CN108241011B - A kind of carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer and its preparation method and application being inlaid with gold - Google Patents
A kind of carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer and its preparation method and application being inlaid with gold Download PDFInfo
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- CN108241011B CN108241011B CN201810095295.3A CN201810095295A CN108241011B CN 108241011 B CN108241011 B CN 108241011B CN 201810095295 A CN201810095295 A CN 201810095295A CN 108241011 B CN108241011 B CN 108241011B
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- G—PHYSICS
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- 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
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Abstract
The invention discloses a kind of carbon nanotube grafting nano combined electrochemical sensing materials of ferrocene polymer and its preparation method and application being inlaid with gold, which is made of the polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate that carbon nanotube, gold nanoparticle and redox with excellent chemical property respond.Its preparation process is related to gold nanoparticle in the modification, complexing and esterification of carbon nano tube surface, and ferrocene-based polymer is then grafted to the carbon nano tube surface being inlaid with gold by atom transfer radical polymerization.Sensing material of the present invention can be used as electrode modified material；It can obtain that there is excellent chemical property with grafting rate by adjustment and control system composition, the electrochemical sensing film of good electrochemistry sensitivity, invertibity, reproducibility, the wide range of linearity and low detection limit.Electrode modified material of the present invention can be used for simple, quick, accurate and effective and reliable food safety detection.
Description
Technical field
The invention belongs to nanocomposites and technical field of function materials, and in particular to a kind of carbon nanotube being inlaid with gold connects
Branch ferrocene polymer sensing material and its preparation method and application.
Background technique
Food is the material base of human survival and development, it provide mankind sustain life, advolution, be engaged in it is various
Activity required energy and nutrition.However as the development of modern industrial or agricultural, the living environment of the mankind is contaminated and breaks ring,
The pollution of poisonous and harmful substance gradually aggravates, and compromises the health and lives safety of the mankind.Food additives and organophosphorus pesticide
It (OPPs) is two kinds of typical poisonous and harmful substances, wherein metrifonate and melamine are one of the most common type OPPs and food additive
Add agent.Their accumulation in environment and food can cause human health direct or potentially hazardous.Metrifonate is in one kind
Equitoxic organophosphorus pesticide.The first reaction when sucking is usually respiratory compromise, including rhinorrhea, cough, chest is uncomfortable, exhales
Inhale difficult or short of breath, asthma.It also results in failure of memory, attention is concentrated, got lost, major depression, irritability,
Puzzlement, headache, dysphasia, delay of response, bad dream, sleep-walking, drowsiness or insomnia.It may also have carcinogenicity, teratogenesis and
Mutagenicity.Melamine is described as " harmful substance eaten, suck or be absorbed by the skin ".Intake melamine may be led
Reproduction damage or bladder or kidney stone are caused, so as to cause bladder cancer.It is general to require in order to ensure food safety and human health
Remaining persticide residue should be controlled in most inefficient level in food additives and food.2006, FAO (Food and Agriculture Organization of the United Nation) and
The maximum residue limit of metrifonate in food additives joint specialist committee confirmation milk milk under the World Health Organization
It (MRLs) is 50 microgram of per kilogram, other fruit and vegetable residue limits standard MRL are 0.5 milligram of per kilogram.In July, 2010, state
Border Codex Committee on Food (CAC) announces that content of melamine is no more than 2.5mg kg in food-1, especially baby formula
In milk powder, the limit value of melamine is 1mg kg-1.Therefore, healthy phase in food or agricultural product is detected quickly, accurately and in time
The residual quantity of related compounds, for ensuring that food safety and human health are very important.
