CN107271508A - Mesoporous carbon nano-composite material of iron oxide and its preparation method and application - Google Patents
Mesoporous carbon nano-composite material of iron oxide and its preparation method and application Download PDFInfo
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- CN107271508A CN107271508A CN201710427576.XA CN201710427576A CN107271508A CN 107271508 A CN107271508 A CN 107271508A CN 201710427576 A CN201710427576 A CN 201710427576A CN 107271508 A CN107271508 A CN 107271508A
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- G—PHYSICS
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Abstract
The invention discloses a kind of iron oxide mesoporous carbon (Fe3O4@C) nano composite material and its preparation method and application.The Fe3O4@C nano composites include：Porous carbon matrix and a plurality of Fe for being at least uniformly distributed in the porous carbon Medium Culture3O4Nano particle.The present invention has been gone back based on the Fe3O4The aptamer sensor of@C nano composites, its preparation method is simple, the Fe used3O4The nanostructured of@C nano composites has hypotoxicity, high stability and electro-chemical activity, the aptamer sensor that there is recognition capability between the fit chain and OTC that are used has high sensitivity and selectivity, so that the specific surface area of the aptamer sensor is high, biological affinity is strong, testing process when being detected for OTC is simple, and detection sensitivity is high, test limit is low.
Description
Technical field
The present invention relates to a kind of aptamer sensor, more particularly to a kind of iron oxide-mesoporous carbon (Fe3O4@C) nano combined material
Material and its preparation method and application, belongs to biological technical field.
Background technology
The antibiotic of now substantial amounts of generation naturally is often used in the growth treated sick animal, promote animal.Its
In, terramycin (OTC) is widely used in treatment agricultural and aquiculture animal as a kind of frequency of use very high antibiotic
Communicable disease.However, due to its relatively low bioavilability, only some OTC can be metabolized suction in animal bodies
Receive, the OTC of residual will be drained and be discharged into soil, in surface water and groundwater, this causes serious environmental problem and potential
Human Health Risk.Therefore, in order that the mankind are from the harm of left drug, the World Health Organization, European Union and Chinese agriculture
Portion provides that MRL of the terramycin in milk is 0.1mgkg-1.So far, the trace for remaining 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 are reliable, sensitive and stably, but their application because some defects such as：
Expensive facility, high cost and sample preparation time length and be restricted.Protected to meet rapid economic development and food security
The requirement of barrier, in the urgent need to formulating new sensing strategy, simple, sensitivity height, just is provided for the OTC residuals of field of food safety
Prompt detection instrument.
Recently, because the order of the oligonucleotides complementary with the targeting binding site of aptamers can be designed, fit base life
Thing sensor detection small molecule target (aptamer sensor) increasingly causes concern.It is fit to pass compared with antibody biology sensor
Sensor has the advantages that simple higher affinity, synthetic method, convenient mark and more preferable stability.Aptamer sensor is integrated
The advantage and the remarkable performance of aptamer sensor of electrochemical techniques, so its development causes the interest of many people.In order to
Seek preferably fixed platform, having explored the material of different modifying electrode includes carbon nanomaterial, metal nanoparticle, conduction
Polymer etc., the bioactivity for improving useful load and probe molecule.
In recent years, as an emerging nano-porous materials, metal-organic framework material (MOFs) is connected by organic ligand
The synthesis of metal node is connect, because it has the adjustability of unique performance, such as high surface area, and 26S Proteasome Structure and Function,
Show good application prospect.And the related nano material prepared by template of MOFs has been widely used for super capacitor
Device, electrode material and catalyst.In these MOFs materials, Fe bases MOFs (Fe-MOFs) shows the chemical stability of brilliance,
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, makes skeleton more stable.In addition, Fe-MOFs is used as having excellent biocompatibility and oxidation during electrode material also
Former activity.However, Fe-MOFs poorly conductive is so as to cause cycle performance poor in actual applications.
The content of the invention
It is a primary object of the present invention to provide a kind of iron oxide-mesoporous carbon nano-composite material and preparation method thereof and answer
With to overcome the deficiencies in the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The invention provides a kind of iron oxide-mesoporous carbon nano-composite material, including porous carbon matrix and at least uniform
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；
It is preferred that, Fe is also distributed with the surface of the porous carbon nanosheet3O4Nano particle；
It is preferred that, the Fe3O4The particle diameter of nano particle is 8-70nm, especially preferably preferably 40-70nm, 60-
70nm；
It is preferred that, the aperture in the porous carbon matrix contained hole hole is 18.5-29.7nm；
It is preferred that, the porous carbon matrix is agraphitic carbon matrix；
It is preferred that, the thickness of the porous carbon nanosheet is 3-8nm, and the aperture of the porous carbon nanosheet is 18.5-
29.7nm；
It is preferred that, the porous carbon matrix and the Fe3O4The mass ratio of particle is 10.64: 1-26.08: 1；
It is preferred that, the specific surface area of the iron oxide-mesoporous carbon nano-composite material is 27.24-315.12m2.g-1。
Present invention also offers a kind of preparation method of iron oxide-mesoporous carbon nano-composite material, including：
Fe-MOFs is provided,
And, by Fe-MOFs in 350-900 DEG C of temperature lower calcination 4-6h, room temperature is subsequently cooled to, iron oxide-Jie is obtained
Hole carbon nano-composite material.
