CN109557159A - A kind of titanium carbide three-dimensional composite material and preparation method thereof and the application in building thrombin aptamers sensor - Google Patents
A kind of titanium carbide three-dimensional composite material and preparation method thereof and the application in building thrombin aptamers sensor Download PDFInfo
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- CN109557159A CN109557159A CN201811582269.XA CN201811582269A CN109557159A CN 109557159 A CN109557159 A CN 109557159A CN 201811582269 A CN201811582269 A CN 201811582269A CN 109557159 A CN109557159 A CN 109557159A
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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
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
- G01N27/3272—Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels
Abstract
This disclosure relates to a kind of titanium carbide three-dimensional composite material and preparation method thereof and the application in building thrombin aptamers sensor, using one step hydro thermal method in Ti3C2TXSurface self-grown TiO2Nanorod shaped is at three-dimensional composite material substrate TiO2/Ti3C2TX, while three-dimensional composite material M NPs/TiO is obtained in three-dimensional material surface reduction noble metal nano particles (M NPs)2/Ti3C2TX.Since a step realizes a variety of enhancings, the current strength of the material is maximum.The three-dimensional structure of composite material can provide king-sized reachable surface area, this is conducive to the anchoring of M NPs.The introducing of transition metal carbonitrides (MXenes) and metal nanoparticle can be improved separation of charge efficiency and accelerate electron transfer rate.By the combination of M NPs and aptamer chain, sensitive unmarked aptamer has been successfully established for measuring zymoprotein.The aptamer sensor proposed has good chemical property, the wider range of linearity, and relatively low detection limit shows M NPs/TiO2/Ti3C2TXThe electrode material that will be held promise in electrochemica biological sensor.
Description
Technical field
The disclosure is more particularly to a kind of titanium carbide three-dimensional composite material and preparation method thereof and in building thrombin aptamers
Application in sensor.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
Fibrin ferment can convert fibrinogen into fibrin.After local application, the blood of lesion surface is acted on
Stable grumeleuse is quickly formed, for controlling capillary, phleborrhagia, or as the bonding of skin and tissue grafts and solid
Determine agent, and is related to various diseases, such as thrombotic disease, leukaemia and inflammatory reaction.It is asked to adapt to Global Health
Topic, especially in developing country, it is highly desirable to which exploitation is used for simple, the inexpensive and effective side of quantitative detection fibrin ferment
Method.Some conventional methods for protein analysis, such as enzyme linked immunosorbent assay (ELISA), Western blotting and polarization measurement are led to
Often face the program of expensive instrument or complexity, the extensive use which has limited them in routine clinical diagnosis.In addition, not
In same available signal reading device, in its low cost, intrinsic signal stability shows Electrochemical Detection with being easy to calibrate aspect
Excellent performance out.In addition, it can be easily integrated with some compact apparatus or on piece lab platform, thus it is portable and
Immediately the manufacture of nursing biosensor has a high potential.However, most of electrochemistry aptamer sensors, which use, is based on enzyme or label
The method for amplifying signal of signal, they are not only expensive but also complicated for operation.
In order to construct electrochemistry aptamer sensor, the selection of electrode substrate materials is crucial.Ti3C2TXIt is a kind of two dimension
Transition metal carbide or carbonitride (MXenes), a kind of two-dimension nano materials similar to graphene.MXenes is as electricity
The modified electrode material of chemical sensor has many advantages, because they have a large amount of come-at-able active sites and short expansion
It dissipates and is based on NH apart from path .Yu et al.3And Ti3C2TXBetween big absorption energy, produce a kind of couple of NH3Show good response
Sensor.Liu et al. has synthesized a kind of two-dimensional layer Ti3C2TXSill, for fixing hemoglobin (Hb), preparation
Biosensor shows good performance in terms of detecting nitrite, has the wide range of linearity, and have extremely low
Detection limit.As indicated by these researchs, this MXenes brand-new material is due to its special characteristic electron and stabilization
Property and become Application in Sensing potential candidate material.
Due to many unique functions, MXenes material have proven to for Application in Sensing high sensitivity and
Selective enumeration method platform.However, MXenes sheet material is easy to stack again during the filtration process, and their small―gap suture interval limit
Electrolyte ion is made, the accessibility of especially big ion, which prevent making full use of for surface area, lead to the electrochemistry of difference
Behavior.The sheet structure of MXenes material is easy to stack, therefore is using Ti3C2TXIt needs to solve when constructing electrochemical sensor
The problem of sheet-stacking.In order to solve this problem, researcher is often inserted into carbon nanotube and ionic liquid among sheet material
(ILs) materials, to prevent sheet-stacking such as.Most of in these methods are to stack different nano materials.Prepare material
Process very complicated.
Summary of the invention
For the deficiency for detecting blood coagulation enzyme method in the prior art, the disclosure develops a kind of no enzyme and unmarked electrification
Aptamer sensor is learned, for detecting fibrin ferment.
The disclosure specifically uses following technical scheme:
In the first aspect of the disclosure, a kind of M NPs/TiO is provided2/Ti3C2TXThe preparation method of composite material, the party
Method includes:
By stratiform Ti3C2TX, precious metal salt and water be uniformly mixed, then hydro-thermal reaction 12~16 is small at 160~200 DEG C
When, 12~15h is stood after cooling, M NPs/TiO can be prepared2/Ti3C2TXComposite material.
In the second aspect of the disclosure, a kind of M NPs/TiO being prepared using the above method is provided2/Ti3C2TX
Composite material.
In terms of the third of the disclosure, a kind of thrombin aptamers sensor is provided, which includes:
Base electrode；
The M NPs/TiO2/Ti3C2TXComposite material, the M NPs/TiO2/Ti3C2TXComposite material is attached to matrix
On electrode, M NPs/TiO is formed2/Ti3C2TXModified base electrode；And
And thrombin aptamers, the thrombin aptamers pass through covalent bond and the M NPs/TiO2/Ti3C2TXModified
M NPs in base electrode is connected.