Currently, food inspection analytical technology includes chemical analysis (CA), infrared spectroscopy and various chromatographic techniques, including thin layer
Chromatography (TCL), gas-chromatography (GC), high performance liquid chromatography (HPLC) etc..Also it has been reported that and carries out trimerization using NMR spectrum
The non-targeted screening of cyanamide quantifies with synchronous.Compared with CA and TCL method, although GC and HPLG sensitivity with higher and accurate
Property, but it is typically necessary expensive equipment, cumbersome preprocessor and higher professional operation skill.In addition, complicated sample
The present context, time-consuming analysis, low analyte concentration and the limited qualitative ability of analysis instrument can all cause trace pesticide
With the difficulty of food additives detection.Therefore, they are not suitable for fast-field evaluation and popularization.Molecular engram, electrochemistry and life
The development and application of object sensing technology compensate for the deficiency of these technologies.It is based particularly on the electrochemical sensing of nanocomposite
Device has many advantages, such as that design is simple, at low cost, chemical property is good, high sensitivity, reacts fast, is widely used to OPPs residual
In detection.It is thus possible to improve sensor is opened in the design of the novel nano composite modified electrode of performance of electrochemical sensors
The detection of hair and subsequent harmful substance is of great significance.Nevertheless, there are still some difficulties for food safety detection.Most
In number situation, need to improve detection limit, reproducibility and stability, so that trace residue object be effectively detected.
Gold nanoparticle (Au NPs) has special quantum skin effect, excellent stability and biocompatibility, unique
Light, electricity, magnetic and catalytic performance and high electro catalytic activity, be therefore widely used in electrochemical sensing, bioanalysis, life
The detection of object medicine, catalysis, anticancer drug, drug delivery, sensor, antioxidant, larvicide, antibacterial agent, nano-fluid and
Agriculture field.In particular, being got in modern food is analyzed and detected based on Au NPs immune labeled Fast Detection Technique
Carry out more applications, has many advantages, such as that simple, quick, high sensitivity, specificity is high, at low cost, sample size is small.Due to carbon nanometer
Managing (CNTs) has excellent physics, machinery, electrochemistry and optical characteristics, quick electron transport property, big specific surface area
The advantages that with strong absorbent energy, CNTs based electrochemical sensor are widely used in metal ion, pesticide and other pollutants
Detection.The modification that Au NPs is carried out on the surface CNTs, can construct has certain attracting light based on its synergistic effect
It learns, the novel nanocomposite materials of electro-catalysis and electrochemical redox characteristic.This combination also contributes to utilizing CNTs and Au
Strong interaction is between NPs to improve the dispersibility of CNTs.On the other hand, ferrocene-based polymer is as a kind of new function
Polymer has unique redox electrochemical properties and semiconductive, optical physics, photoelectron and Electronic Performance, therefore quilt
It is widely used in semiconductor material, phase separation material, catalyst, redox reaction pharmaceutical carrier, biosensor, magnetism
Ceramic precursor and intelligent surface.The electron transmission mistake between electrode surface and modified material can be enhanced due to ferrocene group (Fc)
Journey, therefore electrochemistry or biosensor with preferable sensitivity and stability can be prepared.
Summary of the invention
It is an object of the invention to overcome the above-mentioned problems of the prior art, it is excellent to provide a kind of electrochemical sensing performance
Good, sensitivity, invertibity and favorable reproducibility, the range of linearity is wide, detection is limited down to 10-9mol L-1The nano combined electrochemistry of grade
Sensing material, and a kind of preparation method and application are provided for the sensing material.
In order to achieve the above objectives, present invention design is prepared for a kind of carbon nanotube being inlaid with gold with excellent electrochemical performance
It is grafted the nano combined electrochemical sensing material of polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate, the following institute of the structure of the sensing material
Show:
In formulaAu nanoparticle is represented,Carbon nanotube is represented, the partial size of Au nanoparticle is 5~20nm, and Au is accounted for
Au nanoparticle and 20%~80%, n of carbon nanotube gross mass represent the polymerization of methacrylic acid ferrocene formyl 2-ethoxyethyl acetate
Degree, the nuclear-magnetism grafting rate of polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate are 4.5%~55%.
In above-mentioned sensing material, preferably Au accounts for the 65%~75% of Au nanoparticle and carbon nanotube gross mass, poly- methyl
The nuclear-magnetism grafting rate of acrylic acid ferrocene formyl 2-ethoxyethyl acetate is 30%~40%.
