CN114062470A - 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection - Google Patents

3D printing array type BP-LED-E sensing device for hydrogen peroxide detection Download PDF

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CN114062470A
CN114062470A CN202111155201.5A CN202111155201A CN114062470A CN 114062470 A CN114062470 A CN 114062470A CN 202111155201 A CN202111155201 A CN 202111155201A CN 114062470 A CN114062470 A CN 114062470A
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led
bpe
assembled
sensing device
printing
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CN114062470B (en
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刘爱林
刘萌萌
郭子珍
刘辉
杨元杰
雷云
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Fujian Medical University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components

Abstract

The invention discloses a 3D printing array type BP-LED-E sensing device for detecting hydrogen peroxide. Manufacturing a bipolar electrode device by using different printing consumables, printing by using conductive polylactic acid consumables to prepare a driving electrode of an array structure and a BPE to be assembled, and assembling the BPE to be assembled and a light-emitting diode into an integrated bipolar electrode-light diode structure after activating treatment; the sample carrying pool bottom plate is prepared from non-conductive PLA consumables, and the conductive structure can be assembled with the bottom plate to realize the manufacture of a full-printing sensing device based on the bipolar electrode principle and be applied to the gradient H2O2And (4) synchronously and quantitatively detecting the solution. The array BPE detection device is simple and convenient to manufacture, is miniature and portable, can realize quick semi-quantitative detection through direct visual observation, can also realize accurate quantitative detection by reading numerical experimental results through software, and has important significance in the field of instant detection.

Description

3D printing array type BP-LED-E sensing device for hydrogen peroxide detection
Technical Field
The invention belongs to the technical field of biosensors, and particularly relates to a 3D printing array type BP-LED-E sensor for hydrogen peroxide detection and a manufacturing method thereof.
Background
With the wide application of Conductive Polymer Composites (CPCs) in electromagnetic shielding, radar wave absorption, photoelectric devices, sensors and the like, more and more researchers focus on the CPCs. CPCs are conductive polymer composites obtained by doping conductive fillers (such as carbon black, carbon fibers, carbon nanotubes, graphene, and the like) having excellent conductive properties into a single-phase or multi-phase polymer system. The filling ratio of the conductive filler affects the conductivity of CPCs, and when the conductive filler is filled to a certain critical value, the resistivity of the whole composite system is abruptly reduced, and the quality change from the insulator to the conductor occurs, which is called percolation phenomenon. Additionally, the resistivity of CPCs may also be somewhat responsive to thermal, mechanical, or chemical stimuli.
In recent years, researchers have conducted intensive research in the field of CPCs to provide opportunities for the production of conductive 3D printing consumables. At present, commercial conductive consumables suitable for FDM type 3D printers have appeared on the market. However, the conductive consumables are of a lesser variety, typically polylactic acid (PLA) -based or Acrylonitrile Butadiene Styrene (ABS) -based CPCs. The PLA-based CPCs are widely used, because the PLA has excellent biocompatibility while meeting the requirements of toughness, strength, thermoplasticity and the like required by printing, and can lay a tamped material foundation for the application of printing devices in the medical industry; in addition, the advantages of wide PLA source, low price, easy obtaining and environmental protection and sustainable development provide economic feasibility for the industrial production of conductive PLA consumables. The appearance of novel functional printing material promotes the rapid development of 3D printing, and many researchers utilize 3D printing technology and electrically conductive PLA to develop the research of individualized conductive device in the electrochemistry field: bank topic group has made disc electrodes through graphene/PLA consumables and FDM printer and studied their electrochemistry and physical properties; mu ñ oz and the like, and 3D printing electrodes are manufactured based on carbon black/PLA consumables and are used for analyzing and determining copper ions in the biofuel; the Rodrai guez task group utilizes a dual-nozzle FDM printer to print a PLA material flow pool and embed a graphene-PLA composite electrode into the PLA material flow pool, so that the embedded electrochemical sensor is successfully constructed in one step; kokkinos et al have completely manufactured a multifunctional integrated electrochemical device by means of a 3D printing technology, and the device can be widely applied to the field of electrochemical sensing.
At present, the application of 3D printing in the field of traditional three-electrode analytical chemistry has been reported, but no researchers have applied 3D printing technology to bipolar electrode analytical chemistry. In fact, the flexible manufacturing and rapid forming characteristics of the 3D printing technology can just overcome the defects that the existing BPE construction method cannot realize complex configuration manufacturing, consumes long time and the like, and the use cost of a BPE system is reduced; meanwhile, the commercial production of the conductive PLA consumable material provides material feasibility for the printing and manufacturing of the electrode in the BPE system.