At the 4th aspect of the disclosure, a kind of preparation method of thrombin aptamers sensor, this method packet are provided
Include following steps:
By M NPs/TiO2/Ti3C2TXThe hanging drop of composite material is applied on base electrode, and M NPs/ is prepared
TiO2/Ti3C2TXModified base electrode；
Thrombin aptamers are dripped into M NPs/TiO2/Ti3C2TXReaction, reaction knot are attached on modified base electrode
Then Shu Hou, washing close unreacted active site using bovine serum albumin(BSA), obtain thrombin aptamers sensor.
At the 5th aspect of the disclosure, the M NPs/TiO is provided2/Ti3C2TXComposite material or the fibrin ferment
Application of the aptamer sensor in detection fibrin ferment.
At the 6th aspect of the disclosure, a kind of method for detecting fibrin ferment is provided, this method comprises: using the blood coagulation
Enzyme aptamer sensor Selective recognition fibrin ferment after identification, thrombin aptamers sensor is immersed in methylene blue solution, is not had
Have and adsorb methylene blue with the aptamer of fibrin ferment identification, detects fibrin ferment using the electrochemical signals of methylene blue.
Compared with the relevant technologies that the present inventor knows, the one of technical solution of the disclosure has following beneficial to effect
Fruit:
The disclosure has synthesized a kind of three-dimensional (3D) composite material M NPs/TiO using hydro-thermal method2/Ti3C2TX, utilize a step
Hydro-thermal method is in Ti3C2TXSurface self-grown TiO2Nanorod shaped is at three-dimensional composite material substrate TiO2/Ti3C2TX, while in three-dimensional material
Material surface reduction noble metal nano particles (M NPs) obtains three-dimensional composite material M NPs/TiO2/Ti3C2TX.Since a step is realized
A variety of enhancings, therefore the current strength of the material is maximum.The three-dimensional structure of the composite material can provide king-sized arrive
Up to surface area, this is conducive to the anchoring of M NPs.The introducing of transition metal carbonitrides (MXenes) and metal nanoparticle can be with
It improves separation of charge efficiency and accelerates electron transfer rate.By the combination of M NPs and aptamer chain, it is successfully established sensitive nothing
Label aptamer is for measuring zymoprotein.The aptamer sensor proposed has good chemical property, has 5fM~500nM
Broad linear range, with 2fM lower detection limit, show M NPs/TiO2/Ti3C2TXIt will hold promise for electrochemical student
Electrode material in object sensor.
Detailed description of the invention
The Figure of description for constituting disclosure a part is used to provide further understanding of the disclosure, the signal of the disclosure
Property embodiment and its explanation for explaining the disclosure, do not constitute the improper restriction to the disclosure.
Fig. 1 is M NPs/TiO2/Ti3C2TXSynthesis schematic diagram.
Fig. 2 is TiO2/Ti3C2TXSEM image.
Fig. 3 is M NPs/TiO2/Ti3C2TXTEM image.
Fig. 4 is in the 5.0mM [Fe (CN) containing 0.1M KCl6]4-/3-Electrochemical impedance spectroscopy test result figure in solution.
Fig. 5: (A) blank (curve a), CV characterization of the 5nM TB standard incubations (b) in 0.1M PBS (pH=7.4)；(B)
The DPV of blank characterizes (curve a), characterization of the 5nM TB standard incubations (b) in 0.1M PBS (pH=7.4).
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation and/or their combination.
As background technique is introduced, detecting the method for fibrin ferment in the prior art, there are certain deficiencies, to understand
Technical problem certainly as above, the disclosure devise a kind of unmarked fibrin ferment bio-sensing based on MXenes nanocomposite
Device.In the strategy of the proposition, novel three-dimensional nanocomposite M NPs/TiO has been synthesized by one pot of hydro-thermal method2/
Ti3C2TX, and aptamer chain has been crosslinked with M NPs to realize the specific detection of fibrin ferment.This method has simple, at low cost, spirit
Sensitivity is high, widely used advantage.In addition, Ti3C2TXImportant function has been played in this strategy.As platform, TiO2/
Ti3C2TXConstruct three-dimensional substrate.The three-dimensional structure of the material not only increases proton transport rate, and has load substrate
Bigger specific surface area, to load more noble metal nano particles.Noble metal nano particles are solid by stable M-S chemical bond
Aptamer chain is determined to realize specific detection fibrin ferment.Fibrin ferment may be implemented in addition, the G base on aptamer chain is adsorbed on MB
Unmarked Electrochemical Detection.Finally, a kind of aptamer sensor of fibrin ferment label of our successful designs, can push
Ti3C2TXApplication in unmarked aptamer biosensors.
During the experiment, it has been found that under given conditions, Ti3C2TXLaminate Ti can be oxidized and then be grown to
TiO2Nanometer rods, and precious metal salt is reduced to noble metal nano particles (M NPs) under hydrothermal conditions, and it is compound to form three-dimensional (3D)
Nano material M NPs/TiO2/Ti3C2TX.In Ti3C2TXThe TiO of layer surface growth2Nanometer rods and it is supported on TiO2/Ti3C2TXIn
Noble metal nano particles can prevent Ti3C2TXThe accumulation of piece simultaneously improves proton transport rate, while having fine bio-compatible
The TiO of property2Microenvironment can be shielded for biomolecule such as enzymes to keep its stability and activity.In addition, M NPs/TiO2/
Ti3C2TXWith good electric conductivity, be conducive to its application in electrochemical gaging.Ti3C2TXContain a large amount of hydrophily hydroxyl
Base (- OH), it can improve the hydrophily of material surface.Noble metal nano particles (M NPs) have good electric conductivity and compared with
Big specific surface area can pass through the fixed aptamer chain of M-S key.Furthermore, it was reported that the M NPs being loaded on base material is shown
Excellent antimicrobial acivity out.The fact that surface chemistry and high conductivity can be enhanced in view of 3D-MXenes, both
The combination of material may be used as the ideal electrode substrate of electrochemica biological sensor.
