CN104977343B - A kind of high performance biosensors based on graphene/mesoporous carbon nano-composite material and preparation method thereof - Google Patents
A kind of high performance biosensors based on graphene/mesoporous carbon nano-composite material and preparation method thereof Download PDFInfo
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- CN104977343B CN104977343B CN201510437055.3A CN201510437055A CN104977343B CN 104977343 B CN104977343 B CN 104977343B CN 201510437055 A CN201510437055 A CN 201510437055A CN 104977343 B CN104977343 B CN 104977343B
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
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Abstract
The present invention provides a kind of based on graphene/mesoporous carbon nano-composite material biology sensor and preparation method thereof.The present invention includes preparing graphene/mesoporous carbon nano-composite material using hydrothermal synthesis method, as adsorptive enzyme support material；Using bio-sensing and electrochemical principle, Test paper is made by the method for being combined silk screen and ink jet printing, silk-screen printing is used to print conducting wire, using non-contacting spraying method by sensitive biological element spray printing to electrode support substrate, the wherein quantity for spray of sprayed on material and spray area can control.Nano combined carrier material is in the grown mesoporous carbon in the two sides of graphene sheet layer, graphene/mesoporous carbon composite material is made, as carrier enzyme immobilization, physical mixed is carried out with biological enzyme solutions, modified by ink-jet printer spray printing onto glass-carbon electrode, quick, efficient detection for blood glucose.
Description
Technical field
The invention belongs to the multi-crossed disciplines such as printed electronics, nano material technology, biotechnology field, and in particular to
A kind of high performance biosensors based on graphene/mesoporous carbon nano-composite material and preparation method thereof.
Background technology
Diabetes turn into Community health's problem, global diabetes morbidity rapid development, and diabetes have become
The chronic disease of the third-largest serious threat human health after tumour, cardiovascular pathological changes.Oneself is super by current global diabetic
1.2 hundred million people are crossed, China patient numbers occupy the second in the world, and oneself breaks through 20,000,000.According to the World Health Organization, it is expected that by 2025, entirely
Ball maturity-onset diabetes patient numbers will increase to 300,000,000, and diabetes mellitus in China patient numbers are up to 40,000,000, sugar in coming few decades
Urine disease will be a Chinese serious public health problem.
In modern medical service detection field, detection immediately is quickly grown, and the development of the technology causes patient at home with regard to energy
Carry out self-examination.Glucose biological sensor can be directly to whole blood test and without pre-processing, because of carrying side to blood
Just, high sensitivity, selectivity is good, detection speed is fast, simple to operate and system has the characteristics that intelligent, average family can be entered
Carry out at any time and long-term monitoring, there is good prospect to blood.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of height based on graphene/mesoporous carbon nano-composite material
Imitate biology sensor and preparation method thereof.The drawbacks of graphene/mesoporous carbon nano-composite material can overcome general nano material is high
Effect keeps the activity of enzyme and can carry out the quick transmission of electronics, and with reference to ink-jet technology, the biology sensor of preparation is with reference to supporting
Instrument can quickly and easily obtain test result, and preparation method is simple, facilitate post-production and encapsulation, be advantageous to scale metaplasia
Production.
Technical problem solved by the invention can be realized using following technical scheme.
A kind of biology sensor for detecting glucose, by flexible substrates, print working electrode on a flexible substrate and to electricity
Pole forms, and the working electrode is a kind of bilayer conductive film, biology enzyme electrically conductive ink by water-soluble conducting ink layer and thereon
Composition, described biology enzyme electrically conductive ink is by graphene/mesoporous carbon nano-composite material, glucose oxidase and Nafion film forming
Material forms.
The flexible substrates are using the high polymeric material of a kind of good toughness, insulativity, such as polyvinyl chloride, polyester or poly- carbonic acid
Ester.
Above-mentioned biology sensor, biology enzyme electrically conductive ink is coated with working electrode.Glucose response, and can be catalyzed
Adsorptive enzyme simultaneously can carry out swift electron transmission between enzymic catalytic reaction center and electrode, so form a circuit loop, instead
At once according to the height of the concentration of glucose in blood, correspondingly sized current signal is produced, and detected and read by corresponding tester
Go out.