The above-mentioned carbon nanotube grafting nano combined electrochemical sensing of polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate being inlaid with gold
Material the preparation method is as follows:
1, CNTs@Au nanocomposite is prepared
By in-situ chemical reducing process, carbon nano tube surface after modification inlays Au nanoparticle, obtains CNTs@Au and receives
Nano composite material, the partial size of Au nanoparticle is 5~20nm in the CNTs@Au nanocomposite, and the mass content of Au is
20%~80%.
2, atom transfer radical polymerization initiator is prepared
By molar ratio 1:4~7 of Au and mercaptoethanol, CNTs@Au nanocomposite is reacted with mercaptoethanol (ME)
Generate CNTs@Au-SCH2CH2OH；Then with CNTs@Au-SCH2CH2The meter of the substance of mercaptoethanol in OH, by CNTs@Au-
SCH2CH2OH and 2- bromine isobutyl acylbromide (BIB), triethylamine (TEA) are in molar ratio 1:2~5:2~5, pass through acyl bromination reaction system
For at the carbon nanotube atom transfer radical polymerization initiator being inlaid with gold, it is denoted as CNTs@Au-Br.
3, the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer that preparation is inlaid with gold
Using CuBr as catalyst, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylene tetramines (HMTETA) are ligand, by methyl-prop
Olefin(e) acid ferrocene formyl 2-ethoxyethyl acetate (MAEFc) reacts 12~36h, is inlaid with gold under CNTs Au-Br initiation at 80~90 DEG C
Carbon nanotube be grafted the nano combined electrochemical sensing material of polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate, be denoted as CNTs Au-
g-PMAEFc。
In above-mentioned steps 1, the mass content of Au is 65%~75% preferably in CNTs@Au nanocomposite.
In above-mentioned steps 3, with the meter of the substance of 2- bromine isobutyryl in CNTs@Au-Br, CNTs@Au-Br, MAEFc,
The molar ratio of CuBr, HMTETA are 1:50~400:6:5, preferably 1:100~200:6:5.
CNTs@Au-g-PMAEFc of the present invention can be used as electrode modified material, be used for Electrochemical Detection veterinary antibiotics, food
Content of melamine in the residual quantities such as middle pesticide metrifonate and food additives, detection are limited down to 10-9mol L-1The order of magnitude,
There is very high sensibility to trace residue pesticide and food additives content.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention quantum skin effect special using Au nanoparticle, unique light, electricity, magnetic property and high electricity are urged
It is excellent to change active and CNTs excellent electrochemical properties, quick electron transport property, big specific surface area and strong absorbent energy etc.
Point is prepared with assembling based on synergistic effect in conjunction with the redox electrochemical properties that PMAEFc is excellent by effectively integrating
The nano combined electrochemical sensing material with unique forceful electric power Chemical response.
2, the present invention is obtained by the grafting rate of the composition ratio and PMAEFc of regulation Au nanoparticle and CNTs with excellent
The nano combined electrochemical sensing material of good chemical property.The nano combined electrochemical sensing material can be assembled as with good
The modified electrode film of good electrochemistry sensitivity, invertibity, reproducibility, for residual quantities and foods such as pesticide metrifonate in food
The detection of product additive level, detection are limited down to 10-9mol L-1The order of magnitude has very high sensitive sound to trace residue pesticide
Ying Xing；And within the scope of comparatively wide drug concentration, good linear pass is presented in modified electrode oxidation peak current and drug concentration
System.Electrochemical sensing material of the present invention can be used for simple, quick, accurate and effective and reliable food safety detection.
3, the nano combined electrochemical sensing material modified electrode sensor of the present invention, which has, is better than existing other electrochemistry
The detection of method, chemical analysis, spectroscopic methodology, chromatography and molecular engram solid phase extraction-high performance liquid chromatography joint technology limit and
The significant advantage of the wide range of linearity.
Detailed description of the invention
Fig. 1 is MWCNTs@Au-g-PMAEFc prepared by embodiment 11H nuclear-magnetism figure.
Fig. 2 is the infrared spectrogram of the MWCNTs@Au-g-PMAEFc of MWCNTs and the preparation of embodiment 1.
Fig. 3 is MWCNTs (a) and MWCNTs@Au (b) and MWCNTs@Au-g-PMAEFc (c) prepared by embodiment 1
Raman spectrogram.
