CN106645320A - Flexible electrode based on biocompatible materials, preparation method of flexible electrode and application - Google Patents

Flexible electrode based on biocompatible materials, preparation method of flexible electrode and application Download PDF

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Publication number
CN106645320A
CN106645320A CN201611003241.7A CN201611003241A CN106645320A CN 106645320 A CN106645320 A CN 106645320A CN 201611003241 A CN201611003241 A CN 201611003241A CN 106645320 A CN106645320 A CN 106645320A
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China
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electrode
flexible
biocompatible materials
base material
biological
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刘仁材
陶常冰
颜靖书
陈靖容
赵湛
方震
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University of Chinese Academy of Sciences
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University of Chinese Academy of Sciences
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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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Pathology (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Abstract

The invention discloses a flexible electrode based on biocompatible materials, a preparation method of the flexible electrode and an application. The flexible electrode takes degradable biocompatible materials as a substrate, carbon electrodes are prepared by the aid of screen printing technique, and the biocompatible materials can be biodegradable high-molecular materials such as chitosan, agar and collagen. The method includes the steps: printing carbon electrodes on a biocompatible material substrate by the screen printing technique, and curing the carbon electrodes in a drying oven to obtain bran-new bio-based carbon electrodes; preparing electron transfer medium solution, curing the electron transfer medium solution on working areas of the surfaces of the carbon electrodes; distributing identification molecules into phosphate buffer solution, and curing the phosphate buffer solution on the working areas of the surfaces of the electrodes to prepare a bran-new bio-based electrode detection platform. The flexible electrode is simple in preparation process, low in cost and good in flexibility and has the functions of desensitization, permeability, moisture absorption and the like and important significances for applications of flexible and wearable electronic devices, and the flexible electrode effectively contacts with skins.

