CN115452905A - Electrochemical impedance meter based on smart phone and use method - Google Patents
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- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 6
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- 102000036639 antigens Human genes 0.000 claims description 9
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Abstract
The invention relates to an electrochemical impedance meter based on a smart phone and a using method thereof, and the electrochemical impedance meter specifically comprises a multi-channel electrochemical impedance sensor, an electrochemical impedance detection module and an Android smart phone; the multi-channel electrochemical impedance sensor comprises a plurality of channel working electrodes, a pair of reference electrodes and a pair of counter electrodes; the electrochemical impedance detection module comprises an STM32 main control module, a plurality of single-channel electrochemical impedance modules in communication connection with the STM32 main control module, a Bluetooth transmission module, a liquid crystal display module, a matrix keyboard module and a power supply module; the electrochemical impedance module is in communication connection with an electrode channel of the electrochemical impedance sensor and comprises an AD5933 chip, a low impedance amplifying circuit and a peripheral circuit; the STM32 main control module drives and controls the electrochemical impedance module, and transmits detection data to the Android smart phone through the Bluetooth transmission module; the smart phone displays the detection result in a graph and numerical form and stores the data.
Description
Technical Field
The invention relates to an electrochemical impedance meter, in particular to an electrochemical impedance meter based on a smart phone and a using method thereof.
Background
With the continuous development of sensor technology, the electrochemical sensor is widely concerned by researchers, can be applied to the detection of environmental hormones, utilizes the nanocomposite and the electroactive substance to modify the electrochemical sensor to carry out impedance detection so as to achieve the purpose of detecting the environmental hormones with different concentrations, and becomes a novel detection method. Usually, impedance measurement is mainly realized by using a professional detection instrument, such as an electrochemical workstation Autolab, gamry and the like, but the instrument is expensive in price, large in size, inconvenient to carry, and difficult to meet the requirements of hormone field, rapid and high-sensitivity impedance detection.
Disclosure of Invention
The invention provides an electrochemical impedance meter based on a smart phone, which comprises a multi-channel electrochemical impedance sensor, an electrochemical impedance detection module and an Android smart phone, wherein the multi-channel electrochemical impedance sensor is connected with the electrochemical impedance detection module; the multi-channel electrochemical impedance sensor comprises a plurality of channel working electrodes, a pair of reference electrodes and a pair of counter electrodes; the electrochemical impedance detection module comprises an STM32 main control module, a plurality of single-channel electrochemical impedance modules in communication connection with the STM32 main control module, a Bluetooth transmission module, a liquid crystal display module, a matrix keyboard module and a power supply module; the electrochemical impedance module is in communication connection with an electrode channel of the electrochemical impedance sensor and comprises an AD5933 chip, a low impedance amplifying circuit and a peripheral circuit;
the STM32 main control module drives and controls the electrochemical impedance module, and transmits detection data to the Android smart phone through a Bluetooth transmission module; the Android smart phone displays the detection result in a graph and numerical form, and stores data.
The invention also provides a use method of the electrochemical impedance meter for detecting hormone based on the smart phone, which comprises the following steps: modifying a working electrode of the multi-channel electrochemical impedance sensor by the carbon-based nano composite material and the antibody of the object to be detected, and then repeatedly cleaning by ultrapure water; preparing a series of hormone standard antigen solutions by adopting a proportional dilution method; parameter setting is carried out on an electrochemical impedance meter, hormone standard antigen solutions with different concentrations are measured, corresponding impedance results are obtained, fitting is carried out according to a Randles circuit, and impedance values corresponding to hormones with different concentrations are respectively obtained according to the corresponding relation between the impedance values and impedance curves; and respectively taking hormones with different concentrations and corresponding impedance values obtained by detection of the hormones with different concentrations as horizontal and vertical coordinates, obtaining a fitting curve between the concentration of the hormones and the impedance by using a linear fitting method, and writing the obtained fitting curve into an STM32 main control code for subsequent detection. And dropwise adding a sample solution to be detected to the sample adding position of the multi-channel electrochemical impedance sensor by using a pipette, enabling the sample to be detected to reach the surface of the multi-channel working electrode through the siphonage effect of cellulose filter paper, standing for a preset time, inserting an electrode joint of the multi-channel electrochemical impedance sensor into a slot of an electrochemical impedance meter after an antigen and an antibody are fully reacted, carrying out impedance detection according to the detection method in the step, obtaining a corresponding impedance value according to a multi-channel detection result, and bringing the impedance value into an impedance standard curve equation so as to obtain the concentration of the object to be detected.