Fig. 4 is MWCNTs@Au (c) and MWCNTs@Au- prepared by MWCNTs (a), Au nanoparticle (b) and embodiment 1
The XRD diagram of g-PMAEFc (d).
Fig. 5 is MWCNTs@Au (c) and MWCNTs@Au- prepared by MWCNTs (a), Au nanoparticle (b) and embodiment 1
The UV-vis spectrogram of g-PMAEFc (d).
Fig. 6 is MWCNTs@Au (c) and MWCNTs@Au- prepared by MWCNTs (a), Au nanoparticle (b) and embodiment 1
The XPS of g-PMAEFc (d) schemes.
Fig. 7 is point of the MWCNTs@Au (b) of MWCNTs (a) and the preparation of embodiment 1, MWCNTs@Au-g-PMAEFc (c)
Dissipate Stability Determination result.
Fig. 8 is the TEM figure of MWCNTs@Au-g-PMAEFc prepared by embodiment 1.
Fig. 9 is the SEM figure of MWCNTs@Au-g-PMAEFc prepared by embodiment 1.
Figure 10 is that MWCNTs@Au (b), MWCNTs@Au-g-PMAEFc (c) prepared by MWCNTs (a) and embodiment 4 is repaired
Adorn the CV curve of electrode.
Figure 11 is the CV curve for the MWCNTs@Au-g-PMAEFc modified electrode that in embodiment 1-3 prepared by difference Au content.
Figure 12 is the MWCNTs@Au-g-PMAEFc modified electrode in embodiment 1 and 4 with different PMAEFc grafting rates
CV curve.
Figure 13 is that MWCNTs@Au-g-PMAEFc modified electrode prepared by embodiment 4 is molten for detecting various concentration metrifonate
The differential pulse voltammetry volt-ampere curve of liquid.
Figure 14 is the linear relationship curve between the metrifonate solution concentration obtained by Figure 13 and peak current.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, MWCNTs@Au nanocomposite is prepared
0.2g MWCNTs is added in 40mL acetone, at room temperature ultrasound 30 minutes, is filtered, vacuum drying 24 is small at 80 DEG C
When, ultrasound in 1.0mol/L NaOH aqueous solution is then added and is impregnated 5 hours after 30 minutes, filters, is rinsed with deionized water into
Property, it is dried in vacuo 24 hours at 80 DEG C, then the HF aqueous solution ultrasound for being 5% with 50mL mass concentration continuously stirs again after 30 minutes
It 8 hours, filters, is dried in vacuo 24 hours at 80 DEG C after being rinsed with deionized water to neutrality, obtains modified MWCNTs.It will
Ultrasonic disperse 1 hour in 92mL deionized water the modified MWCNTs of 0.05g, it is 1% that 40mL mass concentration, which is added,
HAuCl4·3H2O aqueous solution and 20mL0.05mol/L two citric acid monohydrate trisodiums aqueous solution, are rapidly added 12mL while stirring
0.1mol/L NaBH4Aqueous solution, it can be seen that solution rapidly goes to claret, continues stirring 24 hours after dripping at room temperature,
Seabed sediment is collected by centrifugation, drying at 80 DEG C obtains MWCNTs@Au nanocomposite, yield 72%.In the composite material
The partial size of Au nanoparticle is 7~15nm, and the mass content of Au is 73.4%.
