CN107271508B - Terramycin electrochemistry aptamer sensor and its preparation method and application - Google Patents
Terramycin electrochemistry aptamer sensor and its preparation method and application Download PDFInfo
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- CN107271508B CN107271508B CN201710427576.XA CN201710427576A CN107271508B CN 107271508 B CN107271508 B CN 107271508B CN 201710427576 A CN201710427576 A CN 201710427576A CN 107271508 B CN107271508 B CN 107271508B
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- terramycin
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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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a kind of terramycin electrochemistry aptamer sensors and its preparation method and application.The Fe3O4@C nano composite material includes: porous carbon matrix and is at least uniformly distributed in a plurality of Fe of the porous carbon Medium Culture3O4Nano particle.The present invention has been gone back based on the Fe3O4The aptamer sensor of@C nano composite material, preparation method is simple, used Fe3O4The nanostructure of@C nano composite material has hypotoxicity, high stability and electro-chemical activity, there are the aptamer sensors of recognition capability to have highly sensitive and selectivity between used aptamer chain and OTC, so that the specific surface area of the aptamer sensor is high, biological affinity is strong, testing process when detecting for OTC is simple, and detection sensitivity is high, detection limit is low.
Description
Technical field
The present invention relates to a kind of aptamer sensor, in particular to a kind of terramycin electrochemistry aptamer sensor and its preparation side
Method and application, belong to field of biotechnology.
Background technique
The growth that the antibiotic largely generated naturally now is often used in and treats sick animal, promotes animal.Its
In, terramycin (OTC) is used as a kind of very high antibiotic of frequency of use, is widely used in treatment agricultural and aquiculture animal
Communicable disease.However, only some OTC can be metabolized suction in animal bodies due to its lower bioavilability
It receives, remaining OTC will be drained and be discharged into soil, in surface water and groundwater, this leads to serious environmental problem and potential
Human Health Risk.Therefore, in order to make the mankind from the harm of left drug, the World Health Organization, European Union and Chinese agriculture
Portion provides that maximum residue limit of the terramycin in milk is 0.1mgkg-1.So far, the trace of residual terramycin is examined
Survey the attention for having attracted many people.The method of traditional detection terramycin has liquid chromatogram, electrophoresis, enzyme linked immunosorbent assay and height
Effect liquid phase chromatogram method.Even if these traditional methods it is reliable, it is sensitive and stablize, but they application because some defects such as:
Expensive facility, high cost and sample preparation time is long and is restricted.It is protected to meet rapid economic development and food safety
The requirement of barrier provides simple, high sensitivity, just there is an urgent need to formulate new sensing strategy for the OTC residual of field of food safety
Prompt detection instrument.
Recently, because the sequence of the oligonucleotides complementary with the targeting binding site of aptamers can design, aptamer base is raw
Object sensor detection small molecule target (aptamer sensor) increasingly causes to pay close attention to.Compared with antibody biosensor, aptamer is passed
Sensor has many advantages, such as that higher affinity, synthetic method are simple, facilitates label and better stability.Aptamer sensor is comprehensive
The brilliant performance of the advantages of electrochemical techniques and aptamer sensor, so its development causes the interest of many people.In order to
Seek preferably fixed platform, the material for having explored different modifying electrode includes carbon nanomaterial, metal nanoparticle, conduction
Polymer etc., for improving the bioactivity of useful load and probe molecule.
In recent years, the nano-porous materials emerging as one, metal-organic framework material (MOFs) are connected by organic ligand
The synthesis of metal node is connect, since it is with unique performance, such as the adjustability of high surface area and structure and function,
Show good application prospect.And super capacitor is had been widely used for using the related nano material that MOFs is prepared as template
Device, electrode material and catalyst.In these MOFs materials, Fe base MOFs (Fe-MOFs) shows brilliant chemical stability,
Because their toxicity is low and rich content, it is most important that their Louis's highly acid, this allow it with carboxylate more
It is coordinated well, keeps skeleton more stable.In addition, being gone back when Fe-MOFs is used as electrode material with excellent biocompatibility and oxidation
Former activity.However, the poorly conductive of Fe-MOFs is in practical applications so as to cause poor circulation.
Summary of the invention
The main purpose of the present invention is to provide a kind of terramycin electrochemistry aptamer sensor and its preparation method and application,
With overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The present invention provides a kind of mesoporous carbon nano-composite material of iron oxide-, including porous carbon matrix and at least uniformly
It is distributed in a plurality of Fe of the porous carbon Medium Culture3O4Nano particle.
Further, the porous carbon matrix is porous carbon nanosheet, and at least described porous carbon nanosheet is embedded in
There are a plurality of Fe3O4Nano particle；
Preferably, Fe is also distributed in the surface of the porous carbon nanosheet3O4Nano particle；
Preferably, the Fe3O4The partial size of nano particle is 8-70nm, preferably 40-70nm, especially preferably 60-
70nm；
Preferably, the aperture in the porous carbon matrix contained hole hole is 18.5-29.7nm；
Preferably, the porous carbon matrix is agraphitic carbon matrix；
Preferably, the porous carbon nanosheet with a thickness of 3-8nm, the aperture of the porous carbon nanosheet is 18.5-
29.7nm；
Preferably, the porous carbon matrix and the Fe3O4The mass ratio of particle is 10.64:1-26.08:1；
Preferably, the specific surface area of the mesoporous carbon nano-composite material of the iron oxide-is 27.24-315.12m2·g-1。
The present invention also provides a kind of preparation methods of the mesoporous carbon nano-composite material of iron oxide-, comprising:
Fe-MOFs is provided,
And then cool to room temperature Fe-MOFs in 350-900 DEG C of temperature lower calcination 4-6h, obtain iron oxide-Jie
Hole carbon nano-composite material.
Further, which comprises by Fe-MOFs with 5-7 DEG C of min-1Heating rate be heated to 350-900
DEG C, and calcining 4-6h is kept the temperature, then cooled to room temperature, obtains the mesoporous carbon nano-composite material of iron oxide-.