Disclosure of Invention
1. The invention aims to provide a 3D printing array type BP-LED-E sensing device for detecting hydrogen peroxide.
The invention aims to realize the 3D printing array type BP-LED-E sensing device for detecting hydrogen peroxide, which is characterized in that a conductive PLA is used for personalized 3D printing to prepare a driving electrode and a bipolar electrode (BPE), a non-conductive PLA is used for personalized preparation of a sample carrying pool bottom plate, and an LED is used as a signal output mode to construct the 3D printing array type BP-LED-E sensing device.
The 3D printing array type BP-LED-E sensing device comprises five parallel groups of BP-LED-E structures, the concave structures of two conductive PLA driving electrodes are fixed at the edges of two rows of grooves of a bottom plate of a sample carrying pool, two lead lamp feet of an LED are respectively inserted into holes of two processed concave structures of a bipolar electrode BPE to be assembled, so that the lead lamp feet are tightly attached to the bipolar electrode BPE to be assembled, the BP-LED-E structure is obtained, and the 3D printing array type BP-LED-E sensing device is formed.
The 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection is characterized in that the gray level value of LED brightness and H are set under the condition that the driving voltage is 3.7V2O2The concentration is 102-105The linear relation is good in the mu M range, and the linear equation is as follows: y = 55.7138X-87.6066, r = 0.98.
The invention discloses a manufacturing method of a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection, which comprises the following steps: (1) construction of a BP-LED-E array sensing device: after the bipolar electrode BPE to be assembled is soaked in acetone for 10 min, the concave structure part is completely immersed in 0.1M NaOH solution, the handle part is connected with a working electrode clamp of an electrochemical workstation, and the treated bipolar electrode BPE to be assembled is obtained after the electric activation is finished; after activation, cutting off the processed strip-shaped handle part of the bipolar electrode BPE to be assembled, and reserving a concave structure with a bottom edge containing holes; bending two lead lamp pins of the LED outwards by 90 degrees along the horizontal direction by using forceps, then respectively inserting the two lamp pins positioned on the same horizontal line into the holes of the two processed concave-shaped structures of the bipolar electrode BPE to be assembled, and bending the exposed parts of the lamp pins penetrating through the holes upwards to enable the parts to be tightly attached to the bipolar electrode BPE to be assembled to obtain a BP-LED-E structure; the five BP-LED-E structures, the driving electrode and the sample loading pool bottom plate are combined, and the concave structures of the five BP-LED-E structures are fixed between two rows of grooves of the white sample loading pool bottom plate; when the solution is added into the groove, the feet of the concave structure can contact the solution; the positive electrode and the negative electrode of the external power supply are connected with two driving electrodes, and the driving electrodes provide the same driving voltage for the five parallel BP-LED-E structures; when the power supply is started, the BP-LED-E structure forms a current loop; (2) BP-LED-E structure for H2O2Detection of (2): 150 mu L PBS is always contained in five cathode cells of the bottom plate of the sample loading cell, and 10 mu M PBS and 10 mu L PBS are sequentially added into the anode cell1.5 μM、102 μM、102.5μM、103 μM、103.5 μM、104 μM、104.5 μM、105 μM、106mu.M different concentrations of H2O2The driving voltage of the solution is 3.7V, and after the power supply is started, the brightness of the LED is required to be stable, and the brightness of the LED in the array type BP-LED-E sensing device is observed, photographed and recorded along with H2O2Obtaining the gray value and H of the LED brightness under the condition of solution concentration change2O2The concentration is 102-105The good linear relationship is present in the μ M range.
2. The BP-LED-E sensing device comprises a non-conductive sample loading pool bottom plate, a conductive driving electrode, a BPE and an LED.
3. According to the BP-LED-E sensing device, 3D printed conductive PLA is used as a driving electrode and a BPE, and an LED is connected with a pair of BPEs, so that concentration gradient H is successfully realized2O2And simultaneously carrying out quantitative detection.
4. According to the BP-LED-E sensing device, BPE obtained through 3D printing needs to be activated before being used so as to obtain high sensitivity and good reproducibility.