2, atom transfer radical polymerization initiator is prepared
By 0.05g MWCNTs@Au nanocomposite be added 50mL deionized water in, ultrasonic disperse 30 minutes, then plus
Enter 0.085mL (1.22mmol) ME, be stirred at room temperature 24 hours, obtains MWCNTs@Au-SCH2CH2OH, yield 78%, wherein ME contains
Amount is 7.65mmol g-1。
By 0.05g MWCNTs@Au-SCH2CH2OH ultrasonic disperse is in 50mL DCM, by 238.6 μ L (1.93mmol) BIB
It is dissolved in 5mL DCM respectively with 267.5 μ L (1.93mmol) TEA, by the DCM solution of BIB under nitrogen protection and condition of ice bath
It is added drop-wise to MWCNTs@Au-SCH2CH2In OH dispersion liquid, about 30min is dripped, and the DCM solution of TEA is added dropwise after dripping again,
About 30min is dripped, and closes N after dripping2, reaction mixture reacts 24 hours at 30 DEG C, is centrifuged, is washed repeatedly with DCM
Unreacted BIB and TEA is removed, drying 24 hours, obtains atom transfer radical polymerization initiator MWCNTs@Au-Br at 60 DEG C,
Yield 70%, wherein the content of 2- bromine isobutyryl is 3.75mmol g-1。
3, the nano combined electrochemistry of carbon nanotube grafting polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate that preparation is inlaid with gold passes
Feel material
By 0.05g MWCNTs@Au-Br, 3.21g (9.375mmol) MAEFc, 0.16g (1.125mmol) CuBr, 239.7
μ L (0.9375mmol) HMTETA is added in the 50mL Shrek bottle for filling 4mL DMF, carries out 3 " freezings-in a closed system
Vacuumize-defrosting-and lead to nitrogen " circular treatment, 90 DEG C are then heated to, is reacted under nitrogen atmosphere for 24 hours.Stop reaction, be centrifuged,
It is cleaned repeatedly with DMF, removes unreacted MAEFc and HMTETA, then cleaned repeatedly with dehydrated alcohol and remove CuBr, then will produced
Object is dried in vacuo 24 hours at 80 DEG C, and the carbon nanotube grafting polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate being inlaid with gold is received
Rice composite electrochemical sensing material (being denoted as MWCNTs@Au-g-PMAEFc).
Inventor uses1H NMR, FTIR, Raman, XRD, TGA, UV-vis and XPS technology prepare above-described embodiment 1
MWCNTs@Au-g-PMAEFc carry out structural characterization and confirmation, as a result as shown in figs. 1 to 6.MWCNTs@Au-g-PMAEFc's1H NMR spectra 1 shows that there is chemical shifts relevant with the ferrocene group of feature and its backbone structure: 4.76 (2H, m,
- C in Cp5H4), 4.34 (4H, m ,-C (O) OCH2-CH2OC (O)-and 2H, m ,-S-CH2 CH2 - OOC-), 4.28 (in 2H, m, Cp-
C5H4), 4.13 (- C in 5H, m, Cp5H5), 1.96 (2H ,-S-CH2 CH2- OOC-), -1.80 (2H, -CH2 C(CH3)-Br),1.48
(2H, on main chain-CH2 ), 1.19 (3H ,-CH3 ), 0.77 (6H ,-(CH3)2 ), grafting rate is about through nucleus magnetic hydrogen spectrum estimation
8.1%.There is vibration peak relevant with PMAEFc and MWCNTs in infrared spectroscopy Fig. 2 of MWCNTs Au-g-PMAEFc,
3105cm-1、2850-2960cm-1、1716cm-1、1015-1140cm-1And 474-510cm-1Locate the absorption peak occurred respectively with two
On luxuriant ring=the flexible of c h bond ,-CH2It is flexible ,-C=O is flexible ,-C-O is flexible and two luxuriant rings on CPThe stretching vibration of-Fe key
It is corresponding, in 1605cm-1、1460cm-1、848cm-1And 720cm-1The absorption peak at place corresponds respectively to benzene in original MWCNTs skeleton
Ring (νC=C) stretching vibration ,-(CH3) asymmetric bending vibration and phenyl ring aromatic series or Ppolynuclear aromatic in hydrocarbon change
Shape vibration.In the Raman spectrogram 3 of MWCNTs@Au-g-PMAEFc, D band, the G band peak intensity ratio of MWCNTs is increased to 1.08.
In the XRD spectra 4 of MWCNTs@Au-g-PMAEFc, the characteristic peak of MWCNTs and Au nanoparticle is it will be clear that appear in
At 25.9 °, 38.1 °, 44.3 °, 64.6 °, 77.5 ° and 81.7 °, however since covalence graft diffraction peak intensity weakens.?
