CN105466991B - Bisphenol-A disposable paper base sensor and its preparation method and application - Google Patents
Bisphenol-A disposable paper base sensor and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to technical field of electrochemical detection, purpose, which is to provide, a kind of can be used to detect bisphenol-A, easy to use, favorable reproducibility, bisphenol-A disposable paper base sensor at low cost and its preparation method and application, including overlay film art paper, one layer of titanium film is coated on overlay film art paper, one layer of golden film, glue belt in golden film are coated on titanium film, adhesive tape layer covers the area of golden film 50%~80%, circular hole is opened up on adhesive tape layer, and one layer of multi-walled carbon nanotube is modified in the golden film at circular hole.Bisphenol-A disposable paper base sensor of the present invention, using overlay film art paper as electrode basement, one layer of titanium film is sputtered on overlay film art paper as binder course, one layer of golden film is sputtered on titanium film again, as modification reaction substrate and good electric conductivity is provided, electron transport ability is accelerated, experiments have shown that paper base sensor of the present invention is good to the response of bisphenol-A.Preparation method of the present invention is easy, and low in cost, material is environmentally protective, can prepare in batches, favorable reproducibility, use easy to process.
Description
Technical field
The invention belongs to technical field of electrochemical detection, more particularly to a kind of bisphenol-A disposable paper base sensor and its
Preparation method and application.
Background technique
Bisphenol-A (Bisphenol A, abbreviation BPA), chemical name 2,2- bis- (4- hydroxy phenyl) propane belong to low toxicity
Property chemical substance, be widely used for producing polycarbonate, the materials such as epoxy resin, be usually used in toy, feeding bottle, water glass, food packet
In the production of the products such as package material.The similar male two pure and mild diethylstilbestrols of its structure, thus have similar with other environmental hormones
Effect plays estrogenic activity, interference organism reproduction, growth and development, nervous system, immune system etc., or even induces cancer
Disease.Corresponding laws and regulations are launched respectively all to forbid the application of bisphenol-A in countries in the world.Therefore, establishing one kind can be to trace
The short-cut method that amount bisphenol-A quickly detects has great importance.Bisphenol-A, which detects common method, at present chromatography, light splitting
Photometry, immunoassay and electrochemical process etc., are compared with other methods, and electrochemical analysis method has easy to operate, analysis
Speed is fast, it is at low cost, be suitable for the advantages such as on-site test.The core of electrochemical detection method is the design of electrochemical sensor,
It can be by the electricity or electrochemical properties of measurement target analytes, to carry out qualitative or quantitative analysis to it.In recent years, sharp
With new function nano material, the hot spot that superior electrochemical sensor has become scientists growing interest is developed.
In the prior art using flat conductor layer as electrode basement, conducting polymer film is flat as binder course
Conductor layer uses ito glass, and conducting polymer film uses carbonaceous conductive glue, but the sensor is simply possible to use in detection Cr VI, can not
For detecting bisphenol-A, and at high cost, when production, need to be cut using specific purpose tool, and production is inconvenient.
The Electrochemical Detection of bisphenol-A mostly uses nanometer-material-modified glass-carbon electrode and metal electrode as work electricity at present
Pole is detected, and electrode preparation cost is higher, and electrode needs Reusability, and bisphenol-A oxidation reaction is irreversible reaction, oxygen
Changing product is easily passivated working electrode surface, and the surface-active site of modified electrode is occupied by bisphenol-A oxidation product, can not
Multiple measurement for bisphenol-A.It, be by complicated so these electrodes are the problem is that require to polish before use every time
Processing, process is troublesome, and effect is deteriorated after processing, poor reproducibility, causes testing result inaccurate, is unable to satisfy practical inspection
The needs of survey.
Summary of the invention
That bisphenol-A, production can be used to detect is simple, easy to use, again the technical problem to be solved in the present invention is to provide a kind of
Existing property is good, bisphenol-A disposable paper base sensor at low cost and its preparation method and application.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of bisphenol-A disposable paper base sensor, including overlay film art paper are coated with one layer of titanium film, titanium on overlay film art paper
One layer of golden film, glue belt in golden film are coated on film, adhesive tape layer covers the area of golden film 50%~80%, opens up on adhesive tape layer
Circular hole modifies one layer of multi-walled carbon nanotube in the golden film at circular hole.