Preferably, the multi-channel working electrode of the multi-channel electrochemical impedance sensor is selected by rotating a switch to select different working electrode channels.
Preferably, the surface of the working electrode of the electrochemical impedance sensor is modified with the carbon-based nanocomposite material.
The invention has the beneficial effects that: the invention adopts a high-precision electrochemical impedance measurement method, and can realize impedance measurement of different modification layers, thereby realizing detection of measured objects with different concentrations. The multi-channel electrochemical impedance sensor comprises a plurality of working electrodes, a reference electrode and a counter electrode, can simultaneously carry out impedance detection on various different objects to be detected, and has high detection efficiency. The wireless Bluetooth module breaks the restriction of traditional wired communication, can realize wireless communication of data, and greatly expands the application range of equipment. The invention has the advantages of accurate detection, lower cost, simple and reasonable structure, small volume, portability and wide market prospect, and can be used at any time.
Drawings
FIG. 1 is a block diagram of the overall structural design of the present invention;
FIG. 2 is a circuit diagram of an electrochemical impedance module of the present invention;
FIG. 3 is a circuit diagram of an electrochemical impedance detection module according to the present invention;
FIG. 4 is a diagram illustrating the results of the impedance test according to the embodiment of the present invention.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as particular circuit diagrams, in order to provide a thorough understanding of the embodiments of the invention. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
The invention provides a multi-channel electrochemical impedance meter based on a smart phone, which comprises a multi-channel electrochemical impedance sensor, an electrochemical impedance detection module and an Android smart phone.
The electrochemical impedance detection module comprises an STM32 main control module, a plurality of single-channel electrochemical impedance modules, a Bluetooth transmission module, a liquid crystal display module, a matrix keyboard module and a power supply module.
As shown in fig. 1, the multi-channel electrochemical impedance sensor is connected with the electrochemical impedance module to convert a hormone concentration signal to be detected into an electrochemical impedance electrical signal, and a detection result of the electrochemical impedance detection module is transmitted to the Android smartphone through the wireless bluetooth module to store and display the electrochemical impedance detection signal. The invention solves the problem of lacking of portable impedance detection equipment for rapid hormone detection.
In the embodiment, the multi-channel electrochemical impedance sensor comprises a plurality of symmetrically arranged multi-channel n (n =6 to 12) working electrodes, a pair of reference electrodes and a pair of counter electrodes, wherein the multi-channel working electrodes can select different working electrode channels by using a rotary change-over switch; the electrochemical impedance sensor surface modified carbon-based nanocomposite is used for hormone detection, and the carbon-based nanocomposite forms a loose porous structure on the sensor surface to adsorb protein molecules and an electroactive substance amplification detection signal; the multi-channel electrochemical impedance sensor is connected with the electrochemical impedance detection module through the connecting component and can be used for simultaneously detecting multiple hormones; the nano material has excellent physical and chemical properties such as quantum size effect, surface effect and the like, so that the amplification of a detection signal can be realized, and the problems of poor result reproducibility, high false positive rate and false negative rate and the like of an immunoassay method can be solved.
The multi-channel electrochemical impedance detection module comprises an STM32 main control module, an electrochemical impedance module, a Bluetooth transmission module, a liquid crystal display module, a matrix keyboard module and a power supply module.
The electrochemical impedance detection module in the embodiment comprises six channels, the requirements of different detection precision ranges can be met, the wireless Bluetooth data transmission function can be realized, the real-time communication function with an Android smart phone is realized, the instant and rapid detection is realized, the detection result is displayed on an Android smart phone interface in a graph and numerical form in real time and is stored in a database inside the mobile phone, and the number of the channels of the electrochemical impedance detection module can be expanded according to the detection precision requirements of a multi-channel electrochemical impedance sensor.
And the STM32 main control module is used for generating an impedance detection control algorithm, driving the electrochemical impedance module and setting an initial parameter value of the electrochemical impedance module. The detection signal is subjected to signal amplification, filtering and other processing through the electrochemical impedance module and then applied to the electrode end of the electrochemical impedance sensor to detect the hormone concentration.