In uv-vis spectra Fig. 5 of MWCNTs@Au-g-PMAEFc, it may be seen that MWCNTs, Au nanoparticle and containing two cyclopentadienyl
The major absorbance peak of the PMAEFc grafted chain of iron, the only remitted its fury at peak.Especially since the grafting of polymer is so that two cyclopentadienyls
Absorption peak red shift of the iron at 308nm is at about 325nm；The absorption peak slight red shift of MWCNTs is at about 270nm；Au nanoparticle
The absorption peak red shift of son is to about 539nm.These results illustrate that there is certain interactions between three kinds of components, and polymer is
Through being successfully grafted to the surface MWCNTs being inlaid with gold.In XPS spectrum Fig. 6 of MWCNTs@Au-g-PMAEFc, in addition to C1s, O1s,
Au4f、Au4d5/2、Au4d3/2Except the electronic signal peak of Au4p, combining at 54.7,103.6 and 711.2-721.3eV of energy
There is new signal peak, corresponds respectively to the characteristic signal peak of Fe3p, Fe3s and Fe2p.Only because the knot being graft-polymerized
Fruit, in the MWCNTs@Au-g-PMAEFc of formation, the signal peak strength of Au4f and Fe2p weaken.In particular, the signal peak of Au
It is even also weaker than in MWCNTs Au nanocomposite.The decrease of signal peak strength is since major part Au receives after polymerizeing
Rice corpuscles is wrapped by caused.
The dispersion behavior for the MWCNTs@Au-g-PMAEFc that inventor further prepares embodiment 1 and pattern use UV-
Vis, TEM, SEM are characterized, as shown in figs. 7-9.It clearly can see by Fig. 7, due to soluble PMAEFc strand
MWCNTs or MWCNTs@Au is prevented to assemble and precipitate, MWCNTs@Au-g-PMAEFc is in CHCl3In have good dispersion
Property.Light transmittance is only 10% after being centrifuged 10min, there was only about 20% after 60min, and there's almost no sedimentation.Fig. 8's and Fig. 9
TEM and SEM shows have one layer of thicker polymer to be closely coated on around MWCNTs@Au nanocomposite, MWCNTs pipe
Diameter significantly thickens.Nevertheless, still it will be clear that some Au nanoparticles are exposed to the polymer of cladding MWCNTs@Au
On coating.MWCNTs@Au-g-PMAEFc with this pattern can disperse well, and can be by between these components
Synergistic effect generates good electrochemical properties.
Embodiment 2
1, MWCNTs@Au nanocomposite is prepared
According to the modified MWCNTs of 1 the method for embodiment.The modified MWCNTs of 0.05g is surpassed in 92mL deionized water
Sound disperses 1 hour, and the HAuCl that 10mL mass concentration is 1% is added4·3H2Bis- citrate hydrate of O aqueous solution and 5mL 0.05mol/L
Sour three sodium water solutions, are rapidly added 3mL 0.1mol/L NaBH while stirring4Aqueous solution, it can be seen that solution rapidly goes to wine
Red continues stirring 24 hours at room temperature after dripping, seabed sediment is collected by centrifugation, and drying at 80 DEG C obtains MWCNTs Au
Nanocomposite, yield 75%.The partial size of Au nanoparticle is 7~15nm in the composite material, and the mass content of Au is
41.9%.