Further, which comprises by FeSO4·7H2O, 4,4'4 "-tricarboxylic acid triphenylamine (H3NTB), N- methyl
After formamide (NMF) and n-methyl-2-pyrrolidone (NMP) mixing, in 140-160 DEG C of heating 3-5d, the Fe- is made
MOFs；
Preferably, the H3NTB and FeSO4·7H2The molar ratio of O is (1-3): (8-10)；
Preferably, the volume ratio of the NMF and NMP is (1-3): (1-3).
The present invention also provides a kind of terramycin electrochemistry aptamer sensors, comprising:
The mesoporous carbon nano-composite material of iron oxide-；
It modifies in the terramycin aptamer chain on the mesoporous carbon nano-composite material of the iron oxide-.
Further, the terramycin electrochemistry aptamer sensor further include: electrode matrix, the Fe3O4@C nano is compound
Material is fixed on the electrode matrix surface；
Preferably, the electrode matrix includes gold electrode；
Preferably, the sequence of the terramycin aptamer chain are as follows: 5 '-CGTA CGGA ATTC GCTA GCCG AGGC ACAG
TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC GAGC TCCA CGTG-3’。
The present invention also provides a kind of preparation methods of terramycin electrochemistry aptamer sensor, comprising:
The mesoporous carbon nano-composite material of iron oxide-is prepared using method above-mentioned；
Solvent, which is dispersed, by the mesoporous carbon nano-composite material of the iron oxide-forms unit for uniform suspension, it will be described uniformly outstanding
Supernatant liquid is applied on electrode matrix and drying；
The nano combined material of iron oxide-mesoporous carbon being fixed on the solution impregnation of terramycin aptamer chain on the electrode matrix
Material makes the modification of terramycin aptamer chain on the mesoporous carbon nano-composite material of iron oxide-, forms the electrochemistry aptamer sensor.
Another aspect of the present invention additionally provides a kind of detection method of terramycin, comprising:
The terramycin electrochemistry aptamer sensor is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, later
Electro-chemical test is carried out using the terramycin electrochemistry aptamer sensor as working electrode, is realized to native in liquid sample
The detection of mycin.
Further, the electrochemical test method includes electrochemical impedance spectroscopy or cyclic voltammetry.
Compared with prior art, the invention has the advantages that
Fe provided by the invention3O4The nanostructure of@C nano composite material has hypotoxicity, high stability and electrochemistry living
Property；
It is provided by the invention to be based on Fe3O4The aptamer sensor preparation method of@C nano composite material is simple, testing process letter
It is single；And the specific surface area of the aptamer sensor is high, biological affinity is strong, detection sensitivity is high, detection limit is low, can be used for fast
Speed accurately detects OTC.
Detailed description of the invention
Fig. 1 a is the coordination mode structural schematic diagram of the NTB ligand of Fe-MOFs in the embodiment of the present invention 1；
Fig. 1 b is the view of the 1-D bar array of Fe-MOFs in the embodiment of the present invention 1；
Fig. 1 c is the 3-D circuit theory schematic diagram of Fe-MOFs in the embodiment of the present invention 1；
Fig. 2 is the crystal structural data schematic diagram of Fe-MOFs in the embodiment of the present invention 1；
Fig. 3 a, Fig. 3 b, Fig. 3 c are Fe-MOFs, Fe in the embodiment of the present invention 2 respectively3O4The XRD of@C nano composite material with
TGA figure；
Fig. 4 a1, Fig. 4 a2, Fig. 4 b1, Fig. 4 b2, Fig. 4 c1, Fig. 4 c2, Fig. 4 d1, Fig. 4 d2, Fig. 4 e1, Fig. 4 e2 are this hair respectively
Fe-MOFs, Fe in bright embodiment 23O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900The XPS of nanocomposite is decomposed
Spectrum；
Fig. 5 is Fe-MOFs, Fe in the embodiment of the present invention 23O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900It is compound
The full spectrogram of the XPS of material；
Fig. 6 a, Fig. 6 b are that Fe-MOFs schemes in 3000 times and 1800 times of SEM in the embodiment of the present invention 2, and figure c, figure d are TEM
Figure；
Fig. 7 a, Fig. 7 b, Fig. 7 c, Fig. 7 d, Fig. 7 e, Fig. 7 f, Fig. 7 g, Fig. 7 h are Fe in the embodiment of the present invention 2 respectively3O4@C350、
Fe3O4@C550、Fe3O4@C700And Fe3O4@C900Nanocomposite low power and high power TEM image, illustration is corresponding
SAED figure；
Fig. 8 is Fe-MOFs and different Fe in the embodiment of the present invention 23O4The nitrogen adsorption-desorption of@C nano composite material
Thermoisopleth；
The EIS curve in CV curve and Fig. 9 b in Fig. 9 a is that use is developed based on Fe-MOF in the embodiment of the present invention 2
Aptamer sensor is in the 5mM [Fe (CN) containing 0.14M NaCl and 0.1M KCl6]3-/4-Solution in detect OTC；
Figure 10 a1, Figure 10 b1, Figure 10 c1, Figure 10 d1, Figure 10 a2, Figure 10 b2, Figure 10 c2, Figure 10 d2 are of the invention real respectively
It applies in example 2 using based on Fe3O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900The aptamer sensor of exploitation is containing
5mM [the Fe (CN) of 0.14M NaCl and 0.1M KCl6]3-/4-Solution in detect OTC CV and EIS curve graph；
Figure 11 is in the embodiment of the present invention 2 using based on Fe-MOF, Fe3O4@C350、Fe3O4@C550、Fe3O4@C700With
Fe3O4@C900The Δ R in each stage of the aptamer sensor detection OTC of exploitationctValue；
Figure 12 a is Apt/Fe in the embodiment of the present invention 23O4@C900/ AE detect various concentration OTC (0,0.005,0.01,
0.05,0.1,0.5 and 1ngmL-1) EIS response curve；
Figure 12 b is Δ R in the embodiment of the present invention 2ctWith the curve of OTC concentration, wherein illustration is the linear portion of calibration curve
Point；
Figure 13 a, Figure 13 b are in the embodiment of the present invention 2 respectively for detecting the Fe of OTC3O4@C900The choosing of base aptamer sensor
Selecting property and reproducibility map；
Figure 14 a, Figure 14 b are that detectable concentration is used in the embodiment of the present invention 2 as 0.005ngmL respectively-1OTC
Fe3O4@C900The stability and reproducibility map of base aptamer sensor.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
The embodiment of the invention provides a kind of mesoporous carbon nano-composite material of iron oxide-, including porous carbon matrix and extremely
It is uniformly distributed in a plurality of Fe of the porous carbon Medium Culture less3O4Nano particle.