Further, methods described includes：By Fe-MOFs with 5-7 DEG C of min-1Heating rate be heated to 350-900
DEG C, and calcining 4-6h is incubated, room temperature is then naturally cooled to, iron oxide-mesoporous carbon nano-composite material is obtained.
Further, methods described includes：By FeSO4·7H2O, 4,4 ' 4 "-tricarboxylic acid triphenylamine (H3NTB), N- methyl
After formamide (NMF) and METHYLPYRROLIDONE (NMP) mixing, 3-5d is heated in 140-160 DEG C, the Fe- is made
MOFs；
It is preferred that, the H3NTB and FeSO4·7H2O mol ratio is (1-3): (8-10)；
It is preferred that, the volume ratio of the NMF and NMP are (1-3): (1-3).
Present invention also offers a kind of terramycin electrochemistry aptamer sensor, including：
The iron oxide-mesoporous carbon nano-composite material；
Modify in the fit chain of terramycin on the iron oxide-mesoporous carbon nano-composite material.
Further, the terramycin electrochemistry aptamer sensor also includes：Electrode matrix, the Fe3O4@C nanos are combined
Material is fixed on the electrode matrix surface；
It is preferred that, the electrode matrix includes gold electrode；
It is preferred that, the sequence of the fit chain of terramycin is：5‘-CGTA CGGA ATTC GCTA GCCG AGGC ACAG
TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC GAGC TCCA CGTG-3’。
Present invention also offers a kind of preparation method of terramycin electrochemistry aptamer sensor, including：
Iron oxide-mesoporous carbon nano-composite material is prepared using foregoing method；
The iron oxide-mesoporous carbon nano-composite material is scattered in solvent formation unit for uniform suspension, will be described uniform outstanding
Supernatant liquid puts on electrode matrix and dried；
The nano combined material of iron oxide-mesoporous carbon being fixed on the solution impregnation of the fit chain of terramycin on the electrode matrix
Material, makes the fit chain of terramycin modify on iron oxide-mesoporous carbon nano-composite material, forms the electrochemistry aptamer sensor.
Another aspect of the present invention additionally provides a kind of detection method of terramycin, including：
The terramycin electrochemistry aptamer sensor is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, afterwards
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, advantages of the present invention includes：
The Fe that the present invention is provided3O4There is the nanostructured of@C nano composites hypotoxicity, high stability and electrochemistry to live
Property；
The present invention provide based on Fe3O4The aptamer sensor preparation method of@C nano composites 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, test limit is low, available for fast
Speed, accurately detect OTC.
Brief description of the drawings
Fig. 1 a are the coordination mode structural representations of the NTB parts of Fe-MOFs in the embodiment of the present invention 1；
Fig. 1 b are the views of the 1-D bar arrays of Fe-MOFs in the embodiment of the present invention 1；
Fig. 1 c are the 3-D circuit theory schematic diagrams 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 composites with
TGA schemes；
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 nano composite material 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 spectrograms of XPS of material；
Fig. 6 a, Fig. 6 b are SEM figures of the Fe-MOFs at 3000 times and 1800 times 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@C900Nano composite material low power and high power TEM image, illustration is corresponding
SAED schemes；
Fig. 8 is Fe-MOFs and different Fe in the embodiment of the present invention 23O4The nitrogen adsorption-desorption of@C nano composites
Thermoisopleth；
The EIS curves in CV curves and Fig. 9 b in Fig. 9 a are used in the embodiment of the present invention 2 based on Fe-MOF exploitations
Aptamer sensor is in the 5mM [Fe (CN) containing 0.14MNaCl 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
Apply to use in example 2 and be based on Fe3O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900The aptamer sensor of exploitation containing
0.14M NaCl and 0.1M KCl 5mM [Fe (CN)6]3-/4-Solution in detect OTC CV and EIS curve maps；
Figure 11 is to use in the embodiment of the present invention 2 to be based on Fe-MOF, Fe3O4@C350、Fe3O4@C550、Fe3O4@C700With
Fe3O4@C900The Δ R in the aptamer sensor detection OTC of exploitation each stagectValue；
Figure 12 a are Apt/Fe in the embodiment of the present invention 23O4@C900/ AE detection various concentrations OTC (0,0.005,0.01,
0.05th, 0.1,0.5 and 1ngmL-1) EIS response curves；
Figure 12 b are 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 the Fe for being used in the embodiment of the present invention 2 detect OTC respectively3O4@C900The choosing of base aptamer sensor
Selecting property and reappearance collection of illustrative plates；
Figure 14 a, Figure 14 b are that to be used for detectable concentration in the embodiment of the present invention 2 be 0.005ngmL respectively-1OTC
Fe3O4@C900The stability and reproducibility collection of illustrative plates of base aptamer sensor.
Embodiment
In view of deficiency of the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical scheme.The technical scheme, its implementation process and principle etc. will be further explained as follows.