5. The invention discloses a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection, which sequentially comprises the following steps:
(1) manufacturing method of BP-LED-E sensing device
And after the BPE to be assembled is soaked in acetone for 10 min, the concave structure part is completely immersed in 0.1M NaOH solution, the handle part is connected with a working electrode clamp of an electrochemical workstation, and the treated BPE to be assembled is obtained after IT (information technology) electric activation is completed. After activation, the processed strip-shaped handle part of the BPE to be assembled is cut off, and a concave structure with holes at the bottom edge is reserved. And (3) folding the two lamp pins of the LED outwards by 90 degrees along the horizontal direction by using tweezers, then respectively inserting the two lamp pins positioned on the same horizontal line into the holes of the two processed concave structures, and bending the exposed parts of the lamp pins penetrating through the holes upwards to enable the parts to be tightly attached to the BPE to be assembled to obtain the BP-LED-E structure. The five BP-LED-E structures, the driving electrode and the bottom plate are combined, and the concave structure is fixed between two rows of grooves of the white bottom plate. When the solution is added into the groove, the feet of the concave structure can contact the solution. The positive electrode and the negative electrode of the external power supply are connected with two driving electrodes, and the driving electrodes can provide the same driving voltage for five parallel BP-LED-E structures. When the power supply is started, the 3D printing array type BP-LED-E sensor (also called BP-LED-E structure) forms a current loop.
(2) Reproducibility inspection of LEDs
A green electrode clamp in an electrochemical workstation is connected with a longer lamp pin of an LED, a white electrode clamp is connected with another lamp pin, the output voltage of the workstation is 1.7V-2.1V, the scanning speed is 100 mV/s, and a CV diagram of 10 circles of scanned LEDs of the same LED under the condition and a CV diagram of 1 circle of scanned LEDs of 5 LEDs under the condition are observed and recorded.
(3) 3D printing array type BP-LED-E sensing device for H2O2Detection of (2)
150 mu L PBS is always contained in five cathode pools of the bottom plate, and 10 mu M and 10 mu L PBS are sequentially added into an anode pool1.5 μM、102μM、102.5 μM、103 μM、103.5 μM、104 μM、104.5 μM、105 μM、106H at μ M concentration2O2The driving voltage of the solution is 3.7V, and after the power supply is started, the brightness of the LED is required to be stable, and the brightness of the LED in the array type BP-LED-E sensing device is observed, photographed and recorded along with H2O2The concentration of the solution varies.
The invention has the advantages that:
the assembly part of the BP-LED-E sensing device is manufactured by a fused deposition type 3D printer and can realize the concentration gradient H2O2Meanwhile, the method has the remarkable advantages of low cost, high response speed, integration and the like.
Drawings
FIG. 1 is a model design drawing and a material object assembly drawing of a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection. (in the figure: 1: the bottom plate of the ocean pond; 2: the groove; 3: the untreated BPE to be assembled; 4: the driving electrode; 5: the treated BPE to be assembled; 6: the LED; 7: the BP-LED-E structure).
Fig. 2 is a CV response diagram of a printing electrode under different processing conditions in a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection according to the present invention.
FIG. 3 is a reproduction investigation diagram of LEDs in a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection according to the invention.
Fig. 4A is a signal output diagram of an unprocessed BPE array electrode in a 3D printing array BP-LED-E sensor device for hydrogen peroxide detection at voltages of 5.5V, 6.0V, and 6.5V according to the present invention.
Fig. 4B is a comparison graph of signal output of the processed bipolar electrode and the unprocessed bipolar electrode under the voltage of 5.0V, 5.5V and 6.5V in the 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection according to the present invention.
FIG. 5 shows the gray-scale value and H of the LED brightness in the 3D printing array type BP-LED-E sensor device for hydrogen peroxide detection according to the present invention2O2A linear relation graph between logarithmic values of concentration and an LED brightness real object graph.
Detailed Description
In order to make the technical problems, technical solutions and effects to be solved by the present invention clearer, the present invention is described in further detail below with reference to embodiments and drawings.
