CN110376364A - A kind of biosensor and preparation method thereof - Google Patents
A kind of biosensor and preparation method thereof Download PDFInfo
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- CN110376364A CN110376364A CN201910616791.3A CN201910616791A CN110376364A CN 110376364 A CN110376364 A CN 110376364A CN 201910616791 A CN201910616791 A CN 201910616791A CN 110376364 A CN110376364 A CN 110376364A
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- nano
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
Abstract
The present invention provides a kind of biosensors and preparation method thereof, comprising: A, obtains the substrate template that surface has nano-channel array；B, by the one side and a silicon substrate soft combination with nano-channel array of the substrate template, nanochannel arrays are formed with combination；C, in bio-ink of the edge of the nanochannel arrays addition with special biological function group, so that the bio-ink fills up the channel array；D, after to the moisture evaporation in the channel array；The substrate template is removed from the silicon substrate, to form the silicon substrate of nano-wire array of the surface with special biological function group；E, contact conductor is set in the two sides of the nano-wire array；Wherein, the contact conductor contacts setting with the nano-wire array and direction is vertical with the nano-wire array direction.
Description
Technical field
The present invention relates to sensor technical fields more particularly to a kind of biosensor and preparation method thereof.
Background technique
The highly sensitive detection of biomolecule is in disease detection, clinical medicine, environmental monitoring, Pharmaceutical Analysis, field of food
Etc. having wide practical use, nano material has the property completely different with block materials, unique electricity, magnetics, light
It learns, thermal property, provides completely new approach for the detection of biomolecule.
Sensor based on nano-structure array can by nanostructure as sensing unit directly with detection substance phase
Mutually contact improves the performance of sensor by the characteristic of low dimensional and nanometer, have can portable, low in energy consumption and sensitivity it is high etc. special
Point.Nanosecond science and technology field is quickly grown in recent years, and the sensor of all kinds of nanostructures is in industrial production, gas detection, disease
Increasingly important role is played in terms of sick medical diagnosis.
Therefore, the biosensor with nano-structure array is obtained, more Sensitive Detection may be implemented.
But the current method of modifying for carrying out biological function group to sensor is more complicated, therefore needs one kind at present
Biosensor and preparation method thereof.To solve the above problems, realizes that simply and effectively preparation has and directly have biological function
Change the biosensor of the nanowire array structure of group.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of biosensors and preparation method thereof.It realizes simple
Effective preparation has the biosensor for directly having biological nanostructures array.
The application provides a kind of preparation method of biosensor, comprising:
A, the substrate template that surface has nano-channel array is obtained；
B, it by the one side and a silicon substrate soft combination with nano-channel array of the substrate template, is formed and is received with combination
Rice grain pattern channel array；
C, in bio-ink of the edge of the nanochannel arrays addition with special biological function group, so that the life
Object ink fills up the channel array；
D, after to the moisture evaporation in the channel array；The substrate template is removed from the silicon substrate, with
Forming surface has the silicon substrate of nano-wire array of special biological function group；
E, contact conductor is set in the two sides of the nano-wire array；Wherein, the contact conductor and the nanometer linear array
Column contact setting.
By upper, the biosensor of the above-mentioned preparation method preparation of the application can be introduced directly into special biological function group, operate
Simple and repeatability is high.And the above-mentioned manufacturing process of the application will not destroy the activity of biological function group.
Preferably, the size range of the nano-wire array line width is 1nm-100 μm；The ruler of the nano-wire array spacing
Very little range is 1nm-100 μm.
Wherein, the line style of the nano wire in the nano-wire array includes: standard straight line style and serpentine bend shape.
Preferably, the bio-ink with special biological function group are as follows: be mixed with special biological function group
The conductive aqueous solutions of polymers of long-chain molecule；
Wherein, the positive elecrtonegativity of the long-chain molecule with special biological function group and the conducting polymer is opposite.
By upper, the opposite benefit of the positive elecrtonegativity is to advantageously allow the two to be bound to each other to form nano wire.All
Bio-ink with special biological function group obtains within protection scope in the application.
Preferably, the polymer with conductive characteristic is PEDOT:PSS；
The long-chain molecule with special biological function group is PLL-g-OEGx-Biotin.
It, can be in manufacture nanometer by the way that the long-chain molecule for having biotin site to be doped in conducting polymer by upper
It is realized in line process and the biotin site of nano wire is modified.The polymer of the conductive characteristic is not limited to the PEDOT:PSS,
Other conductive substances are also within the scope of protection of this application.The long-chain point with special biological function group
Son is PLL-g-OEGx-Biotin.Long-chain molecule of the others with special biological function group is also in the protection scope of the application
Within, all bio-inks with special biological function group obtain within protection scope in the application.