The embodiments of the invention provide a kind of iron oxide-mesoporous carbon nano-composite material, including porous carbon matrix and extremely
A plurality of Fe of the porous carbon Medium Culture are uniformly distributed in 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；
It is preferred that, Fe is also distributed with the surface of the porous carbon nanosheet3O4Nano particle；
It is preferred that, the Fe3O4The particle diameter of nano particle is 8-70nm, especially preferably preferably 40-70nm, 60-
70nm；
It is preferred that, the aperture in the porous carbon matrix contained hole hole is 18.5-29.7nm；
It is preferred that, the porous carbon matrix is agraphitic carbon matrix；
It is preferred that, the thickness of the porous carbon nanosheet is 3-8nm, and the aperture of the porous carbon nanosheet is 18.5-
29.7nm；
It is preferred that, the porous carbon matrix and the Fe3O4The mass ratio of particle is 10.64: 1-26.08: 1；
It is preferred that, the specific surface area of the iron oxide-mesoporous carbon nano-composite material is 27.24-315.12m2·g-1。
Present invention also offers a kind of preparation method of iron oxide-mesoporous carbon nano-composite material, including：
Fe-MOFs is provided,
And, by Fe-MOFs in 350-900 DEG C of temperature lower calcination 4-6h, room temperature is subsequently cooled to, iron oxide-Jie is obtained
Hole carbon nano-composite material.
Further, methods described includes：By Fe-MOFs with 5-7 DEG C of min-1Heating rate be heated to 350-900
DEG C, and calcining 4-6h is incubated, room temperature is then naturally cooled to, iron oxide-mesoporous carbon nano-composite material is obtained.
Further, methods described includes：By FeSO4·7H2O, 4,4 ' 4 "-tricarboxylic acid triphenylamine (H3NTB), N- methyl
After formamide (NMF) and METHYLPYRROLIDONE (NMP) mixing, 3-5d is heated in 140-160 DEG C, the Fe- is made
MOFs；
It is preferred that, the H3NTB and FeSO4·7H2O mol ratio is (1-3): (8-10)；
It is preferred that, the volume ratio of the NMF and NMP are (1-3): (1-3).
Present invention also offers a kind of terramycin electrochemistry aptamer sensor, including：
The iron oxide-mesoporous carbon nano-composite material；
Modify in the fit chain of terramycin on the iron oxide-mesoporous carbon nano-composite material.
Further, the terramycin electrochemistry aptamer sensor also includes：Electrode matrix, the Fe3O4@C nanos are combined
Material is fixed on the electrode matrix surface；
It is preferred that, the electrode matrix includes gold electrode；
It is preferred that, the sequence of the fit chain of terramycin is：5‘-CGTA CGGA ATTC GCTA GCCG AGGC ACAG
TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC GAGC TCCA CGTG-3’。
Present invention also offers a kind of preparation method of terramycin electrochemistry aptamer sensor, including：
Iron oxide-mesoporous carbon nano-composite material is prepared using foregoing method；
The iron oxide-mesoporous carbon nano-composite material is scattered in solvent formation unit for uniform suspension, will be described uniform outstanding
Supernatant liquid puts on electrode matrix and dried；
The nano combined material of iron oxide-mesoporous carbon being fixed on the solution impregnation of the fit chain of terramycin on the electrode matrix
Material, makes the fit chain of terramycin modify on iron oxide-mesoporous carbon nano-composite material, forms the electrochemistry aptamer sensor.
Another aspect of the present invention additionally provides a kind of detection method of terramycin, including：
The terramycin electrochemistry aptamer sensor is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, afterwards
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 scheme, 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),
1-METHYLPYRROLIDONE (NMP) and formic acid can be bought from Shanghai Jing Chun biochemical technologies limited company；Terramycin (OTC),
Tetracycline, fortimicin and aureomycin can be bought from Suo Laibao companies.The water used in following examples is ultra-pure water
(18.2Ωcm-1).All reagents are the pure rank of analysis.The fit sequences of OTC used in the embodiment of the present invention are：5‘-CGTA
CGGA ATTC GCTA GCCG AGGC ACAG TCGC TGGT GCCT ACCT GGTT GCCG TTGT GTGG ATCC
GAGC TCCA CGTG-3’.Feature ssDNA or RNA with uniqueness 3D structures because fit, can with high specific with
Affinity recognizes and combines its homology targets, and these functional chains are mainly for target detection.
The sign equipment and mode used in following examples is as follows：
C, H and N analysis are carried out on Perkin-Elmer 240CHN elemental analysers, the spectrum of Nicolet 850 are used
Instrument (Thermo Electron Corporation, Massachusetts, USA) passes through Fourier transform infrared spectroscopy (FTIR)
Analyze the chemical constitution of nano composite material；Use Cu KαRadiation records X on Rigaku D/Max-2500X x ray diffractometer xs
Ray diffraction measurement (XRD)；With Labsys NETZSCH TG 209Setaram instruments in N2The rate of heat addition is 10 in atmosphere
℃·min-1When measurement thermogravimetric (TGA)；Using the spectrometers of AXIS HIS 165 (Kratos Analytical, Manchester,
UK) using monochrome chromaking Al KαX-ray source (1486.71 eV photons) measurement x-ray photoelectron power spectrum (XPS)；Using Japan
JEOL JEM-2100 high resolution transmission electron microscopies test high resolution transmission electron microscope image (HR-TEM), super
Under high vacuum, in the Belsorp MAX volumetric adsorption equipment with barrier film and turbine pumping system, N is measured2Adsorption-desorption
Data.
