CN115980163A - Portable tumor DNA electrochemiluminescence detection device and method - Google Patents
Portable tumor DNA electrochemiluminescence detection device and method Download PDFInfo
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Abstract
The invention relates to a portable tumor DNA electrochemical luminescence detection device and a method, comprising a main control module, a three-electrode control module, a display module, a Bluetooth module and a photoelectric sensor module; the main controller is connected with the three-electrode sensor through the three-electrode control module, controls the digital-to-analog conversion module to output triangular pulse signals, utilizes cyclic voltammetry in electrochemical principles to scan a three-electrode system, enables electrochemical luminescence reaction to occur in an electrolytic cell, generates optical signals, and enables the photoelectric sensor module to collect the optical signals and convert the optical signals into electric signals to be transmitted to the main controller, so that the technical problems of low signal detection speed, low detection efficiency and poor sensitivity during target ctDNA detection can be solved. In addition, the detection device of the invention has small volume, convenient operation and carrying and high integration level, and can effectively shorten the transmission distance of the light source, thereby reducing the signal interference, improving the sensitivity and stability of the signal and expanding the application scene of the detection target object.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a portable tumor DNA electrochemical luminescence detection device and method.
Background
Circulating tumor gene (ctDNA), an important liquid biopsy tumor marker, is composed of single-stranded or double-stranded DNA and a single-stranded and double-stranded DNA complex, and is extracellular DNA released into the blood circulation system of a human body after tumor cell DNA is shed or cell apoptosis.
In the field of combining optical acquisition and DNA detection, the prior art generally adopts a mode of exciting fluorescence by light source irradiation, and the minimum collected optical signal is a weak fluorescence signal at the pW level, so that the acquisition process is difficult. In addition, because the transmission distance of the light source is too long, signal interference and low sensitivity exist when the signal is acquired, and the follow-up signal analysis, acquisition, device carrying and other work are not facilitated. Therefore, the detection difficulty is greatly improved for unstable and weak signals. Therefore, the sensitivity of sample detection is low, the detection efficiency is low, the background noise is large, and the equipment performance of the lung cancer detection device is greatly reduced.
Disclosure of Invention
The invention aims to provide a portable tumor DNA electrochemiluminescence detection device and method, which utilize cyclic voltammetry in electrochemical principles to scan a three-electrode system, so that electrochemiluminescence reaction occurs in an electrolytic cell to generate an optical signal, a photoelectric sensor module collects the optical signal and converts the optical signal into an electrical signal to be transmitted to a main controller, and the technical problems of low signal detection sensitivity, low detection efficiency and high background noise in the process of detecting the ctDNA concentration of a target object can be solved.
In order to achieve the purpose, the invention designs a portable tumor DNA electrochemiluminescence detection device, which comprises a box body integrated with a main control module, a three-electrode control module and a photoelectric sensor module, wherein the main control module is respectively connected with the three-electrode control module and the photoelectric sensor module; the three-electrode control module is used for manufacturing an electrochemiluminescence biosensor and converting a biological signal into an optical signal; the photoelectric sensor module collects optical signals, converts the optical signals into electric signals and transmits data results to the mobile terminal;
the three-electrode control module comprises a screen printing electrode, a mixed solution of prepared gold nanoparticles, 6-mercapto-1-hexanol and quantum dots (cadmium selenide, cadmium sulfide, carbon nitride, carbon quantum dots and the like) combined with hairpin DNA is added to the surface of a working electrode of the screen printing electrode, and a PBS (phosphate buffer solution) containing a co-reactant potassium persulfate is dripped to form the electrochemical luminescence biosensor; base complementary pairing is carried out between the target object ctDNA and the hairpin DNA, the structure of the hairpin DNA is opened, and the 6-sulfydryl-1-hexanol occupies redundant binding sites on the surface of the gold nanoparticles, so that the distance between a quantum dot and the gold nanoparticles is increased, an electrochemiluminescence signal quenched by adding the hairpin DNA mixed solution is restored again, and the aim of detecting the concentration of the target object ctDNA is fulfilled.
As a preferred scheme, the box body is of a hollow structure and comprises a shell and a partition plate arranged in the middle of a cavity of the box body, wherein the cavity in the box body is divided into a potentiostat area, a main control area and an optical signal acquisition area by the partition plate; the three-electrode control module is arranged in a potentiostat area, the main control module is arranged in a main control area, and the photoelectric sensor module is arranged in an optical signal acquisition area.
As a preferred scheme, an electromagnetic shielding box is arranged in the optical signal acquisition area, the electromagnetic shielding box is of a hollow structure, a photoelectric device fixing plate is arranged on the inner side wall of the electromagnetic shielding box, and the photoelectric sensor module is installed on the photoelectric device fixing plate.