The power supply module is used for providing proper power supply voltage for the STM32 main control module, and the matrix keyboard module is used for inputting parameter values and the like.
Electrochemical impedance detection module: the high-precision impedance conversion chip AD5933 is adopted to realize impedance detection with different precisions; the electrochemical impedance module of each single channel is realized by an AD5933 chip, a low-impedance amplifying circuit and a peripheral circuit.
As shown in fig. 2, AD5933 internally contains a frequency generator and a 12-bit analog-to-digital converter ADC, with a conversion rate of bit 1MSPS. The impedance measurement can control an internal register to set the initial frequency, the frequency resolution and the number of scanning points through an STM32 chip, different output voltage ranges of a frequency generator are selected, an excitation signal generated by the frequency signal generator is applied to two ends of the impedance to be measured, high-speed sampling is carried out through an on-chip ADC (analog to digital converter), fourier variation DFT (discrete Fourier transform) is realized on sampling data through an on-chip DSP (digital signal processor), a measurement result is stored in a corresponding memory, and the impedance measurement is completed through calibration calculation.
The AD5933 chip has the limitations of high output impedance of a drive signal, weak drive capability of drive voltage, non-VDD/2 of direct current bias and the like, which affect the measurement precision, and the measurement precision needs to be improved by optimizing a peripheral circuit. The peripheral circuitry not only removes some of the limitations of the AD5933 chip itself, but also improves the accuracy and precision of the impedance measurements.
The low-impedance amplifying circuit is mainly used for assisting in measuring the resistor to be measured with a small impedance value. The high-precision operational amplifier OPA4364, the T-shaped feedback resistance network and the capacitor are designed to form an amplifying circuit for amplifying a detection signal so as to complete small-impedance resistance measurement.
OPA4364 is a high-performance CMOS operational amplifier with 7MHz bandwidth, 90dB CMRR and 5V/us slew rate. The design utilizes reference power supply chip LM4040 to provide fixed voltage VDD/2 for the positive phase input end of operational amplifier OPA4364, and the voltage is applied to the negative phase input end through 'virtual short', and the T-shaped feedback resistance network can realize different amplification factors through resistance impedance adjustment.
As shown in FIG. 3, the multi-channel electrochemical impedance detection module circuit can select different channels to output measurement ranges through a multi-way switch, so that the measurement of objects to be measured with different concentrations is realized, and the measurement result can pass through I of an STM32 chip 2 The C interface data lines SCL and SDA.
The Bluetooth transmission module: the impedance detection result can be displayed on the liquid crystal display module in real time, and can also be connected with the Android smart phone through the wireless Bluetooth module to perform data transmission, the impedance detection result is stored in the mobile phone in a database mode and used for data management and query, and the impedance detection result can be transmitted to a cloud end and sent to a large detection mechanism. The Bluetooth module adopts an HC-05 module, designs and utilizes a CSR BC417143B chip and a Bluetooth 2.0 protocol, can set the baud rate within the range of 1200-115200bps, and performs Bluetooth data communication with an STM32 chip through TXD and RXD ports. The module has the advantages of low price, small volume and low power consumption, and can be used for mobile detection equipment.
In the invention, the impedance measurement adopts a high-performance AD5933 chip and a low-impedance amplifier circuit to form an impedance measurement circuit to carry out impedance measurement on the multi-channel electrochemical impedance sensor. The measurement is carried out according to the principle that resistance impedances generated between a working electrode and a reference electrode of the electrochemical impedance sensor by substances to be measured with different concentrations are different. Setting an internal register through an STM32 chip, setting an impedance measurement starting frequency, a frequency increment and an increment number, outputting a peak value of a sine waveform, providing a sine wave excitation waveform through a DDS core of a 27-phase accumulator at a transmitting end for exciting the impedance to be detected between electrodes of a sensor to be detected, inputting a generated electric signal into a receiving stage of an AD5933 chip, performing FFT calculation through an internal current-voltage amplifier, a programmable gain amplifier, a filter and an ADC (analog-to-digital converter), obtaining a real part and an imaginary part of the impedance to be detected, storing the real part and the imaginary part into the internal register, and performing FFT calculation through I 2 The C interface signals SCL and SDA are communicated with the STM32 chip to obtain impedance values, and the corresponding concentration of the object to be measured is obtained through the measured impedance values.
