CN105136890B - A kind of N doped graphenes biosensor - Google Patents
A kind of N doped graphenes biosensor Download PDFInfo
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- CN105136890B CN105136890B CN201510660527.1A CN201510660527A CN105136890B CN 105136890 B CN105136890 B CN 105136890B CN 201510660527 A CN201510660527 A CN 201510660527A CN 105136890 B CN105136890 B CN 105136890B
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Abstract
Include insulating properties bottom plate with three-electrode system, insulating layer, the reaction cavity formed around three-electrode system, the reaction reagent layer being equipped in reaction cavity and the coating covered on reaction cavity the invention discloses a kind of N doped graphenes biosensor；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode is the platinum electrode of N doped graphenes modification.N doped graphenes biosensor proposed by the present invention, stablizes, high sensitivity.
Description
Technical field
The present invention relates to biosensor technology field more particularly to a kind of N doped graphenes biosensors.
Background technology
Biosensor is to utilize biological substance (such as enzyme, protein, DNA, antibody, antigen, biomembrane, microorganism, cell
Deng) it is used as recognition component, biochemical reaction is transformed into quantitative physics, chemical signal, thus allows for living matter and change
Learn the device of substance detection and monitoring, it have at low cost, easy to operate, high sensitivity, the good, fast response time of selectivity, can
The advantages that for real-time and field assay.In biology, medicine, chemistry, food, industrial production, environmental monitoring and national security etc.
There is important application value in subject and field.
Currently, scientists are to graphene in nano electron device, low temperature superconducting material, ultracapacitor, micro-
The application of strainer and sensor etc. has made extensive and intensive studies.In numerous application studies of graphene, by it
It is the hot spot direction just risen in recent years applied to building for biosensor.Current existing graphene bio-sensing
There are poorly conductive, the undesirable defects of analytical performance for device.
Invention content
The purpose of the present invention is to solve disadvantages existing in the prior art, and a kind of N doped graphenes life proposed
Object sensor, stablizes, high sensitivity.
To achieve the goals above, present invention employs following technical solutions：
A kind of N doped graphenes biosensor includes insulating properties bottom plate, insulating layer, three electricity with three-electrode system
The covering covered in the reaction reagent layer and reaction cavity being equipped in the reaction cavity that is formed around electrode systems, reaction cavity
Layer；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode is that N doped graphenes are repaiied
The platinum electrode of the platinum electrode of decorations, the N doped graphenes modification is prepared according to following technique：
S1, by weight 100-200 parts of mass fractions be 40-50% graphene oxide solution in 120-150 is added
Part Tris reagents simultaneously stir evenly, and adjust after pH value is 7-8 and 20-50 parts of dopamines are added, be stirred to react 10-20h, reaction terminates
10-15min is centrifuged with the rotating speed of 8000-10000r/min afterwards, is dried in vacuo after being washed with deionized, then in argon gas
It carries out being thermally treated resulting in N doped graphenes under protection, wherein the temperature of heat treatment is 900-1000 DEG C, and the time of heat treatment is
0.5-1.5h；
S2, the solution that N doped graphene ultrasonic disperses are formed to a concentration of 0.001-0.01mg/mL in deionized water,
2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles is added, adjusts a concentration of of 2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles
0.2-0.8mol/L immerses platinum electrode, and then the electro-deposition 50-100s under the current potential of -0.9~-1.2V, is washed with deionized water
It washs, drying at room temperature obtains the platinum electrode of the N doped graphenes modification.
Preferably, the reaction reagent layer includes graphene, acetylcholinesterase and N-Methyl pyrrolidone.
Preferably, described is saturated calomel electrode to electrode.
Preferably, in S1, the temperature of heat treatment is 950-980 DEG C, and the time of heat treatment is 1-1.3h.