Preferably, a potentiostat circuit board is fixed in the potentiostat area, a decorated screen printing electrode is installed on the potentiostat circuit board, and the screen printing electrode is sent into an electromagnetic shielding box of the light signal acquisition area through a three-electrode channel.
As a preferred scheme, the three-electrode control module further comprises a constant potential circuit, an ADC analog-to-digital conversion circuit, a DAC digital-to-analog conversion circuit, a filter circuit, a current/voltage conversion amplifying circuit, an alarm module and a control switch; the input end of the constant potential circuit is connected with the output end of the DAC digital-to-analog conversion circuit after passing through the filter circuit and is used for meeting the scanning requirement of the cyclic voltammetry, and the output end of the constant potential circuit is connected with the input end of the current/voltage conversion amplifying circuit and is used for amplifying signals; the filter circuit is composed of a three-order Butterworth low-pass filter; the alarm circuit adopts a buzzer module, and carries out alarm prompt after the signal acquisition is finished; the control switch is used for controlling whether the current in the screen printing electrode passes through the working electrode or not.
The invention also designs a portable tumor DNA electrochemiluminescence detection method, which comprises the following steps:
s1, controlling a circuit in a three-electrode control module to generate an optical signal;
firstly, the prepared electrochemiluminescence biosensor is used for incubation and combination with a target detection object, and then in a modified screen printing electrode, an excitation voltage is applied through a main control module to generate electrochemiluminescence reaction on the electrochemiluminescence biosensor so as to generate an optical signal;
s2, collecting optical signals and converting the optical signals into electric signals by the photoelectric sensor module;
the photoelectric sensor module collects optical signals in the electrolytic cell, converts the optical signals into electric signals and transmits data results to the main control module;
s3, the main control module transmits the data result to the mobile terminal;
the main control module transmits the data result to the Bluetooth communication module, the Bluetooth communication module receives the data and transmits the data to the mobile terminal, and the mobile phone application program displays the acquired data by using a chart.
Preferably, the method further comprises the step of manufacturing the electrochemiluminescence biosensor before the step S1, wherein the specific manufacturing steps are as follows:
s1.1, uniformly dripping a mixed solution of quantum dots and gold nanoparticles combined with hairpin DNA on the surface of a working electrode of a screen printing electrode, and adding a PBS (phosphate buffer solution) containing a co-reactant into an electrolytic bath; the quantum dot and the coreactant generate electrochemical luminescence reaction under the stimulation of the pulse signal to generate an electrochemical optical signal;
s1.2 hairpin DNA modified by gold nanoparticles is added on the surface of a working electrode to form the electrochemical luminescence biosensor.
Resonance energy transfer occurs between the quantum dots and the gold nanoparticles, and the electrochemical optical signal is quenched; and then adding a target detection object into the electrolytic bath, wherein base complementary pairing is generated between ctDNA of the target detection object and hairpin DNA, the structure of the hairpin DNA is opened, the distance between the quantum dot and the gold nanoparticle is increased, an electrochemiluminescence energy resonance system is damaged, and an electrochemiluminescence signal is recovered.
Preferably, before the step S1.2, a uniform PDDA film is coated on the surface of the working electrode; on one hand, the PDDA film enables the quantum dots to be more stably attached to the surface of the working electrode, on the other hand, the PDDA film is positively charged, the hairpin DNA is negatively charged, and the hairpin DNA modified by the gold nanoparticles is better fixed on the surface of the working electrode through electrostatic interaction.
Preferably, the mixed solution of step S1.1 further contains 6-mercapto-1-hexanol.
Preferably, the co-reactant is K 2 S 2 O 8 . Due to K 2 S 2 O 8 Compared with other solutions, the luminescent reaction effect is better.
The invention has the beneficial effects that:
the system is characterized in that a main control module, a three-electrode control module, a display module, a Bluetooth module and a photoelectric sensor module are arranged; the three-electrode control module comprises a screen printing electrode, a filter circuit, a current/voltage conversion amplifying circuit, a digital-to-analog conversion circuit and an analog-to-digital conversion circuit; the main controller is connected with the three-electrode sensor through the three-electrode control module to control the digital-to-analog conversion module to output triangular pulse signals, the cyclic voltammetry in the electrochemical principle is utilized to stimulate the three-electrode system to generate electrochemical luminescence reaction in the electrolytic cell, and the intensity of the electrochemical luminescence signals and the concentration of the target ctDNA are in a linear relation, so that the method can be used for detecting the concentration of the target ctDNA, and the aim of cyclic tumor gene detection is fulfilled.