Bisphenol-A disposable paper base sensor of the present invention, further, the plating method of the titanium film is as follows: by overlay film copper
Millboard is placed on the sample stage of high vacuum ion sputtering instrument, and using titanium metal plate as sputtering target material, target is away from sample stage
Distance is 5~9cm, and sputtering vacuum degree is not more than 2 × 10-3Mbar, sputtering current be 80~120mA, sputtering time be 50~
150s, to sputter one layer of titanium film on overlay film art paper.
Bisphenol-A disposable paper base sensor of the present invention, further, the method for modifying of the multi-walled carbon nanotube are as follows: will
The multi-walled carbon nanotube aqueous dispersions that 10~30 μ L mass concentrations are 0.5~1 ‰ are added dropwise in circular hole region, cover it uniformly
In the area, it is subsequently placed in 40 DEG C~45 DEG C baking ovens and dries.
Bisphenol-A disposable paper base sensor of the present invention, further, the diameter of the circular hole are 4~6mm.
Bisphenol-A disposable paper base sensor of the present invention further covers circle on the multi-walled carbon nanotube at the circular hole
Shape filter paper.
Bisphenol-A disposable paper base sensor of the present invention, further, the diameter of the circular filter paper piece are 6~8mm, than
Big 1~the 2mm of the diameter of circular hole.
The present invention also provides the preparation methods of above-mentioned bisphenol-A disposable paper base sensor, comprising the following steps:
(1) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, is splashed on overlay film art paper first
The titanium film for penetrating one layer of nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 5~9cm, sputtering
Vacuum degree is not more than 2 × 10-3Mbar, sputtering current are 80~120mA, and sputtering time is 50~150s;Then, then on titanium film
The golden film for sputtering one layer of nanoscale, using gold plaque as sputtering target material, distance of the target away from sample stage is 5~9cm, and sputtering is true
Reciprocal of duty cycle is not more than 2 × 10-3Mbar, sputtering current are 15~50mA, and sputtering time is 50~150s;
(2) the overlay film art paper sputtered is taken out, size required for experiment is cut into, with 4~6mm's of outer diameter
Punch punches on adhesive tape, then by tape-stripping in golden film, makes the area of adhesive tape covering golden film 50%-80%, is formed
Adhesive tape layer;
(3) the multi-walled carbon nanotube aqueous dispersions that 10~30 μ L mass concentrations are 0.5~1 ‰ are added dropwise in circular hole region,
It is uniformly covered on it in region, is subsequently placed in 40 DEG C~45 DEG C baking ovens and dries, bisphenol-A disposable paper of the present invention is made
Based sensor.
The preparation method of bisphenol-A disposable paper base sensor of the present invention, further, after the completion of the step (3), in circle
Bore region pastes the circular filter paper piece that diameter is 6~8mm, and the diameter of filter paper is 1~2mm bigger than the diameter of circular hole.
The present invention also provides application of the above-mentioned bisphenol-A disposable paper base sensor in detection bisphenol-A.
Bisphenol-A disposable paper base sensor of the present invention and its preparation method and application compared with prior art, has following
The utility model has the advantages that
1, bisphenol-A disposable paper base sensor of the present invention is disposable, and detection uses new sensor, nothing every time
It needs to reuse, handles direct use without carrying out, it is easy to use, and guarantee per a piece of result all, reproducibility
Good, testing result is accurate.
2, using overlay film art paper as electrode basement, instead of ito glass or graphite flake substrate, low in cost, material
Expect green and pollution-free, flexibility is good, cuts without special tool(s), easily facilitates processing and uses, greatly reduces electrode
Cost.
3, in the golden film at circular hole modify one layer of multi-walled carbon nanotube, using the high-specific surface area of multi-walled carbon nanotube,
The special electrochemical properties such as good electric conductivity and high absorption property realize the efficient detection for bisphenol-A.
4, using overlay film art paper as electrode basement, the titanium film conduct of one layer of nanoscale is sputtered on overlay film art paper
Binder course, then on titanium film sputter one layer of nanoscale golden film, as modification reaction substrate and good electric conductivity is provided,
Electron transport ability is accelerated, experiments have shown that paper base sensor of the present invention is good to the response of bisphenol-A, is realized to bisphenol-A
Fast electrochemical detection.