As shown in fig. 1, the bipolar electrode (BPE) overall device is divided into a non-conductive portion and a conductive portion. The non-conductive part is a sample loading pool bottom plate 1 with the length of 41 mm, the width of 55 mm and the height of 6 mm. The inside of the sample tank is provided with 3 columns and 5 rows of 15 square grooves 2 which are used for bearing a sample solution and constructing a separated visual BPE; the length and width of each groove structure are 7 mm and the height is 5 mm, and the distance between every two rows of grooves is 5 mm. Designing a three-dimensional model diagram of the base plate in '123D design' software, storing the three-dimensional model diagram as a 'stl' format file, importing the file into 'J-Great' software for slicing, setting printing parameters, storing the file as a 'gcode' format file, and finally transmitting the file to storage equipment of an extreme-gloss Erv A8S 3D printer and printing the file by using white PLA consumables. Setting of printing parameters: layer height: 0.1 mm; thickness of the shell: 1.2 mm; the filling density is 100%; printing speed: 30 mm/s; supporting: none; consumable diameter: 1.75 mm; printing temperature: 190 ℃; temperature of the hot bed: at 45 ℃.
The conductive portion includes the unprocessed BPE3 to be assembled and the driving electrode 4. The untreated BPE3 to be assembled is of a concave structure with a handle, the length, width and height of the bottom edge of the concave part are 9.5 mm multiplied by 2 mm multiplied by 3 mm, and a hole which penetrates through the two ends and has the diameter of 1 mm is arranged in the middle. The left and right feet of the concave structure are cuboids with the length of 2 mm, the width of 2 mm and the height of 4.5 mm, and the distance between the two feet is 5.5 mm. The solid long strip-shaped handle with the length, width and height of 40.5 mm multiplied by 2 mm multiplied by 3 mm is connected with the bottom edge of the concave structure. The two driving electrodes 4 are irregular, five rows of parallel inverted concave structures are spaced by 8 mm, the bottom edge of each concave structure is 5 mm multiplied by 2 mm, and the two feet are respectively 3 mm multiplied by 2 mm multiplied by 4.5 mm (outer side) and 2 mm multiplied by 4.5 mm (inner side). And every two concave structures are connected by a cuboid with the length, width and height of 8 mm multiplied by 2 mm, and a rectangular bulge (6 mm multiplied by 2 mm) is arranged at the center of the outer side of the combined structure and is used for being connected with the anode and the cathode of an external power supply. The three-dimensional model diagram of the conductive part is drawn in '123D design' software and stored as a file in a 'stl' format, then the file is imported into 'XYZware Pro' software for slicing, the file is stored as a file in a '3 w' format after printing parameters are set, and finally the file is transmitted to an XYZ printing 3D printer and printed by using black conductive PLA consumables. Setting of printing parameters: layer height: 0.3 mm; the number of the shell layers is as follows: 2 layers; the filling density is 100%; printing speed: 10 mm/s; supporting: none; consumable diameter: 1.75 mm; printing temperature: 190 ℃; temperature of the hot bed: at 45 ℃.
After untreated BPE3 to be assembled is soaked in Ace for 10 min, the concave structure part is completely immersed in 0.1M NaOH solution, the handle part is connected with a working electrode clamp of an electrochemical workstation, and the treated BPE5 to be assembled is obtained after IT electric activation is completed. After activation, the long-strip-shaped handle part of the BPE to be assembled is cut off, and a concave structure with holes at the bottom edge is reserved. And (3) folding the two lamp pins of the LED6 outwards by 90 degrees along the horizontal direction by using tweezers, then respectively inserting the two lamp pins on the same horizontal line into the holes of the two processed structures in the shape like the Chinese character 'ao', and bending the exposed parts of the lamp pins penetrating through the holes upwards to enable the parts to be tightly attached to the processed BPE5 to be assembled to obtain the BP-LED-E structure 7. Five BP-LED-E7 structures, a driving electrode 4 and a bottom plate 1 are combined, and a concave structure is fixed between two rows of grooves 2 of the white bottom plate 1. When the solution is added to the groove 2, the foot of the concave structure can contact with the solution (0.1M NaOH). The positive electrode and the negative electrode of the external power supply are connected with the two driving electrodes 4, and the driving electrodes 4 can provide the same driving voltage for the five parallel BP-LED-E structures 7. When the power supply is started, the 3D printing array type BP-LED-E sensing device (also called as a BP-LED-E structure) forms a current loop.
Example 1:
a printing electrode CV chart characteristic process under different treatments in a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection is as follows:
an untreated printing electrode (untreated BPE3 to be assembled), which is not treated, a printing electrode soaked in acetone for 10 min, a printing electrode electrically activated for 250 s under the voltage of 2.5V, and a treated printing electrode (treated BPE 5) which is soaked in acetone for 10 min and then electrically activated for 250 s under the voltage of 2.5V are sequentially placed in a 1 mM ferricyanide pair solution for CV detection, the scanning speed is 100 mV/s, and the scanning potential is-0.6V to + 1.0V.