Further, the porous carbon matrix is porous carbon nanosheet, and at least described porous carbon nanosheet is embedded in
There are a plurality of Fe3O4Nano particle；
Preferably, Fe is also distributed in the surface of the porous carbon nanosheet3O4Nano particle；
Preferably, the Fe3O4The partial size of nano particle is 8-70nm, preferably 40-70nm, especially preferably 60-
70nm；
Preferably, the aperture in the porous carbon matrix contained hole hole is 18.5-29.7nm；
Preferably, the porous carbon matrix is agraphitic carbon matrix；
Preferably, the porous carbon nanosheet with a thickness of 3-8nm, the aperture of the porous carbon nanosheet is 18.5-
29.7nm；
Preferably, the porous carbon matrix and the Fe3O4The mass ratio of particle is 10.64:1-26.08:1；
Preferably, the specific surface area of the mesoporous carbon nano-composite material of the iron oxide-is 27.24-315.12m2·g-1。
The present invention also provides a kind of preparation methods of the mesoporous carbon nano-composite material of iron oxide-, comprising:
Fe-MOFs is provided,
And then cool to room temperature Fe-MOFs in 350-900 DEG C of temperature lower calcination 4-6h, obtain iron oxide-Jie
Hole carbon nano-composite material.
Further, which comprises by Fe-MOFs with 5-7 DEG C of min-1Heating rate be heated to 350-900
DEG C, and calcining 4-6h is kept the temperature, then cooled to room temperature, obtains the mesoporous carbon nano-composite material of iron oxide-.
Further, which comprises by FeSO4·7H2O, 4,4'4 "-tricarboxylic acid triphenylamine (H3NTB), N- methyl
After formamide (NMF) and n-methyl-2-pyrrolidone (NMP) mixing, in 140-160 DEG C of heating 3-5d, the Fe- is made
MOFs；
Preferably, the H3NTB and FeSO4·7H2The molar ratio of O is (1-3): (8-10)；
Preferably, the volume ratio of the NMF and NMP is (1-3): (1-3).
The present invention also provides a kind of terramycin electrochemistry aptamer sensors, comprising:
The mesoporous carbon nano-composite material of iron oxide-；
It modifies in the terramycin aptamer chain on the mesoporous carbon nano-composite material of the iron oxide-.
Further, the terramycin electrochemistry aptamer sensor further include: electrode matrix, the Fe3O4@C nano is compound
Material is fixed on the electrode matrix surface；
Preferably, the electrode matrix includes gold electrode；
Preferably, the sequence of the terramycin aptamer chain are as follows: 5 '-CGTA CGGA ATTC GCTA GCCG AGGC ACAG
TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC GAGC TCCA CGTG-3’。
The present invention also provides a kind of preparation methods of terramycin electrochemistry aptamer sensor, comprising:
The mesoporous carbon nano-composite material of iron oxide-is prepared using method above-mentioned；
Solvent, which is dispersed, by the mesoporous carbon nano-composite material of the iron oxide-forms unit for uniform suspension, it will be described uniformly outstanding
Supernatant liquid is applied on electrode matrix and drying；
The nano combined material of iron oxide-mesoporous carbon being fixed on the solution impregnation of terramycin aptamer chain on the electrode matrix
Material makes the modification of terramycin aptamer chain on the mesoporous carbon nano-composite material of iron oxide-, forms the electrochemistry aptamer sensor.
Another aspect of the present invention additionally provides a kind of detection method of terramycin, comprising:
The terramycin electrochemistry aptamer sensor is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, later
Electro-chemical test is carried out using the terramycin electrochemistry aptamer sensor as working electrode, is realized to native in liquid sample
The detection of mycin.
Further, the electrochemical test method includes electrochemical impedance spectroscopy or cyclic voltammetry.
The technical solution, its implementation process and principle etc. will be further explained in conjunction with specific embodiments as follows
It is bright.
Fe (the NO used in following examples of the present invention3)3·9H2O, 4,4', 4 "-nitroso dibenzoic acid (H3NTB),
N-Methyl pyrrolidone (NMP) and formic acid can be bought from Shanghai Jing Chun biochemical technology limited liability company；Terramycin (OTC),
Tetracycline, fortimicin and aureomycin can be bought from Suo Laibao company.The water used in following examples is ultrapure water
(18.2Ωcm-1).All reagents are the pure rank of analysis.The OTC aptamer sequence used in the embodiment of the present invention is: 5 '-CGTA
CGGA ATTC GCTA GCCG AGGC ACAG TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC
GAGC TCCA CGTG-3'.Because aptamer is functional ssDNA or RNA with uniqueness 3D structure, can with high specific with
Affinity identifies and combines its homology targets, these function chains are mainly for target detection.