X-ray single crystal analysis：With installation graphite monochromatic Mo KαOr Cu Kα(λ=0.71073 or) Agilent
The SuperNova monocrystalline crystal meter of scientific ＆ technical corporation measurement data at different temperatures, with SHELXS (direct method) analytic structure,
And be modified in Olex2 bags with SHELXL (complete matrix least square method).All non-hydrogen atoms all use anisotropy displacement
Parameter is redefined, and the hydrogen atom being connected on carbon is placed in into the preferable position of geometry, and repaired using model；Due to frame
Solvent molecule property in frame is highly unordered, it is impossible to directly determine, therefore is carried out using the SQUEEZE programs in PLATON softwares
Processing.Crystal data, TGA and the combination of elementary analysis can determine chemical formula, C372H493Na31N66O164Crystal data (M=
5973.07g.mol-1)：Cube, space group F-43c (numbering 219), a=48.1642 (8), V=111731 (5)Z=
The reflection (6.356 °≤2 of 8, T=293 (2) K, μ (CuK α)=0.640mm-1, Dcalc=0.710gcm-3,15687 measurements
θ≤144.072 °), 7387 unique (Rint=0.0604, Rsigma=0.0594), final R1 is the 0.0954 (σ of I ＞ 2
(I)), wR2For 0.2877.
The electrochemical measurement scheme being related in following examples, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry
(CV) can be using CHI660D electrochemical workstations (Shanghai Chen Hua) measurement.Test is using conventional three-electrode system, wherein wrapping
The gold electrode of a diameter of 3mm as working electrode is included, Ag/AgCl (saturation KCl) electrode and conduct pair as reference electrode
The platinized platinum of electrode；In the 0.5mM [Fe (CN) containing 0.1M KCl6]3-/4-(EIS parameters：Current potential：0.21V；Frequency range：
100kHz to 0.1Hz；Amplitude：EIS curves are measured in 5mV)；Using Zview2 software analysis spectrograms, a non-linear most young waiter in a wineshop or an inn is used
Multiply fitting to determine the component parameters in equivalent circuit.
Embodiment 1：
By mixing 0.242g KH2PO4, 1.445g Na2HPO412H2O, 0.200g KCl and 8.003g NaCl, and
The pH=7.4 that 0.1M HCl solutions adjust mixture is added, phosphate buffer solution (PBS, pH 7.4) is obtained.Prepared with PBS
Fit 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.
22.2mg FeSO is added in the rustless steel container of teflon lining4·7H2The 4 of O, 3.0mg, 4 ' 4 "-tricarboxylic acids
Triphenylamine (H3NTB), the mixture of 2mL N-METHYLFORMAMIDE (NMF) and 2mL METHYLPYRROLIDONE (NMP),
Lower heating 3d in 160 DEG C of baking oven.Brown flat crystal, as Fe-MOFs are obtained after being washed with DMF.Yield：45%, base
In H3NTB parts.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；Elementary analysis (calculated value)：C56H50Fe3N6O16：C, 51.6 (52.5)；H, 4.43 (5.05)；N, 7.40 (6.93) are described
Fe-MOFs crystal structural data 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, calcine 4h~6h at 350 DEG C, 550 DEG C, 700 DEG C and 900 DEG C respectively；Then by sample
Room temperature is naturally cooled to, a series of iron oxide-mesoporous carbon nano-composite materials are obtained, it can be respectively designated as：Fe3O4@
C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900。
Fe-MOFs and Fe3O4The chemical constitution of@C nano composites and component analysis：
Using XPS measuring Fe-MOFs and Fe3O4The chemical composition and local environment of@C nano composites.Five samples
XPS spectrum all shows that they have the characteristic peak related to C, O and Fe and weaker N peaks；C 1s and O 1s characteristic peak come from
In organic ligand, Fe 2p peak is derived from coordination center Fe.Fig. 3 a, 3b, 3c are Fe-MOFs and Fe respectively3O4@C nanos are combined
XRD and the TGA figure of material；
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 contents reduce to a certain extent first, and this is due to waving for carbon containing organic solvent (NMF)
The decomposition of hair and formic acid.As calcining heat is increased to 550 DEG C, 700 DEG C and 900 DEG C, C 1s contents are continuously increased, and show organic
The thermal decomposition of connector part produces porous carbon.For Fe 2p and O 1s contents, Fe3O4@C350Increase first to a certain extent, so
Continuously decline with the rise of calcining heat afterwards, variation tendency is opposite with C 1s contents.