Description

A kind of flexible electrode based on biocompatible materials and its preparation method and application
Technical field
The invention belongs to biosensor technique field, more particularly to a kind of flexible electrode based on biocompatible materials and Its preparation method and application.
Background technology
At present, electrochemica biological sensor has important answering in fields such as medical diagnosis, food security and environment measurings With.It is with low cost etc. because its is portable, convenient particularly when medical diagnostic field is used to detect the blood sugar of diabetic Advantage is widely used.Shown according to the investigation statisticses result of IDF, by 2013, global diabetes were ill Quantity there are about 3.82 hundred million numbers.Therefore, in terms of the field of blood sugar test, electrochemica biological sensor has important application front Scape.On the other hand, with the further investigation of flexible material, in the application in the fields such as artificial skin, wearable electronic equipment Cause extensive concern.Develop the blood-sugar content that a kind of wearable electrode detection platform detects in real time diabetic With more vital meaning, and traditional plastics based electrochemical biology sensor, due to its flexibility it is poor, adhesion Difference, it is difficult to skin surface is attached to, and gas permeability is bad, easily causes the defect such as allergic, it is difficult in wearable device Extensively application.Therefore, a kind of flexible, antianaphylactic biological base material electrode detection test piece good with skin attachment is developed, for Exploitation flexible electronic devices or wearable flexible skin electron detection device have great importance.Biomaterial(Such as shell Glycan, agar, collagen etc.)It is a kind of natural macromolecular material, with excellent biocompatibility, security and micro- life The premium properties such as thing degradability all achieve major progress by extensive concern in the application study of the various fields such as medicine, food. And the biological thin-film material of natural polymer being prepared into by natural macromolecular material, it may have excellent pliability and biofacies Capacitive, being attached to skin surface will not cause allergic, and with good gas permeability and hygroscopicity etc., have to skin Preferable suitability, if biomaterial can be utilized to be the excellent Electrochemical Detection platform of substrate processability, it will obtain Pliability is good, antiallergy, the artificial skin flexible electrode detection platform of excellent performance.With regard to current research, flexible electrode is measured Test piece or platform be all, with undecomposable plastics, to prepare such as PDMS film, but such be simply possible to use in general external inspection Survey, if be separately attached on skin it is easily airtight can also produce allergic phenomena, so the present invention be exactly using biocompatible materials as Soft electronic base material, and the construction detecting element on this base material so as to become a detection platform with biocompatibility, Its electronics artificial skin is made, more can be received by tissue, do not repelled, not allergy, breathed freely. this detection platform for now Either in research or patent, be all without. but at present the research with regard to the electrode detection platform of this respect still falls within Technological gap.
In sum, biomaterial belongs to blank in the application of electrode detection platform.
The content of the invention
It is an object of the invention to provide a kind of flexible electrode based on biocompatible materials and preparation method thereof and should With, it is intended to solve the problems, such as that biomaterial belongs to blank in the application of electrode detection platform.
The present invention is achieved in that a kind of flexible electrode based on biocompatible materials, described based on bio-compatible The flexible electrode of property material prepares carbon electrode with degradable biological material as substrate by screen printing technique;
It can be any one in shitosan, agar, the Biodegradable polymer material of collagen that the biomaterial is Kind, two or three of mixing;Any two or three of mixing according to quality in the shitosan, agar, collagen The ratio of percentage each component is 10% ~ 90%.
Another object of the present invention is to provide a kind of be prepared by the flexible electrode based on biocompatible materials Biological base material electrode detection platform.
Further, the biological base material electrode detection platform is respectively from top to bottom:Identification molecular layer, electron transfer mediator Layer, carbon electrode layer, layer of biological material.
Further, the electron transfer mediator layer is the potassium ferricyanide, methyl ferrocene, methylene blue or 1,4-benzoquinone.
Further, the identification molecular layer is enzyme, antibody, DNA, aptamers or cell.
Another object of the present invention is to a kind of preparation method of described biological base material electrode detection platform is provided, it is described The preparation method of biological base material electrode detection platform includes:
Step one, in biomaterial substrate carbon electrode is printed with, and by screen printing technique carbon electrode is printed, and moves into baking oven In solidified, obtain brand-new biological base material carbon electrode;
Step 2, prepares electron transfer mediator solution, and is fixed on the working region of carbon electrodes;
Step 3, identification molecule is allocated into phosphate buffer, and is fixed in the working region of electrode surface, is prepared Biological base material electrode detection platform.
Another object of the present invention is to provide a kind of be prepared by the flexible electrode based on biocompatible materials For detecting the degradable flexible biological base material electrode detection test piece of glucose.
Another object of the present invention is to provide a kind of be prepared by the flexible electrode based on biocompatible materials Flexible artificial skin electrode detection platform.
Another object of the present invention is to provide a kind of be prepared by the flexible electrode based on biocompatible materials Wearable electrode detection platform.
Flexible electrode based on biocompatible materials that the present invention is provided and its preparation method and application, with degradable Biomaterial prepares carbon electrode, and the suitable potassium ferricyanide of fixation and grape glycosyloxy as substrate by screen printing technique Change enzyme, prepare the flexible biological electrode of the substrate test strip of brand-new degradable detection glucose.Prepared detection grape The biological base material electrode detection test piece of sugar shows the plastic basis material glucose electrode test piece tool commercial with it by electro-chemical test There is same good chemical property.The flexible biological electrode of the substrate test strip of brand-new detection glucose is used to detect Portugal Grape sugar, its result illustrates that this test piece can accurately for detecting the glucose solution in the range of finite concentration, and with spirit Sensitivity is high(0.97 μA cm-2), detection time is short(Less than 40 s), otherness is little(Relative standard deviation is less than 2.41 %, N= 3)The advantages of.The flexible biological electrode of the substrate detection platform that the present invention is provided, preparation process is simple, low cost is flexible, with skin Skin contact is good, and with functions such as antianaphylaxis, gas permeability and hygroscopicity, for deflection, wearable electronic equipment Application have great importance, be to prepare flexible artificial skin electronic product or the application in wearable electronic product is provided New method and approach.With degradable biological material as substrate, carbon electrode is prepared by screen printing technique, and it is fixed Suitable electron transfer mediator and identification molecule, prepare a kind of brand-new biological base material electrode detection platform.Prepared biology Electrode of the substrate detection platform is shown with excellent chemical property by cyclic voltammetry, for detecting glucose solution When, high with accuracy, sensitivity is high, and detection time is short, the advantages of favorable reproducibility and good stability.
Description of the drawings
Fig. 1 is the preparation method flow chart of flexible biological electrode of the substrate detection platform provided in an embodiment of the present invention.
Fig. 2 is flexible biological electrode of the substrate detection platform structural representation provided in an embodiment of the present invention;
In figure:1st, molecule is recognized;2nd, electron transfer mediator;3rd, carbon electrode;4th, biomaterial substrate.
Fig. 3 is the chemical property analysis chart of flexible biological electrode of the substrate detection platform provided in an embodiment of the present invention.
Fig. 4 is that flexible biological electrode of the substrate test strip provided in an embodiment of the present invention is used to detect the linear model of glucose Enclose and sensitivity schematic diagram.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention Limit the present invention.
The application principle of the present invention is explained in detail below in conjunction with the accompanying drawings.
Flexible electrode based on biocompatible materials provided in an embodiment of the present invention is with degradable biological material as base Bottom, by screen printing technique carbon electrode is prepared.It can be shitosan, agar, the biology of collagen that the biomaterial is In degradable high polymer material any one, two or three of mixing;In the shitosan, agar, collagen arbitrarily The ratio according to mass percent each component of two or three of mixing is 10% ~ 90%.
As shown in figure 1, the preparation method of the biological base material electrode detection platform of the embodiment of the present invention is comprised the following steps:
S101:With degradable biological material as substrate, carbon electrode is prepared by screen printing technique, and move into baking oven and carry out Solidification, obtains the carbon electrode of biomaterial substrate;
S102:Electron transfer mediator solution is prepared, and is fixed in carbon electrodes;
S103:Identification molecule is allocated into phosphate buffer, and is fixed in the working region of electrode surface, preparing can The brand-new biological base material electrode detection platform of degraded.
As shown in Fig. 2 the flexible biological electrode of the substrate detection platform of the embodiment of the present invention mainly by:Identification molecule 1, electronics Transfer Medium 2, carbon electrode 3, biomaterial 4 are constituted.
Carbon electrode 3 is printed with biological base material 4, one end of carbon electrode 3 is placed with electron transfer mediator 2, electronics Identification molecular layer 1 is placed with Transfer Medium 2.
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1:
(1)With chitosan material as substrate, carbon electrode is prepared by a step screen printing technique, and move into carry out in baking oven it is solid Change, obtain brand-new chitosan biological base material carbon electrode;
(2)200 mMs per liter of potassium ferricyanide solution is prepared, the solution of 2 ~ 5 μ L is fixed on into carbon electrodes, and be placed on In 25 DEG C ~ 30 DEG C of baking oven, preserve 10 ~ 30 minutes;
(3)It is the glucose oxidase of 10 K international units by activity, allocates the carboxymethylcellulose calcium containing 0.05 gram per liter into In the phosphate buffer of 50 mMs per liter of sodium, the solution of 2 ~ 5 μ L is fixed on into carbon electrodes, and is placed on 25 DEG C ~ 30 DEG C Baking oven in, preserve 10 ~ 30 minutes, prepare detection glucose flexible chitosan biological electrode of the substrate test strip.
Embodiment 2:
(1)With agar material as substrate, carbon electrode is prepared by a step screen printing technique, and moves into baking oven and solidified, Obtain brand-new agar biological base material carbon electrode;
(2)50 mMs per liter of methyl solution of ferrocene is prepared, the solution of 20 ~ 50 μ L is fixed on into carbon electrodes, and put In 25 DEG C ~ 30 DEG C of baking oven, preserve 10 ~ 30 minutes;
(3)It is the cholesterol oxidase of 10 K international units by activity, allocates the carboxymethylcellulose calcium containing 0.05 gram per liter into In the phosphate buffer of 50 mMs per liter of sodium, the solution of 20 ~ 50 μ L is fixed on into carbon electrodes, and is placed on 25 DEG C ~ 30 DEG C baking oven in, preserve 10 ~ 30 minutes, prepare the flexible agar biological base material electrode detection test piece of cholesterol detection.
The schematic diagram of prepared brand-new flexible biological electrode of the substrate test strip, as shown in Figure 2.
The application effect of the present invention is explained in detail with reference to experiment.
(1)By the brand-new flexible biological electrode of the substrate detection platform for preparing, by the electrochemical workstations of CHI 400 profit The performance of biological base material electrode detection platform is analyzed with cyclic voltammetry, as shown in Figure 3.Its result explanation biological base material electrode inspection The electrochemical reaction for surveying platform is mainly limited by granule surface contral, further calculates its Apparent electron transfer rate constant for 4.49 ×10-3, larger electron transfer rate constant shows that prepared flexible biological electrode of the substrate detection platform has excellent electricity Chemical property.
(2)By the flexible biological electrode of the substrate test strip of the brand-new detection glucose for preparing, variable concentrations are added dropwise Glucose solution in the working region of biological base material electrode detection test piece, timing is utilized by the electrochemical workstations of CHI 400 Current method detects the relation between response current and concentration of glucose, as shown in Figure 4.Its result explanation has higher sensitivity (0.97 μA cm-2), and brand-new flexible biological electrode of the substrate test strip for detect glucose when with shorter Detection time(Less than 40 s), and less otherness(Relative standard deviation is less than 2.41 %, N=3).
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (9)