The photoelectric sensor module collects fluorescent signals in the electrolytic cell, converts the optical signals into electric signals and transmits the electric signals to the main controller, the main controller transmits data results to the Bluetooth, the Bluetooth communication module receives the data and transmits the data to the mobile terminal, and the mobile phone application program displays the collected data by using a chart. Therefore, the invention can effectively solve the technical problems of low signal detection speed, low detection efficiency and poor sensitivity when the ctDNA concentration of the target object is detected. The invention has the advantages of high sensitivity, high detection speed, wide dynamic range and good portability.
In addition, the detection device is small in size, convenient to operate and carry, high in integration level due to the fact that the main control module, the three-electrode control module and the photoelectric sensor module are integrated, and capable of effectively shortening the transmission distance of a light source, so that signal interference can be reduced, and the sensitivity and the stability of signals can be improved. The application scene of detecting the target object is expanded.
Drawings
FIG. 1 is a basic block diagram of a detection system of the present invention;
FIG. 2 is a schematic diagram of the three-electrode circuit of the present invention;
FIG. 3 is a schematic diagram of a screen printed electrode structure according to the present invention;
FIG. 4 is a schematic diagram of the operation of an electrochemiluminescence biosensor;
FIG. 5 is a schematic perspective view of the detecting device of the present invention;
FIG. 6 is a schematic cross-sectional view of the detecting device of the present invention;
FIG. 7 is a schematic side view of the detecting device of the present invention.
Description of reference numerals:
the device comprises a constant potential rectifier area 1, a main control area 2, a three-electrode channel 3, an optical signal acquisition area 4, an electromagnetic shielding box 5, a partition plate 6, a photoelectric device fixing plate 7, a shell 8, a chute 9, an electromagnetic shielding box channel 10, an upper cover plate slide rail 11, a fixing hole 12, an upper cover plate plane 13, an upper cover plate 14, a counter electrode 15, a working electrode 16, an electrolytic cell 17 and a reference electrode 18.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted and the technical effects achieved by the present invention clearer, the technical solutions of the present invention are further described below by way of specific embodiments with reference to the accompanying drawings. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. It should be further noted that, for the convenience of description, only some but not all of the elements associated with the present invention are shown in the drawings.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Wherein the terms "first position" and "second position" are two different positions.
In the description of the present invention, it should be noted that unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection or a removable connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The invention relates to a portable tumor DNA electrochemiluminescence detection device and method, which utilizes quantum dot materials to prepare a high-sensitivity electrochemiluminescence biosensor for detecting ctDNA concentration of a target object. The quantum dots can be any one of cadmium selenide, cadmium sulfide, carbon nitride and carbon quantum dots.
As shown in FIG. 1, the present invention relates to a portable tumor DNA electrochemiluminescence detection device, which comprises a box body integrated with a main control module, a three-electrode control module, a display module, a Bluetooth module, a power supply voltage stabilization module and a photoelectric sensor module. The main control module is respectively connected with the three-electrode control module and the photoelectric sensor module; the three-electrode control module is used for manufacturing an electrochemiluminescence biosensor and converting biological signals in the screen-printed electrode into optical signals; the photoelectric sensor module collects optical signals and converts the optical signals into electric signals to be transmitted to the mobile terminal;
the three-electrode control module comprises a screen printing electrode, the prepared mixed solution of gold nanoparticles, 6-sulfydryl-1-hexanol and quantum dots which are combined with hairpin DNA is added on the surface of a working electrode of the screen printing electrode, and PBS buffer solution containing co-reactant is dripped to form the electrochemical luminescence biosensor; when a solution containing a target substance ctDNA with a certain concentration is added to the surface of the working electrode, base complementary pairing occurs between the target substance ctDNA and the hairpin DNA, the structure of the hairpin DNA is opened, and the 6-mercapto-1-hexanol occupies redundant binding sites on the surface of the gold nanoparticles, so that the distance between the quantum dot and the gold nanoparticles is increased, an electrochemiluminescence signal quenched by the addition of the hairpin DNA mixed solution is restored again, and the purpose of detecting the concentration of the target substance ctDNA is achieved.
The main control module comprises an STM32 singlechip minimum system control unit, a connecting terminal, a reset circuit, a crystal oscillator circuit and a clock circuit. The minimum system control unit of STM32 singlechip is hereinafter referred to as main control unit, belongs to prior art, and the main control chip model is STM32f103c8t6.