A kind of biology sensor preparation method based on graphene/mesoporous carbon nano-composite material, it comprises the following steps：
1）By conductive black, graphite, water-based acrylic resin, deionized water, 25 ~ 28wt% ammoniacal liquor with 10:5:15:15:3
Mass ratio be sufficiently mixed and uniformly prepare water-soluble conducting ink, it is standby；
2）The metal of 200-400 mesh numbers or nylon polyesters material web are fixed on square light-weight metal framework, dark
Coat photoresists, drying for standby in interior；
3）It is placed on photoresists by the working electrode of computer drawing and to electrode negative film, is exposed under 20-40 watts of ultraviolet
Light 15-30 minutes, the unhardened photoresists covered by electrode negative film are washed with giant, screen template is formed after drying；
4）It will be installed on working electrode and to the screen template of electrode pattern on screen process press, using waterborne conductive
Ink prints working electrode, to electrode；
5）Rate activity is dissolved in pH7.0 phosphate buffer for >=150u/mg glucose oxidase and is configured to concentration
For 10mg/ml enzyme solutions, it is standby fully to shelve 0 DEG C of refrigerator after dissolving；
6）Using graphene/mesoporous carbon nano-composite material as carrier material, it is added in enzyme solutions, mix 10~
36h, it is standby for adsorbing glucose oxidase；
7）The Nafion filmogen solution that mass fraction is 0.5% is prepared, adds step 6）In obtained mixed solution,
30min is mixed, biology enzyme electrically conductive ink is made, is then printed onto working electrode surface by the way of spraying, at room temperature
Immobilized and electrode the modification of enzyme can be completed by drying 24h, and biology sensor is made.
Such scheme step 6）The preparation of middle graphene/mesoporous carbon nano-composite material concretely comprises the following steps：
Take 1.5~2g molecular guide agent be dissolved in 10~30ml deionized water mix 10~30min, add 1~
2ml concentration is that 1M HCl continues to stir；30~50mg graphene and 1.5~2g beta-schardinger dextrin are sequentially added, is stirred
0.5~1h, mixed liquor is then transferred in reactor 24~36h of heat treatment reaction at 120~150 DEG C, finally in tubular type
In stove under the protection of nitrogen, 10 DEG C/min programming rate is to reacting 3~5h at 700~800 DEG C, you can nano combined material
Material.
The preparation of the graphene, using cheap electrically conductive graphite raw material, using electrophoresis, by adjusting electrophoresis
The composition of liquid, pH value, applied voltage value etc., separating high-purity high conductivity few layer (<10 layers) graphene.Characterized in that,
Electrophoretic voltage is arranged to 60-100V；The graphene refers to single-layer graphene, few layer graphene（＜ 10）Or their mixing
It is any in thing.
The present invention does conducting effect, so as to reduce the requirement of technique making, silk-screen using silk-screen printing printing conducting wire
Material and screen printing device special need not be processed, and can be obtained by commercially available channel, cost is very low；Carried using electrophoresis from graphite
Few layer of graphite for preparing good conductivity is taken, simple and easy, raw material are easy to get, and cost is relatively low；Prepared using hydrothermal synthesis method and compare table
Area is big, graphene/mesoporous carbon nano-composite material of good biocompatibility, good conductivity, not only can be with immobilized grape glycosyloxy
Change enzyme, while modify to transmission of the electronics between enzyme active center and electrode is accelerated on electrode, increase the sensitive of sensor
Degree；Using the quantity for spray and area of spraying printing technology control biological sensitive materials, make the precision of final products and repeated
Ensured to abundant.
Beneficial effects of the present invention are：
1）The method being combined using silk-screen printing and spraying printing, can not only simplify silk-screen printing technique process, reduce
Cost, and can eliminate adverse effect of the composite filament India side formula to biological sensitive materials-enzyme, and the mode of printing of spraying can be controlled effectively
The quantity for spray and spray area of biological sensitive materials-enzyme processed, whole technological operation is simple and easy, and cost is cheap, can be advised greatly
Mould produces；
2）Electrophoresis goes out few layer graphene from graphite cheap and easy to get, with the existing method ratio method letter for preparing graphene
Single, cost is low, and obtained graphene conductive performance is good；
3）Graphene/mesoporous the carbon nano-composite material prepared using hydro-thermal method, has good biocompatibility, porous
The advantages such as property and specific surface area are big are advantageous to the immobilized of enzyme, and the interface resistance of composite is small, good conductivity, may advantageously facilitate
The transfer of electronics；
4）Using the graphene composite material modified electrode of good conductivity, be advantageous to increase the sensitivity of biology sensor,
Response time and detection range.This invention can be greatly facilitated the detection of Portable household blood sugar concentration.