As shown in fig. 2, only the treated electrode (treated BPE5 to be assembled) of the four test electrodes, which was soaked in acetone and then activated electrically, could sweep a CV curve with a distinct redox peak pattern and good symmetry in the solution of the ferricyanide couple, and the peak current intensity was much greater than that of the untreated electrode (untreated BPE3 to be assembled). Compared with the other three electrodes, the treated electrode (treated BPE5 to be assembled) which is soaked in acetone and then is electrically activated plays a certain role in promoting the redox reaction generated in the electrolyte solution, so that the ionic reaction in the electrolyte solution is more complete.
Example 2:
a reproducibility investigation process of LEDs in a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection is as follows:
the green electrode clamp in the electrochemical workstation is connected with the longer lamp pin of the LED6, the white electrode clamp is connected with the other lamp pin, the output voltage of the workstation is 1.7V-2.1V, the scanning speed is 100 mV/s, and a CV diagram of 10 circles scanned by the same LED6 under the condition and a CV diagram of 1 circle scanned by 5 LEDs 6 under the condition are observed and recorded.
As shown in fig. 3, five LEDs 6 are scanned at the same voltage to obtain almost a uniform CV pattern; in addition, the same LED6 is scanned for 10 circles in a circulating mode under the voltage of 1.7-2.1V, the obtained 10 circles of CV graphs are similar in height (an illustration in fig. 3), and the fact that the LED6 used in the experiment has good reproducibility and no obvious difference exists between lamp beads shows that the introduction of the LED6 cannot cause deviation to signal output, and the reliability of signals of the LED6 is guaranteed.
Example 3:
a feasibility study of a 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection:
150 mu L of PBS is added into the anode sample loading pool and the cathode sample loading pool of the bottom plate, the untreated BPE3 to be assembled and the LED6 are selected to be assembled into a BP-LED-E structure 7, the power supply is started after the whole device is built, the voltage is gradually increased, and the light emitting condition of the LED6 is observed. And then the power supply is turned off, the unprocessed BPE3 to be assembled in the BP-LED-E structure 7 of the 1 st, 3 rd and 5 th rows is replaced by the processed BPE5 to be assembled, the power supply is started again, and the change of the brightness of the LED6 along with the rise of the voltage is recorded.
As shown in fig. 4A, at a voltage of 5.5V, the LEDs 6 in the five untreated BPE3 array electrodes to be assembled emit light weakly, and as the voltage increases, the brightness of the LEDs 6 also increases in turn, which indicates that the conductive parts in the device have excellent conductivity and can be used as a substitute for conventional conductors. In addition, five LEDs 6 in the array device keep basically consistent brightness under the same voltage, and stably output optical signals in parallel, so that the constructed platform can realize array type visual output, and the feasibility of the platform is preliminarily verified. As shown in fig. 4B, when the row 1, 3, 5 is the processed BPE5 to be assembled, and the row 2, 4 is the unprocessed BPE3 to be assembled, the row 1, 3, 5 LEDs 6 can emit light at a voltage of 5.0V, while the row 2, 4 LEDs 6 do not emit light. With the rise of voltage, the LEDs 6 in the rows 1, 3 and 5 emit light more intensely, and the LEDs 6 in the rows 2 and 4 only emit light weakly under the voltage of 6.5V, so that the conductivity of the processed BPE5 to be assembled is proved to be stronger than that of the unprocessed BPE to be assembled, and the processed BPE5 to be assembled is selected to construct the BP-LED-E structure 7, so that the platform can analyze the object to be tested under lower driving voltage.
Example 4:
3D printing array type BP-LED-E sensing device for hydrogen peroxide detection has gray value and H of LED brightness under optimal driving voltage of 3.7V2O2The linear relationship between the logarithmic values of the concentrations was determined as follows:
150 mu L PBS is always contained in five cathode pools of the bottom plate, and H with different concentrations is sequentially added into an anode pool2O2Solution (10. mu.M, 10)1.5 μM、102 μM、102.5 μM、103 μM、103.5 μM、104 μM、104.5 μM、105 μM、106Mu M), the driving voltage is 3.7V, after the power supply is started, the brightness of the LED6 in the array type BP-LED-E structure 7 system is observed, photographed and recorded along with H after the brightness of the LED is stable2O2The concentration of the solution varies.