The three-electrode control module comprises a screen printing electrode, a constant potential circuit, a current/voltage conversion circuit, an ADC (analog to digital conversion) circuit, a DAC (digital to analog conversion) circuit, a filter circuit, an alarm module and a control switch. The output end of the three-electrode amplifying circuit is connected with the signal input ends of the AD analog-to-digital conversion circuit and the DA digital-to-analog conversion circuit and is used for amplifying signals; the filter circuit is formed by connecting two capacitors of an electrolytic capacitor and a ceramic capacitor in parallel; the alarm circuit adopts a buzzer module, and carries out alarm prompt after the signal acquisition is finished; the control switch is used for controlling whether the current in the screen printing electrode passes through the working electrode or not.
As shown in fig. 2 and 3, the current and voltage scanning modes of the three-electrode control module are controlled by the mobile phone end, and an instruction is sent to the bluetooth control module through the mobile phone end application program, the bluetooth control module transmits the received instruction to the main control chip, and the main control chip controls the scanning mode in the three electrodes through the DAC digital-to-analog conversion module. The processed reagent is loaded on a screen printing electrode in the three-electrode control module, if a target object ctDNA exists in a target detection object, a solution in which a three-electrode system is located generates a strong fluorescence signal under the stimulation of a scanning mode of cyclic voltammetry, and if the target object ctDNA does not exist in the target detection object, a weaker fluorescence signal is generated under the stimulation of the three electrodes in the scanning mode of the cyclic voltammetry. The screen printing electrode is fixed in an electrode groove of the three-electrode control module, when a target detection object is in an electrolytic tank of the screen printing electrode, the moving end transmits a control command to the main controller through Bluetooth communication, and the main controller switches and changes a scanning mode program to control a pulse signal generated by the DAC circuit. The three-electrode circuit on the screen printing electrode is connected to an ADC (analog-to-digital converter) module, the ADC module is connected to an I/O (input/output) port of the main controller, voltage values of the three electrodes are returned to the main controller, and data are transmitted to the mobile terminal through Bluetooth. And the DAC analog-to-digital conversion electric circuit is controlled by the main controller to generate a pulse signal. ADC digital-to-analog conversion is carried out, voltage signals obtained after amplification and conversion are sampled by the three electrodes, the voltage signals are converted into digital signals after filtering, data are transmitted to the main control chip, meanwhile, the main controller sends instructions to the Bluetooth communication module through the serial port, the Bluetooth communication module receives the instructions and then transmits the instructions to the mobile phone end, and the mobile phone end application program displays corresponding voltage values. The signal amplification chip adopted by the three-electrode circuit is a wide-bandwidth self-stabilizing zero amplifier (ADC 8608ARZ-REEL 7) and has rail-to-rail input and output swing amplitude and low noise characteristics. The ADC digital-to-analog conversion chip adopts a high-precision digital converter (LTC 2470CMS # TRPBF) with 16-bit resolution. The DAC analog-to-digital conversion circuit chip outputs digital-to-analog conversion (DAC 8831) by adopting 16-bit double-circuit voltage. The filter circuit is a three-order Butterworth low-pass filter with cutoff frequency of 30KHz, and the AD8656 is used as an operational amplifier chip. The alarm circuit adopts a buzzer module, and after the signal acquisition is finished, an alarm is given. The DAC is selected from DAC8831 of TI company, the DAC8831 is a 16-bit voltage output type digital-to-analog converter of the TI company, and the digital-to-analog converter has the advantages of high conversion speed, ultralow power consumption (the lowest 15 mu W), high precision (the maximum linearity error of DAC8831ICD does not exceed +/-1 LSB), low output noise, high-speed SPI interface (the highest can reach 50 MHz), automatic zero calibration during power-on and the like, and is very suitable for small instruments and handheld mobile equipment. The DAC8831 can be combined with an external operational amplifier to realize two output modes of unipolar and bipolar, and the potentiostat must use positive and negative voltage scanning, so that bipolar output is adopted.
The Bluetooth module is HC-05 in model, can interact data with the mobile terminal, collects and regulates and controls data through mobile phone application program software, sends a mark instruction for program switching to the main control chip when a scanning mode needs to be changed, and finally displays the collected data on a display screen of the mobile terminal.
The power supply voltage stabilizing module comprises a 5v charge-discharge power supply circuit and a +/-3.3 v power supply circuit. The power supply voltage stabilizing module is used for connecting the main controller, the Bluetooth module and the photoelectric sensor module, the power supply voltage stabilizing module can directly supply power through a USB and provide +5V voltage, the voltage stabilizing circuit is completed by adopting an LM1117T-3.3V voltage stabilizing chip, and the power supply circuit is completed by adopting ICL7660 and RT9193-33 GB.