Difference Fe after the Fe-MOFs of table 1 and thermal cracking3O4The atomic percent of@C nano composites
In order to further appreciate that Fe-MOFs and Fe before and after thermal decomposition3O4Chemical composition the C 1s and Fe of@C nano composites
2p, also analyzes their XPS figures (shown in such as Fig. 4 (a1, a2, b1, b2, c1, c2, d1, d2, e1, e2)).Original Fe-
MOFs (Fig. 4 a1) C 1s, which decompose spectrum, can be divided into 5 main peaks ,~283.7 ,~284.8 ,~285.6 and~287.9eV,
C-C/C-H, C-N, C-O, COO are corresponded to respectively-With π-π * group, these peaks will originate from organic linking part.As for not
The material of synthermal lower thermal cracking, such as Fe3O4@C350(Fig. 4 b1), has and C=O groups in C 1s high-resolution XPS spectrums
Corresponding~286.8eV additional peaks；For Fe3O4@C550And Fe3O4@C700(Fig. 4 c1 and d1), C 1s high-resolution XPS spectrums
In combination can position and Fe-MOFs combination can be consistent, but intensity is different, as Fe3O4@C900, in C 1s high scores
In resolution XPS spectrum (Fig. 4 e1) also observe distribute to C=O groups~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 original Fe-MOFs (Fig. 4 a2) Fe 2p spectrum~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) have~711.0 and~724.8eV two
Individual peak, it is consistent with Fe-MOFs.With the rise of calcining heat, Fe3O4@C550The Fe 2p spectrum of (Fig. 4 c2) are divided into 5 peaks, point
Not Wei~709.3 ,~711.4 ,~717.7 ,~722.3 and~724.1eV, with reference to can be for 711.4 and 724.1eV peak
Fe3+Characteristic peak, and combination can be due to Fe for 709.3 and 722.3eV peak value2+.In addition, combination can be 717.7eV peak
It is due to Fe2+And Fe3+The satellite peak that collective effect is produced.When temperature rises to 700 DEG C and 900 DEG C, Fe3O4@C700And Fe3O4@C900
Fe 2p optical spectroscopies 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 Fe-MOFs SEM and TEM image, and can be seen that Fe-MOFs from image is block structure, most of
Crystal illustrates the Fe-MOFs prepared more like polycrystalline or dusty material more than tens or even hundreds of microns, size uneven distribution；
Fe-MOFs discontinuity causes their poorly conductive, therefore electro-chemical activity is bad.As shown in fig. 7, can from TEM figures
To find out the Fe under different pyrolysis temperatures3O4The metamorphosis of@C nano composites；At first 350 DEG C of temperature, retain
Fe-MOFs bulk morphologies, at the edge of composite are observed that Fe2O3, it is most of as shown in figs. 7 a and 7b
Fe3O4@C350Nano composite material 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@C350Nano composite material is polycrystalline, and 0.247 and 0.283nm lattice vacancy is correspondence
In (311) and (220) crystal face, it was demonstrated that Fe3O4@C formation.
As shown in figs. 7 c and 7d, in second stage (550 DEG C), it is found that bigger spheric granules is formed and is embedded into many
In the carbon nanosheet of hole, and most of particle agglomerations obtain size between 100-150nm nanosphere (nanosphere be Fe3O4
Granuloplastic aggregate).This is probably because organic remains makes Fe as reducing agent2O3It is converted into Fe3O4, and in system
What may be disperseed when being ready for use on TEM sample is incomplete.In addition, such as Fig. 7 d, SAED pattern displayings in illustration Fe2O3With
Fe3O4Lattice, wherein the Fe3O4Nano particle is rendered as monodisperse status.Such as Fig. 7 e figures, Fig. 7 f, Fig. 7 g and Fig. 7 h institutes
Show, when calcining heat is further improved to 700 DEG C and 900 DEG C, because ferric oxide particles caused by crystal accumulation meeting increase.As schemed
Shown in 7e and 7f, the Fe-MOFs calcined at 700 DEG C TEM image is it can be seen that nano composite material is composite construction, therefrom
It can be seen that average diameter is the 40nm Fe being individually wrapped by thin carbon border3O4Nano particle, and these particles be dispersed in it is many
Its content of hole carbon and/or surface, as shown in Fig. 7 g and Fig. 7 h, in Fe3O4@C900Observed in nano composite material similar
Situation, Fe3O4The average-size (particle diameter) of particle increases to 60-70nm, and porous carbon is used as Fe3O4The buffering area of particle aggregation makes
Crystal is distributed evenly, and the illustration SAED explanations in Fig. 7 f and 7h have formed typical Fe3O4Lattice, is further demonstrated
Fe3O4Formation.
Fe-MOFs and different Fe3O4The N of@C nano composites2Adsorption-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：
5min is incubated at 90 DEG C by fit, is then slowly cooled to room temperature, by the Fe prepared by embodiment 13O4@C350Powder
Last (0.5mg) is added in ethanol and thoroughly ultrasonic until obtaining uniform Fe3O4@C350Suspension；Then, by 10 μ L's
Fe3O4@C350Suspension (0.5mgmL-1) spread on gold electrode (AE) surface, then it is dried at room temperature for 5h；Then,
By 2h in the electrode immersion aptamer solutions (100nM) of modification, it is ensured that fit chain is fixed at the electrode surface until reaching saturation shape
State；In this process, fit and Fe3O4@C nanos composite is combined by fit chain with target specific moiety formation amido link,
This will cause redox probe to reduce the AE of modification surface degree of closeness, therefore electro-chemical activity will reduce.Finally, will
The Fe of fit fixation3O4@C350Electro-chemical test is carried out in/AE immersion OTC solution.In Electrochemical Detection, part can be formed
There is the stranded structures of G- tetra- of high-affinity with OTC.
In order to compare, also construct in an identical manner based on foregoing Fe-MOFs, Fe3O4@C550、Fe3O4@C700And Fe3O4@
C900Aptamer sensor as a comparison.