The characterization equipment and mode used in following examples is as follows:
The analysis that C, H and N are carried out on 240 CHN elemental analyser of Perkin-Elmer, uses Nicolet850 spectrum
Instrument (Thermo Electron Corporation, Massachusetts, USA) passes through Fourier transform infrared spectroscopy (FTIR)
Analyze the chemical structure of nanocomposite；Use Cu KαRadiation records X on Rigaku D/Max-2500X x ray diffractometer x
Ray diffraction measurement (XRD)；With Labsys NETZSCH TG 209Setaram instrument in N2The rate of heat addition is 10 in atmosphere
℃·min-1When measure thermogravimetric (TGA)；Using 165 spectrometer of AXIS HIS (Kratos Analytical, Manchester,
UK monochrome chromaking Al K) is usedαX-ray source (1486.71eV photon) measures x-ray photoelectron spectroscopy (XPS)；Using Japan
JEOL JEM-2100 high resolution transmission electron microscopy tests high resolution transmission electron microscope image (HR-TEM), super
Under high vacuum, in the Belsorp MAX volumetric adsorption equipment with diaphragm and turbine pumping system, N is measured2Adsorption-desorption
Data.
X-ray single crystal analysis: with installation graphite monochromatic MoKαOr CuKα(λ=0.71073 or) Agilent section
The SuperNova monocrystalline crystal meter of skill company measurement data at different temperatures, with SHELXS (direct method) analytic structure, and
It is modified in Olex2 packet with SHELXL (complete matrix least square method).All non-hydrogen atoms, which are all displaced with anisotropy, joins
Number redefines, and the hydrogen atom being connected on carbon is placed in the ideal position of geometry, and repaired using model；Due to frame
In solvent molecule property it is highly disordered, cannot directly determine, thus using the SQUEEZE program in PLATON software at
Reason.Crystal data, TGA and the combination of elemental analysis can determine chemical formula, C372H493Na31N66O164Crystal data (M=
5973.07g·mol-1): cube, space group F-43c (number 219), a=48.1642 (8), Z
(6.356 ° of reflection of=8, T=293 (2) K, μ (CuK α)=0.640mm-1, Dcalc=0.710gcm-3,15687 measurement
≤ 2 θ≤144.072 °), 7387 unique (Rint=0.0604, Rsigma=0.0594), final R1 are the 0.0954 (σ of I > 2
(I)), wR2It is 0.2877.
Electrochemical measurement scheme involved in following examples, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry
(CV) it can be measured using CHI660D electrochemical workstation (Shanghai Chen Hua).Test is using conventional three-electrode system, wherein wrapping
The gold electrode for being 3mm as the diameter of working electrode is included, as Ag/AgCl (saturation KCl) electrode of reference electrode and as right
The platinized platinum of electrode；In the 0.5mM [Fe (CN) containing 0.1M KCl6]3-/4-(EIS parameter: current potential: 0.21V；Frequency range:
100kHz to 0.1Hz；Amplitude: 5mV) in measure EIS curve；Using Zview2 software analysis of spectra, non-linear minimum two are used
Multiply fitting to determine the component parameters in equivalent circuit.
Embodiment 1:
By mixing 0.242g KH2PO4, 1.445g Na2HPO4·12H2O, 0.200g KCl and 8.003g NaCl, and
The pH=7.4 that 0.1M HCl solution adjusts mixture is added, obtains phosphate buffer solution (PBS, pH 7.4).It is prepared with PBS
Aptamer and OTC solution, by by 1.650g K3Fe(CN)6With 2.111g K4Fe(CN)6Electrolysis can be prepared by being dissolved in 1L PBS
Matter solution.
The FeSO of 22.2mg is added in the rustless steel container of teflon lining4·7H2The 4 of O, 3.0mg, 4'4 "-tricarboxylic acid
Triphenylamine (H3NTB), the mixture of the n-methyl-2-pyrrolidone (NMP) of the N-METHYLFORMAMIDE (NMF) and 2mL of 2mL,
It is lower in 160 DEG C of baking oven to heat 3d.Brown flat crystal, as Fe-MOFs are obtained after being washed with DMF.Yield: 45%, base
In H3NTB ligand.IR (KBr, cm-1): 3414w (br), 1682m, 1654m, 1592vs, 1555m, 1505m, 1398vs,
1354m, 1318m, 1266m, 1173m, 1102w, 1013w, 840w, 784m, 713w, 671w, 629w, 583w, 532w, 513w,
436w；Elemental analysis (calculated value): C56H50Fe3N6O16: C, 51.6 (52.5)；H, 4.43 (5.05)；N, 7.40 (6.93) are described
The crystal structural data of Fe-MOFs is as shown in Figure 1, 2.
Prepared Fe-MOFs is placed in tube furnace and with 5 DEG C of min-1~7 DEG C of min-1Heating rate rise to
350 DEG C, 550 DEG C, 700 DEG C and 900 DEG C, respectively in 350 DEG C, 550 DEG C, 700 DEG C and 900 DEG C calcining 4h~6h；Then by sample
Cooled to room temperature obtains a series of mesoporous carbon nano-composite material of iron oxide-, can be respectively designated as: Fe3O4@
C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900。
Fe-MOFs and Fe3O4The chemical structure and component analysis of@C nano composite material:
Using XPS measuring Fe-MOFs and Fe3O4The chemical component and local environment of@C nano composite material.Five samples
XPS spectrum all shows that they have characteristic peak relevant to C, O and Fe and the weaker peak N；The characteristic peak of C 1s and O 1s come from
Coordination center Fe is derived from the peak of organic ligand, Fe 2p.Fig. 3 a, 3b, 3c are Fe-MOFs and Fe respectively3O4@C nano is compound
The XRD and TGA of material scheme；
Table 1 is the percentage composition of each atom, after being pyrolyzed as can be seen from Table 1 for Fe-MOFs at different temperatures
Material, such as Fe3O4@C350, C 1s content reduces to a certain extent first, this is because carbon containing organic solvent (NMF's) waves
The decomposition of hair and formic acid.As calcination temperature is increased to 550 DEG C, 700 DEG C and 900 DEG C, C 1s content is continuously increased, and is shown organic
The thermal decomposition of connector ligand generates porous carbon.For Fe 2p and O 1s content, Fe3O4@C350Increase first to a certain extent, so
Continuously decline with the raising of calcination temperature afterwards, variation tendency is opposite with C 1s content.