The photoelectric sensor module belongs to the prior art, the model is H10721-110 of Binchong, and the +5v power supply of DC is adopted for power supply. The photoelectric sensor module comprises a photomultiplier tube matched with the power supply voltage stabilizing module, a voltage boosting and reducing circuit, a sensor amplifying circuit and a compensating circuit. The photoelectric sensor module is provided with a voltage boosting, voltage reducing and voltage stabilizing circuit which is matched with the power supply voltage stabilizing module and is positioned in an integrated module of the photoelectric sensor module. The photoelectric sensor module is connected with the main controller, converts light signals into electrical signal transmission to the main controller, the main controller interacts with the mobile terminal through the Bluetooth, mobile phone application programs in the mobile terminal collect, store and analyze data, and meanwhile, commands can be sent to the main controller, and welded DuPont wires can be directly adopted when signal connection is carried out. The photoelectric sensor module is placed right above the screen printing electrode in a sealed and light-tight manner and is placed in the electromagnetic shielding box together, so that signal interference is reduced, and light signal collection is facilitated.
As shown in fig. 5 to 7, the box body is a rectangular parallelepiped with a hollow structure, and includes a housing 8, a partition plate 6 disposed in the middle of the cavity of the box body, and an upper cover plate 14 covering the housing 8. The housing 8 is made of a common ABS material, and the partition 6 divides the cavity of the housing 8 into three regions: a potentiostat area 1, a main control area 2 and an optical signal acquisition area 4. The three-electrode control module is arranged in a potentiostat area 1, the main control module is arranged in a main control area 2, and the photoelectric sensor module is arranged in an optical signal acquisition area 4.
A potentiostat circuit board is fixed in the potentiostat area 1, a decorated screen printing electrode is arranged on the circuit board, the screen printing electrode is sent into the optical signal acquisition area 4 through a chute 9 on the bottom plate through a three-electrode channel 3, and the potentiostat circuit board is connected with the circuit board of the main control area 2.
Main control area 2 internal fixation has main control chip STM32, LED lamp, bee calling organ, bluetooth module, switch and power cord, and the USB line that provides the main power draws outside the casing. The power can be supplied by a mobile power supply.
The optical signal acquisition area 4 is fixedly provided with an optical signal acquisition module, an electromagnetic shielding box 5 and a photoelectric device fixing plate 7; the optical signal acquisition area 4 is also internally provided with a three-electrode channel 3, a chute 9 and an electromagnetic shielding box channel 10.
The photoelectric sensor module connects the signal transmission line to the main control chip, generates an optical signal on the modified screen printing electrode in the electromagnetic shielding box 5 through an electrochemiluminescence reaction, collects data by the photoelectric sensor module and transmits the data to the main control chip, and transmits the data to the mobile phone through the Bluetooth module.
An upper cover plate plane 13 for installing an upper cover plate 14 is arranged at the upper end of the shell 8, upper cover plate sliding rails 11 are arranged on two sides of the upper cover plate plane 13, a fixing hole 12 is formed in the upper end of the side face of the shell 8, and the shell 8 is connected with the upper cover plate 14 in a sealing mode through the upper cover plate sliding rails 11 and the fixing hole 12 to form a cassette environment.
The signal transmission process in the device is as follows: the main controller is connected with the three-electrode control module, the power supply module, the Bluetooth module and the photoelectric sensor module. The specific connection mode is that a digital interface of the main controller is connected with an ADC (analog-to-digital converter) circuit and a DAC (digital-to-analog converter) circuit, an input end of the ADC and a signal output end of the DAC are connected with an output end and an input end of a filter circuit, an input end of a constant potential circuit is connected with a circuit output end filtered by a DAC (digital-to-analog converter) module, an output end of the constant potential circuit is connected with an input end of a current/voltage conversion amplifier, an output end of the current/voltage conversion amplifier is connected with an input end of the ADC module, a read-write interface of the main controller is connected with a Bluetooth module, the Bluetooth module and a mobile data end use a mobile phone end application program to perform data interaction, a signal input port of the main controller is connected with a signal output port of a photoelectric sensor module, and a control signal output end of the main controller is connected with a signal input port of an LED indicator lamp. The main controller communicates with the mobile phone through the Bluetooth module, and sends instructions to control the scanning mode through the application program of the mobile phone. The main control chip controls the DAC analog-to-digital conversion circuit, thereby realizing the scanning mode of a three-electrode system in the constant potential circuit and realizing the scanning mode of the cyclic voltammetry. In addition, the electrochemical luminescence reaction has the characteristics of direct feedback, high reliability, simplicity and convenience in operation, low detection limit, low cost and the like, the master controller controls the DAC (digital-to-analog converter) module to generate triangular wave pulses, and stimulates and scans the three-electrode system by utilizing a scanning mode of cyclic voltammetry in electrochemical principles, so that the electrochemical luminescence reaction is generated in the electrolytic bath to generate an optical signal. The photoelectric sensor module collects optical signals in the electrolytic cell, converts the optical signals into electric signals and transmits the electric signals to the main controller, the main controller transmits the data to the Bluetooth, the Bluetooth communication module receives the data and outputs the data to the mobile terminal, and the mobile phone application program displays the collected data by using a chart.