Brief description of the drawings
Fig. 1 is biology sensor Test paper structure chart prepared by the present invention；
Fig. 2 is biological sensor electrode schematic diagram prepared by the present invention；
Fig. 3 is the preparation flow figure of biological sensor electrode prepared by the present invention；
Fig. 4 is graphene/mesoporous carbon composite material fundamental diagram.
Embodiment
Further illustrated with reference to embodiment.
Embodiment 1
1）Weigh 10g graphite, 5g conductive black, 15g water-based acrylic resin, 15g deionized water, 3g ammonia
Water mixed grinding stirs 1h, prepares water-soluble conducting ink, standby.
2）The metal of 200 mesh or nylon polyesters material are fixed on square light-weight metal framework, Ke is coated in darkroom
Up to photoresists, drying for standby；
3）It is placed in by the working electrode of computer drawing and to electrode negative film on photoresists, exposes 15 under 25 watts of uviol lamps
Minute, the unhardened photoresists covered by electrode negative film are washed with giant, silk-screen template is formed after drying；
4）It will be installed on working electrode and to the screen template of electrode pattern（SYP）On type screen printer, use is water-based
Electrically conductive ink prints working electrode, to electrode；
5）Rate activity is dissolved in pH7.0 phosphate buffer for >=150u/mg glucose oxidase and is configured to concentration
For 10mg/ml enzyme solutions, 0 DEG C of refrigerator fully is shelved after dissolving, it is standby；
6）Prepare few layer graphene：Surfactant, ammonia conduction liquid and water are made into electrolyte, two panels copper by a certain percentage
Piece is wired on the positive and negative electrode of electrophoresis apparatus, and the distance between upper and lower two electrode about 10~15cm, electrophoretic voltage are set
60-100V is set to, is ionized；
7）Prepare graphene/mesoporous carbon composite material：Taking 1.5g molecular guide agent -- triblock copolymer F127 is dissolved in
10min is stirred in 20ml deionized water, the HCl that the concentration for adding 1ml is 1M continues to stir；Sequentially add 30mg right 2
Step 2）The graphene of preparation and 1.5g beta-schardinger dextrin, stir 0.5h.Then mixed liquor is transferred in reactor at 130 DEG C
Lower heat treatment reaction 24h, finally in tube furnace under the protection of nitrogen, 10 DEG C/min programming rate to reacting 3h at 750 DEG C,
It is standby that nano composite material is made.
8）By step 7）The graphene of preparation/mesoporous carbon nano-composite material is added to step 5 as carrier material）Enzyme is molten
In liquid, absorption 10h is mixed；The Nafion filmogen solution that mass fraction is 0.5% will be prepared and be added to obtained mixing
In solution, 30min is mixed, using spraying method by gained mixed solution, is printed onto on working electrode, dries at room temperature
24h can complete immobilized and electrode the modification of enzyme, and the high performance biosensors based on graphene/mesoporous carbon are made.
Embodiment 2
The present embodiment is roughly the same with embodiment 1, and difference is, step 6）Middle electrophoresis is prepared when lacking layer graphene
Impressed DC voltage increases to 100V, and other conditions are constant.
Embodiment 3
The present embodiment is roughly the same with embodiment 1, and difference is, step 7）In in tube furnace calcining heat be raised to
800 DEG C, other conditions are constant.
Embodiment 4
The present embodiment is roughly the same with embodiment 1, and difference is, step 8）In suction of the nano composite material to enzyme
The attached time rises to 24h, and other conditions are constant.
The present invention prepares circuit and naked carbon electrode using the method for silk-screen printing, and low manufacture cost is convenient and easy；Using spray
Ink print mode is printed biology enzyme in the case where can effectively control the amount of sprayed on material and the size of covering
Brush；Two kinds of carbon nanomaterials with high biology enzyme adsorption capacity and high conductivity are combined with each other simultaneously, are advantageous to electronics
Fast transfer, realize the highly sensitive detection of biology sensor.Graphene is modified using the mode of surface direct growth, no
The laminated structure of graphene two dimension and high electric conductivity are only remained, overcomes the difficult point of the high interface resistance of nano composite material,
And solve the problems, such as easily to reunite between graphene sheet layer, while the porous of the mesoporous carbon grown is the preferable of enzyme offer
Biological microenvironment, be advantageous to the immobilized of enzyme.In addition, aperture by regulating and controlling mesoporous carbon etc., which can prepare, is suitable for different scale life
The fixation matrix of thing molecule, heterogeneous electron is promoted to shift and improve the biological electro catalysis performance of immobilized protein, this to be situated between
Hole carbon is valuable in terms of redox protein matter Direct Electrochemistry, while has widened the development way of carbon-based biology sensor
Footpath.