Difference Fe after 1 Fe-MOFs of table and thermal cracking3O4The atomic percent of@C nano composite material
In order to further appreciate that thermal decomposition front and back Fe-MOFs and Fe3O4Chemical component the C 1s and Fe of@C nano composite material
2p also analyzes their XPS figure (shown in such as Fig. 4 (a1, a2, b1, b2, c1, c2, d1, d2, e1, e2)).Original Fe-
The C 1s of MOFs (Fig. 4 a1), which decomposes spectrum, can be divided into 5 main peaks, in~283.7 ,~284.8 ,~285.6 and~287.9eV,
Respectively correspond C-C/C-H, C-N, C-O, COO-With the group of π-π *, these peaks will originate from organic linking ligand.As for not
The material of synthermal lower thermal cracking, such as Fe3O4@C350(Fig. 4 b1) has and C=O group in C 1s high-resolution XPS spectrum
Corresponding~286.8eV additional peak；For Fe3O4@C550And Fe3O4@C700(Fig. 4 c1 and d1), in C1s high-resolution XPS spectrum
Combination can position and the combination of Fe-MOFs can be consistent, but intensity is different, as Fe3O4@C900, in C 1s high-resolution
Also observed in rate XPS spectrum (Fig. 4 e1) distribute to C=O group~286.8eV at additional peak.
It is observed that from the Fe 2p core spectrum of five samples (Fig. 4 a2, Fig. 4 b2, Fig. 4 c2, Fig. 4 d2 and Fig. 4 e2) bright
Aobvious difference.In the Fe 2p spectrum of original Fe-MOFs (Fig. 4 a2)~711.1 and~724.9eV, correspond respectively to Fe
2p3/2With Fe 2p1/2.After Fe-MOFs pyrolysis, Fe3O4@C350The Fe 2p spectrum of (Fig. 4 b2) has~711.0 and~724.8eV two
A peak, it is consistent with Fe-MOFs.With the raising of calcination temperature, Fe3O4@C550The Fe 2p spectrum of (Fig. 4 c2) is divided into 5 peaks, point
Not Wei~709.3 ,~711.4 ,~717.7 ,~722.3 and~724.1eV, in conjunction with can be for the peak of 711.4 and 724.1eV
Fe3+Characteristic peak, and in conjunction with can be due to Fe for the peak value of 709.3 and 722.3eV2+.In addition, in conjunction with the peak that can be 717.7eV
It is due to Fe2+And Fe3+The satellite peak that collective effect generates.When temperature rises to 700 DEG C and 900 DEG C, Fe3O4@C700And Fe3O4@C900
Fe 2p optical spectroscopy to similar situation (Fig. 4 d2 and Fig. 4 e2)；Fe3+、Fe2+The combination of characteristic peak and satellite peak can distinguish
In 712.5,725.3,710.0,723.0,717.5eV and 711.3,724.0,709.2,722.1,717.6eV, sample
Fe2+And Fe3+Presence further demonstrate Fe3O4Formation.
Fig. 6 is the SEM and TEM image of Fe-MOFs, most of as can be seen that Fe-MOFs is block structure from image
Crystal is more than tens or even several hundred microns, and size uneven distribution illustrates the Fe-MOFs of preparation more like polycrystalline or dusty material；
The discontinuity of Fe-MOFs leads to their poorly conductive, therefore electro-chemical activity is bad.As shown in fig. 7, can from TEM figure
To find out the Fe under different pyrolysis temperatures3O4The metamorphosis of@C nano composite material；At first 350 DEG C of temperature, retain
The bulk morphologies of Fe-MOFs, at the edge of composite material are observed that Fe2O3, most of as shown in figs. 7 a and 7b
Fe3O4@C350Nanocomposite has equally distributed chondritic, and the chondritic is Fe3O4Nano particle, average-size
About 8-10nm.In addition, the electron diffraction diagram in selected areas electronic diffraction (SAED, Fig. 7 b, illustration) is several lattice compositions
Circular concentric, show Fe3O4@C350Nanocomposite is polycrystalline, and the lattice vacancy of 0.247 and 0.283nm is to correspond to
In (311) and (220) crystal face, it was demonstrated that Fe3O4The formation of@C.
As shown in figs. 7 c and 7d, in second stage (550 DEG C), it is found that bigger spheric granules forms and is embedded into more
In the carbon nanosheet of hole, and most of particle agglomerations obtain size between 100-150nm nanosphere (nanosphere be Fe3O4
The aggregate that particle is formed).This may be because organic remains is as reducing agent makes Fe2O3It is converted into Fe3O4, and making
What may be dispersed when being ready for use on the sample of TEM is incomplete.In addition, such as Fig. 7 d, SAED pattern displaying in illustration Fe2O3With
Fe3O4Lattice, wherein the Fe3O4Nano particle is rendered as monodisperse status.If Fig. 7 e schemes, Fig. 7 f, Fig. 7 g and Fig. 7 h institute
Show, when calcination temperature is further increased to 700 DEG C and 900 DEG C, the ferric oxide particles due to caused by crystal accumulation meeting increase.Such as figure
Shown in 7e and 7f, the TEM image of the Fe-MOFs calcined at 700 DEG C can be seen that nanocomposite is composite construction, therefrom
It can be seen that average diameter is the Fe of 40nm being individually wrapped by thin carbon boundary3O4Nano particle, and these particles be dispersed in it is more
The content of hole carbon and/or surface, as shown in Fig. 7 g and Fig. 7 h, in Fe3O4@C900It is observed in nanocomposite similar
Situation, Fe3O4The average-size (partial size) of particle increases to 60-70nm, and porous carbon is as Fe3O4The buffer area of particle aggregation makes
Crystal is distributed more evenly, and the illustration SAED explanation in Fig. 7 f and 7h has formed typical Fe3O4Lattice further demonstrates
Fe3O4Formation.
