CN115452908A - Preparation method and application of graphene microelectrode based on smartphone detection - Google Patents
Preparation method and application of graphene microelectrode based on smartphone detection Download PDFInfo
- Publication number
- CN115452908A CN115452908A CN202211161136.1A CN202211161136A CN115452908A CN 115452908 A CN115452908 A CN 115452908A CN 202211161136 A CN202211161136 A CN 202211161136A CN 115452908 A CN115452908 A CN 115452908A
- Authority
- CN
- China
- Prior art keywords
- electrode
- graphene
- detection
- graphene microelectrode
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 238000001514 detection method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 96
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 48
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 48
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 48
- 239000003814 drug Substances 0.000 claims abstract description 22
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 16
- 229940079593 drug Drugs 0.000 claims abstract description 14
- 210000004243 sweat Anatomy 0.000 claims abstract description 7
- 210000002700 urine Anatomy 0.000 claims abstract description 7
- 239000012488 sample solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000004458 analytical method Methods 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000840 electrochemical analysis Methods 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000012491 analyte Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229940126586 small molecule drug Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000007648 laser printing Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 239000012472 biological sample Substances 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 3
- 229930182837 (R)-adrenaline Natural products 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 3
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229960005139 epinephrine Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229960000304 folic acid Drugs 0.000 description 3
- 235000019152 folic acid Nutrition 0.000 description 3
- 239000011724 folic acid Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229940116269 uric acid Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013060 biological fluid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005220 pharmaceutical analysis Methods 0.000 description 2
- -1 potassium ferricyanide Chemical compound 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 1
- SBJKKFFYIZUCET-UHFFFAOYSA-N Dehydroascorbic acid Natural products OCC(O)C1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000020960 dehydroascorbic acid Nutrition 0.000 description 1
- 239000011615 dehydroascorbic acid Substances 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940088679 drug related substance Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002558 medical inspection Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000029501 response to L-ascorbic acid Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention relates to a preparation method and application of a graphene microelectrode based on smartphone detection, and belongs to the technical field of biosensing. The invention designs a direct-insertion type three-electrode pattern compatible with a U-disk type electrochemical analyzer, prepares a miniature flexible graphene electrode by combining a Laser Induced Graphene (LIG) technology, uses the PalmSens U-disk type electrochemical analyzer, combines with smart phone detection, adopts a cyclic voltammetry, and is used for detecting micromolecular drugs such as ascorbic acid. The designed graphene microelectrode is compatible with a PalmSens U-disk electrochemical analyzer, has good stability and sensitivity, and the constructed drug detection method has good repeatability, precision and selectivity, can be used for detecting biological samples such as sweat, urine and the like, and further promotes portable, green, low-cost and intelligent drug detection.
Description
Technical Field
The invention belongs to the technical field of electroanalytical chemistry, and particularly relates to a graphene microelectrode preparation method based on smart phone detection and application thereof.
Background
Analytical detection methods are important means for human beings to know knowledge and understand unknown matters at present. The development of society whether to quickly acquire accurate information of a detected object is now available. The analysis and detection of the medicine can research the composition, physicochemical property, authenticity identification, purity check and content determination of the effective components of the medicine and the preparation thereof, and ensure that the medicine is safe, reasonable and effective for people. After decades of development, the analysis of drugs in our country has been rapidly advanced, and the analysis methods adopted for controlling the quality of drugs are increasing, for example: electrochemical analysis, gas chromatography, liquid chromatography and the like, and the used instruments are gradually advanced, the used detection methods are gradually increased, and when the coming of the intelligent equipment era, the current pharmaceutical analysis technology tends to be in the direction of fine, sensitive, simple, portable and automatic intelligence. And with the development of microelectronic technology and computer technology and the popularization of intelligent equipment, instruments are developed towards portability, refinement and convenience. Therefore, we must fully pay attention to the development and application of new technology and new equipment, so that the drug analysis method and the more advanced level of the world are shortened. The medicine is a special medicine closely related to the health of human bodies, the truth or the quality of the medicine is accurately checked, and advanced, rapid and accurate qualitative and quantitative means are needed. The task of pharmaceutical analysis is therefore to detect, identify and quantify certain components in samples of different origin and composition for different purposes and requirements in the various fields of pharmacy.
