1. Calculate the current response formula of the redundant electrode sensor; The current response formula is Ic=F1(C)*F2(T)*F3(t), where C is the solution concentration, T is the solution temperature, and t is the working time of the sensor; The specific forms and parameters of F1(C), F2(T), and F3(t) are obtained by testing and fitting the redundant electrode sensors, including: Concentration function F1 (C) = k*C + b, where k and b are constants; Temperature function F2 (T) = a2*T2+ a1*T+ a0, where a0, a1, and a2 are constants; The time function is F3(t)=log(a4) / log(t), where a4 is a constant obtained by fitting after measurement; S2, removing the redundant electrode sensor to obtain the original electrode sensor; S3, use the original electrode sensor to measure the current signal It, solution temperature T, and sensor working time t at a certain moment; S4, using the characteristics of the redundant electrode sensor to predict the results of the original electrode sensor; Step S4 includes: S401, substitute the parameters measured in step S3 into the formula It=F1(C)*F2(T)*F3(t) Substitute the known quantities It, F2(T) and F3(t) into the formula It=F1(C)*F2(T)*F3(t); S402, inversely calculating the glucose concentration of the solution in which the original electrode sensor is located; By inferring F1(C), we can obtain the glucose concentration C of the solution where the original electrode sensor is located.

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