1. a kind of flexible electrode based on biocompatible materials, it is characterised in that described based on the soft of biocompatible materials Property electrode prepares carbon electrode with degradable biological material as substrate by screen printing technique;
It can be any one in shitosan, agar, the Biodegradable polymer material of collagen that the biomaterial is Kind, two or three of mixing;Any two or three of mixing according to quality in the shitosan, agar, collagen The ratio of percentage each component is 10% ~ 90%.
2. the biological base material electrode detection that prepared by a kind of flexible electrode by described in claim 1 based on biocompatible materials is put down Platform.
3. biological base material electrode detection platform as claimed in claim 2, it is characterised in that the biological base material electrode detection is put down Platform is respectively from top to bottom:Identification molecular layer, electron transfer mediator layer, carbon electrode layer, layer of biological material.
4. biological base material electrode detection platform as claimed in claim 3, it is characterised in that the electron transfer mediator layer is iron Potassium cyanide, methyl ferrocene, methylene blue or 1,4-benzoquinone.
5. biological base material electrode detection platform as claimed in claim 3, it is characterised in that the identification molecular layer is enzyme, is resisted Body, DNA, aptamers or cell.
6. a kind of preparation method of biological base material electrode detection platform as claimed in claim 2, it is characterised in that the biology The preparation method of electrode of the substrate detection platform includes:
Step one, in biomaterial substrate carbon electrode is printed with, and by screen printing technique carbon electrode is printed, and moves into baking oven In solidified, obtain brand-new biological base material carbon electrode;
Step 2, prepares electron transfer mediator solution, and is fixed on the working region of carbon electrodes;
Step 3, identification molecule is allocated into phosphate buffer, and is fixed in the working region of electrode surface, is prepared Brand-new biological base material electrode detection platform.
7. what prepared by a kind of flexible electrode by described in claim 1 based on biocompatible materials can for detect glucose Degraded flexible biological electrode of the substrate test strip.
8. the flexible artificial skin electrode inspection that prepared by a kind of flexible electrode by described in claim 1 based on biocompatible materials Survey platform.
9. the wearable electrode detection that prepared by a kind of flexible electrode by described in claim 1 based on biocompatible materials is put down Platform.
CN201611003241.7A 2016-11-15 2016-11-15 Flexible electrode based on biocompatible materials, preparation method of flexible electrode and application Pending CN106645320A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108593719A (en) * 2018-06-26 2018-09-28 浙江大学 A kind of immunosensor based on flexible electrode
WO2019062326A1 (en) * 2017-09-29 2019-04-04 清华大学 Ultra-thin, skin-like flexible glucose measuring sensor and manufacturing method thereof