The wide application of Electrochemical analysis (Electrochemical analysis) in drug detection is realized based on the mechanism that a drug substance can generate Electrochemical properties in a solution phase. The electrochemical analysis method has the characteristics of extremely high sensitivity and accuracy, good selectivity, high precision, high analysis speed, wide application range and the like. At present, the automation of analysis work can be realized after the joint control of an analytical instrument and a modern computer. Meanwhile, the electrochemical analysis method is widely applied to various fields such as industry, agriculture, medicine and health, food inspection, environmental protection, medical inspection and the like.
The Laser Direct Writing (LDW) technology is a preparation method without mask and reprocessing, processes and prepares pollution-free and ultra-fine electronic elements by a non-contact means, is different from the preparation method of the traditional semiconductor, can meet the requirement of circuit pattern fineness by the Laser direct writing technology, has the advantages of precise spatial distribution, large scanning area, high processing speed, no pollution to the environment and the like, can be compatible with the modern electronic industry integrated design technology, and enables the preparation of the graphene micro electronic device to be possible. By using a single laser direct writing technology and combining auxiliary means such as electrochemical deposition, 3D printing, photoetching and the like, the graphene electronic component can be prepared on the flexible substrate by one step, for example: electrodes/circuits, sensors, etc.
After the second quarter in 2013, the number of global smart phones and tablet computers has already exceeded that of personal computers, and the smart phones and tablet computers become the most used smart devices in the world. In 2013, the number of users of the Chinese smart phones reaches 3.54 hundred million, and the Chinese smart phone becomes the country which uses the smart phones most in the world beyond the United states. Investigation by the U.S. Pituee research agency 2016 for 2 months showed that smart phones have a prevalence in the adult population of 72% in the United states, 37% in emerging economies, and 58% in China. Today, many smart mobile devices typically have multiple wireless network communication functions, such as wireless network (WiFi), fourth or fifth generation digital communication technology (4G or 5G), bluetooth (Bluetooth), etc. The wired data interface of the equipment comprises Type-C, HDMI, and the Type-C ports are the most numerous in the wired data interface of the Chinese smart phone. These wireless or wired communication means allow the smart device to exchange data with peripheral devices or other hosts in the network in a variety of ways. Meanwhile, the Type-C interface can be used as a data transmission interface and can provide a power supply for external equipment. Many researchers have been dedicated to using smart mobile devices as analysis and detection devices, the electrochemical sensor usually needs external power supply when working, the lithium polymer battery equipped in the smart phone can be used as power supply, and the Type-C port can provide the connection path and power supply of the device for the external electrochemical sensor. PalmSens USB Type electrochemical analyzer that the company of leydirt promoted has Type-C port and connects, can insert the smart mobile phone through Type-C port, uses as electrochemical analysis software through computer end or android version PSTrace software. The dimensions are only: 43 by 25 by 11mm, have advantages such as portable, fast, accurate, can use under any scene that can not carry too big equipment.
Disclosure of Invention
The invention aims to provide a preparation method and application of a graphene microelectrode based on smartphone detection, the prepared graphene microelectrode is compatible with a PalmSens U-disk electrochemical analyzer, has good stability and sensitivity, and the constructed medicine detection method has good repeatability, precision and selectivity and can be used for detection of biological samples such as sweat, urine and the like. Further promote portable, green, low-cost, intelligent drug detection.
In order to achieve the purpose, the technical scheme of the invention is as follows: a graphene microelectrode preparation method based on smart phone detection comprises the following steps:
1) Designing a three-electrode system microelectrode pattern by adopting CAD drawing software, and printing a graphene microelectrode on a high-insulation PI film by adopting a laser;
2) And coating Ag/AgCl slurry on the reference electrode, taking the conductive silver slurry as a signal output connector, and fixing the area of a working area by using a PI film with adhesive, thereby forming a laser direct writing graphene electrode (LIG electrode).
The three-electrode pattern obtained in the step 1) is printed, and the size of the printed graphene electrode is as follows: the total length is 30mm, the width of the electrode joint is 2mm, the total width of the tail end is 10mm, the diameter of a working area disc is 5mm, the width of the three electrodes is 1.5mm, and the interval between the three electrodes is 1mm.