The invention also relates to a portable tumor DNA electrochemiluminescence detection method, which comprises the following steps:
before detection, firstly, an electrochemiluminescence biosensor is manufactured, and the specific manufacturing steps are as follows:
s1.1, uniformly dropwise adding a mixed solution of quantum dots, 6-mercapto-1-hexanol and gold nanoparticles combined with hairpin DNA onto the surface of a working electrode of a screen-printed electrode, and adding a PBS (phosphate buffer solution) containing a co-reactant into an electrolytic bath; adopting an electrochemiluminescence method in an electrochemical research method, and using a cyclic voltammetry excitation voltage to enable the quantum dots and the co-reactant to generate an electrochemiluminescence reaction to generate an electrochemical optical signal, wherein the electrochemiluminescence reaction is shown as ECL1 in figure 4; the coreactant is K 2 S 2 O 8 (Potassium persulfate) due to K 2 S 2 O 8 Compared with other solutions, the luminescent reaction effect is better.
S1.2, covering a layer of uniform PDDA film on the surface of a working electrode; hairpin DNA modified with gold nanoparticles is then added to form an electrochemiluminescence biosensor. The PDDA membrane is a membrane formed by polydiallyldimethylammonium chloride, and the hairpin DNA is a single-stranded DNA capable of forming a hairpin-like configuration with a stem-loop connection. On one hand, the PDDA film enables the quantum dots to be more stably attached to the surface of the working electrode, on the other hand, the PDDA film is positively charged, the hairpin DNA is negatively charged, and the hairpin DNA modified by the gold nanoparticles is better fixed on the surface of the working electrode through electrostatic interaction. Due to the resonance energy transfer between the quantum dots and the gold nanoparticles, the electrochemical optical signal is quenched, as shown in ECL2 in fig. 4. Base complementary pairing occurs between ctDNA of the target and hairpin DNA, the structure of the hairpin DNA is opened, and 6-sulfydryl-1-hexanol occupies redundant binding sites on the surface of the gold nanoparticles, so that the distance between the quantum dots and the gold nanoparticles is increased, an electrochemiluminescence energy resonance system is destroyed, and an electrochemiluminescence signal quenched by adding a hairpin DNA mixed solution is recovered again, as shown in ECL3 in FIG. 4. Within a certain range, the intensity of the electrochemiluminescence signal and the concentration of the target ctDNA are in a linear relation, so that the method can be used for detecting the target ctDNA, and the aim of detecting the ctDNA content is fulfilled.
S1, controlling a circuit in a three-electrode control module to generate an optical signal;
firstly, incubating and combining a target object by using the prepared electrochemiluminescence biosensor, then dropwise adding PBS (phosphate buffer solution) containing a coreactant onto the modified screen-printed electrode, and applying a pulse signal through a main control module to enable the electrochemiluminescence reaction to occur in an electrolytic bath subjected to screen printing so as to generate a light signal;
electrode reaction: the method comprises the steps that a command is sent to a Bluetooth module on a control panel through a mobile phone end application program, the Bluetooth communication module receives the command and sends the command to a main controller through a serial port, when the main controller confirms that a certain voltage scanning mode is selected, the scanning mode of the cyclic voltammetry is selected in the embodiment, corresponding triangular pulses are applied to a Counter Electrode (CE) through a DAC (digital-to-analog converter) circuit, a closed loop is formed between the Counter Electrode (CE) and a Working Electrode (WE), current signals are collected through a gain amplification circuit after I/V (input/output) conversion, and then the voltage of the sampling circuit is sampled through analog-to-digital conversion.
Under the action of voltage, the surface of the Working Electrode (WE) is subjected to chemical reaction. Since a loop is formed between the Working Electrode (WE) and the Reference Electrode (RE) at this time, the current generated by the redox reaction is output through the Reference Electrode (RE), and the voltage between the Working Electrode (WE) and the Reference Electrode (RE) is also changed according to the change of the reaction current. Therefore, the Reference Electrode (RE) is set to be at a constant potential, a reference potential is provided, and the potential of the Reference Electrode (RE) is adjusted through a negative feedback adjusting system, so that the voltage of the Working Electrode (WE) relative to the Reference Electrode (RE) is maintained at a constant value.