Claims (3)
1. it is a kind of detect glucose biology sensor preparation method, described biology sensor by flexible substrates, be imprinted on it is soft
Property substrate on working electrode and to electrode form, the working electrode is a kind of bilayer conductive film, by water-soluble conducting ink
Layer and thereon biology enzyme electrically conductive ink composition, described biology enzyme electrically conductive ink by graphene/mesoporous carbon nano-composite material,
Glucose oxidase and Nafion filmogens composition；
It is characterized in that comprise the following steps：
1）By conductive black, graphite, water-based acrylic resin, deionized water, 25 ~ 28wt% ammoniacal liquor with 10:5:15:15:3 matter
Amount ratio, which is sufficiently mixed, uniformly prepares water-soluble conducting ink, standby；
2）The metal of 200-400 mesh numbers or nylon polyesters material web are fixed on square light-weight metal framework, in darkroom
Coat photoresists, drying for standby；
3）It is placed in by the working electrode of computer drawing and to electrode negative film on photoresists, exposes 15- under 20-40 watts of ultraviolet
30 minutes, the unhardened photoresists covered by electrode negative film are washed with giant, screen template is formed after drying；
4）It will be installed on working electrode and to the screen template of electrode pattern on screen process press, using water-soluble conducting ink
Print working electrode, to electrode；
5）Rate activity is dissolved in for >=150u/mg glucose oxidase and is configured to concentration in pH7.0 phosphate buffer and is
It is standby that 0 DEG C of refrigerator is shelved after 10mg/ml enzyme solutions, fully dissolving；
6）Using graphene/mesoporous carbon nano-composite material as carrier material, it is added in enzyme solutions, mixes 10~36h,
It is standby for adsorbing glucose oxidase；
7）The Nafion filmogen solution that mass fraction is 0.5% is prepared, adds step 6）In obtained mixed solution, mixing
30min is stirred, biology enzyme electrically conductive ink is made, then working electrode surface is printed onto by the way of spraying, dries at room temperature
24h can complete immobilized and electrode the modification of enzyme, and biology sensor is made.
2. preparation method according to claim 1, it is characterised in that step 6）The middle nano combined material of graphene/mesoporous carbon
The preparation process of material is：
Take 1.5~2g molecular guide agent to be dissolved in 10~30ml deionized water 10~30min of mixing, add 1~2ml's
Concentration is that 1M HCl continues to stir；Sequentially add 30~50mg graphene and 1.5~2g beta-schardinger dextrin, stirring 0.5~
1h, mixed liquor is then transferred in reactor 24~36h of heat treatment reaction at 120~150 DEG C, finally the nitrogen in tube furnace
Under the protection of gas, 10 DEG C/min programming rate is to reacting 3~5h at 700~800 DEG C, you can nano composite material.
3. preparation method according to claim 2, it is characterised in that the graphene uses electrically conductive graphite raw material, adopts
Prepared with electrophoresis method.
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| CN105597803B (en) * | 2015-12-14 | 2017-11-03 | 江南大学 | A kind of mesoporous carbon nitride photocatalyst and preparation method thereof |
| CN105699453A (en) * | 2016-01-24 | 2016-06-22 | 西南大学 | Preparation method and application of ink jet printing plane three-electrode system |
| CN105973962A (en) * | 2016-04-25 | 2016-09-28 | 陈前伟 | Preparation method of glucose sensor based on graphene nano wall |
| CN107966478A (en) * | 2016-10-19 | 2018-04-27 | 华邦电子股份有限公司 | Sensor array, its manufacture method and method for sensing |
| CN107167503B (en) * | 2017-05-27 | 2019-02-19 | 山东农业大学 | A kind of chloramphenicol electrochemical sensor detection method |
| CN111855774A (en) * | 2020-05-19 | 2020-10-30 | 大连理工大学 | Prussian blue-based intelligent wearable enzyme-based biosensor and preparation method and application thereof |
| CN111803087B (en) * | 2020-06-12 | 2021-11-09 | 同济大学 | Organism nondestructive blood sugar detection device and preparation method thereof |
| CN114609204B (en) * | 2022-03-15 | 2023-09-15 | 肇庆学院 | CMK-8 and GNs combined modified electrode, electrochemical sensor and application |
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