Preferably, the step A, comprising:
A1, a substrate is obtained；
A2, the upper surface of the substrate is subjected to oxygen plasma treatment, and thermoplastic material mr-I T85 is spin-coated on
The upper surface of the substrate；
A3, surface is provided with to the silicon substrate of nano-wire array as nano-imprint stamp；And by nano-imprint stamp
Being provided with the side of nano-wire array and spin coating has the upper surface of the substrate of thermoplastic material to be bonded, and is put into later to nano impression
It is heated in machine and applies pressure so that the nano-wire array on nano-imprint stamp, which squeezes the surface spin coating, thermoplasticity material
The substrate of material is to form nano-channel in the corresponding part for being extruded recess；
A4, the nano-imprint stamp and the substrate are taken out and separated from marking press, to obtain surface with nanometer
The substrate template of channel array.
By upper, be conducive to obtain a substrate template with nano-channel array.
Preferably, the step A2 further include: it is pre-processed before using nano-imprint stamp, including cleaning and surface
Hydrophobic treatment.
By upper, the cleaning is conducive to remove the most organic matter in its surface and other particles.At the surface hydrophobicity
Reason can form the orderly monomolecular film of 1-2nm thickness on nano-imprint stamp surface, not to the nano impression structure greater than 10nm
It will cause influence, while the antiacid alkali of this monomolecular film, high temperature resistant, the adhesion with polymer can be effectively prevented.
By upper, be conducive to be prepared the electrode that the nano-wire array is acted on after being powered.
Preferably, the upper surface by the substrate carries out oxygen plasma treatment, comprising: to the surface of the substrate
The oxygen stream that the pressure of application is 10mTorr, power 10W, flow velocity 20sccm, time are 15s is to carry out the substrate
Oxygen plasma treatment.
Wherein, the rate by thermoplastic material, the spin coating for being spin-coated on substrate surface be 3000rad/s, spin coating when
Between be 1 minute.
By upper, the upper surface of the substrate is subjected to oxygen plasma treatment, the surface for being conducive to improve the substrate is attached
Put forth effort.Above-mentioned spin coating rate and spin-coating time are conducive to that thermoplastic material is preferably spin-coated on substrate surface.
Preferably, the material of substrate described in step A1 is polydimethylsiloxane.Preferably, the acquisition of the substrate
Mode are as follows:
Liquid PDMS and curing agent are mixed according to specified mass ratio, and toasted 45 minutes at 85 DEG C of heat drier.
By upper, substrate needed for being conducive to acquisition the application.
Preferably, the mass ratio is 10:1~7:1.
By upper, the benefit of aforementioned proportion is to be conducive to preferably form soft or hard suitable required substrate.
The application also provides a kind of biosensor based on above method preparation, comprising:
Silicon substrate,
Nano-wire array is set on the silicon substrate；Wherein, the nano-wire array is by having special biological function group
Bio-ink constitute；
Contact conductor is set to the two sides of the nano-wire array, and contacts setting with the nano-wire array, and described
The direction of contact conductor is vertical with the nano-wire array direction.
Preferably, the contact conductor shape includes: rectangle, circle, triangle, rectangular, rectangle, diamond shape, parallel four
Side shape, ellipse, polygon and combinations thereof.
Wherein, the contact conductor all contacts setting with all nano wires in the nano-wire array
In conclusion the conducting polymer that the biosensor of the above-mentioned preparation method preparation of the application is opposite by two kinds of electrical property
Doping forms the ink that can directly roll into a ball with special biological function, and then using the method preparation structure array of Soft lithograph.Favorably
In being introduced directly into special biological function group, easy to operate and repeated height.And the above-mentioned manufacturing process of the application will not destroy spy
The activity of different biological function group.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method of biosensor provided by the present application；
Fig. 2 is the process that the variation in the form of graphic structure of the preparation method of biosensor provided by the present application indicates
Schematic diagram；
Fig. 3 is the structural schematic diagram of biosensor provided by the present application.
Specific embodiment
Technical solution of the present invention is described in detail referring to each attached drawing.As shown in Figure 1, being provided by the present application
The flow diagram of the preparation method of biosensor；It is illustrated in figure 2 the preparation method of biosensor provided by the present application
The flow diagram that indicates of the variation in the form of graphic structure.
Specifically, the preparation method of biosensor provided by the present application, comprising:
S101 obtains a substrate.Wherein, the material of the substrate is polydimethylsiloxane, used PDMS
Substrate is mixed by liquid PDMS and curing agent according to mass ratio 10:1 ratio, and is toasted 45 minutes at 85 DEG C of heat drier.For
The enabling capabilities for increasing the PDMS substrate are embedded in small sheet glass during manufacturing PDMS substrate.
The upper surface of the substrate is carried out oxygen plasma treatment, and thermoplastic material is spin-coated on substrate table by S102
Face.Corresponding structure is as shown in 210 in Fig. 2, wherein 211 indicate substrate, 212 indicate the thermoplastic material layer of spin coating.
Surface is provided with the silicon substrate of nano-wire array as nano-imprint stamp by S103；On nano-imprint stamp
Nano-wire array uniform parallel arrangement, without apparent flaw.And by the nano-wire array of being provided with of nano-imprint stamp
Side and spin coating have the upper surface of the substrate of thermoplastic material to be bonded, and are put into later and heat into nano marking press and apply pressure
So that the nano-wire array on nano-imprint stamp, which squeezes the surface spin coating, has the substrate of thermoplastic material in corresponding quilt
The part for squeezing recess forms nano-channel.Corresponding structure is as shown in 220 in Fig. 2, wherein 221 indicate nano impression mould
Plate.
Wherein, before to the nano-imprint stamp use, further include it is carried out cleaning and surface hydrophobicity processing it is pre-
Processing.
S104 takes out from marking press and separates the nano-imprint stamp and the substrate, with obtain surface have receive
The substrate template of rice channel array.Corresponding structure is as shown in 230 in Fig. 2, wherein 231 indicate nano-channel array.We
The made PDMS substrate template of method.It is used multiple times, to improve the repeatability of nanowire structure.
S105 passes through one silicon substrate (Si/SiO of oxygen plasma treatment2Substrate)；And the surface had into nano-channel
The substrate template of array and the silicon substrate soft combination, to form nanochannel arrays；Corresponding structure such as 240 institutes in Fig. 2
Show, wherein 241 indicate silicon substrate.Give enough supports and conformal effect.
The bio-ink with special biological function group is added dropwise at the edge of the nanochannel arrays, so that institute in S106
It states bio-ink and fills up the channel array；Wherein, the bio-ink with special biological function group are as follows: be mixed with and have
The conducting polymer aqueous solution of the long-chain molecule in biotin site.Wherein, the long-chain molecule with special biological function group
It is opposite with the positive elecrtonegativity of the conducting polymer.For example, the polymer with conductive characteristic can be PEDOT:PSS；
The long-chain molecule with special biological function group can be PLL-g-OEGx-Biotin；Wherein x=1-100.Wherein, institute
PLL-g-OEGx-Biotin (1mol/L) and PEDOT:PSS (1mol/L) water-soluble polyelectrolyte solution are stated with volume ratio (1:9
~1:7) ratio mixing.By upper, by the way that the long-chain molecule for having biotin site is doped in conducting polymer aqueous solution,
The biotin site modification to nano wire can be realized during manufacturing nano wire.And the PLL-g-OEGx- of aforementioned proportion
Biotin is mixed into PEDOT:PSS solution, will not influence the surface topography of conductive polymer nanometer line, the nano wire of array is still
It is continuous in a big way, not broken；It will not influence the electrology characteristic of conductive polymer nanometer line.
S107, after the moisture evaporation in the channel array；The substrate template is removed from the silicon substrate,
To form the silicon substrate of nano-wire array of the surface with biotin group；Corresponding structure is as shown in 260 in Fig. 2, wherein
261 indicate nano-wire array；262 indicate special biological function group.Wherein, the size range of the nano-wire array line width is
1nm-100μm；The size range of the nano-wire array spacing is 1nm-100 μm.Wherein, the nanometer in the nano-wire array
The line style of line includes: standard straight line style and serpentine bend shape.
Contact conductor is arranged in S108；Wherein, the contact conductor contacted with the nanometer linear array setting and direction with it is described
Nano-wire array direction is vertical.Corresponding structure is as shown in 270 in Fig. 2, wherein 271 indicate contact conductor.The electrode draws
Wire shaped includes: rectangle, circle, triangle, rectangular, rectangle, diamond shape, parallelogram, ellipse, polygon and its group
It closes；Wherein, the contact conductor all contacts setting with all nano wires in the nano-wire array.The contact conductor is used for will
The electric signal of detection exports.In conclusion the biosensor of the above-mentioned preparation method preparation of the application can be introduced directly into special life
Object functional group (such as biotin site), easy to operate and repeated height.And the above-mentioned manufacturing process of the application will not destroy spy
The activity of different biological function group.