5, the titanium film and golden film of nanoscale are coated with respectively using ion sputtering process, manufacturing process is simple, it can prepare in batches,
Production Time is short, is easy to use.
Bisphenol-A disposable paper base sensor of the invention and its preparation method and application is made with reference to the accompanying drawing further
Explanation.
Detailed description of the invention
Fig. 1 is the cross-sectional view of bisphenol-A disposable paper base sensor of the present invention;
Fig. 2 is that the bisphenol-A disposable paper base sensor prepared using embodiment 2 measures various concentration bisphenol-A standard solution
Electrochemical response map;
Fig. 3 is the bisphenol-A canonical plotting that embodiment 4 measures;
Fig. 4 is the bisphenol-A canonical plotting that embodiment 5 measures;
Fig. 5 is the bisphenol-A canonical plotting that embodiment 6 measures;
Fig. 6 is the electrification for detecting bisphenol-A standard solution respectively using paper base sensor of the present invention and prior art sensor
Learn response map.
Specific embodiment
As shown in Figure 1, bisphenol-A disposable paper base sensor of the present invention includes overlay film art paper 1, plated on overlay film art paper 1
There is the titanium film 2 of one layer of nanoscale, the golden film 3 of one layer of nanoscale, glue belt 4 in golden film 3, adhesive tape are coated on titanium film 2
Layer 4 covers the area of golden film 50%~80%, and adhesive tape layer 4 is using the adhesive waterproof tape with insulation performance, such as normal transparent adhesive tape.
The circular hole 5 that diameter is 4~6mm is opened up on adhesive tape layer 4, modifies one layer of multi-walled carbon nanotube 6, multi wall carbon in the golden film 3 at circular hole 5
Circular filter paper piece 7 is covered on nanotube 6, the diameter of filter paper 7 is 6~8mm, 1~2mm bigger than the diameter of circular hole 5.
The preparation method of bisphenol-A disposable paper base sensor of the present invention, comprising the following steps:
(1) overlay film art paper being cut into certain size with scissors, the size of overlay film art paper is determined according to sputter model,
The full-size that sputter can sputter cannot be greater than;
(2) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, is splashed on overlay film art paper first
The titanium film for penetrating one layer of nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 5~9cm, sputtering
Vacuum degree is not more than 2 × 10-3Mbar, sputtering current are 80~120mA, and sputtering time is 50~150s;Then, then on titanium film
The golden film for sputtering one layer of nanoscale, using gold plaque as sputtering target material, distance of the target away from sample stage is 5~9cm, and sputtering is true
Reciprocal of duty cycle is not more than 2 × 10-3Mbar, sputtering current are 15~50mA, and sputtering time is 50~150s;
(3) the overlay film art paper sputtered is taken out, size required for being cut into experiment with scissors, with outer diameter 4
The punch of~6mm punches on adhesive tape, then by tape-stripping in golden film, makes the face of adhesive tape covering golden film 50%-80%
Product forms adhesive tape layer;
(4) the multi-walled carbon nanotube aqueous dispersions that 10~30 μ L mass concentrations are 0.5~1 ‰ are added dropwise in circular hole region,
It is uniformly covered on it in region, is subsequently placed in 40 DEG C~45 DEG C baking ovens and dries;
(5) circular filter paper piece that diameter is 6~8mm is pasted in circular hole region, the diameter of filter paper is bigger than the diameter of circular hole by 1
Bisphenol-A disposable paper base sensor of the present invention is made in~2mm.