The laser printing or laser induction conditions in the step 1) are as follows: the laser is a continuous semiconductor laser with the wavelength of 450nm, the output power of 5.5W, the relative laser intensity of 20-50 percent and the relative printing depth of 5-30 percent.
Preferably, the laser printing or laser inducing conditions in step 1) above are: the laser is a continuous semiconductor laser with the wavelength of 450nm, the output power of 5.5W, the relative laser intensity of 35 percent and the relative printing depth of 20 percent.
The PI film in the step 1) is 0.08 mu m thick, the reverse side is provided with adhesive and is stuck to the surface of the PET substrate, and the PET substrate is cut into the required size with the thickness of 180 mu m.
The conductive silver paste coating signal output connector in the step 2) can not be adhered to each other within the coating range of 2mm x 4mm, so that the conductive silver paste can be fully contacted with the interface of the electrochemical analyzer, and a good conductive effect is achieved. The curing temperature of the Ag/AgCl paste and the conductive silver paste is 80-100 ℃, and the curing time is 2-3 h.
The invention also provides application of the graphene microelectrode based on smartphone detection, which comprises the following steps:
1) The prepared LIG electrode is directly inserted into a miniature electrochemical analyzer and connected with a mobile phone, and an electrochemical mobile phone intelligent detection device is set up.
2) The sample solution is dropped onto the surface of the electrode, covered with three electrodes, and the current signal is monitored by electrochemical analysis to detect the target analyte.
The micro electrochemical analyzer used in the step 1) is as follows: palmSens USB flash disk electrochemical analyzer, cell-phone are the android system, and the cell-phone interface is Type-C interface, and used APP software is PStouch 2.7.
The volume of the sample solution in the step 2) is 50-150 mul, the sample solution can be serum, sweat and urine, the concentration is 0.01-0.5 mg/mL, and the target analyte is one of micromolecular medicines or biomolecules such as ascorbic acid, glucose and the like.
The ascorbic acid detection in the step 2) adopts cyclic voltammetry, the scanning range is-0.2-0.5V, and the scanning speed is 0.1V/s.
The invention discloses an application of a graphene microelectrode based on smartphone detection, and the prepared LIG electrode is applied to drug analysis.
Compared with the prior art, the invention has the following beneficial effects:
1) The planar microelectrode prepared by the laser direct writing technology is simple and convenient to operate, does not need an organic solvent, is green and environment-friendly, has extremely low cost, can be used for patterning an electrode in a microscale, can be prepared in batches, creates special requirements for an electrode system in a micrometer size range, and is beneficial to designing a miniaturized electrochemical sensor. The LIG technology can induce a Polyimide (PI) substrate to directly generate graphene with a three-dimensional porous structure, shows large specific surface area and high conductivity, and is beneficial to adsorbing more small-molecule drugs on the surface of an electrode to generate the change of electrochemical properties.
2) The PalmSens U-disk Type electrochemical analyzer enables electrochemical detection to be carried out in any scene, is connected with a mobile phone port through a Type-C interface, does not need to additionally carry a power supply or an external power supply, and simultaneously controls and shares a detection result in real time. The problems that a large-scale electrochemical workstation is not easy to carry and needs an external power supply are solved, and an idea is provided for monitoring the physical health condition of people in real time.
3) The prepared graphene microelectrode detected by the smart phone has good stability, precision and selectivity for sensing small-molecule drugs such as ascorbic acid and glucose, and can be repeatedly used.
4) The graphene microelectrode detected by the smart phone can be used for detecting ascorbic acid by using biological fluids such as human sweat, urine and the like, can also be used for analyzing micromolecular medicines such as glucose and the like, and can be used for noninvasive monitoring of diabetes and the like. And by combining a smart phone detection system, the miniature flexible wearable equipment has a good application prospect.