Afterwards by blank AE, the aptamer sensor based on foregoing Fe-MOFs, based on foregoing each iron oxide-mesoporous carbon nanometer
The aptamer sensor of composite is in the 5mM [Fe (CN) 6] containing finite concentration OTC, 0.14M NaCl 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 curves in Fig. 9 a, there are a pair of clear and definite reversible redox peaks, peak-to-peak potential difference in blank AE figures
(ΔEp) it is 248mV.AE is through Fe-MOFs modified (Fe-MOF/AE), Δ EpIncrease to 292mV, redox peak current is corresponding
Reduction, illustrates that Fe-MOFs is coated on AE rear conductance reduction.Fe-MOF/AE surfaces are fixed on when OTC targets fit chain (Apt)
When (Apt/Fe-MOF/AE), Δ Ep311mV is slightly increased to, redox peak current is almost unchanged, shows Apt for Fe-
MOF/AE influence is not obvious.However, when using prepare Apt/Fe-MOF/AE detect OTC when (OTC/Apt/Fe-MOF/
AE), Δ Ep369mV is further increased to, redox peak current is further reduced, it was demonstrated that OTC/Apt/Fe-MOF/AE's
Electric conductivity and electrochemistry reduction.Four kinds of AEs of detection OTC different phase electricity can be drawn from the EIS figures 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 is reduced successively after Apt and OTC, RctAs a result variation tendency is consistent with above-mentioned CV results.
Test is based on foregoing Fe in the same way3O4@C350、Fe3O4@C550、Fe3O4@C700And Fe3O4@C900It is fit
The CV curves of sensor, as a result as shown in Figure 10 a1,10b1,10c1,10d1.Wherein, 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.As a result show, 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
Plus, redox peak current declines, and four kinds are based on Fe3O4The electro-chemical activity of the aptamer sensor of@C nano composites is corresponding
Reduction.It is that four kinds of Fe based on calcining at different temperatures are represented with EIS as shown in Figure 10 a2,10b2,10c2,10d23O4@C
Nano composite material aptamer sensor detects OTC whole process.For blank AE, there is small semicircle at upper frequency,
(a) Fe is corresponded to respectively3O4@C350, (b) Fe3O4@C550, (c) Fe3O4@C700Fe (d)3O4@C900RctBe worth for 122.7,
39.26th, 69.17 and 42.24 Ω.With four kinds of Fe3O4@C nanos composite distinguishes modified, RctValue is significantly increased respectively
260.7th, 98.4,133.3 and 119.6 Ω, shows Fe3O4The electrical conductivity of@C nano composites is relatively poor；When OTC targetings are suitable
Body (Apt) chain is fixed on Fe3O4During@C/AEs surfaces, Apt/Fe3O4@C/AE RctValue is further increased respectively to respectively
330.3rd, 183.0,236.8 and 334.1 Ω, because the negatively charged phosphate included in fit 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.Made when using
Standby Fe3O4@C bases aptamer sensors are determined during OTC, and the semicircle of EIS curves further increases, 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 fit chain of OTC targetings with OTC by tying
Close and change its conformation, conjuncted to form the chains of G- tetra-, this will prevent electric charge transfer.In addition, such as in N2In adsorption-desorption isothermal
Discussed, Fe3O4@C nano composites have meso-hole structure and high-specific surface area, therefore OTC can be adsorbed onto Fe3O4@C
In nano composite material, substantial amounts of OTC is adsorbed to Apt/Fe3O4@C/AEs surface, further makes electric charge transfer become tired
It is difficult.Therefore, OTC obstruction and blocking effect results in Apt/Fe3O4@C/AE electro-chemical activity is significantly reduced.
Fe is based in order to compare Fe-MOFs and four kinds3O4The electrochemistry aptamer sensor of@C nano composites is to detection
OTC different Detection results, the invention provides the R that foregoing five bio-sensing systems are often walkedctIt is worth (Δ Rct) change and table
Show in fig. 11.ΔRctThe difference of value as shown in the block diagram in Figure 11, from block diagram as can be seen that with other four kinds of material phases
Than Fe3O4@C900The Apt adsorbances on/AE surfaces are maximum, due to Fe3O4@C900/ AE specific surface area and meso-hole structure highest, because
This can further help to absorb most of OTC, and with maximum Δ Rct(RCt, Apt-RCt, material) and Δ Rct(RCt, OTC--
RCt, Apt).Therefore, the optimum electrode material of measurement electrochemistry is Fe3O4@C900。
Apt/Fe3O4@C900/ AE sensitivity test：By by Apt/Fe3O4@C900/ AE is together with the OTC of various concentrations
It is incubated, then in [Fe (CN)6]3-/4-Their EIS collection of illustrative plates is determined in solution.Figure 12 a are the OTC for detecting various concentrations
Apt/Fe3O4@C900/ AE EIS figures, because effective identification of the aptamer sensor to OTC, RctValue with OTC concentration increasing
Plus (from 0.005 to 1.0ngmL-1) and gradually increase.This is probably because with the increase of OTC concentration, in nano combined electricity
More molecular recognitions between antigen-antibody complex are generated on the surface of pole, so as to result in RctThe enhancing of value.Sensor exists
Detect the Δ R before and after OTCctThe numerical value (referring to Figure 12 b) being to determine, and as the logarithm value (logC of OTC concentrationOTC)