Embodiment 1
A kind of preparation method of bisphenol-A disposable paper base sensor, comprising the following steps:
(1) overlay film art paper is cut into certain size with scissors, the size of overlay film art paper is determined according to sputter model;
(2) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, is splashed on overlay film art paper first
The titanium film for penetrating one layer of nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 5cm, and sputtering is true
Reciprocal of duty cycle is not more than 2 × 10-3Mbar, sputtering current 80mA, sputtering time 50s;Then, then on titanium film sputter one layer of nanometer
The golden film of scale, using gold plaque as sputtering target material, distance of the target away from sample stage is 5cm, sputtering vacuum degree no more than 2 ×
10-3Mbar, sputtering current 15mA, sputtering time 50s;
(3) the overlay film art paper sputtered is taken out, size required for being cut into experiment with scissors uses outer diameter
The punch of 4mm punches on adhesive tape, then by tape-stripping in golden film, makes the area of adhesive tape covering golden film 50%, is formed
Adhesive tape layer;
(4) the multi-walled carbon nanotube aqueous dispersions that 30 μ L mass concentrations are 0.5 ‰ are added dropwise in circular hole region, make it uniformly
Covering in the area, be subsequently placed in 40 DEG C of baking ovens and dry;
(5) circular filter paper piece that diameter is 6mm is pasted in circular hole region, the diameter of filter paper is 2mm bigger than the diameter of circular hole,
Bisphenol-A disposable paper base sensor of the present invention is made.
Embodiment 2
A kind of preparation method of bisphenol-A disposable paper base sensor, comprising the following steps:
(1) overlay film art paper is cut into certain size with scissors, the size of overlay film art paper is determined according to sputter model;
(2) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, is splashed on overlay film art paper first
The titanium film for penetrating one layer of nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 9cm, and sputtering is true
Reciprocal of duty cycle is not more than 2 × 10-3Mbar, sputtering current 100mA, sputtering time 100s;Then, then one layer is sputtered on titanium film to receive
The golden film of metrical scale, using gold plaque as sputtering target material, distance of the target away from sample stage is 9cm, sputtering vacuum degree no more than 2 ×
10-3Mbar, sputtering current 34mA, sputtering time 80s;
(3) the overlay film art paper sputtered is taken out, size required for being cut into experiment with scissors uses outer diameter
The punch of 5mm punches on adhesive tape, then by tape-stripping in golden film, makes the area of adhesive tape covering golden film 60%, is formed
Adhesive tape layer;
(4) the multi-walled carbon nanotube aqueous dispersions that 20 μ L mass concentrations are 1 ‰ are added dropwise in circular hole region, keep it uniform
Covering in the area, is subsequently placed in 45 DEG C of baking ovens and dries;
(5) circular filter paper piece that diameter is 7mm is pasted in circular hole region, the diameter of filter paper is 2mm bigger than the diameter of circular hole,
Bisphenol-A disposable paper base sensor of the present invention is made.
Embodiment 3
A kind of preparation method of bisphenol-A disposable paper base sensor, comprising the following steps:
(1) overlay film art paper is cut into certain size with scissors, the size of overlay film art paper is determined according to sputter model;
(2) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, is splashed on overlay film art paper first
The titanium film for penetrating one layer of nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 7cm, and sputtering is true
Reciprocal of duty cycle is not more than 2 × 10-3Mbar, sputtering current 120mA, sputtering time 150s;Then, then one layer is sputtered on titanium film to receive
The golden film of metrical scale, using gold plaque as sputtering target material, distance of the target away from sample stage is 7cm, sputtering vacuum degree no more than 2 ×
10-3Mbar, sputtering current 50mA, sputtering time 150s;
(3) the overlay film art paper sputtered is taken out, size required for being cut into experiment with scissors uses outer diameter
The punch of 6mm punches on adhesive tape, then by tape-stripping in golden film, makes the area of adhesive tape covering golden film 80%, is formed
Adhesive tape layer;
(4) the multi-walled carbon nanotube aqueous dispersions that 10 μ L mass concentrations are 1 ‰ are added dropwise in circular hole region, keep it uniform
Covering in the area, is subsequently placed in 40 DEG C of baking ovens and dries;
(5) circular filter paper piece that diameter is 7mm is pasted in circular hole region, the diameter of filter paper is 1mm bigger than the diameter of circular hole,
Bisphenol-A disposable paper base sensor of the present invention is made.
Bisphenol-A disposable paper base sensor of the present invention can be used to complete the measurement of trace amount of bisphenol A in solution.
It, first will be to electrode and reference electricity with plastic clip when being detected using bisphenol-A disposable paper base sensor of the present invention
Pole is fixed on adhesive tape layer, is made to be in close contact the front end of electrode and reference electrode and filter paper, is constituted three-electrode system.To electricity
Using Pt to electrode, reference electrode uses Ag/AgCl reference electrode for pole.