Drawings
FIG. 1 LIG electrode layout (unit: mm);
FIG. 2 is a flow chart of smartphone drug detection;
fig. 3 SEM image of LIG electrode graphene material;
fig. 4 TEM image of LIG electrode graphene material;
fig. 5 CV diagram of LIG electrode in potassium ferricyanide solution: 5mmol/L KCl containing 0.1mol/L, sweep rate: 0.1V/s;
fig. 6 LIG electrode detection of ascorbic acid in different pH solution environments. Ascorbic acid concentration: 0.1mg/mL;
figure 7 CV scan overlay of ascorbic acid with multiple repeated use of the same electrode, scan rate: 0.1V/s, pH =1, ascorbic acid concentration: 0.1mg/mL;
fig. 8 is a graph of peak current versus number of repeated uses, pH =1, ascorbic acid concentration: 0.1mg/mL;
figure 9 same batch electrode precision test, pH =1, ascorbic acid concentration: 0.1mg/mL;
fig. 10 LIG electrode vs series concentration ascorbic acid CV plot, sweep rate: 0.1V/s, pH =1;
FIG. 11 is a graph of peak current versus concentration;
figure 12 CV scans of the prepared electrode against different sample solutions, sweep rate: 0.1V/s, pH =1, and the solution concentrations were all 0.025mg/mL;
FIG. 13 is a CV diagram of smartphone test sweat and its addition of ascorbic acid at different concentrations;
figure 14 CV graph of smartphone assay urine and its addition of different concentrations of ascorbic acid.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples and accompanying drawings which are set forth to illustrate, but are not to be construed as the limit of the present invention. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The instrument comprises the following steps: nano Pro-iii laser printer (tianjin jia silver nanotechnology limited);
PalmSens U disk electrochemical analyzer (Redtite).
The preparation of the LIG electrode and the detection and analysis process of the smart phone are shown in fig. 2: the specific process comprises the steps of a) laser direct writing three-electrode patterned graphene; b) Preparing an LIG electrode; c) And (3) analyzing the drug of the smartphone detection system, and recording the difference value (delta I) between the peak current and the initial current as a response signal.
Example 1
Adopting CAD drawing software to design a microelectrode pattern of a three-electrode system, wherein the specific size is shown in figure 1: the total length is 30mm, the width of the electrode joint is 2mm, the total width of the tail end is 10mm, the diameter of a working area disc is 5mm, the width of the three electrodes is 1.5mm, and the interval between the three electrodes is 1mm. And a 450nm laser is adopted, the output power is 5.5W, the laser relative intensity is 35%, and the printing relative depth is 20%. And (3) sticking the high-insulation PI film on the surface of the PET substrate, and cutting into the required size. And printing an LIG electrode graphene pattern on the PI film, and leaching the electrode with water and ethanol in sequence and drying. Ag/AgCl paste is coated on a reference electrode, conductive silver paste is coated at the tail end of the three electrodes to serve as a signal output connector, and the curing time is 2 hours at 80 ℃. And fixing the circular area of the working area by using a high-insulation PI film to prevent the dropwise added test sample solution from diffusing, thereby preparing the LIG electrode.
Example 2
The surface morphology of the LIG electrode prepared in example 1 was characterized by a Scanning Electron Microscope (SEM) (fig. 3), in which the spatial network structure of graphene is shown, indicating that the high-insulation PI film was successfully induced into a graphene material by the laser direct writing technique. The macroporous/mesoporous structure of the graphene endows the graphene material with ultrahigh specific surface area and excellent electron transfer rate, and provides good conditions for small molecule drug analysis of the graphene electrode.
Example 3
The graphene material was collected with a scraper on the electrode working interface prepared in example 1, and was ground and dispersed, and the morphology of the graphene material was characterized with a Transmission Electron Microscope (TEM). As shown in fig. 4, the graphene material has a lamellar stacked thin-layer structure, and the prepared graphene is a multi-layer graphene, so that a three-dimensional cavity network structure is formed, and the graphene material has an ultra-high specific surface area.
Example 4
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer (see fig. 2) connected to a smart phone of android system, and subjected to electrochemical performance test using cyclic voltammetry, and 50 μ L of a 5mmol/L potassium ferricyanide solution containing 0.1mol/L KCl was transferred to a working area of the electrode. Opening PStouch 2.7APP on the smart phone, and performing electrochemical scanning by adopting cyclic voltammetry, wherein the scanning range is as follows: -0.6V, sweep rate: 0.1V/s, and the click test results are shown in FIG. 5. Can seeThe obvious oxidation reduction peak of the LIG electrode, the peak current of the LIG electrode is 300 mu A, and the peak-to-peak separation voltage (delta E) P ) And the smaller size shows that the graphene electrode prepared by the laser direct writing technology has excellent measurement sensitivity and good electrochemical performance.