Utilize 3D TiO2/Ti3C2TXMultifunctionality and M NPs conductivity, we are prepared for a kind of based on 3D TiO2/
Ti3C2TXElectrochemical cyclic voltammetry (CV) or differential pulse voltammetry (DPV) detection fibrin ferment (TB) novel aptamer sensing
Device, as shown in Figure 1.M NP is encapsulated in 3D composite nano materials M NPs/TiO by one pot of hydro-thermal method2/Ti3C2TXIn, it obtains
Composite nano materials M NPs/TiO2/Ti3C2TX.Secondly, by composite nano materials M NPs/TiO2/Ti3C2TXTo the surface ITO, so
It is fixed thrombin aptamers (TBA) by metal-sulfur key afterwards.Third uses in order to avoid possible non-specific protein absorption
Bovine serum albumin(BSA) covers the active site on electrode surface as sealer.Finally, TBA/M NPs/TiO2/Ti3C2TXIt repairs
The indium-tin oxide electrode (ITO) of decorations is used for Selective recognition fibrin ferment.4th, by TB/TBA/M NPs/TiO2/Ti3C2TXIt repairs
The ITO of decorations immerses in methylene blue (MB) solution, and the aptamer with fibrin ferment identification can not adsorb MB, utilizes the electrochemistry of MB
Signal detects fibrin ferment.Performance is analyzed using CV or DPV technical research, even if as the result is shown in diluted human serum sample
In, aptamer sensor shows satisfactory fibrin ferment detection performance.
Specifically include the technical solution of the following aspects:
In first typical embodiment of the disclosure, one kind is provided to construct unmarked fibrin ferment electrification student
The M NPs/TiO of object sensor2/Ti3C2TXThe preparation method of composite material, this method comprises:
By stratiform Ti3C2TX, precious metal salt and water be uniformly mixed, then hydro-thermal reaction 12~16 is small at 160~200 DEG C
When, 12~15h is stood after cooling, M NPs/TiO can be prepared2/Ti3C2TXComposite material.
Noble metal nano particles (M NPs) are directly reverted to composite material using one pot of hydro-thermal method by the disclosure
TiO2/Ti3C2TXIn, while TiO is carried out after hydro-thermal reaction2The growth of nanometer rods, the TiO of acquisition2For nanorod structure
And size is bigger, inventors be surprised to learn that the structure is more advantageous to and struts Ti3C2TXLayer structure is conducive to improve proton biography
Defeated rate, to be more advantageous to the detection of fibrin ferment.
It keeps reaction kettle closed after the completion of hydro-thermal reaction and does not move, carry out cooling down static 12h or more to promote lamella material
TiO on material2Crystal seed is grown to TiO2Nanometer rods.
In one of the disclosure or some embodiments, by using hydrofluoric acid (HF) from Ti3AlC2Selective etch Al
To prepare stratiform Ti3C2TX。
Further, the disclosure provides that a kind of structure is relatively stable and surface hydrophilicity hydroxyl group stratiform more abundant
Ti3C2TXPreparation method, this method specifically includes: by 2g to 4g Ti3AlC24 DEG C to 6 DEG C of the 9M of 20mL to 40mL is added
In HF solution, mixed solution is obtained；Mixed solution is stirred 10~30 minutes at 4 DEG C to 6 DEG C, is then stirred at 42~47 DEG C
It mixes 22~26 hours, obtains Ti3C2TXThe suspension of thin slice；Then it is centrifuged until the pH of suspension reaches 6~7；By super
10~12 hours acquisition stratiform Ti of sonication3C2TXColloidal solution, be then centrifuged for remove sediment.
In one of the disclosure or some embodiments, the precious metal salt includes but is not limited to silver nitrate (Ag
NO3), six hydration gold chlorides, six hydration chloroplatinic acids etc..
In one of the disclosure or some embodiments, stratiform Ti3C2TX, precious metal salt and water ratio be (30~
120) mg:(15~30) mL:(50~80) mg.By verification experimental verification, the material rate of the range can make final sensor
Obtain more highly sensitive detection effect.
In one of the disclosure or some embodiments, a kind of M NPs/TiO is provided2/Ti3C2TXThe tool of composite material
Preparation, method includes the following steps:
By 15~20mL (2~6mg/mL) Ti3C2TXSolution is dispersed in 5mL water, and 50~80mg precious metal salt is added, and is surpassed
Sonication 1~1.5 hour to obtain uniform suspension；
Then, suspension is transferred in autoclave and is heated 12~16 hours at 160~200 DEG C；
After being cooled to room temperature, 12~15 hours are allowed to rest for form TiO2The growth of nanometer rods；
The three-dimensional composite nano materials M NPs/TiO of synthesis2/Ti3C2TXIt is washed with water, is then stored in pure water.
In second typical embodiment of the disclosure, the M NPs/ being prepared using the above method is provided
TiO2/Ti3C2TXComposite material, wherein M is the abbreviation of noble metal, including but not limited to silver-colored (Ag), golden (At), platinum (Pt) etc.,
Ti3C2TXIn TXRefer to surface group (such as O-, OH-, F-).
The M NPs/TiO2/Ti3C2TXThe microscopic appearance of composite material are as follows: TiO2Nanometer rods are closely uniformly adhered to or are worn
It is inserted in stratiform Ti3C2TXOn, M NPs is uniformly adhered to TiO2Nanometer rods and stratiform Ti3C2TXOn, wherein TiO2Nanometer rods it is straight
Diameter is 5~30nm, and the ratio of diameter and length is 1:(3~8), M NPs size is 12~18nm.Experiment proves that this is specific
The M NPs/TiO of pattern2/Ti3C2TXComposite material helps to improve the detection sensitivity of fibrin ferment.