In N doped graphenes biosensor of the present invention, select the platinum electrode that N doped graphites are modified for work electricity
Pole avoids the reunion of graphene because surface is covered with dopamine in N doped graphenes, so as to get graphene have big
Specific surface area and meso-hole structure, are deposited onto working electrode surface, are evenly distributed, and density is controllable, are used as working electrode
Obtained biosensor stability is good, the high sensitivity of detection.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1
A kind of N doped graphenes biosensor includes insulating properties bottom plate, insulating layer, three electricity with three-electrode system
The covering covered in the reaction reagent layer and reaction cavity being equipped in the reaction cavity that is formed around electrode systems, reaction cavity
Layer；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode is that N doped graphenes are repaiied
The platinum electrode of the platinum electrode of decorations, the N doped graphenes modification is prepared according to following technique：
S1, by weight 100 parts of mass fractions be 50% graphene oxide solution in be added 120 parts of Tris reagents simultaneously
It stirs evenly, adjusts after pH value is 8 and 20 parts of dopamines are added, 20h is stirred to react, after reaction with the rotating speed of 8000r/min
15min is centrifuged, is dried in vacuo after being washed with deionized, then carries out being thermally treated resulting in N doping stones under protection of argon gas
Black alkene, wherein the temperature of heat treatment is 900 DEG C, and the time of heat treatment is 1.5h；
S2, the solution that N doped graphene ultrasonic disperses are formed to a concentration of 0.001mg/mL in deionized water are added 2,
5- bis- (2- thiophene) -1- para Toluic Acid pyrroles adjusts a concentration of 0.8mol/ of 2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles
L immerses platinum electrode, and then the electro-deposition 100s under the current potential of -0.9V, is washed with deionized, and drying at room temperature obtains the N and mixes
The platinum electrode of miscellaneous graphene modified.
Wherein, the reaction reagent layer includes graphene, acetylcholinesterase and N-Methyl pyrrolidone；It is described to electrode
For saturated calomel electrode.
Embodiment 2
A kind of N doped graphenes biosensor includes insulating properties bottom plate, insulating layer, three electricity with three-electrode system
The covering covered in the reaction reagent layer and reaction cavity being equipped in the reaction cavity that is formed around electrode systems, reaction cavity
Layer；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode is that N doped graphenes are repaiied
The platinum electrode of the platinum electrode of decorations, the N doped graphenes modification is prepared according to following technique：
S1, by weight 200 parts of mass fractions be 40% graphene oxide solution in be added 150 parts of Tris reagents simultaneously
It stirs evenly, adjusts after pH value is 7 and 50 parts of dopamines are added, 10h is stirred to react, after reaction with the rotating speed of 10000r/min
10min is centrifuged, is dried in vacuo after being washed with deionized, then carries out being thermally treated resulting in N doping stones under protection of argon gas
Black alkene, wherein the temperature of heat treatment is 1000 DEG C, and the time of heat treatment is 0.5h；
S2, the solution that N doped graphene ultrasonic disperses are formed to a concentration of 0.01mg/mL in deionized water are added 2,
5- bis- (2- thiophene) -1- para Toluic Acid pyrroles adjusts a concentration of 0.2mol/ of 2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles
L immerses platinum electrode, and then the electro-deposition 50s under the current potential of -1.2V, is washed with deionized, and drying at room temperature obtains the N and mixes
The platinum electrode of miscellaneous graphene modified.
Wherein, the reaction reagent layer includes graphene, acetylcholinesterase and N-Methyl pyrrolidone；It is described to electrode
For saturated calomel electrode.
Embodiment 3
A kind of N doped graphenes biosensor includes insulating properties bottom plate, insulating layer, three electricity with three-electrode system
The covering covered in the reaction reagent layer and reaction cavity being equipped in the reaction cavity that is formed around electrode systems, reaction cavity
Layer；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode is that N doped graphenes are repaiied
The platinum electrode of the platinum electrode of decorations, the N doped graphenes modification is prepared according to following technique：
S1, by weight 150 parts of mass fractions be 46% graphene oxide solution in be added 130 parts of Tris reagents simultaneously
It stirs evenly, adjusts after pH value is 8 and 40 parts of dopamines are added, 16h is stirred to react, after reaction with the rotating speed of 9000r/min
12min is centrifuged, is dried in vacuo after being washed with deionized, then carries out being thermally treated resulting in N doping stones under protection of argon gas
Black alkene, wherein the temperature of heat treatment is 950 DEG C, and the time of heat treatment is 1h；
S2, the solution that N doped graphene ultrasonic disperses are formed to a concentration of 0.005mg/mL in deionized water are added 2,
5- bis- (2- thiophene) -1- para Toluic Acid pyrroles adjusts a concentration of 0.5mol/ of 2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles
L immerses platinum electrode, and then the electro-deposition 70s under the current potential of -1V, is washed with deionized, and drying at room temperature obtains the N doping
The platinum electrode of graphene modified.