Example 5
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer connected to an android system smartphone, and electrochemical tests were performed on ascorbic acid in solutions of different pH using cyclic voltammetry. Firstly, 0.1mol/L potassium chloride solution is prepared, ascorbic acid is added, and then hydrochloric acid and potassium hydroxide are used for adjusting the pH of the solution, so as to obtain 0.1mg/mL ascorbic acid solution with the pH values of 1, 2, 4, 6, 7, 8 and 10 in sequence. The labeling was pH 1, pH 2, pH 4, pH 6, pH 7, p H, pH 10, in that order, depending on the pH environment of the solution. And (2) taking 50 mu L of ascorbic acid solution on the surface of a working area of the LIG motor, and performing electrochemical scanning by adopting cyclic voltammetry, wherein the scanning range is as follows: -0.2-0.5V, sweep rate: 0.1V/s, ascorbic acid solutions of different pH were tested sequentially and the results are shown in FIG. 6. The peak current under the neutral condition is the smallest, the peak current is reduced on the contrary as the pH value of the solution is increased, the smaller the pH value is, namely the peak current is larger on the contrary when the acidity is stronger, and the analysis on the ascorbic acid shows that the sensitivity is the largest under the strong acidic condition and the effect is the best. This is because the rate of ascorbic acid to dehydroascorbic acid varies at different pH conditions, which affects the electron transfer rate.
Example 6
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer connected to an android system smartphone, and a repeated electrochemical test was performed on an ascorbic acid solution with pH =1 using cyclic voltammetry. Dropwise adding an ascorbic acid solution with the value of 1 of 50 mu LpH to the surface of a working area of an electrode, and performing electrochemical scanning by adopting a cyclic voltammetry method, wherein the scanning range is as follows: -0.2-0.5V, sweep rate: the same electrode was scanned seven times at 0.1V/s, and the results are shown in FIGS. 7 and 8. The difference between the first scanning result and other six times is larger, because the electrochemical performance of the electrode is not fully activated during the first scanning, and the solution does not infiltrate into the electrode; the difference of the results from the second time to the seventh time is small, and the peak current is stable, which indicates that the repeatability of the prepared electrode is good, so that the subsequent experimental tests take the second scanning as the standard.
Example 7
Five electrodes are simultaneously prepared by the method of embodiment 1, the electrodes are inserted into a PalmSens U disk electrochemical analyzer connected with an android system smart phone, a prepared ascorbic acid solution with the concentration of 50 μ LpH of 1 and the concentration of 0.1mg/mL is dripped on the surface of a working area of the electrodes, a cyclic voltammetry method is used for detection, and the scanning range is as follows: -0.2-0.5V, sweep rate: 0.1V/s, and testing whether the electrochemical performance of the electrodes prepared in the same batch is different, wherein the result is shown in figure 9. The peak current to electrode RSD =3.14% calculated using the following formula, and both the experimental results and RSD of the peak current indicate that the precision of the experimental method is high and the difference between the same batch of electrodes has less influence on the peak current.
Example 8
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer connected to an android system smartphone, and electrochemical tests were performed on ascorbic acid solutions of different concentrations of pH =1 using cyclic voltammetry. Firstly, 0.1mol/L potassium chloride solution is prepared, ascorbic acid with different amounts is added, and then hydrochloric acid and potassium hydroxide are utilized to adjust the pH of the solution to 1, so as to obtain the ascorbic acid solution with the concentration of 0.01, 0.025, 0.05, 0.1, 0.2 and 0.5mg/mL in sequence. And (3) dripping 50 mu L of ascorbic acid solution on the surface of a working area of the electrode, and performing cyclic voltammetry scanning, wherein the scanning range is as follows: -0.2-0.5V, sweep rate: 0.1V/s. A batch of six electrodes with substantially identical signals was tested for six different concentrations of ascorbic acid solution using the method of example 7 and the experiment was repeated three times to obtain the results shown in figure 10. The results show that the ascorbic acid has obvious oxidation peak current at the potential of about 0.25V, and the peak current is gradually increased along with the increase of the concentration.