In the typical embodiment of third of the disclosure, a kind of thrombin aptamers sensor is provided, the sensor packet
It includes:
Base electrode；
The M NPs/TiO2/Ti3C2TXComposite material, the M NPs/TiO2/Ti3C2TXComposite material is attached to matrix
On electrode, M NPs/TiO is formed2/Ti3C2TXModified base electrode；
And thrombin aptamers, the thrombin aptamers pass through covalent bond and the M NPs/TiO2/Ti3C2TXModified
M NPs in base electrode is connected.
In one of the disclosure or some embodiments, described matrix electrode is indium-tin oxide electrode (ITO electrode),
Ordinary skill in the art means can be used in its preparation.Experiment proves that helping to mention using ITO electrode as base electrode
The detection sensitivity of high fibrin ferment.
Thrombin aptamers in the disclosure are the one section of widows referred to high affinity and specificity in conjunction with fibrin ferment
Nucleotide sequence, in one of the disclosure or some embodiments, including but not limited to following sequence: 5'-SH- (CH2)6-GGT
TGGTGTGGT TGG-3'。
Further, the thrombin aptamers of the terminal modified sulfydryl of the M NPs connection 5 ', the two are keyed by M-S.
In the 4th typical embodiment of the disclosure, a kind of preparation side of thrombin aptamers sensor is provided
Method, method includes the following steps:
By M NPs/TiO2/Ti3C2TXThe hanging drop of composite material is applied on base electrode, and M NPs/ is prepared
TiO2/Ti3C2TXModified base electrode；
Thrombin aptamers are dripped into M NPs/TiO2/Ti3C2TXReaction, reaction knot are attached on modified base electrode
Then Shu Hou, washing close unreacted active site using bovine serum albumin(BSA), obtain thrombin aptamers sensor.
In the 5th typical embodiment of the disclosure, the M NPs/TiO is provided2/Ti3C2TXComposite material or
Application of the thrombin aptamers sensor described in person in detection fibrin ferment.
In the 6th typical embodiment of the disclosure, a kind of method for detecting fibrin ferment is provided, this method comprises:
Fibrin ferment is identified using the thrombin aptamers sensor selectivity, after identification, thrombin aptamers sensor is immersed into methylene
In base indigo plant solution, the aptamer with fibrin ferment identification does not adsorb methylene blue, is detected using the electrochemical signals of methylene blue
Fibrin ferment.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment of body.
Reagent used in following embodiments, material and instrument:
Reagent and material:
With 5'-SH- (CH2)6The thrombin aptamers of-GGT TGGTGTGGT TGG-3' sequence are purchased from Sangon
Biotech Co., Ltd.(Chinese Shanghai, http://www.sangon.com/).Fibrin ferment, bovine serum albumin(BSA) (BSA) and
Human serum albumins (HSA) is purchased from Sangon Biotech Co., Ltd.(Chinese Shanghai, http: //
www.sangon.com/)。
MAX-Ti3AlC2Powder comes from Forsman Scientific Co., Ltd (BeiJing, China), potassium chloride (KCl), hydrogen
Fluoric acid (HF), dichloride sodium (NaCl) come from traditional Chinese medicines chemical reagent Co., Ltd.(Shanghai, China).Precious metal salt [silver nitrate
(Ag NO3), six hydration gold chlorides, six hydration chloroplatinic acids], all chemicals are analytical-reagent grade, are used as it is.At this
In experiment, select by NaH2PO4And Na2HPO4The 0.1M phosphate buffer solution (PBS) of the pH 7.4 of preparation is molten as electrolyte
Liquid.Distilled water is used in the entire experiment process.
Instrumentation and testing:
Electrochemistry experiment and measurement are carried out on the CHI660E electrochemical workstation with conventional three-electrode system.It uses
Exposure or modified ITO are used as working electrode, use platinum column as to electrode, and use saturated calomel electrode (SCE) as joining
It examines.Scanning electron microscope (SEM) image is collected on JEOL JSM-6700F with 5.0kV.It is penetrated by using DX2700 powder X-ray
The phase of line diffraction (XRD) pattern characterization catalyst.Electrochemical impedance spectroscopy (EIS) is measured by Princeton electrochemical workstation
(USA) it carries out.
Embodiment 1
MXenes-Ti3C2TXSynthesis
By 3g Ti3AlC2It is slowly added in the 9M HF solution of 5 DEG C of 30mL, obtains mixed solution.By mixed solution 5
It is stirred at DEG C 20 minutes, is then stirred 24 hours at 45 DEG C, obtain Ti3C2TXThe suspension of thin slice.Then be centrifuged until
The pH of suspension reaches 6.5, by being ultrasonically treated 11 hours acquisition stratiform Ti3C2TXColloidal solution, then with 3500rpm from
The heart 35 minutes to remove sediment.
TiO2/Ti3C2TXThe synthesis of hydrogel
By 20mL (4mg/mL) Ti3C2TXSolution is dispersed in 5mL water, is ultrasonically treated 1.2 hours to obtain uniform suspend
Liquid.Then, suspension is transferred in the autoclave of Teflon sealing and is heated 14 hours at 180 DEG C.After being cooled to room temperature,
14 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite nano materials TiO of synthesis2/Ti3C2TXIt is washed with water
It washs, is then stored in pure water.
Obtain TiO2/Ti3C2TXThe SEM image of material is as shown in Fig. 2, which show TiO2Nanometer rods are closely equably anchored
In Ti3C2TXIn substrate.TiO2The diameter of nanometer rods is in the range of 5-30nm.In addition, these nanometer rods equably cover
Ti3C2TXThe surface of substrate.Also it is clearly observed many TiO2Nanometer rods are also well embedded in adjacent Ti3C2TXNanoscale twins it
Between space in.TiO2Nanometer rods can be to avoid Ti3C2TXIt stacks.The unique nanostructure of the composite material provides big connect
Touch interface and ion transmission channel abundant, it is ensured that TiO2/Ti3C2TXNanocomposite has high conductivity.