Fe-MOFs and different Fe3O4The N of@C nano composite material2Adsorption-desorption isothermal as shown in figure 8, Fe-MOFs and
The specific surface area of calcined product is respectively 846.19,27.24,119.45,315.12 and 258.03m2·g-1。
Embodiment 2:
Aptamer is incubated for 5min at 90 DEG C, is then slowly cooled to room temperature, by Fe prepared by embodiment 13O4@C350Powder
Last (0.5mg) is added in ethyl alcohol and thorough ultrasound is until obtain uniform Fe3O4@C350Suspension；Then, by 10 μ L's
Fe3O4@C350Suspension (0.5mgmL-1) spread on the surface of gold electrode (AE), then it is dried at room temperature for 5h；Then,
The electrode of modification is immersed into 2h in aptamer solutions (100nM), guarantees that aptamer chain is fixed at the electrode surface until reaching saturation shape
State；In this process, aptamer and Fe3O4@C nano composite material is formed in conjunction with amido bond by aptamer chain with target specific moiety,
This will lead to redox probe and reduces to the surface degree of closeness of the AE of modification, therefore electro-chemical activity will reduce.Finally, will
The fixed Fe of aptamer3O4@C350/ AE, which immerses in OTC solution, carries out electro-chemical test.In Electrochemical Detection, ligand can be formed
There is tetra- stranded structure of G- of high-affinity with OTC.
In order to compare, also construct in an identical manner based on aforementioned Fe-MOFs, Fe3O4@C550、Fe3O4@C700And Fe3O4@
C900Aptamer sensor as a comparison.
Later by blank AE, the aptamer sensor based on aforementioned Fe-MOFs, based on aforementioned each iron oxide-mesoporous carbon nanometer
The aptamer sensor of composite material is in the 5mM [Fe (CN) 6] containing a certain concentration OTC, 0.14MNaCl and 0.1M KCl3-/4-'s
OTC is detected in solution, wherein the electrochemical detection method used is CV and EIS.
As shown in the CV curve in Fig. 9 a, there are a pair of specific reversible redox peak, peak-to-peak potential difference in blank AE figure
(ΔEp) it is 248mV.AE is through Fe-MOFs modified (Fe-MOF/AE), Δ EpIncrease to 292mV, redox peak current is corresponding
It reduces, illustrates that Fe-MOFs is coated on AE rear conductivity and reduces.When OTC targeting aptamer chain (Apt) is fixed on the surface Fe-MOF/AE
When (Apt/Fe-MOF/AE), Δ EpIt is slightly increased to 311mV, redox peak current is almost unchanged, shows Apt for Fe-
The influence of MOF/AE is unobvious.However, (the OTC/Apt/Fe-MOF/ when detecting OTC using the Apt/Fe-MOF/AE of preparation
AE), Δ EpIt is further increased to 369mV, redox peak current further decreases, it was demonstrated that OTC/Apt/Fe-MOF/AE's
Electric conductivity and electrochemistry reduce.It can be concluded that the electricity of four kinds of AEs of the different phase of detection OTC from the EIS figure in Fig. 9 b
Lotus transfer resistance (Rct) it is respectively 141.2,366.6,427.5 and 478.1 Ω, show to be fixed with Fe-MOFs on blank AE,
Electro-chemical activity reduces successively after Apt and OTC, RctAs a result variation tendency is consistent with above-mentioned CV result.
Test is based on aforementioned Fe in the same way3O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900Aptamer
The CV curve of sensor, as a result as shown in Figure 10 a1,10b1,10c1,10d1.Wherein, it is based on Fe3O4@C350Sensor (Apt/
Fe3O4@C350/ AE) four AEs Δ EpRespectively 271,301,354 and 399mV；Based on Fe3O4@C550Sensor (Apt/
Fe3O4@C550/ AE) four AEs Δ EpRespectively 256,305,402 and 463mV；Based on Fe3O4@C700Sensor (Apt/
Fe3O4@C700/ AE) four AEs Δ EpRespectively 243,354,433 and 500mV；Based on Fe3O4@C900Sensor (Apt/
Fe3O4@C900/ AE) four AEs Δ EpFor 251,283,354 and 420mV.The result shows that Δ EpWith redox peak current
Variation tendency meet identical rule, i.e., in blank AE by Fe3O4After@C, Apt and OTC are continuously fixed, Δ EpIt is continuous to increase
Add, the decline of redox peak current, four kinds are based on Fe3O4The electro-chemical activity of the aptamer sensor of@C nano composite material is corresponding
It reduces.It is to be indicated with EIS based on the four kinds of Fe calcined at different temperatures as shown in Figure 10 a2,10b2,10c2,10d23O4@C
Nanocomposite aptamer sensor detects the whole process of OTC.For blank AE, there is small semicircle at upper frequency,
Respectively correspond (a) Fe3O4@C350, (b) Fe3O4@C550, (c) Fe3O4@C700(d) Fe3O4@C900RctValue for 122.7,
39.26,69.17 and 42.24 Ω.With four kinds of Fe3O4@C nano composite material distinguishes modified, RctValue significantly increases respectively
260.7,98.4,133.3 and 119.6 Ω, shows Fe3O4The conductivity of@C nano composite material is relatively poor；When OTC targeting is suitable
Body (Apt) chain is fixed on Fe3O4When the surface C/AEs@, Apt/Fe3O4The R of@C/AEctValue further increases respectively to respectively
330.3,183.0,236.8 and 334.1 Ω, because of the negatively charged phosphate for including in aptamer chain and [Fe (CN)6]3-/4-Oxygen
Change repulsive interaction of the reduction between, so the R of the interface between analyte solution and electrodectIncrease.It is made when using
Standby Fe3O4@C base aptamer sensor is come when measuring OTC, the semicircle of EIS curve is further increased, the corresponding R of half-round curvectValue
The Ω of respectively 409.6,288.2,375.3 and 507.3, in the presence of OTC, the aptamer chain of OTC targeting with OTC by tying
It closes and changes its conformation, conjuncted to form tetra- chain of G-, this will prevent electric charge transfer.In addition, such as in N2In adsorption-desorption isothermal
It is discussed, Fe3O4@C nano composite material has meso-hole structure and high-specific surface area, therefore OTC can be adsorbed onto Fe3O4@C
On nanocomposite, a large amount of OTC is adsorbed to Apt/Fe3O4The surface of@C/AEs further makes electric charge transfer become tired
It is difficult.Therefore, the obstruction of OTC and blocking effect result in Apt/Fe3O4The electro-chemical activity of@C/AE significantly reduces.