The peak current changes with concentration are shown in FIG. 11, the peak current value of the LIG electrodeAnd the concentration of the ascorbic acid solution is in a linear relation, and the linear equation is as follows: y =661.13x +22.91, linear correlation coefficient R 2 =0.9906. The prepared LIG electrode has good current response to ascorbic acid when the concentration of the ascorbic acid is 0.01-0.5 mg/mL, and the constructed method can be used for the quantitative analysis of the ascorbic acid.
Example 9
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer connected to an android system smartphone, and the selectivity of the LIG electrode to ascorbic acid was tested using cyclic voltammetry. Respectively preparing folic acid, ascorbic acid, epinephrine and uric acid solutions with the pH value of 1 and the concentration of 0.025mg/mL, then preparing a bottle of mixed solution of folic acid, ascorbic acid, epinephrine and uric acid with the pH value of 1 and the concentration of 0.025mg/mL, respectively dripping 50 mu L to five electrode working area surfaces with consistent electric signals into the five solutions, and performing electrochemical scanning by adopting a cyclic voltammetry, wherein the scanning range is as follows: -0.2-0.5V, sweep rate: 0.1V/s, the results are shown in FIG. 12. At the potential of about 0.25V, obvious oxidation peaks appear in the ascorbic acid and the mixed solution, and electrochemical response does not appear in the folic acid, the epinephrine and the uric acid solution, which indicates that the prepared LIG electrode shows good selectivity at the potential of 0.25V and is slightly interfered by other substances.
Example 10
The LIG electrode prepared in example 1 was inserted into a PalmSens usb disk electrochemical analyzer connected to an android smartphone, and the effect of different sample solutions on the LIG electrode detection of ascorbic acid was tested using cyclic voltammetry. Firstly, respectively preparing artificial urine, artificial sweat and a potassium chloride solution according to the weight ratio of 1:19 volume ratio of mother liquor, then adding ascorbic acid, adjusting the pH of the solution to 1 by utilizing hydrochloric acid and potassium hydroxide, and obtaining ascorbic acid sample solutions with the concentrations of 0, 0.01, 0.05 and 0.5mg/mL in sequence. Preparing eight electrodes with consistent electrochemical signals, sequentially taking 50 mu L of ascorbic acid sample solutions with different concentrations, dripping the ascorbic acid sample solutions to the surface of a working area of the electrode, and performing electrochemical scanning by adopting a cyclic voltammetry method, wherein the scanning range is as follows: -0.2-0.5V, sweep rate: 0.1V/s, the results shown in FIGS. 13 and 14 were obtained. The result shows that the prepared LIG electrode can still have an obvious electrochemical oxidation peak for ascorbic acid in a complex solution environment, and the electrochemical response is good.
From the results in the figure, the recovery rate of ascorbic acid addition in the sample solution was calculated (table 1). The results show that the sample solution has certain influence on the detection of the ascorbic acid, but the recovery rate is about 80% on average in general, which indicates that the prepared LIG electrode for intelligent mobile phone detection can be suitable for analyzing the ascorbic acid by more complicated biological fluids.
TABLE 1 LIG electrode test results in sample solution
The above are preferred embodiments of the present invention, and all changes made according to the technical solutions of the present invention that produce functional effects do not exceed the scope of the technical solutions of the present invention belong to the protection scope of the present invention.
Claims (10)
1. A graphene microelectrode preparation method based on smart phone detection is characterized by comprising the following steps:
1) Designing a three-electrode system graphene microelectrode pattern by adopting CAD drawing software, and printing a graphene microelectrode on a high-insulation polyimide PI film by adopting a laser;
2) Coating Ag/AgCl slurry on a reference electrode, coating a signal output connector with conductive silver slurry, and fixing the working area by a PI film with adhesive to form a laser direct writing graphene electrode (LIG electrode).
2. The graphene microelectrode preparation method based on smartphone detection according to claim 1, wherein the printed graphene microelectrode patterns in the step 1) are as follows: total length 30mm, electrode joint width 2mm, tip total width 10mm, working area disc diameter 5mm, triple electrode width 1.5mm, triple electrode spacing 1mm.
3. The graphene microelectrode preparation method based on smartphone detection according to claim 1, wherein the conditions of laser printing or laser induction in step 1) are as follows: the laser is a continuous semiconductor laser, the wavelength is 450nm, the output power is 5.5W, the relative laser intensity is 20-50%, and the relative printing depth is 5-30%.