Ag NPs/TiO2/Ti3C2TXThe synthesis of hydrogel
By 20mL (4mg/mL) Ti3C2TXSolution is dispersed in 5mL water, and 60mg silver nitrate is added, and is ultrasonically treated 1.2 hours
To obtain uniform suspension.Then, suspension is transferred in the autoclave of Teflon sealing and at 180 DEG C heating it is 14 small
When.After being cooled to room temperature, 14 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite nano materials M of synthesis
NPs/TiO2/Ti3C2TXIt is washed with water, is then stored in pure water.
TEM is for further studying the Ag NPs/TiO of synthesis2/Ti3C2TXThe microstructure of sample.It can from Fig. 3
Out, some TiO2Nanometer rods are supported on Ti3C2TXIn substrate.Fig. 3 shows that Ag NPs is uniformly adhered to TiO2/Ti3C2TXSurface
On, and the size with about 15nm.TiO2/Ti3C2TXThe SEM and TEM image of nanostructure have good consistency, it was demonstrated that
TiO2Nanometer rods are successfully fixed on Ti3C2TXOn surface.
By in the 5.0mM [Fe (CN) containing 0.1M KCl6]4-/3-The electrochemistry of electrochemical impedance spectroscopy (EIS) in solution
It tests to characterize the property of the material of preparation.As shown in figure 4, half circular diameter of EIS is equal to Ret in nyquist diagram.When
Small semicircle (Fig. 4, curve a), it means that electrode surface has good electric conductivity are observed when modifying Ag NPs on ITO.
When modifying TiO on ITO2/Ti3C2TXWhen, similar to the radius of M NPs, (Fig. 4, curve b), this is attributed to half circular diameter
Ti3C2TXSuperior electrical conductivity.As Ag NPs/TiO2/Ti3C2TXWhen modified on ITO, half diameter of a circle reduces (Fig. 4, curve
c).The reason is that Ag NPs is modified to TiO2/Ti3C2TXHole, this is conducive to electronics transfer.
Manufacture modified electrode
ITO electrode can be obtained by conventional technical means.By under ultrasonic agitation by the Ag NPs/TiO of 2.0mg2/
Ti3C2TXIt is dispersed in 1.0mL secondary water and prepares 2mg mL-1Ag NPs/TiO2/Ti3C2TXSuspension.Then, by 20 μ L institutes
Hanging drop is obtained to 0.5cm2On the ITO slice of fixed-area, and it is dry under infrared lamp.Hereafter, in order to preferably solid
Determine material and prevent material from falling off during the experiment, 10 μ L chitosan solutions is covered on it and dry in surrounding air
To obtain Ag NPs/TiO2/Ti3C2TXModified ITO electrode.
In order to compare, Ag NPs/ITO and TiO are obtained by method similar to the above2/Ti3C2TXModified ITO electricity
Pole.
The preparation of thrombin aptamers sensor
By 5 μm of olL of 10 μ L-1Thrombin aptamers (TBA) solution is dripped to Ag NPs/TiO2/Ti3C2TXModified ITO electricity
On extremely.Reaction carries out 12 hours at 4 DEG C, is successfully consolidated with ensuring that aptamer passes through the covalent bond formed between Ag and the sulfydryl of TBA
It is scheduled on Ag NPs/TiO2/Ti3C2TXOn/ITO, TBA/Ag NPs/TiO is obtained2/Ti3C2TX/ITO.After completion of the reaction, PBS is used
Electrode is rinsed to remove Physical Absorption.Then, it is small that electrode is covered to 1 with 1% bovine serum albumin(BSA) (BSA) of 10 μ L at 4 DEG C
When, so that the unreacted active site on electrode surface inactivates, then thoroughly washing.
In order to compare, Ag NPs/ITO sensor and TiO are obtained by method similar to the above2/Ti3C2TXModified
ITO sensor.
Experiment measurement
By the TBA/Ag NPs/TiO of preparation2/Ti3C2TX/ ITO electrode is in 10 μ containing various concentration thrombin solution
It is incubated 40 minutes in L0.1MPBS in 37 DEG C.Fibrin ferment is fixed on the surface of modified electrode by specific recognition affinity
Then reaction between TBA and fibrin ferment is thoroughly washed with PBS.Then, TB/TBA/Ag NPs/TiO is successfully developed2/
Ti3C2TX/ ITO electrode simultaneously is used to detect fibrin ferment.Next, the aptamer sensor of acquisition is immersed in 20 μM of MB solution 5 minutes
It is reacted with completing the identification of the MB aptamer chain unidentified with fibrin ferment, washs electrode gently with ultrapure water then to obtain MB/TB/
TBA/Ag NPs/TiO2/Ti3C2TX/ITO。
In order to compare, we are also prepared for MB/TB/TBA/M NPs/ITO and MB/TB/TBA/TiO2/Ti3C2TX/ ITO electricity
Pole.
Electrochemistry experiment and measurement are carried out on the CHI660E electrochemical workstation with conventional three-electrode system, and
Electrochemical impedance spectroscopy (EIS) measurement is carried out by Princeton Applied Research (USA).By modified electrode in 0.1M
CV test is carried out in PBS (pH7.4), and is containing 5mM [Fe (CN)6]4-/3-Solution in carry out EIS test.CV experiment with
0.1V s-1Sweep speed carry out.EIS is determined under the frequency window of 0.1Hz to 10kHz and the replacement voltage of 5mV.DPV is real
It tests and is carried out in the potential range of -0.6 to 0.0V (relative to SCE) in 0.1M PBS buffer solution (pH7.4).