Fe is based in order to compare Fe-MOFs and four kinds3O4The electrochemistry aptamer sensor of@C nano composite material is to detection
The different detection effects of OTC, the present invention provides the R of the every step of aforementioned five bio-sensing systemsctIt is worth (Δ Rct) variation and table
Show in Figure 11.ΔRctThe difference of value is as shown in the histogram in Figure 11, from histogram as can be seen that with other four kinds of material phases
Than Fe3O4@C900The Apt adsorbance on the surface /AE is maximum, due to Fe3O4@C900The specific surface area and meso-hole structure highest of/AE, because
This can further help to absorb most of OTC, and have maximum Δ Rct(Rct,Apt-RCt, material) and Δ Rct(Rct,OTC-
Rct,Apt).Therefore, the optimum electrode material for measuring electrochemistry is Fe3O4@C900。
Apt/Fe3O4@C900The sensitivity test of/AE: by by Apt/Fe3O4@C900/ AE is together with the OTC of various concentration
It is incubated for, then in [Fe (CN)6]3-/4-Their EIS map is measured in solution.Figure 12 a is the OTC for detecting various concentration
Apt/Fe3O4@C900The EIS of/AE schemes, because of effective identification of the aptamer sensor to OTC, RctValue with OTC concentration increasing
Add (from 0.005 to 1.0ngmL-1) and gradually increase.This may be because of the increase with OTC concentration, in nano combined electricity
More molecular recognitions between antigen-antibody complex are produced in pole surface, so as to cause RctThe enhancing of value.Sensor exists
Detect the Δ R before and after OTCctIt is determining numerical value (2b refering to fig. 1), and works as the logarithm (logC of OTC concentrationOTC)
When range from -2.301 to 0, Δ RctValue and logCOTCDirectly proportional, its equation of linear regression is Δ Rct=0.676logCOTC+
1.762, related coefficient (R2) it is 0.9944.According to Langmuir adsoption equation, when signal-to-noise ratio (s/n) is than being 3, analog detection
(LOD) is limited down to 0.027pgmL-1。
Apt/Fe3O4@C900The selectivity and stability test of/AE: Apt/Fe is used3O4@C900/ AE detects possibility respectively
It is 10 with the concentration that OTC coexists-3The antibiotic of nM (10 times of OTC concentration) includes tetracycline, Doxycycline, aureomycin and blank
PBS buffer solution.As depicted in fig. 13 a, Δ R significant with detection OTCctResponse is on the contrary, interfere obtained sound by adding other
It should change negligible.Therefore, there is high degree of specificity, electrochemistry aptamer sensor pair between its corresponding probe aptamer of OTC
OTC selectivity with higher；Reproducibility is the important indicator of assessment exploitation aptamer sensor performance, is prepared under the same conditions
Five be based on Fe3O4@C900The aptamer sensor of nanocomposite is dissolved in PBS under room temperature (25 DEG C) by detecting
10-5Δ R caused by the OTC of nMctValue tests the reproducibility (Figure 13 b) of aptamer sensor.Simultaneously with five aptamer sensors
Detect the Δ R of the OTC of same concentrationsctThe relative standard deviation (RSD) of value is 2.6%, shows reproducibility between sensor very
It is good.
In addition, stability and reproducibility are also to assess the important indicator of aptamer sensor performance.Within a couple of days, survey every time
Electrode is immersed in ultrapure water after amount and is saved it in 4 DEG C of refrigerator and the Δ R of recording electrodectValue, with these Δs RctValue
To indicate Fe3O4@C900The stability (Figure 14 a) of aptamer sensor.The R of 60nM OTC is not found after 15 daysctIt significantly reduces；Again
One week is spent, RctAfter value decline about 10%, one month, about 17% is had dropped.It will be combined with the nanometer combined electrode of OTC at room temperature
It immerses in 1.0M NaOH and 80 minutes and is washed with water, survey its RctThen value is immersed 2 hours in the OTC solution of same concentrations again and is surveyed
Its RctValue repeats the step for several times, compares RctIt is worth and assesses reproducibility.As shown in fig. 14b, in preceding 5 regeneration runtimes
Between, observe the Δ R of aptamer sensorctIt is worth no substantial variations, shows easily to regenerate.It is all these the result shows that,
Aptamer sensor provided by the invention not only has highly sensitive and selectivity, but also has good reproducibility, stability and
Reproducibility.
Embodiment 3:
Actual sample is tested using a series of sensors made from embodiment 2, which is milk.Accordingly
Test process include:
In 50mL centrifuge tube, by the mixing of 12mL raw milk and 18mL ultrapure water and 6mL 10% trichloroacetic acid and chloroform
Mixing 1min is under vortex concussion with the organic substance in depositing proteins and dissolved matrix for object, then by mixture at 20 DEG C
It is ultrasonically treated 15min, and with 13000rpm centrifugation 10min to separate deposit；Supernatant is transferred in another centrifuge tube,
And with 10000rpm centrifugation 10min to remove deposit again；A certain amount of OTC is added in stoste, then according to above-mentioned step
Suddenly it is pre-processed and is analyzed；The solution is detected according to the above method, mark-on sample is analyzed by HPLC and is proposed with verifying
Analysis method reliability.