4. The graphene microelectrode preparation method based on smartphone detection according to claim 1, wherein in the step 1), the PI film is 0.08 μm thick, the reverse side is provided with adhesive and attached to the surface of a PET substrate, and the PET substrate is cut into required sizes, wherein the thickness of the PET substrate is 180 μm.
5. The graphene microelectrode preparation method based on smartphone detection according to claim 1, wherein in the step 2), a signal output connector is coated with conductive silver paste, and the conductive silver paste is coated within a range of 2mm by 4mm and cannot be adhered to each other, so that sufficient contact with an interface of a micro electrochemical analyzer is ensured, and a good conductive effect is achieved; the curing temperature of the Ag/AgCl paste and the conductive silver paste is 80 to 100 ℃, and the curing time is 2 to 3 hours.
6. The application of the graphene microelectrode based on the detection of the smart phone is characterized by comprising the following steps:
1) Directly inserting the LIG electrode prepared according to any one of claims 1 to 5 into a miniature electrochemical analyzer, connecting a mobile phone, and building an electrochemical mobile phone intelligent detection device;
2) The sample solution is dripped on the surface of the LIG electrode, the three electrodes are covered, and the current signal is monitored by adopting an electrochemical analysis method to detect the target analyte.
7. The application of the graphene microelectrode based on the detection of the smart phone as claimed in claim 6, wherein the micro electrochemical analyzer used in step 1) is a PalmSens U disk electrochemical analyzer, the mobile phone system is an android system, the mobile phone interface is a Type-C interface, and the APP software is PStouch 2.7.
8. The application of the graphene microelectrode based on the smartphone detection of claim 6, wherein the volume of the sample solution in the step 2) is 50 to 150 μ L, the sample solution comprises sweat and urine, the concentration of the sample solution is 0.01 to 0.5mg/mL, and the target analyte is one of a small molecule drug or a biomolecule including ascorbic acid and glucose.
9. The application of the graphene microelectrode based on the detection of the smart phone as claimed in claim 8, wherein the ascorbic acid detection is performed by cyclic voltammetry, with a scanning range of-0.2 to 0.5V and a scanning speed of 0.1V/s.
10. Use of a graphene microelectrode based on smartphone detection, characterized in that the LIG electrode prepared according to any of claims 1 to 5 is used in drug analysis.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211161136.1A CN115452908A (en) | 2022-09-22 | 2022-09-22 | Preparation method and application of graphene microelectrode based on smartphone detection |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211161136.1A CN115452908A (en) | 2022-09-22 | 2022-09-22 | Preparation method and application of graphene microelectrode based on smartphone detection |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115452908A true CN115452908A (en) | 2022-12-09 |
Family
ID=84306229
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211161136.1A Pending CN115452908A (en) | 2022-09-22 | 2022-09-22 | Preparation method and application of graphene microelectrode based on smartphone detection |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115452908A (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111735863A (en) * | 2020-05-26 | 2020-10-02 | 中国地质大学(北京) | Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof |
CN113295748A (en) * | 2021-05-21 | 2021-08-24 | 闽江学院 | Preparation of laser direct-writing graphene/precious metal nanoparticle composite electrode and application of immunosensing |
CN113311044A (en) * | 2021-06-19 | 2021-08-27 | 中国地质大学(北京) | Sensor capable of rapidly detecting nitrite in water environment and detection method |
US20210332489A1 (en) * | 2020-04-27 | 2021-10-28 | Iowa State University Research Foundation, Inc. | Laser-induced graphene electrodes adaptable for electrochemical sensing and catalysis |
WO2022077027A2 (en) * | 2020-10-09 | 2022-04-14 | The Trustees Of The University Of Pennsylvania | Low-cost rapid diagnostic for covid-19 and other pathogens |
CN114705736A (en) * | 2022-03-21 | 2022-07-05 | 山东大学 | Portable multi-channel detection electrochemical sensing system and application thereof |
CN115015345A (en) * | 2022-08-08 | 2022-09-06 | 湖南农业大学 | Non-modified flexible electrochemical sensor for rapidly detecting heavy metal ions and preparation method and application thereof |