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CN103448308A (en) * 2013-09-18 2013-12-18 电子科技大学 Biodegradable flexible conductive base plate and preparation method thereof
CN104941705A (en) * 2015-06-30 2015-09-30 华南师范大学 Three-carbon electrode electrochemiluminescence base fabric micro-fluidic chip and preparation method and application thereof
CN105004781A (en) * 2015-07-27 2015-10-28 南通大学 Dopamine detecting method based on paper-base electrochemistry device
CN105606682A (en) * 2016-01-26 2016-05-25 南通大学 Method for determining glucose based on paper-based electrochemical device
CN105954331A (en) * 2016-05-04 2016-09-21 中国科学院大学 Paper-based electrode detection platform for biochemical analysis, and preparation method thereof
CN205607915U (en) * 2016-03-25 2016-09-28 中国科学院重庆绿色智能技术研究院 Glucose sensor based on three -dimensional graphite alkene

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013036617A1 (en) * 2011-09-06 2013-03-14 President And Fellows Of Harvard College Microfluidic devices for multiplexed electrochemical detection
CN102920465A (en) * 2012-10-26 2013-02-13 浙江大学 Glucose sensor
CN103448308A (en) * 2013-09-18 2013-12-18 电子科技大学 Biodegradable flexible conductive base plate and preparation method thereof
CN104941705A (en) * 2015-06-30 2015-09-30 华南师范大学 Three-carbon electrode electrochemiluminescence base fabric micro-fluidic chip and preparation method and application thereof
CN105004781A (en) * 2015-07-27 2015-10-28 南通大学 Dopamine detecting method based on paper-base electrochemistry device
CN105606682A (en) * 2016-01-26 2016-05-25 南通大学 Method for determining glucose based on paper-based electrochemical device
CN205607915U (en) * 2016-03-25 2016-09-28 中国科学院重庆绿色智能技术研究院 Glucose sensor based on three -dimensional graphite alkene
CN105954331A (en) * 2016-05-04 2016-09-21 中国科学院大学 Paper-based electrode detection platform for biochemical analysis, and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019062326A1 (en) * 2017-09-29 2019-04-04 清华大学 Ultra-thin, skin-like flexible glucose measuring sensor and manufacturing method thereof
CN108593719A (en) * 2018-06-26 2018-09-28 浙江大学 A kind of immunosensor based on flexible electrode

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Application publication date: 20170510