2, atom transfer radical polymerization initiator is prepared
By 0.05g MWCNTs@Au nanocomposite be added 50mL deionized water in, ultrasonic disperse 30 minutes, then plus
Enter 0.044mL (0.63mmol) ME, be stirred at room temperature 24 hours, obtains MWCNTs@Au-SCH2CH2OH, yield 78%, wherein ME contains
Amount is 5.56mmol g-1。
By 0.05g MWCNTs@Au-SCH2CH2OH ultrasonic disperse is in 50mL DCM, by 137.5 μ L (1.112mmol)
BIB and 154.1 μ L (1.112mmol) TEA are dissolved in respectively in 5mL DCM, by the DCM of BIB under nitrogen protection and condition of ice bath
Solution is added drop-wise to MWCNTs@Au-SCH2CH2In OH dispersion liquid, about 30min is dripped, and the DCM that TEA is added dropwise after dripping again is molten
Liquid, about 30min drip, and close N after dripping2, reaction mixture reacts 24 hours at 30 DEG C, is centrifuged, repeatedly with DCM
Unreacted BIB and TEA is washed away, drying 24 hours, obtains atom transfer radical polymerization initiator MWCNTs@Au- at 60 DEG C
Br, yield 69%, wherein the content of 2- bromine isobutyryl is 3.39mmol g-1。
3, the nano combined electrochemistry of carbon nanotube grafting polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate that preparation is inlaid with gold passes
Feel material
By 0.05g MWCNTs@Au-Br, 2.90g (8.475mmol) MAEFc, 0.15g (1.017mmol) CuBr, 216.7
μ L (0.8475mmol) HMTETA is added in the 50mL Shrek bottle for filling 4mL DMF, carries out 3 " freezings-in a closed system
Vacuumize-defrosting-and lead to nitrogen " circular treatment, 90 DEG C are then heated to, is reacted under nitrogen atmosphere for 24 hours.Stop reaction, be centrifuged,
It is cleaned repeatedly with DMF, removes unreacted MAEFc and HMTETA, then cleaned repeatedly with dehydrated alcohol and remove CuBr, then will produced
Object is dried in vacuo 24 hours at 80 DEG C, obtains MWCNTs@Au-g-PMAEFc, and nuclear-magnetism grafting rate is 4.5%.
Embodiment 3
1, MWCNTs@Au nanocomposite is prepared
According to the modified MWCNTs of 1 the method for embodiment.The modified MWCNTs of 0.05g is surpassed in 92mL deionized water
Sound disperses 1 hour, and the HAuCl that 20mL mass concentration is 1% is added4·3H2O aqueous solution and 10mL 0.05mol/L bis- are hydrated lemon
Lemon three sodium water solutions of acid, are rapidly added 6mL 0.1mol/L NaBH while stirring4Aqueous solution, it can be seen that solution is rapidly gone to
Claret continues stirring 24 hours at room temperature after dripping, seabed sediment is collected by centrifugation, and drying at 80 DEG C obtains MWCNTs
Au nanocomposite, yield 73%.The partial size of Au nanoparticle is 7~15nm in the composite material, and the mass content of Au is about
It is 58.4%.
2, atom transfer radical polymerization initiator is prepared
By 0.05g MWCNTs@Au nanocomposite be added 50mL deionized water in, ultrasonic disperse 30 minutes, then plus
Enter 0.063mL (0.90mmol) ME, be stirred at room temperature 24 hours, obtains MWCNTs@Au-SCH2CH2OH yield is 76%, wherein ME
Content is 6.61mmol g-1。
By 0.05g MWCNTs@Au-SCH2CH2OH sound is scattered in 50mL DCM, by 163.4 μ L (1.322mmol) BIB
It is dissolved in 5mL DCM respectively with 183.8 μ L (1.322mmol) TEA, by the DCM solution of BIB under nitrogen protection and condition of ice bath
It is added drop-wise to MWCNTs@Au-SCH2CH2In OH dispersion liquid, about 30min is dripped, and the DCM solution of TEA is added dropwise after dripping again,
About 30min is dripped, and closes N after dripping2, reaction mixture reacts 24 hours at 30 DEG C, is centrifuged, is washed repeatedly with DCM
Unreacted BIB and TEA is removed, drying 24 hours, obtains atom transfer radical polymerization initiator MWCNTs@Au-Br at 60 DEG C,
Yield is 70%, and wherein the content of 2- bromine isobutyryl is 3.52mmol g-1。
3, the nano combined electrochemistry of carbon nanotube grafting polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate that preparation is inlaid with gold passes
Feel material
By 0.05g MWCNTs@Au-Br, 3.01g (8.800mmol) MAEFc, 0.15g (1.056mmol) CuBr, 225.0
μ L (0.880mmol) HMTETA is added in the 50mL Shrek bottle for filling 4mL DMF, carries out 3 " freezings-in a closed system
Vacuumize-defrosting-and lead to nitrogen " circular treatment, 90 DEG C are then heated to, is reacted under nitrogen atmosphere for 24 hours.Stop reaction, be centrifuged,
It is cleaned repeatedly with DMF, removes unreacted MAEFc and HMTETA, then cleaned repeatedly with dehydrated alcohol and remove CuBr, then will produced
Object is dried in vacuo 24 hours at 80 DEG C, obtains MWCNTs@Au-g-PMAEFc, and nuclear-magnetism grafting rate is 6.7%.