Control variable experiment, the machine of research experiment are carried out using cyclic voltammetry (CV) or differential pulse voltammetry (DPV)
Manage feasibility.Shown in experimental result such as Fig. 5 (A).In the case where fibrin ferment is not present, significant current signal is detected, because
Not form the compound of fibrin ferment and aptamer at the electrode surface, to allow a large amount of MB in conjunction with aptamer.Work as presence
When fibrin ferment, Thrombin specificity bind thrombin aptamer nucleic acid sequence, to reduce the combination of MB and aptamer.In conjunction with MB
Variation of the amount of aptamer in response to electric current.When not having fibrin ferment, aptamer adsorbs more MB, and sensor has bigger electric current
(curve a), when there are fibrin ferment, aptamer fibrin ferment combines the current-responsive of the absorption for reducing MB and sensor to reduce for response
(curve b).We also use differential pulse voltammetry (DPV) to carry out control variable experiment, further to study the machine of the experiment
Manage feasibility.As shown in Fig. 5 (B), when not having fibrin ferment, aptamer can adsorb more MB, and sensor has more greatly
Current-responsive (curve a).When there are fibrin ferment, aptamer reduces the absorption of MB in conjunction with fibrin ferment, and sensor
Current-responsive reduces (curve b).As a result identical as CV test result.The experimental results showed that based on the absorption detection blood coagulation of MB aptamer
The biosensor of enzyme can be used as the new method of detection fibrin ferment.
Embodiment 2
MXenes-Ti3C2TXSynthesis
By 3g Ti3AlC2It is slowly added in the 9M HF solution of 5 DEG C of 30mL, obtains mixed solution.By mixed solution 5
It is stirred at DEG C 20 minutes, is then stirred 24 hours at 45 DEG C, obtain Ti3C2TXThe suspension of thin slice.Then be centrifuged until
The pH of suspension reaches 6.5, by being ultrasonically treated 11 hours acquisition stratiform Ti3C2TXColloidal solution, then with 3500rpm from
The heart 35 minutes to remove sediment.
TiO2/Ti3C2TXThe synthesis of hydrogel
By the Ti of 20mL (4mg/mL)3C2TXSolution is dispersed in 5mL water, is ultrasonically treated 1.2 hours to obtain uniform hang
Supernatant liquid.Then, suspension is transferred in the autoclave of Teflon sealing and is heated 14 hours at 180 DEG C.It is cooled to room temperature
Afterwards, 14 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite nano materials TiO of synthesis2/Ti3C2TXUse water
Washing, is then stored in pure water.
Obtain TiO2/Ti3C2TXThe SEM image of material is as shown in Fig. 2, which show TiO2Nanometer rods are closely equably anchored
In Ti3C2TXIn substrate.TiO2The diameter of nanometer rods is in the range of 5-30nm.In addition, these nanometer rods equably cover
Ti3C2TXThe surface of substrate.Also it is clearly observed many TiO2Nanometer rods are also well embedded in adjacent Ti3C2TXNanoscale twins it
Between space in.TiO2Nanometer rods can be to avoid Ti3C2TXIt stacks.The unique nanostructure of the composite material provides big connect
Touch interface and ion transmission channel abundant, it is ensured that TiO2/Ti3C2TXNanocomposite has high conductivity.
Au NPs/TiO2/Ti3C2TXThe synthesis of hydrogel
By 15mL (4mg/mL) Ti3C2TXSolution is dispersed in 5mL water, and 50mg six is added and is hydrated gold chloride, ultrasonic treatment 1
Hour is to obtain uniform suspension.Then, suspension is transferred in the autoclave of Teflon sealing and is heated at 160 DEG C
16 hours.After being cooled to room temperature, 12 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite Nano material of synthesis
Expect Au NPs/TiO2/Ti3C2TXIt is washed with water, is then stored in pure water.
Manufacture modified electrode
ITO electrode can be obtained by conventional technical means.By under ultrasonic agitation by the Au NPs/TiO of 2.0mg2/
Ti3C2TXIt is dispersed in 1.0mL secondary water and prepares 2mg mL-1M NPs/TiO2/Ti3C2TXSuspension.It then, will be obtained by 20 μ L
Hanging drop is to 0.5cm2On the ITO slice of fixed-area, and it is dry under infrared lamp.Hereafter, in order to preferably fixed
Material simultaneously prevents material from falling off during the experiment, 10 μ L chitosan solutions are covered on it and in surrounding air dry with
Obtain Au NPs/TiO2/Ti3C2TXModified ITO electrode.
In order to compare, Au NPs/ITO and TiO are obtained by method similar to the above2/Ti3C2TXModified ITO electricity
Pole.
The preparation of thrombin aptamers sensor
By 5 μm of olL of 10 μ L-1Thrombin aptamers (TBA) solution is dripped to Au NPs/TiO2/Ti3C2TXModified ITO electricity
On extremely.Reaction carries out 12 hours at 4 DEG C, is successfully consolidated with ensuring that aptamer passes through the covalent bond formed between Au and the sulfydryl of TBA
It is scheduled on M NPs/TiO2/Ti3C2TXOn/ITO, TBA/Au NPs/TiO is obtained2/Ti3C2TX/ITO.After completion of the reaction, PBS is used
Electrode is rinsed to remove Physical Absorption.Then, it is small that electrode is covered to 1 with 1% bovine serum albumin(BSA) (BSA) of 10 μ L at 4 DEG C
When, so that the unreacted active site on electrode surface inactivates, then thoroughly washing.
In order to compare, Au NPs/ITO sensor and TiO are obtained by method similar to the above2/Ti3C2TXModified
ITO sensor.
Experiment measurement
By the TBA/Au NPs/TiO of preparation2/Ti3C2TX/ ITO electrode is in 10 μ containing various concentration thrombin solution
It is incubated 40 minutes in L0.1MPBS in 37 DEG C.Fibrin ferment is fixed on the surface of modified electrode by specific recognition affinity
Then reaction between TBA and fibrin ferment is thoroughly washed with PBS.Then, TB/TBA/Au NPs/TiO is successfully developed2/
Ti3C2TX/ ITO electrode simultaneously is used to detect fibrin ferment.Next, the aptamer sensor of acquisition is immersed in 20 μM of MB solution 5 points
Clock is reacted with the identification for completing the MB aptamer chain unidentified with fibrin ferment, washs electrode gently with ultrapure water then to obtain MB/
TB/TBA/Au NPs/TiO2/Ti3C2TX/ITO。
In order to compare, we are also prepared for MB/TB/TBA/Au NPs/ITO and MB/TB/TBA/TiO2/Ti3C2TX/ITO
Electrode.