S2, collecting optical signals and converting the optical signals into electric signals by the photoelectric sensor module;
the photoelectric sensor module collects optical signals in the electrolytic cell, converts the optical signals into electric signals and transmits data results to the main control module;
starting signal acquisition: the target ctDNA is fixed on the surface of the modified working electrode in the three electrodes by base complementary pairing with the hairpin DNA, and the target ctDNA contains 0.1 mol/L K 2 S 2 O 8 Measuring in PBS buffer solution of co-reactant, applying excitation voltage and generating optical signal, and electrically connecting with photoelectric sensor moduleThe light signal in the cell is collected, is converted into an electric signal, and transmits a data result to the main controller, the main controller transmits the data to the Bluetooth, the Bluetooth communication module receives the data and outputs the data to the mobile terminal, and the mobile phone application program displays the acquired data by using a chart.
S3, the main control module transmits the data result to the mobile terminal;
the main control module transmits the data result to the Bluetooth communication module, the Bluetooth communication module receives the data and transmits the data to the mobile terminal, and the mobile phone application program displays the acquired data by using a chart.
S3.1, connecting and detecting a front-end device and an Android intelligent device connecting electrode in a matched mode;
the switch for detecting the front-end equipment is pressed to be turned on, the green system work indicator lamp is normally on at the moment, and the blue indicator lamp flickers to indicate that the equipment is in an unconnected state. The method comprises the steps of running an application program on the Android equipment, entering a starting interface, clicking a button of a connection detector to search and connect detection front-end equipment, if the equipment is located in a searching range, finding the equipment and displaying the equipment in a searching list, selecting the equipment needing to be connected to connect, and after the equipment is successfully connected, displaying corresponding prompt information on the interface, and meanwhile, detecting that a blue indicator lamp on the front-end equipment is in a normally-on state. If the front-end equipment and the Android equipment are detected to be interconnected for the first time or to be paired and deleted, pairing needs to be performed first, if the password needs to be paired, if the password is 1234, 1234 is input, the connection can be performed after the pairing is successful, and the pairing is not needed after the connection is performed again.
S3.2, starting detection;
after the connection is successful, a button of 'start new detection' can be clicked to start new detection for one time. The new test setup interface can set up relevant information including the initial and final voltages, scan periods and scan rates to be set up in cyclic voltammetry. After the confirmation, the program enters a detection operation main interface, operation steps are listed on the interface according to a detection sequence, and the operation steps are completed only according to the sequence.
S3.3, measuring a standard solution;
after calibration of the blank solution, different concentrations of standard solutions were measured. The concentration of the standard solution is determined according to the concentration range of the sample to be detected. The user may predict the concentration of the sample fluid to select the appropriate concentration of the standard fluid, or may first perform a trial and error test to aid in the prediction.
In this embodiment, the standard solution is a mixed solution of ctDNA of the target object and PBS buffer, and the PBS buffer is the most widely used buffer in biochemical research and contains Na as a main component 2 HPO 4 、KH 2 PO 4 NaCl and KCl, generally act as solvents to solubilize the protective agent. In this example, 7 concentrations of standard solutions were selected for calibration, 100 pmol/L, 10 pmol/L, 1 pmol/L, 100 fmol/L, 10 fmol/L, 1 fmol/L and 0.1 fmol/L, followed by 0.1 mol/L of co-reagent K 2 S 2 O 8 And measuring in the solution to obtain a group of data of electrochemical fluorescence signal intensity peaks of 7 samples to be detected.
S3.4, data processing;
after the reaction on the three electrodes is completed by one period, the photoelectric sensor module is collected by the mobile phone end, the main controller sends an instruction to the alarm module, the buzzer buzzes, and the screen printing electrode is taken out of an electrode groove in the circuit.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A portable electrochemical luminescence detection device for tumor DNA is characterized in that: the device comprises a box body integrating a main control module, a three-electrode control module and a photoelectric sensor module, wherein the main control module is respectively connected with the three-electrode control module and the photoelectric sensor module; the three-electrode control module is used for manufacturing an electrochemiluminescence biosensor and converting biological signals in the screen-printed electrode into optical signals; the photoelectric sensor module collects optical signals and converts the optical signals into electric signals to be transmitted to the mobile terminal;
the three-electrode control module comprises a screen printing electrode, wherein a mixed solution of quantum dots and gold nanoparticles combined with hairpin DNA is added to the surface of a working electrode of the screen printing electrode, and then a PBS (phosphate buffer solution) containing a co-reactant is dripped to form the electrochemical luminescence biosensor; base complementary pairing occurs between the target object ctDNA and the hairpin DNA, the structure of the hairpin DNA is opened, the distance between the quantum dot and the gold nanoparticles is increased, and an electrochemiluminescence signal quenched by adding the hairpin DNA mixed solution is restored again, so that the aim of detecting the target object ctDNA concentration is fulfilled.