Wherein, the reaction reagent layer includes graphene, acetylcholinesterase and N-Methyl pyrrolidone；It is described to electrode
For saturated calomel electrode.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of N doped graphenes biosensor, which is characterized in that include insulating properties bottom plate with three-electrode system, absolutely
The reaction reagent layer and reaction cavity overlying being equipped in the reaction cavity that is formed around edge layer, three-electrode system, reaction cavity
The coating of lid；The three-electrode system is formed by reference electrode, working electrode and to electrode, and the working electrode adulterates for N
The platinum electrode of the platinum electrode of graphene modified, the N doped graphenes modification is prepared according to following technique：
S1,120-150 parts are added in the graphene oxide solution that 100-200 parts of mass fractions are 40-50% by weight
Tris reagents simultaneously stir evenly, and adjust after pH value is 7-8 and 20-50 parts of dopamines are added, be stirred to react 10-20h, after reaction
10-15min is centrifuged with the rotating speed of 8000-10000r/min, is dried in vacuo after being washed with deionized, is then protected in argon gas
It carries out being thermally treated resulting in N doped graphenes under shield, wherein the temperature of heat treatment is 900-1000 DEG C, and the time of heat treatment is
0.5-1.5h；
S2, the solution that N doped graphene ultrasonic disperses are formed to a concentration of 0.001-0.01mg/mL in deionized water are added
2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles adjust a concentration of 0.2- of 2,5- bis- (2- thiophene) -1- para Toluic Acid pyrroles
0.8mol/L immerses platinum electrode, and then the electro-deposition 50-100s under the current potential of -0.9~-1.2V, is washed with deionized, room
Temperature is dried to obtain the platinum electrode of the N doped graphenes modification.
2. N doped graphenes biosensor according to claim 1, which is characterized in that the reaction reagent layer includes stone
Black alkene, acetylcholinesterase and N-Methyl pyrrolidone.
3. N doped graphenes biosensor according to claim 1, which is characterized in that described is saturation calomel to electrode
Electrode.
4. N doped graphenes biosensor according to claim 1, which is characterized in that in S1, the temperature of heat treatment is
950-980 DEG C, the time of heat treatment is 1-1.3h.
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| CN101101273A (en) * | 2007-06-29 | 2008-01-09 | 浙江大学 | Carbon nano tube modified blood sugar biosensor |
| CN102520038A (en) * | 2011-12-16 | 2012-06-27 | 江南大学 | Method for preparing graphene biosensor |
| CN103601181A (en) * | 2013-12-04 | 2014-02-26 | 南京大学扬州化学化工研究院 | Method for preparing nitrogen-doped graphene with polydopamine as raw material |
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| KR101159012B1 (en) * | 2010-11-18 | 2012-06-21 | 경희대학교 산학협력단 | Electrode for electrochemical biosensor and biosensor including the same |
| US9678036B2 (en) * | 2013-03-15 | 2017-06-13 | The Regents Of The University Of California | Graphene-based gas and bio sensor with high sensitivity and selectivity |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101273A (en) * | 2007-06-29 | 2008-01-09 | 浙江大学 | Carbon nano tube modified blood sugar biosensor |
| CN102520038A (en) * | 2011-12-16 | 2012-06-27 | 江南大学 | Method for preparing graphene biosensor |
| CN103601181A (en) * | 2013-12-04 | 2014-02-26 | 南京大学扬州化学化工研究院 | Method for preparing nitrogen-doped graphene with polydopamine as raw material |
Non-Patent Citations (1)
| Title |
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| 氮掺杂石墨烯和碳化钼/石墨烯复合纳米材料的电催化性能研究;王平;《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》;20141015(第10期);第31-34页 * |
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