The invention also provides a using method of the device for detecting the hormone, aiming at the requirement of simultaneously detecting various hormones, the multichannel electrochemical impedance sensor is combined, and the rapid high-sensitivity detection of the object to be detected is realized by utilizing the multichannel electrochemical impedance meter based on the intelligent mobile phone. The hormone is used as a detection object, a multichannel electrochemical impedance sensor structure formed by a multichannel working electrode, a pair of reference electrodes and a counter electrode is designed, and the sensor is modified by using a carbon-based nano composite material and different electroactive substances, so that simultaneous detection of multiple hormones is realized.
The standard curve of the hormone impedance can be obtained by an impedance measurement mode, then the standard curve equation is written into a program of an impedance meter, and finally, a corresponding concentration value is obtained according to the standard curve impedance value corresponding to each hormone in the measurement.
Taking the detection of FSH as an example, the specific steps are as follows:
(1) Preparing a sufficient amount of prepared carbon-based nano composite material and a multi-channel electrochemical impedance sensor modified by an antibody of an object to be detected, and repeatedly cleaning the multi-channel electrochemical impedance sensor by using ultrapure water for later use;
(2) Preparing a series of FSH standard antigen solutions by adopting a proportional dilution method: 0 mIU mL -1 、5 mIU mL -1 、25 mIU mL -1 、50 mIU mL -1 ；
(3) The parameters of the multi-channel electrochemical impedance meter are set, and the frequency range is as follows: 1 to 10 5 Hz, measuring FSH standard antigen solutions with different concentrations to obtain corresponding impedance results, fitting according to a Randles circuit, and respectively obtaining impedance values corresponding to the FSH with different concentrations according to the corresponding relation between the impedance values and the impedance curve;
(4) And respectively taking FSH with different concentrations and corresponding impedance values obtained by detection as horizontal and vertical coordinates, obtaining a fitting curve between the FSH concentration and the impedance by using a linear fitting method, and writing the obtained fitting curve into an STM32 main control code for subsequent detection.
The detection steps of the FSH to be detected are as follows:
firstly, a sample solution to be detected is dripped to the sample adding position of the multi-channel electrochemical impedance sensor by using a pipette, the sample to be detected reaches the surface of a multi-channel working electrode through the siphon effect of cellulose filter paper, the multi-channel electrochemical impedance sensor is kept stand for 25 minutes, after an antigen and an antibody fully react, an electrode joint of the multi-channel electrochemical impedance sensor is inserted into a slot of the multi-channel electrochemical impedance meter, impedance detection is carried out according to the detection method in the steps, a corresponding impedance value is obtained according to the detection result of six channels, and the impedance value is brought into an impedance standard curve equation, so that the concentration of an object to be detected can be obtained.
The results of impedance measurements of different concentrations of FSH are shown in fig. 4.
The invention has the beneficial effects that:
(1) The multi-channel electrochemical impedance sensor comprises a plurality of working electrodes, a reference electrode and a counter electrode, can simultaneously carry out impedance detection on six different objects to be detected, and has high detection efficiency.
(2) The invention adopts a high-precision electrochemical impedance measurement method, and can realize impedance measurement of different modification layers, thereby realizing detection of measured objects with different concentrations.
(3) The impedance meter provided by the invention adopts the Bluetooth wireless module to realize communication between the portable impedance meter and the Android smart phone, and can display the acquired data on the smart phone in real time and perform data processing and management. The use of the Bluetooth wireless module breaks through the restriction of traditional wired communication, can realize wireless communication of data, and greatly expands the application range of equipment.
(4) Low-cost low-power consumption design: the audio interface is used as a power supply mode, so that the defect of a traditional short board for battery endurance is overcome, and the power consumption of the equipment can be greatly reduced by the audio power supply mode; and meanwhile, the USB and the button battery are used as standby power supplies, so that more power supply modes are provided for the equipment. The equipment adopts an ARM STM32F103RCT6 chip with low power consumption, and the inside of the chip comprises a 12-bit ADC and a DAC, so that the design cost is greatly reduced compared with the design mode of singly adopting the ADC and the DAC; and the power consumption of the whole equipment is further reduced by selecting the low-power-consumption Bluetooth module.