The measurement of trace amount of bisphenol A in 4 solution of embodiment
Experimentation is as follows:
(1) the bisphenol-A standard buffer solution of various concentration is prepared, concentration is respectively 0.2mg/L, 0.5mg/L, 1mg/L,
2mg/L, 5mg/L, 10mg/L;
(2) it using the paper base sensor of 6 embodiments 2 preparation, is fixed respectively to electricity on the filter paper of each sensor
Pole and reference electrode constitute three-electrode system;
(3) solution to be measured of 20 μ L various concentrations is added dropwise on filter paper respectively, after placing a period of time, with electrochemistry work
Make station connection, the bisphenol-A in sample is detected using linear sweep voltammetry, obtains electrochemical signals as shown in Figure 2
Curve, peak height are related with the concentration of bisphenol-A solution.
Linear relationship as shown in figure 3, bisphenol A concentration in the range of 0.2~10mg/L, linear equation Y=21.423X
+ 2.331, related coefficient 0.9979.
Embodiment 5
Using paper base sensor made from embodiment 1, according to the step of (1) in embodiment 4~(3) to the bis-phenol in sample
A is measured, obtained linear relationship as shown in figure 4, bisphenol A concentration in the range of 0.2~10mg/L, linear equation Y
=4.876X-0.567, related coefficient 0.9986.
Embodiment 6
Using paper base sensor made from embodiment 3, according to the step of (1) in embodiment 4~(3) to the bis-phenol in sample
A is measured, obtained linear relationship as shown in figure 5, bisphenol A concentration in the range of 0.2~10mg/L, linear equation Y
=18.392X+0.847, related coefficient 0.9978.
From the foregoing, it will be observed that bisphenol-A disposable paper base sensor of the present invention has very good linear response, energy to bisphenol-A
For completing the measurement of trace amount of bisphenol A in solution, and it is easy to use.
Embodiment 7
Result reproducibility between different sensors:
(1) the step of using embodiment 1 prepares 20 paper base sensors, fixes respectively on the filter paper of each sensor
To electrode and reference electrode, three-electrode system is constituted;
(2) the bisphenol-A standard buffer solution that 20 μ L concentration are 1mg/L is added dropwise on the filter paper of 20 sensors respectively,
Bisphenol-A in solution is measured, measures the detection error between Different electrodes less than 8.30%.
Equally, it using 20 paper base sensors are prepared the step of embodiment 2, is measured according to above-mentioned steps (1), (2),
The detection error between Different electrodes is measured less than 7.20%.
Equally, it using 20 paper base sensors are prepared the step of embodiment 3, is measured according to above-mentioned steps (1), (2),
The detection error between Different electrodes is measured less than 7.80%.
From the foregoing, it will be observed that bisphenol-A disposable paper base sensor favorable reproducibility produced by the present invention, testing result are accurate.
Embodiment 8
Bisphenol-A disposable paper base sensor of the present invention and prior art testing result compare:
Using ito glass as electrode basement, using carbonaceous conductive glue as binder course, one layer of golden film is coated on carbonaceous conductive glue,
And pasted in golden film and set round-meshed adhesive tape layer, one layer of multi-walled carbon nanotube is modified in the golden film at circular hole, and in circular hole
Place's covering filter paper, circular hole and the size of filter paper, the method for modifying of multi-walled carbon nanotube are identical as the embodiment of the present invention 2, obtain
To sensor one.
Detection process is as follows:
(1) it is fixed respectively to electrode on the filter paper of the paper base sensor made from sensor one and the embodiment of the present invention 2
And reference electrode, constitute three-electrode system;
(2) the bisphenol-A standard solution that 20 μ L concentration are 1mg/L is added dropwise on the filter paper of two sensors respectively, utilizes
Linear sweep voltammetry is measured the bisphenol-A in solution, and testing result is as shown in fig. 6, a is paper base of the present invention sensing in figure
The linear scan curve of device, b are the linear scan curve of sensor one.