As can be seen from FIG. 5, the LED6 signal obtained by the BP-LED-E structure 7 array sensing platform, i.e. the relative gray-scale value and H2O2There is a good linear relationship between the log values of the concentrations, the linear equation being Y = 55.7138X-87.6066 (where Y represents the average relative optical density value of three measurements and X represents H2O2Logarithmic value of concentration), r = 0.98, linear range 102 - 105And mu.M. From the inset, following H2O2The brightness of the LED6 is gradually enhanced due to the increase of the concentration, and semi-quantitative detection can be realized by visual observation.

Claims (4)

1. A3D printing array type BP-LED-E sensing device for detecting hydrogen peroxide is characterized in that a conductive PLA (polylactic acid) is used for personalized 3D printing to prepare a driving electrode and a bipolar electrode (BPE), a non-conductive PLA is used for personalized preparation of a sample carrying pool bottom plate, and an LED is used as a signal output mode to construct the 3D printing array type BP-LED-E sensing device.
2. The 3D printing array type BP-LED-E sensing device for detecting hydrogen peroxide according to claim 1, wherein the 3D printing array type BP-LED-E sensing device comprises five parallel groups of BP-LED-E structures, the concave-shaped structures of two conductive PLA driving electrodes are fixed on the edges of two rows of grooves of the bottom plate of the sample carrying pool, two lead lamp pins of an LED are respectively inserted into holes of two processed concave-shaped structures of a bipolar electrode BPE to be assembled, so that the lead lamp pins are tightly attached to the bipolar electrode BPE to be assembled, the BP-LED-E structure is obtained, and the 3D printing array type BP-LED-E sensing device is formed.
3. The 3D printing array type BP-LED-E sensing device for hydrogen peroxide detection according to claim 2, wherein, under the driving voltage of 3.7V, the gray value of the LED brightness and H are2O2The concentration is 102-105The linear relation is good in the mu M range, and the linear equation is as follows: y = 55.7138X-87.6066, r = 0.98.
4. A method of making a 3D printed array BP-LED-E sensor device for hydrogen peroxide detection according to any of claims 1 to 3, comprising the steps of: (1) construction of a BP-LED-E array sensing device: after the bipolar electrode BPE to be assembled is soaked in acetone for 10 min, the concave structure part is completely immersed in 0.1M NaOH solution, the handle part is connected with a working electrode clamp of an electrochemical workstation, and the treated bipolar electrode BPE to be assembled is obtained after the electric activation is finished; after activation, cutting off the processed strip-shaped handle part of the bipolar electrode BPE to be assembled, and reserving a concave structure with a bottom edge containing holes; bending two lead lamp pins of the LED outwards by 90 degrees along the horizontal direction by using forceps, then respectively inserting the two lamp pins positioned on the same horizontal line into the holes of the two processed concave-shaped structures of the bipolar electrode BPE to be assembled, and bending the exposed parts of the lamp pins penetrating through the holes upwards to enable the parts to be tightly attached to the bipolar electrode BPE to be assembled to obtain a BP-LED-E structure; the five BP-LED-E structures, the driving electrode and the sample loading pool bottom plate are combined, and the concave structures of the five BP-LED-E structures are fixed between two rows of grooves of the white sample loading pool bottom plate; when the solution is added into the groove, the foot of the concave structure can be connectedContacting the solution; the positive electrode and the negative electrode of the external power supply are connected with two driving electrodes, and the driving electrodes provide the same driving voltage for the five parallel BP-LED-E structures; when the power supply is started, the BP-LED-E structure forms a current loop; (2) BP-LED-E structure for H2O2Detection of (2): 150 mu L PBS is always contained in five cathode cells of the bottom plate of the sample loading cell, and 10 mu M PBS and 10 mu L PBS are sequentially added into the anode cell1.5 μM、102 μM、102.5μM、103 μM、103.5 μM、104 μM、104.5 μM、105 μM、106mu.M different concentrations of H2O2The driving voltage of the solution is 3.7V, and after the power supply is started, the brightness of the LED is required to be stable, and the brightness of the LED in the array type BP-LED-E sensing device is observed, photographed and recorded along with H2O2Obtaining the gray value and H of the LED brightness under the condition of solution concentration change2O2The concentration is 102-105The good linear relationship is present in the μ M range.
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