During scope from -2.301 to 0, Δ RctValue and logCOTCIt is directly proportional, its equation of linear regression is Δ Rct=0.676logCOTC+
1.762, coefficient correlation (R2) it is 0.9944.According to Langmuir adsoption equations, when signal to noise ratio (s/n) is than being 3, analog detection
Limit (LOD) as little as 0.027pgmL-1。
Apt/Fe3O4@C900/ AE selectivity and stability test：Use Apt/Fe3O4@C900/ AE detects possibility respectively
It is 10 with the concentration that OTC coexists-3NM (10 times of OTC concentration) antibiotic includes tetracycline, Doxycycline, aureomycin and blank
PBS.As depicted in fig. 13 a, with the detection significant Δ R of OTCctResponse is on the contrary, by adding the sound that other interference are obtained
It should change negligible.Therefore, there is high degree of specificity, electrochemistry aptamer sensor pair between its corresponding probe aptamers of OTC
OTC has higher selectivity；Repeatability is to assess the important indicator of exploitation aptamer sensor performance, is prepared under the same conditions
Five be based on Fe3O4@C900The aptamer sensor of nano composite material, is dissolved in PBS by detecting under room temperature (25 DEG C)
10-5Δ R caused by nM OTCctValue tests the repeatability (Figure 13 b) of aptamer sensor.With five aptamer sensors simultaneously
Detect the OTC of same concentrations Δ RctThe relative standard deviation (RSD) of value is 2.6%, shows reappearance 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
After amount by electrode immerse in ultra-pure water and save it in 4 DEG C of refrigerator and recording electrode Δ RctValue, with these Δs RctValue
To represent Fe3O4@C900The stability (Figure 14 a) of aptamer sensor.60nM OTC R is not found after 15 daysctSignificantly reduce；Again
Cross one week, RctAfter value declines about 10%, one month, about 17% have dropped.OTC nanometer combined electrode will be combined with room temperature
80 minutes and it is washed with water in immersion 1.0M NaOH, surveys its RctValue, then immerses 2 hours in the OTC solution of same concentrations and surveys again
Its RctValue, repeats the step for several times, compares RctIt is worth and assesses reproducibility.As shown in fig. 14b, the runtime is regenerated at first 5 times
Between, it was observed that the Δ R of aptamer sensorctIt is worth no substantial variations, shows easily to regenerate.All these results show,
The aptamer sensor that the present invention is provided not only has high sensitivity and selectivity, and with good repeatability, stability and
Reproducibility.
Embodiment 3：
Actual sample is tested using a series of sensors made from embodiment 2, the actual sample is milk.Accordingly
Test process include：
In 50mL centrifuge tubes, by the mixing of 12mL raw milk and 18mL ultra-pure waters and the trichloroacetic acids of 6mL 10% and chloroform
Mixing 1min is with the organic substance in depositing proteins and dissolved matrix under vortex concussion for thing, then by mixture at 20 DEG C
Ultrasonically treated 15min, and centrifuge 10min to separate deposit with 13000rpm；Supernatant is transferred in another centrifuge tube,
And centrifuge 10min to remove deposit again with 10000rpm；A certain amount of OTC is added in stoste, then according to above-mentioned step
Suddenly pre-processed and analyzed；The solution is detected according to the above method, analyze mark-on sample by HPLC is proposed to verify
Analysis method reliability.
Result is obtained according to Figure 12 b standard curve.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 with HPLC in milk
OTC, show that the result for the aptamer sensor that the present invention is provided complies fully with HPLC requirement by comparing, these all show this
New strategy has very high reappearance, accuracy and feasibility for the OTC in quick detection milk.
OTC in the 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 composites, at these
Fe in nano composite material3O4Nano particle is embedded in mesoporous amorphous carbon substrate so that these nano composite materials are respectively provided with
Specific surface area is high, good biocompatibility, the advantages of biological affinity is strong, Fe particularly therein3O4@C900Detection to OTC shows
Optimal electro-chemical activity is shown, therefore can be used for building electrochemistry aptamer sensor.Especially, based on Fe3O4@C900Exploitation
OTC aptamer sensors show high sensitivity, in OTC concentration from 0.005 to 1ngmL-1The wide line in the range of test limit
As little as 0.027pgmL-1, while the sensor also have high selectivity, good repeatability, stability, reproducibility and be applicable
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 can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all
The equivalent change or modification made according to spirit of the invention, should all be included within the scope of the present invention.
Claims (10)
1. a kind of iron oxide-mesoporous carbon nano-composite material, it is characterised in that be uniformly distributed including porous carbon matrix and at least
In a plurality of Fe of the porous carbon Medium Culture3O4Nano particle.