-
2022
- 2022-09-22 CN CN202211161136.1A patent/CN115452908A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210332489A1 (en) * | 2020-04-27 | 2021-10-28 | Iowa State University Research Foundation, Inc. | Laser-induced graphene electrodes adaptable for electrochemical sensing and catalysis |
CN111735863A (en) * | 2020-05-26 | 2020-10-02 | 中国地质大学(北京) | Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof |
WO2022077027A2 (en) * | 2020-10-09 | 2022-04-14 | The Trustees Of The University Of Pennsylvania | Low-cost rapid diagnostic for covid-19 and other pathogens |
CN113295748A (en) * | 2021-05-21 | 2021-08-24 | 闽江学院 | Preparation of laser direct-writing graphene/precious metal nanoparticle composite electrode and application of immunosensing |
CN113311044A (en) * | 2021-06-19 | 2021-08-27 | 中国地质大学(北京) | Sensor capable of rapidly detecting nitrite in water environment and detection method |
CN114705736A (en) * | 2022-03-21 | 2022-07-05 | 山东大学 | Portable multi-channel detection electrochemical sensing system and application thereof |
CN115015345A (en) * | 2022-08-08 | 2022-09-06 | 湖南农业大学 | Non-modified flexible electrochemical sensor for rapidly detecting heavy metal ions and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Tu et al. | A miniaturized electrochemical system for high sensitive determination of chromium (VI) by screen-printed carbon electrode with gold nanoparticles modification | |
Abunahla et al. | MOMSense: metal-oxide-metal elementary glucose sensor | |
Zhou et al. | Fabrication of a microfluidic Ag/AgCl reference electrode and its application for portable and disposable electrochemical microchips | |
CN112179964B (en) | Self-calibration electrode array based on polystyrene/gold sensing material and application | |
Beitollahi et al. | A sensitive electrochemical DNA biosensor for anticancer drug topotecan based on graphene carbon paste electrode | |
CN102944596A (en) | Preparation method of graphene modified glassy carbon electrode and application thereof | |
Veloso et al. | Flow-through amperometric determination of ampicillin using a copper electrode in a batch injection analysis system | |
CN101021529A (en) | High-flux detection system of multianalyte simultaneous detection and electrochemical immunoanalytical method | |
CN101303357A (en) | Method for manufacturing rapid blood sugar test paper | |
CN101387617A (en) | Silk-screen printing electrode and method for synthesizing chloramphenicol molecular imprinting film | |
Khashaba et al. | Complexation based voltammetric determination of pantoprazole sodium in pharmaceutical formulations and rabbit plasma | |
Qiu et al. | A low-cost wireless intelligent portable sensor based on disposable laser-induced porous graphene flexible electrode decorated by gold nanoshells for rapid detection of sulfonamides in aquatic products | |
TWI695166B (en) | A multi-ion sensing electrode array chip and sensing device thereof | |
CN104330452B (en) | A kind of screen printing electrode of soft material modification and preparation method and application | |
Kulapina et al. | Screen-printed potentiometric sensors based on carbon materials for determining cefotaxime and cefuroxime | |
Hendawy et al. | A Zirconium Oxide Nanoparticle Modified Screen‐printed Electrode for Anodic Stripping Determination of Daclatasvir Dihydrochloride | |
CN105004781A (en) | Dopamine detecting method based on paper-base electrochemistry device | |
Li et al. | A novel strategy of electrochemically treated ZrOCl2 doped carbon paste electrode for sensitive determination of daidzein | |
Soleymanpour et al. | Liquid membrane/polyaniline film coated glassy carbon sensor for highly sensitive and selective determination of fluvoxamine in pharmaceutical and biological samples | |
Li et al. | All-solid-state carbonate-selective electrode based on screen-printed carbon paste electrode | |
CN115452908A (en) | Preparation method and application of graphene microelectrode based on smartphone detection | |
Mümin et al. | Electrochemical determination of brucine in urine with a poly (Alizarin Red S)-modified glassy carbon electrode | |
Dilgin | Determination of calcium dobesilate by differential pulse voltammetry at a disposable pencil graphite electrode | |
Ren et al. | A miniaturized electrochemical nitrate sensor and the design for its automatic operation based on distributed model | |
Schwarz et al. | All-solid-state screen-printed sensors for potentiometric calcium (II) determinations in environmental samples |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |