CN108181366A - Using titanium dioxide-molybdenum disulfide-gold trielement composite material as the construction method of the optical electro-chemistry aptamer sensor of stent - Google Patents
Using titanium dioxide-molybdenum disulfide-gold trielement composite material as the construction method of the optical electro-chemistry aptamer sensor of stent Download PDFInfo
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- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- 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
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
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- 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
- G01N27/307—Disposable laminated or multilayered electrodes
Abstract
The present invention relates to a kind of using titanium dioxide molybdenum disulfide gold trielement composite material as the construction method of the optical electro-chemistry aptamer sensor of stent, specially：TiO is first prepared using sol-gal process2Ball template is then prepared into shaggy anatase TiO2Ball, then using hydro-thermal method by MoS2Nanometer sheet is closely supported on TiO2The surface of nanosphere forms TiO2‑MoS2Heterojunction structure；Finally by trisodium citrate reduction method by its surface of Au nanoparticle depositions, TiO is formed2‑MoS2Au tri compound nano materials.The trielement composite material has great specific surface area and good biocompatibility, considerably increases the load capacity of biomolecule, also possesses excellent electric conductivity and stronger electricity conversion etc., therefore is adapted to structure biosensor.DNA aptamers are fixed on TiO2‑MoS2Au trielement composite materials surface, the optical electro-chemistry aptamer sensor that research has shown that prepare in this way can quickly detect kanamycins, and sensitivity is higher, the range of linearity is larger, detection limit is relatively low.
Description
Technical field
The invention belongs to optical electro-chemistry aptamer sensor constructing technology fields, and in particular to one kind is with TiO2-MoS2-Au
Construction method of the trielement composite material for the optical electro-chemistry aptamers biosensor of load bracket, the optical electro-chemistry aptamers pass
Sensor can be used for detecting kanamycins.
Background technology
For antibiotic as a kind of anti-infectives, main function is to inhibit bacteria infection, kills pathogenic bacteria or other
Active material, be widely used in the fields such as medicine, agriculture and forestry, aquatic products industry and animal husbandry.Antibiotics are various, kanamycins
It is the common basic amine group glycoside antibiotic of one of which, with water solubility is strong, has a broad antifungal spectrum, bactericidal effect are apparent, price
The features such as cheap and medication facilitates.But it is unreasonable drug resistance can be caused to enhance using antibiotic, endotoxic generation and residual
It stays in food-borne animal body, is then enriched in human body by biological cycle system, cause the damage that human body is different degrees of, institute
Harmful effect either can all be generated to food quality or human health with the residual of kanamycins.To ensure human health,
Countries in the world government organs are to the maximum allowable residue limits of the yapamicin relict in milk（MRL）Regulation requirement has been done,
European Union perform more stringent standard, it is specified that in cow's milk kanamycins the μ gkg of MRL≤100-1, China is defined as 200 μ
g·kg-1.Therefore, easy to operate, portable, specific good, high sensitivity and economical and practical detection method, for adding are established
The residual quantity control of kanamycins, improves foodsafety and is of great significance in strong animal derived product.
The present invention establishes the optical electro-chemistry detection based on aptamer for the qualitative and quantitative analysis of kanamycins
Method.Aptamer (aptamer) is by SELEX technologies（The aglucon phyletic evolution technology of index concentration）Screen obtained widow
Nucleotide sequence.These sequences can be that DNA can also be RNA, can be combined with high specificity and affinity with target molecule,
Aptamer has many advantages, such as to be easy to synthesize and modify in vitro simultaneously, target cell-range is wide, chemical property stabilization.And by core
The detection method that sour aptamers are used to build Photoelectrochemistrbiosensor biosensor is a kind of analysis side developed rapidly in recent years
Method, basic testing principle are that the generation reacted based on bio-identification in sensing system can cause to detect the variation of signal.The party
Method is because of its high sensitivity, favorable reproducibility, equipment are simple and it is at low cost etc. unique the advantages of and its it is latent in future biological sensing
Power receives more and more attention, and is also had made great progress in detection performance and bio-sensing application etc..In structure light
During electrochemica biological sensor, it is effective that the photo activating material with high photoelectricity conversion performance is often used as biological compatibility carrier
Fixing biological molecules.Wherein, TiO2Due to good photoelectric conversion efficiency, bigger serface, superior bio compatibility, more
The advantages that kind nano shape, easily prepared, chemical and engineering properties are stablized, and obtained in photoelectric sensor field more and more
Application.However, the TiO of Detitanium-ore-type2Energy gap is 3.2 eV, and light absorption range is limited to ultraviolet region（λ<387 nm), this
The utilization rate of sunlight is not only limited, and ultraviolet light is also damaged to a certain extent the biological sample activity in experimentation
Effect.Further, since TiO2Characteristic of semiconductor, electric conductivity is poor, does not meet the requirement of high-performance sensors.Therefore, it is
Overcome these defects, need using certain methods to TiO2Material is modified, and the present invention mainly uses semiconductors coupling method
To widen TiO2Light abstraction width, make gained composite material also have notable absorption in visual field；It is deposited simultaneously using gold nano
Method enhances the electric conductivity and biocompatibility of composite material.
Hexagonal crystal system MoS2It is the two-dimensional material with anisotropic class graphene layer structure, passes through model between layers
De Huali is combined, and energy gap is 1.2 ~ 1.8 eV, can absorb large-scale visible ray, and with good electric conductivity etc.
Feature.MoS2It can be with TiO2Heterojunction structure is compounded to form, effectively enhances the transfer of photo-electric charge and separative efficiency, reduction electricity
Son-hole is to compound, enhancing visible absorption, promotion photocatalysis performance.Xiang et al. is by hydro-thermal method by graphene/MoS2
Common modification TiO2Nano particle, it is proposed that a kind of cheap photochemical catalyst without precious metal, and electricity conversion is notable
Raising is arrived.
The advantage of both plurality of advantages based on aptamers and optical electro-chemistry sensor, present invention joint is set up a kind of new
Type yapamicin relict detection method.In the present invention, first using sol-gel method be prepared for smooth surface is smooth, size is uniform, point
Dissipate the good no crystal form TiO of property2Nanometer ball template, then using hydro-thermal method by TiO2Ball template is prepared into shaggy anatase
TiO2Ball not only increases its photoelectrochemical behaviour, and its surface is made to be more easy to adhere to other nano materials；Then in order to enhance
TiO2Visible absorption performance, using hydro-thermal method by MoS2Nanometer sheet is closely supported on TiO2The surface of nanosphere is formed
TiO2-MoS2Heterojunction structure；Finally by trisodium citrate reduction method by Au nanoparticle depositions in TiO2-MoS2Hetero-junctions
Body structure surface forms TiO2-MoS2- Au tri compound nano materials.Wherein Au nano particles and MoS2Nanometer sheet is conducive to carry
High TiO2Electric conductivity and electricity conversion and biocompatibility.Present invention employs X-ray powder diffraction (XRD), scannings
Electron microscope（SEM）, x-ray photoelectron spectroscopy（XPS）, electrochemical impedance（EIS）This ternary is answered etc. different characterization methods
Nano material is closed to be characterized.Then the trielement composite material is scattered in chitosan solution and modified in ITO electrode table
Face, the sulfydryl and trielement composite material surface gold on aptamers surface are combined in a manner of Au-SH keys, and aptamers are modified in electricity
Pole surface, for detecting kanamycins.The present invention overcomes the range of linearity occurred in the prior art is relatively narrow, detection limit it is higher with
And stability it is poor the shortcomings of, yet there are no relevant report.
Invention content
Present invention aims to overcome that prior art defect, provides one kind with TiO2-MoS2- Au trielement composite materials are negative
Carry stent optical electro-chemistry aptamers biosensor construction method, the optical electro-chemistry aptamer sensor can quickly, have
The detection kanamycins of effect, and high sensitivity, the range of linearity are big, detection limit is relatively low.
To achieve the above object, the present invention adopts the following technical scheme that:
One kind is with TiO2-MoS2- Au trielement composite materials are the optical electro-chemistry of stent（PEC）The structure side of aptamer sensor
Method specifically includes following steps：
①TiO2-MoS2The preparation of-Au tri compound nano materials：
TiO2The preparation of nanosphere：Weigh 1.75 g cetylamine HDA, be dispersed in absolute ethyl alcohol, then add in KCl aqueous solutions and
Ultra-pure water adds in isopropyl titanate TIP while agitating, keeps HDA：Ultra-pure water：KCl：Absolute ethyl alcohol：The molar ratio of TIP is
0.5: 5: 5.5×10-3: 236.5: 1.0；Continue to stir 30 min, stand, white precipitate is collected by centrifugation, it is washed, dry
Obtain the smooth TiO in surface2Nanosphere is collected spare；
By the TiO that 0.5 g surfaces are smooth2Nanosphere is dispersed in the mixed solution of absolute ethyl alcohol and ultra-pure water, then at 160 DEG C
90 min of lower holding, are collected by centrifugation precipitation, washed, be dried to obtain anatase TiO2Nanosphere, it is spare；
TiO2-MoS2The preparation of binary composite：By 0.08 g anatases TiO2Nanosphere is dispersed in absolute ethyl alcohol and ultra-pure water
Mixed solution in, then add in 0.35 g sodium molybdates（NaMoO4·2H2O）With 0.52 g thiocarbamides（H2NCSNH2）, after mixing
20 h of hydro-thermal reaction at 220 DEG C, cooled to room temperature after reaction, after gained Dark grey precipitation is washed, it is dry after,
Powder is collected, grinds, is denoted as TiO2-MoS2Binary composite, it is spare；
TiO2-MoS2The preparation of-Au trielement composite materials:By 40 mg TiO2-MoS2Binary composite is dispersed in ultra-pure water
In, add in HAuCl under stirring condition4Aqueous solution, end-capping reagent trisodium citrate aqueous solution and sodium borohydride aqueous solution, in ice-water bath
30 min are stirred, then continue to stand overnight after stirring 30 min at room temperature, are collected by centrifugation precipitation, it is washed, be dried to obtain
TiO2-MoS2- Au trielement composite materials；
2. the preparation of modified electrode:
Take 1. TiO that step prepares2-MoS220 mg of-Au trielement composite materials is dispersed in 1 mL containing 0.2 wt% shells
In the HAc solution of glycan, then measure 25 μ L be added dropwise clean dried ITO electrode surface, be stored in refrigerator, spare, institute
The modified electrode of preparation is denoted as TiO2-MoS2- Au/ITO electrodes；
3. the structure of aptamer sensor：
Measure 25 μ L, 1.5 μM of mercapto-modified DNA adaptations liquid solutions are added dropwise and 2. prepare the dry TiO of gained in step2-
MoS2- Au/ITO electrode surfaces are placed in refrigerator and are incubated 12 h, take out, and 25 μ L are then added dropwise, 3% bovine serum albumin aqueous solution is made
It is ion sealer to get aptamer/TiO2-MoS2- Au/ITO electrodes, as optical electro-chemistry aptamer sensor.
Specifically, step 1. middle preparation TiO2-MoS2During-Au trielement composite materials, 2 mL, concentration 0.01 M are added in
HAuCl4Aqueous solution, 2 mL, 0.01 M of concentration trisodium citrate aqueous solution, 2 mL, the fresh configurations of 0.1 M sodium borohydride water
Solution.
Compared to the prior art, the advantageous effect of the method for the present invention：
The present invention first using sol-gel method be prepared for smooth surface is smooth, size is uniform, good dispersion without crystal form TiO2Nanometer
Ball template；Then hydro-thermal method is used by TiO2Ball template is prepared into shaggy anatase TiO2Ball not only increases its photoelectricity
Chemical property, and its surface is made to be more easy to adhere to other nano materials；Then it is enhancing TiO2Visible absorption performance, use
Hydro-thermal method is by MoS2Nanometer sheet is closely supported on anatase TiO2The surface of nanosphere forms TiO2-MoS2Heterojunction structure；Most
Afterwards by trisodium citrate chemical reduction method by Au nanoparticle depositions in TiO2-MoS2Heterojunction structure surface forms TiO2-
MoS2- Au tri compound nano materials.Wherein MoS2Nanometer sheet is improved significantly due to its great specific surface area to biomolecule
Load capacity, and MoS2Be conducive to improve TiO with Au nano particles2Electric conductivity and electricity conversion and biofacies
Capacitive, so as to improve the sensitivity of the aptamer sensor.Present invention employs X-ray powder diffraction (XRD), scanning electricity
Sub- microscope（SEM）, x-ray photoelectron spectroscopy（XPS）, electrochemical impedance（EIS）Etc. different characterization methods to this tri compound
Nano material is characterized.Then the trielement composite material is scattered in chitosan solution and modified in ITO electrode surface,
The sulfydryl and trielement composite material surface gold on aptamers surface are combined in a manner of Au-SH keys, and aptamers are modified in electrode
Surface, for detecting kanamycins.The present invention overcomes the range of linearity occurred in the prior art is relatively narrow, detection limit it is higher and
The shortcomings of stability is poor yet there are no relevant report.
Description of the drawings：
Fig. 1 is that the SEM of different nano materials schemes, and wherein A and B are respectively without crystal form TiO2Nanosphere and anatase TiO2Nanometer
Ball；C is simple MoS2The SEM figures of nanometer sheet；D is TiO2-MoS2The SEM figures of binary composite；E and F is respectively to deposit Au to receive
TiO after different amplification after rice grain2-MoS2The SEM figures of-Au trielement composite materials；
Fig. 2 is the XRD spectrum of different materials, and wherein a is anatase TiO2Nanosphere；B is MoS2Nanometer sheet；C is TiO2-MoS2
Binary composite nano flower；D is the trielement composite material TiO deposited after Au nano particles2-MoS2- Au nano flowers；
Fig. 3 is TiO2-MoS2The XPS collection of illustrative plates of-Au trielement composite material nano flowers, wherein A are TiO2-MoS2- Au nano flowers
The full spectrograms of XPS;B, C, D, E, F are respectively Ti2p, O1s, the XPS high-resolution collection of illustrative plates of Mo 3d, S 1s and Au 4f；
Fig. 4 is nyquist diagram, wherein a, b, c, and d represents naked ITO electrode, TiO respectively2/ITO、TiO2-MoS2/ITO、
TiO2-MoS2The impedance spectrum of-Au/ITO electrodes, e and f represent aptamer/TiO respectively2-MoS2- Au/ITO electrodes are using
Impedance spectrum before and after BSA sealers；
Fig. 5 is the photocurrent response collection of illustrative plates of different modifying electrode；Wherein a, b, c, d, e represent MoS respectively2/ITO、TiO2/
ITO、TiO2-MoS2/ITO、TiO2-MoS2-Au/ITO、aptamer/TiO2-MoS2The photoelectric current collection of illustrative plates of-Au/ITO electrodes；
Fig. 6 is the optimization for being adapted to bulk concentration；
When Fig. 7 is photocurrent response, alive optimization is applied；
Fig. 8 is the photocurrent response of various concentration kanamycins；
Fig. 9 is photoelectric current with the increased linearity curve of kanamycins concentration；
Figure 10 is the interference that disturbance object measures kanamycins.
Specific embodiment
Technical scheme of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
In following embodiments, used kanamycins and mercapto-modified DNA aptamers (5 '-HS- (CH2)6-
TGG-GGG-TTG-AGG-CTA-AGC-CGA-3 ') it is purchased from raw work bioengineering Shanghai limited company.
Embodiment 1：
One kind is with TiO2Construction method of the nanosphere composite nano materials for the optical electro-chemistry aptamer sensor of load bracket,
Include the following steps：
①TiO2-MoS2The preparation of-Au tri compound nano materials：
Anatase TiO2The preparation of nanosphere:
Weigh 1.75 g cetylamines（HDA）, it is dispersed in by way of stirring in 200 mL absolute ethyl alcohols, after dispersion completely,
The KCl aqueous solutions and 0.51 mL ultra-pure waters of 0.80 mL, 0.1 M is added in, adds in 4.32 mL isopropyl titanates while agitating
（TIP）, that is, keep HDA：Ultra-pure water：KCl：Absolute ethyl alcohol：The molar ratio of TIP is 0.5: 5: 5.5×10-3: 236.5:
1.0.Continue after stirring 30 min, stand 18 h, white precipitate is collected by centrifugation, after being washed with absolute ethyl alcohol, under the conditions of 60 DEG C
Dry 4 h obtain the smooth no crystal form TiO in surface2Nanosphere is collected spare；
The relatively rough anatase TiO in surface in order to obtain2Nanosphere takes 0.5 g no crystal form TiO obtained above2Nanosphere
It is dispersed in the mixed solution of 20 mL absolute ethyl alcohols and 10 mL ultra-pure waters, this mixed solution is transferred to 50 after being completely dispersed
ML is using polytetrafluoroethylene (PTFE) as in the autoclave of liner, precipitation is collected by centrifugation, through anhydrous in 90 min of hydro-thermal reaction at 160 DEG C
Ethyl alcohol washs, dry, obtains anatase TiO2Nanosphere, it is spare；
TiO2Nanosphere-MoS2Nanometer sheet（TiO2-MoS2）The preparation of binary composite：
By 0.08 g anatase TiO obtained above2Nanosphere is dispersed in the mixing of 10 mL absolute ethyl alcohols and 20 mL ultra-pure waters
In solution, 0.35 g sodium molybdates are then added in（NaMoO4·2H2O）With 0.52 g thiocarbamides（H2NCSNH2）, uniformly rear turn to be mixed
50 mL are moved to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, 20 h of hydro-thermal reaction at 220 DEG C.After reaction,
It treats reaction kettle cooled to room temperature, gained Dark grey precipitation is used after using absolute ethyl alcohol, milli-Q water successively, it is true at 60 DEG C
Dry 10 h, collect powder in empty drying box, grind, are denoted as TiO2-MoS2Binary composite, it is spare；
In order to compare, using above-mentioned same method, it is being added without TiO2In the case of nanosphere, simple MoS is prepared2It receives
Rice piece, is denoted as MoS2Nanometer sheet；
TiO2Nanosphere-MoS2Nanometer sheet-Au nano particles（TiO2-MoS2-Au）The preparation of trielement composite material:
By 40 mg TiO2-MoS2Binary composite is dispersed in 40 mL ultra-pure waters, after being uniformly dispersed, in stirring condition
The lower HAuCl for adding in 2 mL, 0.01 M4The end-capping reagent trisodium citrate aqueous solution of 0.01 M of aqueous solution and 2 mL, then 30
The NaBH of the fresh configurations of 2 mL, 0.1 M is added dropwise in min4Aqueous solution（0-4 DEG C of ice-water bath）, 30 are stirred in ice-water bath
Min, then continue to stand overnight after stirring 30 min at room temperature, it centrifuges, collects gained precipitation with successively with absolute ethyl alcohol, ultrapure
After water washing, it is dried overnight in 60 DEG C of vacuum drying chambers, is denoted as TiO2-MoS2- Au trielement composite materials, it is spare；
2. the preparation of modified electrode:
The anatase TiO prepared in weighing step respectively 1.2Nanosphere, MoS2Nanometer sheet, TiO2-MoS2Binary composite wood
Material and TiO2-MoS2Each 20 mg of-Au trielement composite materials is scattered in respectively in HAc solution of 1 mL containing 0.2 wt% chitosans,
20 min of ultrasound are until be completely dispersed.Meanwhile ITO electrode is dried in the air at room temperature respectively with acetone, absolute ethyl alcohol and milli-Q water
It is dry, it is spare.Then the dropwise addition of 25 μ L dispersion liquids is respectively measured with liquid-transfering gun（Modification）In the ITO electrode surface of clean dried, will modify
Good ITO electrode is stored in 4 DEG C of refrigerator, spare.Prepared modified electrode is denoted as TiO respectively2/ITO、MoS2/ITO、
TiO2-MoS2/ITO、TiO2-MoS2- Au/ITO electrodes；
3. the structure of aptamer sensor：
The mercapto-modified DNA adaptations liquid solutions of 1.5 μM of 25 μ L are measured with liquid-transfering gun to be added dropwise（Modification）Gained is 2. prepared in step
Dry TiO2-MoS2- Au/TO electrode surfaces are placed in 4 DEG C of refrigerator and are incubated 12 h, take out, 25 μ L 3% are then added dropwise（w/
v）Bovine serum albumin（BSA）Aqueous solution is as ion sealer to get aptamer/TiO2-MoS2- Au/TO electrodes, as photoelectricity
Chemical aptamer sensor.
By prepared aptamer/TiO2-MoS2- Au/ITO electrodes（PEC aptamer sensors）It is stored in 4 DEG C of ice
It is spare in case.
The present invention uses SEM Technique on T iO2-MoS2The pattern of-Au tri compound nano materials is characterized.Such as Fig. 1
It is shown, figure A be with sol-gel method prepare without crystal form TiO2Nanometer ball template, as seen from the figure, synthesized TiO2Nanosphere table
Face is smooth, size is uniform, is uniformly dispersed, a diameter of ~ 400 nm of ball；It is by TiO to scheme B2Nanosphere hydrothermal template method is simply located
The Detitanium-ore-type TiO obtained after reason2The SEM figures of nanosphere.With presoma TiO2Template is compared, hydro-thermal method treated TiO2It receives
Rice ball dispersibility is still preferable, size is more uniform, and diameter is without significant change, but ball surface becomes very coarse；Figure C is hydro-thermal method
The simple MoS prepared2The SEM figures of nanometer sheet, it can be seen from the figure that simple MoS2Size is random, but can be seen that apparent
Laminated structure, and there are a large amount of folds on surface；Figure D is TiO2-MoS2The SEM figures of binary composite, can from figure
It arrives, MoS2Nanometer sheet is by TiO2Nanosphere closely wraps up completely, and like flower-shaped, diameter significantly increases, and average-size is ~ 600
Nm, and disperse more uniform；Scheme the TiO that E and F is different amplification2-MoS2The SEM figures of-Au tri compound nano materials, from figure
In it can clearly be seen that：Au nano particles are relatively uniformly dispersed throughout TiO2-MoS2The surface of nanosphere fold, the size of Au particles
Only several nanometers.Therefore, it is known that by SEM figures：TiO2-MoS2Preferable shape has been fully achieved in-Au tri compound nano materials
Looks.
The present invention uses XRD Technique on T iO2-MoS2The crystalline structure and composition of-Au trielement composite materials are characterized.
A illustrates rough surface TiO in Fig. 22The XRD diagram of nanosphere, wherein in 2 θ=25.3o, 37.8o, 48.0o, 53.9 o,
55.1oWith 62.7oDiffraction maximum correspond to TiO respectively2Anatase (101), (004), (200), (105), (211) and
(204) crystal face（JCPDS 21-1272）；B is simple MoS in Fig. 22The XRD spectrum of nanometer sheet, wherein 14.2o, 33.3o,
39.5oWith 58.6oThe diffraction maximum at place corresponds to MoS respectively2(002), (100), (103) and (110) crystal face；C is TiO in Fig. 22-
MoS2The XRD spectrum of binary composite, in 2 θ=14.2o, 33.3o, 39.5o, 58.6oThe diffraction maximum at place derives from MoS2
Nanometer sheet, 25.3o, 48.0oTwo peaks at place correspond to anatase TiO2(101), the diffraction crystal face of (200), wherein anatase
TiO2The main reason for diffraction maximum is weaker is TiO2Nanosphere is by MoS2Nanometer sheet is closely wrapped in the inside；D is TiO in Fig. 22-
MoS2The XRD spectrum of-Au trielement composite materials, from the XRD spectrum, not only it is observed that anatase TiO2And MoS2Nanometer
The characteristic peak of piece, it is important that the characteristic diffraction peak of Au nano particles can also be observed, in 2 θ=38.6o, 44.8o,
64.9o, 77.8oThe diffraction maximum difference corresponding A u nano particles (101) that place occurs, (110), (220), (311) crystal face, this
Illustrate the successful deposition and TiO of Au nano particles2-MoS2The successful preparation of-Au trielement composite materials.
To study TiO2-MoS2The element composition of-Au trielement composite materials, the present invention have carried out table using XPS technologies to it
Sign, Fig. 3 TiO2-MoS2The XPS collection of illustrative plates of-Au trielement composite materials.A is TiO in Fig. 32-MoS2- Au trielement composite materials
The full spectrograms of XPS, as seen from the figure this trielement composite material be mainly made of five kinds of elements of Ti, O, Mo, S, Au；B is corresponded in Fig. 3
TiO2-MoS2The XPS high-resolution collection of illustrative plates of Ti 2p in-Au trielement composite materials, two peaks at 459.2 eV and 464.98 eV
Ti is corresponded to respectively4+Ti 2p3/2With Ti 2p1/2The characteristic peak of track；C is the XPS High-Resolution Maps of O 2p in Fig. 3, and collection of illustrative plates can
It is synthesized to be located at two peaks at 530.5 eV and 532.0 eV, is respectively belonging to TiO2In middle Ti-O-Ti keys and hydroxyl (- OH)
Oxygen；D is the XPS High-Resolution Maps of Mo 3d in Fig. 3, wherein two peaks are respectively belonging at 232.3 eV and 229.1 eV
MoS2Middle Mo4+Mo 3d3/2With Mo 3d5/2The characteristic peak of track；E is TiO in Fig. 32-MoS2The S 2p of-Au trielement composite materials
XPS High-Resolution Maps, the peak at 162.9 eV and 161.7 eV is belonging respectively to the S 2p of S elements in material1/2With S 2p3/2Rail
The characteristic peak in road；F is the high-resolution collection of illustrative plates of Au 4f in Fig. 3, and two peaks at 87.9 eV and 84.1 eV are Au respectively
4f5/2With Au 4f7/2Spin-orbit splitting photoelectron spectroscopy, this is combined with the standard of Au and can be identical, and shows Au nanometers
Grain is by successful deposition in TiO2-MoS2On composite nano materials.XPS collection of illustrative plates demonstrates again that TiO2-MoS2- Au trielement composite materials
Successful preparation.
Test process:
The 2. and 3. TiO of middle preparation by step2/ITO、MoS2/ITO、TiO2-MoS2/ ITO and aptamer/TiO2-MoS2-Au/
ITO electrode is clipped respectively with work electrode holder, is placed in containing 40 mL, 0.1 M PBS buffer solution（PH=7.4）Transparent electrolytic cell
In, reference electrode is also positioned in this electrolytic cell electrode, forms three-electrode system.Then it is placed on a flight data recorder
In, with a 300 W xenon lamps（Containing a 400 nm edge filters）As excitation light source（400-780 nm）To irradiate modification
ITO working electrodes afterwards.The applied voltage for applying 0.6 V by CHI630D electrochemical workstations records respectively in working electrode
Photocurrent response under open and close lamp.Wherein aptamer/TiO2-MoS2- Au/ITO electrodes are exactly photoelectrochemical constructed by the present invention
Aptamers biosensor is learned, was testing aptamer/TiO2-MoS2It, then will be different dense after the photoelectric current of-Au/ITO electrodes
The kanamycins of degree is injected in this electrolytic cell, equally its photocurrent response is surveyed under the voltage for applying 0.6 V, with quantitative test card
That mycin.
Electrochemical impedance（EIS）Method monitors the assembling process of aptamer sensor：
As assessment dynamic process and the effective tool of modified electrode interface performance, electrochemical impedance is used to the monitoring present invention
The assembling process of optical electro-chemistry aptamer sensor prepared by embodiment 1.
Impedance experiment is in the 5 mM K containing 0.1 M KCl electrolyte3[FeCN)6]/K4[Fe(CN)6] in solution into
Row applies DC voltage as 0.20 V, the alternating voltage of 5 mV of laminated thereto.Impedance experiment is in the mHz of 100 KHz~100
Record nyquist diagram in frequency range.For all nyquist diagrams in Fig. 4 in high frequency region comprising a semicircle, it corresponds to electricity
Son transfer resistance（Ret）；A straight line portion is showed in low frequency range, it corresponds to diffusion controlled process.Half circular diameter and modification electricity
The potassium ferricyanide electron transmission coefficient of pole surface is inversely proportional, this provides an intuitive judgment standard for research material electric conductivity.
As shown in figure 4, curve a, b, c, d are respectively naked ITO electrode, TiO2/ITO、TiO2-MoS2/TO、TiO2-MoS2-
The impedance spectrum of Au/ITO electrodes, e and f represent aptamer/TiO respectively2-MoS2- Au/ITO electrodes are before BSA sealers are used
Impedance spectrum afterwards.Wherein naked ITO electrode（Curve a）The semicircle of a very little is showed, represents sheet resistance very little, belongs to expansion
Dissipate control process.In contrast, pure TiO2Nanosphere（Curve b）Radius is maximum, shows TiO2Electric conductivity is poor.But work as TiO2
Through hydro-thermal method in one layer of MoS of area load2Nanometer sheet forms TiO2-MoS2After binary composite, the electric conductivity of material significantly increases
Greatly（That is curve c）；Work as TiO2-MoS2After binary composite is supported Au nano particles, electric conductivity greatly enhances（Curve
d）.Curve e, f represent TiO2-MoS2- Au/ITO electrodes are modified upper aptamer and BSA successively, it can be seen from the figure that adjoint
Modification, half circular diameter gradually increases, and this is mainly due to the low electric conductivities and steric effect of protein, hinder electrification
Electron transmission of the probe to electrode surface is learned, while also shows a variety of materials and is assembled in electrode surface layer by layer.
Photocurrent response method monitors the assembling process of aptamer sensor：
Fig. 5 is 0.1 M PBS buffer solution of the different modifying electrode in 40 mL（pH=7.4）Photoelectric current under the conditions of middle open and close lamp
Collection of illustrative plates is responded, experiment applies voltage as 0.6 V.Wherein a, b, c, d, e represent MoS respectively2/ITO、TiO2/ITO、
TiO2-MoS2/ITO、TiO2-MoS2-Au/ITO、aptamer/TiO2-MoS2The photoelectric current collection of illustrative plates of-Au/ITO electrodes.As schemed
Show, in all modified electrodes, pure MoS2Electrode, that is, MoS of nanometer sheet modification2The photoelectric current of/ITO electrode（Curve a）Minimum,
This is mainly due to photo-generate electron-hole pair it is quick it is compound caused by；Meanwhile TiO2/ ITO electrode generate photoelectric current also compared with
It is small（Such as curve b）, this is because TiO2Greater band gap, to visible light-responded difference.However, TiO2-MoS2Binary composite is repaiied
The photoelectric current for adoring ITO electrode is approximately TiO26 times of/ITO electrode（Curve c）, this is mainly due to TiO2And MoS2Intimate contact
Heterojunction structure is formd, the absorption to visible ray is greatly strengthened, effectively promotes separation of charge；When in TiO2-MoS2Two
After Au nano particles being deposited on first composite material, TiO2-MoS2The photoelectric current that-Au/ITO is generated is maximum（Curve d）, it is approximately TiO2-
MoS21.9 times of/ITO photoelectric currents, this is because the electric conductivity that Au nano-particles are extremely strong, the transmission for greatly strengthening electronics is fast
Rate further promotes separation of charge；Finally, in TiO2-MoS2Aptamer/ is formed after aptamer is fixed on-Au/ITO
TiO2-MoS2- Au/ITO electrodes, then its photoelectric current be substantially reduced（Curve e）If this is since aptamers belong to large biological molecule,
Its space steric effect seriously hinders the transmission of light induced electron, is more easy to it compound with photohole.
The optimization of optical electro-chemistry aptamer sensor testing conditions:
To obtain better optical electro-chemistry signal, adaptation bulk concentration is optimized in the present invention and applying the testing conditions such as voltage.This
Two Optimal Experimentals are in the 0.1 M PBS buffer solution containing 200 nM kanamycins（pH=7.4）Middle progress.In general,
The concentration of DNA adaptation liquid solutions is bigger, and the adaptation volume density modified on electrode is bigger, and the detection signal of target molecule is got over
Greatly；The concentration of DNA adaptation liquid solutions is smaller, then electrode surface adaptation volume density is lower, and photoelectric current is with regard to smaller.But when adaptation
When body molecular surface density is excessively high, space resistance effect also leads to photoelectric current reduction.
As shown in fig. 6, when the concentration of DNA aptamers is from when increasing to 1.5 μM for 0.5 μM, photoelectric current is remarkably reinforced, when dense
More than 1.5 μM, photoelectric current is obviously reduced degree, therefore, selects 1.5 μM of best compound concentrations as DNA aptamers.In addition,
Applied voltage be also influence optical electro-chemistry signal an important factor for one of, therefore the present invention investigated applied voltage from 0.2 V to
Photocurrent response in the range of 0.8 V, is as a result shown in Fig. 7.Fig. 7's the result shows that：Applied voltage is in the range of 0.2 V-0.6 V
When, photocurrent response gradually increases with the increase of applied voltage, but since 0.6 V, and photocurrent response starts to tend to be steady
It is fixed, therefore we select the applied voltage of 0.6 V to apply voltage as final.
That mycin of quantitative test card：
The present invention that mycin of quantitative test card under optimum determining condition, is as a result shown in Fig. 8 and 9.As can see from Figure 8：Photoelectricity
Stream response increases with the increase of kanamycins concentration, when there is radiation of visible light, originally in MoS2Photoproduction electricity in valence band
Son has been excited to conduction band, is then delivered to TiO2Conduction band, lead to MoS2Valence band on leave a large amount of photohole.And
The presence of Au nano-particles substantially increases the transfer rate of electronics.It, can be by light in the presence of having kanamycins in system
Raw Hole oxidation, kanamycins concentration is bigger, and the photohole of consumption is more so that the recombination rate of photohole and light induced electron
It further reduces, photoelectric current is caused to increase.It can from curve graph of the photocurrent response in Fig. 9 with kanamycins concentration
Go out：Good linear relationship is presented with photocurrent response in the concentration of kanamycins, and the range of linearity is 1 nM to 450 nM, phase relation
Number is 0.998（n=3）；Under conditions of signal-to-noise ratio is 3, the detection of kanamycins is limited down to 0.2 nM.
Reproducibility, selectivity and stability test：
In order to probe into the accuracy of optical electro-chemistry aptamer sensor of the present invention and reproducibility, 4 are prepared respectively under the same conditions
Root electrode, and analysis test is carried out under identical conditions, acquired results relative standard deviation（RSD）For 4.9 %, show the present invention
Aptamer sensor has good accuracy and reproducibility.
For the specificity of optical electro-chemistry aptamer sensor that the present invention is examined to prepare（Selectivity）, spy introduces several
Possible chaff interferent does contrast test.It is mould to containing 100 nM kanamycins, chlorine respectively with the DNA optical electro-chemistry aptamer sensor
Element, erythromycin, streptomysin, fortimicin, Ciprofloxacin and Ofloxacin 0.1 M PBS buffer solution（pH=7.4）It is examined
It surveys.The results are shown in Figure 10, which has kanamycins great response, and response current is caused to have and is significantly changed
Become, and to other materials without obvious responsing to or responding very little, this shows that this DNA aptamer sensor has good selectivity.
In addition, in order to assess the stability of optical electro-chemistry aptamer sensor of the present invention, the present invention compares them at 4 DEG C
Under the conditions of store 2 weeks before and after photocurrent response signal variation.The result shows that：88.7% photo-signal is able to after two weeks
Retain, this illustrates that this aptamer sensor is with good stability.
Claims (2)
- It is 1. a kind of using titanium dioxide-molybdenum disulfide-gold trielement composite material as the structure of the optical electro-chemistry aptamer sensor of stent Construction method, which is characterized in that include the following steps：①TiO2-MoS2The preparation of-Au tri compound nano materials：TiO2The preparation of nanosphere：Weigh 1.75 g cetylamine HDA, be dispersed in absolute ethyl alcohol, then add in KCl aqueous solutions and Ultra-pure water adds in isopropyl titanate TIP while agitating, keeps HDA：Ultra-pure water：KCl：Absolute ethyl alcohol：The molar ratio of TIP is 0.5: 5: 5.5×10-3: 236.5: 1.0；Continue to stir 30 min, stand, white precipitate is collected by centrifugation, it is washed, dry Obtain the smooth TiO in surface2Nanosphere is collected spare；By the TiO that 0.5 g surfaces are smooth2Nanosphere is dispersed in the mixed solution of absolute ethyl alcohol and ultra-pure water, then at 160 DEG C 90 min of lower holding, are collected by centrifugation precipitation, washed, be dried to obtain anatase TiO2Nanosphere, it is spare；TiO2-MoS2The preparation of binary composite：By 0.08 g anatases TiO2Nanosphere is dispersed in absolute ethyl alcohol and ultra-pure water Mixed solution in, then add in 0.35 g sodium molybdates and 0.52 g thiocarbamides, after mixing at 220 DEG C 20 h of hydro-thermal reaction, instead Cooled to room temperature after answering after gained Dark grey precipitation is washed, after drying, collects powder, and grinding is denoted as TiO2- MoS2Binary composite, it is spare；TiO2-MoS2The preparation of-Au trielement composite materials：By 40 mg TiO2-MoS2Binary composite is dispersed in ultra-pure water, HAuCl is added under stirring condition4Aqueous solution, end-capping reagent trisodium citrate aqueous solution and sodium borohydride aqueous solution are stirred in ice-water bath 30 min are mixed, then continue to stand overnight after stirring 30 min at room temperature, are collected by centrifugation precipitation, it is washed, be dried to obtain TiO2- MoS2- Au trielement composite materials；2. the preparation of modified electrode:Take 1. TiO that step prepares2-MoS220 mg of-Au trielement composite materials is dispersed in 1 mL and gathers containing 0.2 wt% shells Sugar HAc solution in, then measure 25 μ L be added dropwise clean dried ITO electrode surface, be stored in refrigerator, it is spare, it is made Standby modified electrode is denoted as TiO2-MoS2- Au/ITO electrodes；3. the structure of aptamer sensor：Measure 25 μ L, 1.5 μM of mercapto-modified DNA adaptations liquid solutions are added dropwise and 2. prepare the dry TiO of gained in step2-MoS2- Au/ITO electrode surfaces are placed in refrigerator and are incubated 12 h, take out, 25 μ L are then added dropwise, 3% bovine serum albumin aqueous solution be used as from Sub- sealer obtains aptamer/TiO2-MoS2- Au/ITO electrodes, as optical electro-chemistry aptamer sensor.
- 2. as described in claim 1 using titanium dioxide-molybdenum disulfide-gold trielement composite material as the optical electro-chemistry aptamers of stent The construction method of sensor, which is characterized in that step 1. middle preparation TiO2-MoS2During-Au trielement composite materials, 2 mL, dense are added in Spend the HAuCl of 0.01 M4Aqueous solution, 2 mL, 0.01 M of concentration trisodium citrate aqueous solution, 2 mL, 0.1 M fresh configurations Sodium borohydride aqueous solution.
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