Result is obtained according to the standard curve of Figure 12 b.As shown in table 2, the rate of recovery of the aptamer sensor be 98% to
104%, RSD are less than 3.0%.Meanwhile according to chinese national standard GB/T22990-2008, also determined in milk with HPLC
OTC show that the result of aptamer sensor provided by the invention complies fully with the requirement of HPLC by comparing, these all show this
New strategy is for quickly detecting the OTC in milk with very high reproducibility, accuracy and feasibility.
The OTC in aptamer sensor detection milk sample that table 2 is developed
The present invention is by the way that Fe-MOFs to be pyrolyzed to form a series of Fe in different temperatures3O4@C nano composite material, at these
Fe in nanocomposite3O4Nano particle is embedded in mesoporous amorphous carbon substrate, so that these nanocomposites all have
The advantages that specific surface area is high, good biocompatibility, biological affinity is strong, Fe especially therein3O4@C900It is aobvious to the detection of OTC
Optimal electro-chemical activity is shown, therefore can be used for constructing electrochemistry aptamer sensor.Especially, it is based on Fe3O4@C900Exploitation
OTC aptamer sensor show high sensitivity, in OTC concentration from 0.005 to 1ngmL-1The wide range of linearity in detection limit
Down to 0.027pgmL-1, while the sensor also has highly selective, a good reproducibility, stability, reproducibility and is applicable in
The features such as property.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (17)
1. a kind of terramycin electrochemistry aptamer sensor, characterized by comprising:
The mesoporous carbon nano-composite material of iron oxide-；
It modifies in the terramycin aptamer chain on the mesoporous carbon nano-composite material of the iron oxide-；
Wherein, the mesoporous carbon nano-composite material of the iron oxide-includes porous carbon nanosheet and Fe3O4Nano particle, middle part
Divide the Fe3O4Nano particle is evenly distributed on the surface of porous carbon nanosheet, the part Fe3O4Described in nano particle insertion
In porous carbon nanosheet, the porous carbon nanosheet and the Fe3O4The mass ratio of particle is 10.64:1 26.08:1.
2. terramycin electrochemistry aptamer sensor according to claim 1, it is characterised in that it further include electrode matrix, it is described
The mesoporous carbon nano-composite material of iron oxide-is fixed on the electrode matrix surface.
3. terramycin electrochemistry aptamer sensor according to claim 2, it is characterised in that: the electrode matrix includes gold
Electrode.
4. terramycin electrochemistry aptamer sensor according to claim 2, it is characterised in that: the terramycin aptamer chain
Sequence are as follows: 5 '-CGTA CGGA ATTC GCTA GCCG AGGC ACAG TCGC TGGT GCCT ACCT GGTT GCCG
TTGT GTGG ATCC GAGC TCCA CGTG-3’。
5. terramycin electrochemistry aptamer sensor according to claim 1, it is characterised in that: the Fe3O4Nano particle
Partial size is 8 70 nm.
6. terramycin electrochemistry aptamer sensor according to claim 5, it is characterised in that: the Fe3O4Nano particle
Partial size is 40 70 nm.
7. terramycin electrochemistry aptamer sensor according to claim 5, it is characterised in that: the Fe3O4Nano particle
Partial size is 60 70 nm.
8. terramycin electrochemistry aptamer sensor according to claim 1, it is characterised in that: the porous carbon nanosheet is
Agraphitic carbon matrix.
9. terramycin electrochemistry aptamer sensor according to claim 1, it is characterised in that: the porous carbon nanosheet
With a thickness of 38 nm, the aperture of the porous carbon nanosheet is 18.5 29.7 nm.
10. terramycin electrochemistry aptamer sensor according to claim 1, it is characterised in that: the iron oxide-mesoporous carbon
The specific surface area of nanocomposite is 27.24 315.12 m2·g−1。
11. such as the preparation method of terramycin electrochemistry aptamer sensor of any of claims 1-10, feature exists
In including:
Prepare the mesoporous carbon nano-composite material of iron oxide-；
Solvent is dispersed by the mesoporous carbon nano-composite material of the iron oxide-and forms unit for uniform suspension, by the unit for uniform suspension
It is applied on electrode matrix and dry；
The mesoporous carbon nano-composite material of iron oxide-being fixed on the electrode matrix with the solution impregnation of terramycin aptamer chain,
Make the modification of terramycin aptamer chain on the mesoporous carbon nano-composite material of iron oxide-, forms the electrochemistry aptamer sensor.
12. according to the preparation method described in claim 11, characterized by comprising:
Ferrous metals organic framework materials are provided,
And by ferrous metals organic framework materials with 57 DEG C of min-1Heating rate be heated to 350 900 DEG C, and keep the temperature
46 h are calcined, then cooled to room temperature, obtains the mesoporous carbon nano-composite material of iron oxide-.
13. according to the preparation method described in claim 12, characterized by comprising: by FeSO4∙7H2O, 4,4'4''- tricarboxylic acids three
After aniline, N-METHYLFORMAMIDE and n-methyl-2-pyrrolidone mixing, in 140 160 DEG C of 35 d of heating, it is made described iron-based
Metal-organic framework material.
14. according to the preparation method described in claim 13, it is characterised in that: 4, the 4'4''- tricarboxylic acid triphenylamine and FeSO4∙
7H2The molar ratio of O is 1-3:8-10.
15. according to the preparation method described in claim 13, it is characterised in that: the N-METHYLFORMAMIDE and N- methyl -2- pyrroles
The volume ratio of alkanone is 1-3:1-3.
16. a kind of detection method of terramycin, characterized by comprising:
Terramycin electrochemistry aptamer sensor of any of claims 1-10 is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, later with institute
Terramycin electrochemistry aptamer sensor is stated as working electrode and carries out electro-chemical test, is realized to terramycin in liquid sample
Detection.
17. the detection method of terramycin according to claim 16, it is characterised in that: the electrochemical test method includes
Electrochemical impedance spectroscopy or cyclic voltammetry.
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