Embodiment two
As shown in figure 3, the application also provides a kind of biosensor of method preparation based on embodiment one, comprising:
Silicon substrate 241,
Nano-wire array 261 is set on the silicon substrate 241；Wherein, the nano-wire array 261 is by with special
The bio-ink of biological function group 262 is constituted.
Contact conductor 271 contacts setting and direction and 261 direction of nano-wire array with the nano-wire array 261
Vertically.Wherein, the shape of the contact conductor can be parallel, interdigitated, it is any it is round, triangle is rectangular, polygon, square
The shapes such as shape, ellipse, parallelogram, diamond shape and combinations thereof, the electric signal export that the contact conductor is used to will test.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of preparation method of biosensor characterized by comprising
A, the substrate template that surface has nano-channel array is obtained；
B, by the one side and a silicon substrate soft combination with nano-channel array of the substrate template, it is logical that nanometer is formed with combination
Channel array；
C, in bio-ink of the edge of the nanochannel arrays addition with special biological function group, so that the biology ink
Water fills up the channel array；
D, after to the moisture evaporation in the channel array；The substrate template is removed from the silicon substrate, to be formed
Surface has the silicon substrate of the nano-wire array of special biological function group；
E, contact conductor is set in the two sides of the nano-wire array；Wherein, the contact conductor connects with the nano-wire array
Touching setting.
2. preparation method according to claim 1, which is characterized in that the size range of the nano-wire array line width is
1nm-100μm；The size range of the nano-wire array spacing is 1nm-100 μm.
Wherein, the line style of the nano wire in the nano-wire array includes: standard straight line style and serpentine bend shape.
3. the method according to claim 1, wherein the bio-ink with special biological function group are as follows:
It is mixed with the conductive aqueous solutions of polymers of the long-chain molecule with special biological function group；
Wherein, the positive elecrtonegativity of the long-chain molecule with special biological function group and the conducting polymer is opposite.
4. according to the method described in claim 3, it is characterized in that, the polymer with conductive characteristic is PEDOT:PSS；
Wherein, the long-chain molecule with special biological function group is PLL-g-OEGx-Biotin。
5. the method according to claim 1, wherein the step A, comprising:
A1, a substrate is obtained；
A2, the upper surface of the substrate is subjected to oxygen plasma treatment, and thermoplastic material is spin-coated on the upper of the substrate
Surface；
A3, surface is provided with to the silicon substrate of nano-wire array as nano-imprint stamp；And by the setting of nano-imprint stamp
The upper surface for having the side of nano-wire array and spin coating to have the substrate of thermoplastic material is bonded, and is put into later into nano marking press
It heats and applies pressure so that the nano-wire array on nano-imprint stamp, which squeezes the surface spin coating, thermoplastic material
Substrate is to form nano-channel in the corresponding part for being extruded recess；
A4, the nano-imprint stamp and the substrate are taken out and separated from marking press, to obtain surface with nano-channel
The substrate template of array.
6. according to the method described in claim 5, it is characterized in that, the step A2 further include:
It is pre-processed before using nano-imprint stamp, including cleaning and surface hydrophobicity processing.
7. according to the method described in claim 5, it is characterized in that, the upper surface by the substrate carries out oxygen plasma
Processing, comprising:
The oxygen that the pressure applied to the surface of the substrate is 10mTorr, power 10W, flow velocity 20sccm, time are 15s
Air-flow is to carry out oxygen plasma treatment to the substrate.
8. according to the method described in claim 5, it is characterized in that, the material of substrate described in step A1 is dimethyl silicone polymer
PDMS；Wherein, the acquisition modes of the substrate are as follows:
Liquid PDMS and curing agent are mixed according to specified mass ratio, and toasted 45 minutes at 85 DEG C of heat drier.
9. according to the method described in claim 8, it is characterized in that, the mass ratio is 10:1~7:1.
10. a kind of biosensor of the method preparation based on any one of claim 1-9 characterized by comprising
Silicon substrate,
Nano-wire array is set on the silicon substrate；Wherein, the nano-wire array is by the life with special biological function group
Object ink is constituted；
Contact conductor is set to the two sides of the nano-wire array, and contacts setting with the nano-wire array.
11. biosensor according to claim 10, which is characterized in that the contact conductor shape include: rectangle,
Circle, triangle, rectangle, diamond shape, polygon and combinations thereof；
Wherein, the contact conductor is all connected with each nano wire in the nano-wire array.
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Cited By (1)
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| CN111924799A (en) * | 2020-07-02 | 2020-11-13 | 天津大学 | Preparation method of metal oxide nanowire array and nanowire array prepared by same |
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