Electrochemistry experiment and measurement are carried out on the CHI660E electrochemical workstation with conventional three-electrode system, and
Electrochemical impedance spectroscopy (EIS) measurement is carried out by Princeton Applied Research (USA).By modified electrode in 0.1M
CV test is carried out in PBS (pH7.4), and is containing 5mM [Fe (CN)6]4-/3-Solution in carry out EIS test.CV experiment with
0.1V s-1Sweep speed carry out.EIS is determined under the frequency window of 0.1Hz to 10kHz and the replacement voltage of 5mV.DPV is real
It tests and is carried out in the potential range of -0.6 to 0.0V (relative to SCE) in 0.1M PBS buffer solution (pH7.4).
Control variable experiment, the machine of research experiment are carried out using cyclic voltammetry (CV) or differential pulse voltammetry (DPV)
Manage feasibility.
Embodiment 3
MXenes-Ti3C2TXSynthesis
By 3g Ti3AlC2It is slowly added in the 9M HF solution of 5 DEG C of 30mL, obtains mixed solution.By mixed solution 5
It is stirred at DEG C 20 minutes, is then stirred 24 hours at 45 DEG C, obtain Ti3C2TXThe suspension of thin slice.Then be centrifuged until
The pH of suspension reaches 6.5, by being ultrasonically treated 11 hours acquisition stratiform Ti3C2TXColloidal solution, then with 3500rpm from
The heart 35 minutes to remove sediment.
TiO2/Ti3C2TXThe synthesis of hydrogel
By 20mL (4mg/mL) Ti3C2TXSolution is dispersed in 5mL water, is ultrasonically treated 1.2 hours to obtain uniform suspend
Liquid.Then, suspension is transferred in the autoclave of Teflon sealing and is heated 14 hours at 180 DEG C.After being cooled to room temperature,
14 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite nano materials TiO of synthesis2/Ti3C2TXIt is washed with water
It washs, is then stored in pure water.
Obtain TiO2/Ti3C2TXThe SEM image of material is as shown in Fig. 2, which show TiO2Nanometer rods are closely equably anchored
In Ti3C2TXIn substrate.TiO2The diameter of nanometer rods is in the range of 5-30nm.In addition, these nanometer rods equably cover
Ti3C2TXThe surface of substrate.Also it is clearly observed many TiO2Nanometer rods are also well embedded in adjacent Ti3C2TXNanoscale twins it
Between space in.TiO2Nanometer rods can be to avoid Ti3C2TXIt stacks.The unique nanostructure of the composite material provides big connect
Touch interface and ion transmission channel abundant, it is ensured that TiO2/Ti3C2TXNanocomposite has high conductivity.
Pt NPs/TiO2/Ti3C2TXThe synthesis of hydrogel
By the Ti of 15mL (4mg/mL)3C2TXSolution is dispersed in 5mL water, and 50mg six is added and is hydrated chloroplatinic acid, ultrasonic treatment
1 hour to obtain uniform suspension.Then, suspension is transferred in the autoclave of Teflon sealing and is added at 160 DEG C
Heat 16 hours.After being cooled to room temperature, 12 hours are allowed to rest for form TiO2The growth of nanometer rods.The three-dimensional composite Nano of synthesis
Material Pt NPs/TiO2/Ti3C2TXIt is washed with water, is then stored in pure water.
Manufacture modified electrode
ITO electrode can be obtained by conventional technical means.By under ultrasonic agitation by 2.0mg Pt NPs/TiO2/
Ti3C2TXIt is dispersed in 1.0mL secondary water and prepares 2mg mL-1M NPs/TiO2/Ti3C2TXSuspension.It then, will be obtained by 20 μ L
Hanging drop is to 0.5cm2On the ITO slice of fixed-area, and it is dry under infrared lamp.Hereafter, in order to preferably fixed
Material simultaneously prevents material from falling off during the experiment, 10 μ L chitosan solutions are covered on it and in surrounding air dry with
Obtain Pt NPs/TiO2/Ti3C2TXModified ITO electrode.
In order to compare, Pt NPs/ITO and TiO are obtained by method similar to the above2/Ti3C2TXModified ITO electricity
Pole.
The preparation of thrombin aptamers sensor
By 5 μm of olL of 10 μ L-1Thrombin aptamers (TBA) solution is dripped to Pt NPs/TiO2/Ti3C2TXModified ITO electricity
On extremely.Reaction carries out 12 hours at 4 DEG C, is successfully consolidated with ensuring that aptamer passes through the covalent bond formed between Pt and the sulfydryl of TBA
It is scheduled on M NPs/TiO2/Ti3C2TXOn/ITO, TBA/Pt NPs/TiO is obtained2/Ti3C2TX/ITO.After completion of the reaction, PBS is used
Electrode is rinsed to remove Physical Absorption.Then, it is small that electrode is covered to 1 with 1% bovine serum albumin(BSA) (BSA) of 10 μ L at 4 DEG C
When, so that the unreacted active site on electrode surface inactivates, then thoroughly washing.
In order to compare, Pt NPs/ITO sensor and TiO are obtained by method similar to the above2/Ti3C2TXModified
ITO sensor.