2. The portable tumor DNA electrochemiluminescence detection apparatus of claim 1, wherein: the box body is of a hollow structure and comprises a shell and a partition plate arranged in the middle of a cavity of the box body, and the cavity in the box body is divided into a potentiostat area, a main control area and an optical signal acquisition area by the partition plate; the three-electrode control module is arranged in a potentiostat area, the main control module is arranged in a main control area, and the photoelectric sensor module is arranged in an optical signal acquisition area.
3. The portable electrochemiluminescence detection apparatus for tumor DNA according to claim 2, wherein: the optical signal acquisition area is internally provided with an electromagnetic shielding box which is of a hollow structure, the inner side wall of the electromagnetic shielding box is provided with a photoelectric device fixing plate, and the photoelectric sensor module is installed on the photoelectric device fixing plate.
4. The portable tumor DNA electrochemiluminescence detection apparatus of claim 3, wherein: a potentiostat circuit board is fixed in the potentiostat area, a modified screen printing electrode is installed on the potentiostat circuit board, and the screen printing electrode is sent into an electromagnetic shielding box of the optical signal acquisition area through a three-electrode channel.
5. The portable tumor DNA electrochemiluminescence detection apparatus of claim 1, wherein: the three-electrode control module also comprises a constant potential circuit, an ADC (analog-to-digital converter) circuit, a DAC (digital-to-analog converter) circuit, a filter circuit, a current/voltage conversion amplifying circuit, an alarm module and a control switch; the input end of the constant potential circuit is connected with the output end of the DAC digital-to-analog conversion circuit after passing through the filter circuit and is used for meeting the scanning requirement of the cyclic voltammetry, and the output end of the constant potential circuit is connected with the input end of the current/voltage conversion amplifying circuit and is used for amplifying signals; the filter circuit is composed of a three-order Butterworth low-pass filter; the alarm circuit adopts a buzzer module, and carries out alarm prompt after the signal acquisition is finished; the control switch is used for controlling whether the current in the screen printing electrode passes through the working electrode or not.
6. A portable tumor DNA electrochemical luminescence detection method is characterized in that: the method comprises the following steps:
s1, controlling a circuit in a three-electrode control module to generate an optical signal;
firstly, incubating and combining a target object by using the prepared electrochemiluminescence biosensor, then dropwise adding PBS (phosphate buffer solution) containing a coreactant onto the modified screen-printed electrode, and applying a pulse signal through a main control module to enable the electrochemiluminescence reaction to occur in an electrolytic bath subjected to screen printing so as to generate a light signal;
s2, collecting optical signals and converting the optical signals into electric signals by the photoelectric sensor module;
the photoelectric sensor module collects optical signals in the electrolytic cell, converts the optical signals into electric signals and transmits data results to the main control module;
s3, the main control module transmits the data result to the mobile terminal;
the main control module transmits the data result to the Bluetooth communication module, the Bluetooth communication module receives the data and transmits the data to the mobile terminal, and the mobile phone application program displays the acquired data by using a chart.
7. The portable electrochemiluminescence detection method of tumor DNA according to claim 6, wherein: before the step S1, the method also comprises the manufacture of the electrochemiluminescence biosensor, and the specific manufacture steps are as follows:
s1.1, uniformly dripping a mixed solution of quantum dots and gold nanoparticles combined with hairpin DNA on the surface of a working electrode of a screen printing electrode, and adding a PBS (phosphate buffer solution) containing a co-reactant into an electrolytic bath;
s1.2 hairpin DNA modified by gold nanoparticles is added on the surface of a working electrode to form the electrochemical luminescence biosensor.
8. The portable electrochemiluminescence detection method of tumor DNA as claimed in claim 7, wherein: before step S1.2, the surface of the working electrode is covered with a uniform PDDA film.
9. The portable electrochemiluminescence detection method of tumor DNA according to claim 7, wherein: the mixed solution of step S1.1 also contains 6-mercapto-1-hexanol.
10. The portable electrochemiluminescence detection method of tumor DNA according to any one of claims 6 to 9, wherein: the coreactant is K 2 S 2 O 8 。
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