2. iron oxide according to claim 1-mesoporous carbon nano-composite material, it is characterised in that：The porous carbon matrix
For porous carbon nanosheet, and at least described porous carbon nanosheet has been embedded in a plurality of Fe3O4Nano particle；
It is preferred that, Fe is also distributed with the surface of the porous carbon nanosheet3O4Nano particle；
It is preferred that, the Fe3O4The particle diameter of nano particle is 8-70nm, especially preferably preferably 40-70nm, 60-70nm；
It is preferred that, the aperture in the porous carbon matrix contained hole hole is 18.5-29.7nm；
It is preferred that, the porous carbon matrix is agraphitic carbon matrix；
It is preferred that, the thickness of the porous carbon nanosheet is 3-8nm, and the aperture of the porous carbon nanosheet is 18.5-29.7nm；
It is preferred that, the porous carbon matrix and the Fe3O4The mass ratio of particle is 10.64: 1-26.08: 1；
It is preferred that, the specific surface area of the iron oxide-mesoporous carbon nano-composite material is 27.24-315.12m2·g-1。
3. a kind of preparation method of iron oxide-mesoporous carbon nano-composite material, it is characterised in that including：
Fe-MOFs is provided,
And, by Fe-MOFs in 350-900 DEG C of temperature lower calcination 4-6h, room temperature is subsequently cooled to, iron oxide-mesoporous carbon is obtained
Nano composite material.
4. preparation method according to claim 3, it is characterised in that including：By Fe-MOFs with 5-7 DEG C of min-1Heating
Speed is heated to 350-900 DEG C, and is incubated calcining 4-6h, then naturally cools to room temperature, obtains iron oxide-mesoporous carbon nanometer multiple
Condensation material.
5. according to the preparation method described in claim 3, it is characterised in that including：By FeSO4·7H2O, 4,4 ' 4 "-front three triphenyl phosphates
Amine (H3NTB), after N-METHYLFORMAMIDE (NMF) and METHYLPYRROLIDONE (NMP) are mixed, 3- is heated in 140-160 DEG C
5d, is made the Fe-MOFs；
It is preferred that, the H3NTB and FeSO4·7H2O mol ratio is (1-3): (8-10)；
It is preferred that, the volume ratio of the NMF and NMP are (1-3): (1-3).
6. a kind of terramycin electrochemistry aptamer sensor, it is characterised in that including：
Iron oxide-mesoporous carbon nano-composite material any one of claim 1-2；
Modify in the fit chain of terramycin on the iron oxide-mesoporous carbon nano-composite material.
7. terramycin electrochemistry aptamer sensor according to claim 6, it is characterised in that described also including electrode matrix
Fe3O4@C nano composites are fixed on the electrode matrix surface；
It is preferred that, the electrode matrix includes gold electrode；
It is preferred that, the sequence of the fit chain of terramycin is：5‘-CGTA CGGA ATTC GCTA GCCG AGGC ACAG
TCGC TGGT GCCTACCT GGTT GCCG TTGT GTGG ATCC GAGC TCCA CGTG-3’。
8. a kind of preparation method of terramycin electrochemistry aptamer sensor, it is characterised in that including：
Iron oxide-mesoporous carbon nano-composite material is prepared using the method described in claim any one of 3-5；
The iron oxide-mesoporous carbon nano-composite material is scattered in solvent formation unit for uniform suspension, by the unit for uniform suspension
Put on electrode matrix and dry；
The iron oxide being fixed on the solution impregnation of the fit chain of terramycin on the electrode matrix-mesoporous carbon nano-composite material,
The fit chain of terramycin is modified on iron oxide-mesoporous carbon nano-composite material, form the electrochemistry aptamer sensor.
9. a kind of detection method of terramycin, it is characterised in that including：
Terramycin electrochemistry aptamer sensor any one of claim 6-7 is provided；
The terramycin electrochemistry aptamer sensor is impregnated in may be in the liquid sample containing terramycin, afterwards 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.
10. the detection method of terramycin according to claim 9, it is characterised in that：The electrochemical test method includes
Electrochemical impedance spectroscopy or cyclic voltammetry.
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| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN108226244A (en) * | 2018-01-12 | 2018-06-29 | 湖南大学 | For detecting electrochemical sensor of lead ion and/or cadmium ion and its preparation method and application |
| CN110243904A (en) * | 2019-05-31 | 2019-09-17 | 山西大学 | A kind of preparation method of the aptamers electrochemical sensor for terramycin detection |
| CN110243903A (en) * | 2019-05-31 | 2019-09-17 | 山西大学 | A kind of application method of aptamers electrochemical sensor |
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| CN110514716A (en) * | 2019-09-09 | 2019-11-29 | 山东省农业科学院农业质量标准与检测技术研究所 | For detecting the preparation method of the current type aptamer sensor of pesticide residue |
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| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN108226244A (en) * | 2018-01-12 | 2018-06-29 | 湖南大学 | For detecting electrochemical sensor of lead ion and/or cadmium ion and its preparation method and application |
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| CN110243903A (en) * | 2019-05-31 | 2019-09-17 | 山西大学 | A kind of application method of aptamers electrochemical sensor |
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| CN110514716A (en) * | 2019-09-09 | 2019-11-29 | 山东省农业科学院农业质量标准与检测技术研究所 | For detecting the preparation method of the current type aptamer sensor of pesticide residue |
| CN111422912A (en) * | 2020-04-11 | 2020-07-17 | 石河子大学 | Fe 3O4Preparation method and application of @ C modified electrode material |
| CN111422912B (en) * | 2020-04-11 | 2023-04-21 | 石河子大学 | Fe (Fe) 3 O 4 Preparation method and application of modified electrode material @ C |
| CN113336274A (en) * | 2021-06-09 | 2021-09-03 | 长沙理工大学 | Fe3O4Mesoporous graphitized carbon composite and preparation method and application thereof |
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