Experiment measurement
By the TBA/Pt NPs/TiO of preparation2/Ti3C2TX/ ITO electrode is in 10 μ containing various concentration thrombin solution
It is incubated 40 minutes in L0.1MPBS in 37 DEG C.Fibrin ferment is fixed on the surface of modified electrode by specific recognition affinity
Then reaction between TBA and fibrin ferment is thoroughly washed with PBS.Then, TB/TBA/Pt NPs/TiO is successfully developed2/
Ti3C2TX/ ITO electrode simultaneously is used to detect fibrin ferment.Next, the aptamer sensor of acquisition is immersed in 20 μM of MB solution 5 minutes
It is reacted with completing the identification of the MB aptamer chain unidentified with fibrin ferment, washs electrode gently with ultrapure water then to obtain MB/TB/
TBA/Pt NPs/TiO2/Ti3C2TX/ITO。
In order to compare, we are also prepared for MB/TB/TBA/Pt NPs/ITO and MB/TB/TBA/TiO2/Ti3C2TX/ITO
Electrode.
Electrochemistry experiment and measurement are carried out on the CHI660E electrochemical workstation with conventional three-electrode system, and
Electrochemical impedance spectroscopy (EIS) measurement is carried out by Princeton Applied Research (USA).By modified electrode in 0.1M
CV test is carried out in PBS (pH7.4), and is containing 5mM [Fe (CN)6]4-/3-Solution in carry out EIS test.CV experiment with
0.1V s-1Sweep speed carry out.EIS is determined under the frequency window of 0.1Hz to 10kHz and the replacement voltage of 5mV.DPV is real
It tests and is carried out in the potential range of -0.6 to 0.0V (relative to SCE) in 0.1M PBS buffer solution (pH7.4).
Control variable experiment, the machine of research experiment are carried out using cyclic voltammetry (CV) or differential pulse voltammetry (DPV)
Manage feasibility.
Above-described embodiment is the preferable embodiment of the disclosure, but embodiment of the present disclosure is not by above-described embodiment
It limits, made changes, modifications, substitutions, combinations, simplifications under other any spiritual essence and principles without departing from the disclosure,
It should be equivalent substitute mode, be included within the protection scope of the disclosure.
Claims (10)
1. a kind of M NPs/TiO2/Ti3C2TXThe preparation method of composite material, characterized in that this method comprises:
By stratiform Ti3C2TX, precious metal salt and water be uniformly mixed, then hydro-thermal reaction 12~16 hours at 160~200 DEG C, cold
But 12~15h is stood afterwards, and M NPs/TiO can be prepared2/Ti3C2TXComposite material.
2. preparation method as described in claim 1, characterized in that stratiform Ti3C2TXPreparation method, this method specifically includes:
By 2g to 4g Ti3AlC2It is added in 4 DEG C to 6 DEG C of the 9M HF solution of 20mL to 40mL, obtains mixed solution；By mixed solution
It is stirred at 4 DEG C to 6 DEG C 10~30 minutes, is then stirred 22~26 hours at 42~47 DEG C, obtain Ti3C2TXThin slice hangs
Supernatant liquid；Then it is centrifuged until the pH of suspension reaches 6~7；By being ultrasonically treated 10~12 hours acquisition stratiform Ti3C2TX
Colloidal solution, be then centrifuged for remove sediment；
Further, the precious metal salt includes silver nitrate, six hydration gold chlorides and six hydration chloroplatinic acids.
3. preparation method as described in claim 1, characterized in that stratiform Ti3C2TX, precious metal salt and water ratio be (30~
120) mg:(15~30) mL:(50~80) mg.
4. the M NPs/TiO being prepared using method according to any one of claims 1 to 32/Ti3C2TXComposite material,
It is characterized in, the M NPs/TiO2/Ti3C2TXThe microscopic appearance of composite material are as follows: TiO2Nanometer rods are closely uniformly adhered to or are worn
It is inserted in stratiform Ti3C2TXOn, M NPs is uniformly adhered to TiO2Nanometer rods and stratiform Ti3C2TXOn, wherein TiO2Nanometer rods it is straight
Diameter is 5~30nm, and the ratio of diameter and length is 1:(3~8), M NPs size is 12~18nm.
5. a kind of thrombin aptamers sensor, characterized in that the sensor includes:
Base electrode；
M NPs/TiO as claimed in claim 42/Ti3C2TXComposite material, the M NPs/TiO2/Ti3C2TXComposite material attachment
On base electrode, M NPs/TiO is formed2/Ti3C2TXModified base electrode；
And thrombin aptamers, the thrombin aptamers pass through covalent bond and the M NPs/TiO2/Ti3C2TXModified matrix
M NPs in electrode is connected.
6. thrombin aptamers sensor as claimed in claim 5, characterized in that described matrix electrode is indium tin oxide electricity
Pole.
7. thrombin aptamers sensor as claimed in claim 6, characterized in that the sequence of the thrombin aptamers is 5'-SH-
(CH2)6-GGT TGGTGTGGT TGG-3'。
8. the preparation method of thrombin aptamers sensor described in claim 5 or 6, characterized in that this method includes following step
It is rapid:
By M NPs/TiO2/Ti3C2TXThe hanging drop of composite material is applied on base electrode, and M NPs/TiO is prepared2/
Ti3C2TXModified base electrode；
Thrombin aptamers are dripped into M NPs/TiO2/Ti3C2TXReaction is attached on modified base electrode, after reaction,
Then washing closes unreacted active site using bovine serum albumin(BSA), obtains thrombin aptamers sensor.
9. M NPs/TiO as claimed in claim 42/Ti3C2TXComposite material or thrombin aptamers described in claim 4 or 5
Application of the sensor in detection fibrin ferment.
10. a kind of method for detecting fibrin ferment, characterized in that this method comprises: using fibrin ferment described in claim 4 or 5
Aptamer sensor Selective recognition fibrin ferment after identification, thrombin aptamers sensor is immersed in methylene blue solution, is not had
Methylene blue is adsorbed with the aptamer of fibrin ferment identification, detects fibrin ferment using the electrochemical signals of methylene blue.
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| CN109975382B (en) * | 2019-04-04 | 2021-06-22 | 北京工商大学 | Tyrosinase biosensor with phosphorus-doped MXene modified electrode and preparation method and application thereof |
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