From fig. 6 it can be seen that bisphenol-A disposable paper base sensor of the present invention will be significantly larger than the response of bisphenol-A
Response of the prior art sensor to bisphenol-A.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (8)
1. a kind of bisphenol-A disposable paper base sensor, it is characterised in that: including overlay film art paper, be coated with one on overlay film art paper
Layer titanium film, one layer of golden film, glue belt in golden film are coated on titanium film, and adhesive tape layer covers the area of golden film 50%~80%, glue
Circular hole is opened up on belt, and one layer of multi-walled carbon nanotube is modified in the golden film at circular hole;
Overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, using titanium metal plate as sputtering target material, target
Distance of the material away from sample stage is 5~9cm, and sputtering vacuum degree is not more than 2 × 10-3Mbar, sputtering current are 80~120mA, sputtering
Time is 50~150s, to sputter one layer of titanium film on overlay film art paper.
2. bisphenol-A disposable paper base sensor according to claim 1, it is characterised in that: the multi-walled carbon nanotube
Method of modifying are as follows: the multi-walled carbon nanotube aqueous dispersions that 10~30 μ L mass concentrations are 0.5~1 ‰ are added dropwise in circular hole region,
It is uniformly covered on it in region, is subsequently placed in 40 DEG C~45 DEG C baking ovens and dries.
3. bisphenol-A disposable paper base sensor according to claim 1, it is characterised in that: the diameter of the circular hole be 4~
6mm。
4. bisphenol-A disposable paper base sensor according to claim 3, it is characterised in that: the multi wall carbon at the circular hole
Circular filter paper piece is covered on nanotube.
5. bisphenol-A disposable paper base sensor according to claim 4, it is characterised in that: the circular filter paper piece it is straight
Diameter is 6~8mm, 1~2mm bigger than the diameter of circular hole.
6. the preparation method of bisphenol-A disposable paper base sensor described in claim 1, it is characterised in that the following steps are included:
(1) overlay film art paper is placed on the sample stage of high vacuum ion sputtering instrument, sputters one on overlay film art paper first
The titanium film of layer nanoscale, using titanium metal plate as sputtering target material, distance of the target away from sample stage is 5~9cm, sputters vacuum
Degree is not more than 2 × 10-3Mbar, sputtering current are 80~120mA, and sputtering time is 50~150s;Then, then on titanium film sputter
The golden film of one layer of nanoscale, using gold plaque as sputtering target material, distance of the target away from sample stage is 5~9cm, sputters vacuum degree
No more than 2 × 10-3Mbar, sputtering current are 15~50mA, and sputtering time is 50~150s;
(2) the overlay film art paper sputtered is taken out, size required for experiment is cut into, with the punching of 4~6mm of outer diameter
Device punches on adhesive tape, then by tape-stripping in golden film, makes the area of adhesive tape covering golden film 50%-80%, forms adhesive tape
Layer;
(3) the multi-walled carbon nanotube aqueous dispersions that 10~30 μ L mass concentrations are 0.5~1 ‰ are added dropwise in circular hole region, make it
It is uniformly covered in the region, is subsequently placed in 40 DEG C~45 DEG C baking ovens and dries, bisphenol-A disposable paper base of the present invention is made and passes
Sensor.
7. the preparation method of bisphenol-A disposable paper base sensor according to claim 6, it is characterised in that: the step
(3) after the completion of, the circular filter paper piece that diameter is 6~8mm is pasted in circular hole region, the diameter of filter paper is bigger than the diameter of circular hole by 1
~2mm.
8. application of the described in any item bisphenol-A disposable paper base sensors of claim 1-5 in detection bisphenol-A.
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CN109142480A (en) * | 2018-09-17 | 2019-01-04 | 河北工程大学 | A kind of electrochemical sensor and its preparation method and application based on carbon nanotube |
CN110887710A (en) * | 2019-11-08 | 2020-03-17 | 华中科技大学 | Sample preparation method for analyzing elements in water body based on laser-induced breakdown spectroscopy technology |
CN113702477A (en) * | 2021-04-30 | 2021-11-26 | 广州钰芯智能科技研究院有限公司 | Gold film modified electrode for heavy metal detection and preparation method thereof |
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CN205263027U (en) * | 2015-12-30 | 2016-05-25 | 中国检验检疫科学研究院 | Formula paper base sensor can be thrown to bisphenol A |
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