Claims (5)
1. An electrochemical impedance meter based on a smart phone is characterized by comprising a multi-channel electrochemical impedance sensor, an electrochemical impedance detection module and an Android smart phone;
the multi-channel electrochemical impedance sensor comprises a plurality of channel working electrodes, a pair of reference electrodes and a pair of counter electrodes; the multi-channel working electrode selects different working electrode channels through a rotary selector switch;
the electrochemical impedance detection module comprises an STM32 main control module, a plurality of single-channel electrochemical impedance modules in communication connection with the STM32 main control module, a Bluetooth transmission module, a liquid crystal display module, a matrix keyboard module and a power supply module;
the electrochemical impedance module is in communication connection with an electrode channel of the electrochemical impedance sensor and comprises an AD5933 chip, a low impedance amplifying circuit and a peripheral circuit;
the STM32 main control module drives and controls the electrochemical impedance module, and transmits detection data to the Android smart phone through a Bluetooth transmission module;
the Android smart phone displays the detection result in a graph and numerical form, and stores data.
2. The smart-phone-based electrochemical impedance meter according to claim 1, wherein the surface of the working electrode of the electrochemical impedance sensor is modified with a carbon-based nanocomposite material.
3. The electrochemical impedance meter based on the smart phone as claimed in claim 1, wherein the low impedance amplifying circuit comprises an operational amplifier OPA4364, a T-type feedback resistance network and a capacitor to form an amplifying circuit for amplifying the detection signal.
4. The electrochemical impedance meter based on the smart phone according to claim 1, wherein the STM32 main control module selects an ARM STM32F103RCT6 chip with low power consumption, and adopts an audio interface as a power supply mode.
5. The method for using the electrochemical impedance meter to detect hormones as claimed in any one of claims 1 to 4, comprising:
(1) Modifying a working electrode of the multi-channel electrochemical impedance sensor by the carbon-based nano composite material and the antibody of the object to be detected, and then repeatedly cleaning by ultrapure water;
(2) Preparing a series of hormone standard antigen solutions by adopting a proportional dilution method;
(3) Parameter setting is carried out on an electrochemical impedance meter, hormone standard antigen solutions with different concentrations are measured, corresponding impedance results are obtained, fitting is carried out according to a Randles circuit, and impedance values corresponding to hormones with different concentrations are respectively obtained according to the corresponding relation between the impedance values and impedance curves;
(4) Respectively taking hormones with different concentrations and corresponding impedance values obtained by detection of the hormones as horizontal and vertical coordinates, obtaining a fitting curve between the concentration of the hormones and the impedance by using a linear fitting method, and writing the obtained fitting curve into an STM32 main control code for subsequent detection;
(5) And (3) dropwise adding a sample solution to be detected to the sample adding position of the multi-channel electrochemical impedance sensor by using a pipette, enabling the sample to be detected to reach the surface of the multi-channel working electrode through the siphon effect of cellulose filter paper, standing for a preset time, inserting an electrode connector of the multi-channel electrochemical impedance sensor into a slot of an electrochemical impedance instrument after the antigen and the antibody fully react, carrying out impedance detection according to the detection methods in the steps (2) and (3), obtaining a corresponding impedance value according to the detection result of the multi-channel, and bringing the impedance value into an impedance standard curve equation so as to obtain the concentration of the object to be detected.
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| CN111912976A (en) * | 2020-06-30 | 2020-11-10 | 无锡市妇幼保健院 | Electrochemical impedance biosensor and preparation method and application thereof |
| CN113281386A (en) * | 2021-04-01 | 2021-08-20 | 中山大学 | Multi-channel electrochemical sensor detection device and detection method thereof |
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- 2022-11-04 CN CN202211373912.4A patent/CN115452905A/en active Pending
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| CN203933543U (en) * | 2014-05-17 | 2014-11-05 | 徐云鹏 | A kind of T-shaped filter amplification circuit of fast detector |
| CN107255665A (en) * | 2017-07-03 | 2017-10-17 | 武汉科技大学 | A kind of mancarried device of quick detection human body female hormone and progestational hormone |
| CN111404491A (en) * | 2020-03-25 | 2020-07-10 | 杭州顾宸科技有限公司 | T-shaped resistance network trans-impedance amplifying circuit with automatic voltage compensation function |
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Application publication date: 20221209 |