Embodiment 4
In the step 3 of the present embodiment, by 0.05g MWCNTs Au-Br, (content of 2- bromine isobutyryl is 3.75mmol
g-1), 9.72g (28.425mmol) MAEFc, 0.17g (1.137mmol) CuBr, 257.7 μ L (0.9475mmol) HMTETA be added
It fills in the 50mL Shrek bottle of 8mL DMF, carries out 3 times " freeze-vacuumizing-thaw-lead to nitrogen " in a closed system and recycle
Processing, then heats to 90 DEG C, for 24 hours, other steps are same as Example 1 for confined reaction under nitrogen atmosphere, obtain MWCNTs@
Au-g-PMAEFc, nuclear-magnetism grafting rate are 38%.
Embodiment 5
MWCNTs@Au-g-PMAEFc prepared by embodiment 1-4 is used to oppose in vegetables as glassy carbon electrode decorative material
The application of hundred worm residues detections, specific electrode modification and trace metrifonate detection method are as follows:
By naked glassy carbon electrode (GCE) successively with 0.3 μm and 0.05 μm of Al2O3Powder is polished to mirror surface, with dehydrated alcohol and
Distilled water ultrasonic cleaning is stand-by.By MWCNTs@Au-g-PMAEFc ultrasonic disperse 30min in chloroform, 6 μ of its suspension is taken
L is uniformly dripped on the surface GCE handled well, and standing is dried, and obtains MWCNTs@Au-g-PMAEFc/GCE modified electrode sensor.
The CHI660E type electrochemical workstation produced using Shanghai Chen Hua Instrument Ltd., with MWCNTs Au-g-PMAEFc/GCE
Modified electrode sensor is working electrode, saturated calomel electrode is reference electrode, platinum electrode is to electrode, in 0.2M pH=7
PBS buffer solution (by 0.2M H3PO4、0.2M NaH2PO4And 0.2M Na2HPO4The PBS buffer solution of preparation, and use 1.0M
HCl and 1.0M NaOH adjust pH) and 0.2M KCl aqueous solution composition electrolyte solution in using cyclic voltammetry (CV) measurement
The electrochemical redox performance of MWCNTs@Au-g-PMAEFc is detected.In order to compare, respectively by MWCNTs,
MWCNTs@Au is prepared into MWCNTs/GCE according to the above method, MWCNTs@Au/GCE modified electrode sensor carries out electrochemical oxidation
Reducing property detection.Experimental result is as shown in Figure 10~12.
By the CV curve of Figure 10, it is apparent that MWCNTs@Au-g-PMAEFc modification prepared by the embodiment of the present invention 4
The redox electrochemical process of electrode sensor will definitely be inverse, and chemical property is also remarkably reinforced, and is a kind of excellent
Electrochemical Modification electrode material.It can be seen from figure 11 that with the increase of Au nanoparticle content, pair of redox peak shape
Title property improves；Increased by the redox peak current that Au nanoparticle and the ferrocene segment of grafting generate；Oxidation peak potential subtracts
Small and reduction peak potential increases, thus nano combined electrochemical sensing material has better electrochemical response.And due to Au
The anode and cathode spike potential difference Δ E that nanoparticle and ferrocene units generatepValue is gradually reduced, anode and cathode peak current
Than (Ip,a/Ip,c) level off to integer 1.Therefore, the symmetry and invertibity of nano combined electrochemical sensing material improve.Therefore,
It can be obtained by regulating and controlling each component ratio with excellent electrochemical response and the reversible MWCNTs@Au-g- of response
PMAEFc.In particular, when the mass content of Au is 73.4% in MWCNTs@Au nanocomposite, MWCNTs@Au-g-
The redox property and electrochemical reversibility of PMAEFc is optimal.From the MWCNTs@Au-g- of Figure 12 difference PMAEFc grafting rate
The CV curve of PMAEFc is, it is apparent that with the increase for being grafted ferrocene segment content, by Au nanoparticle and ferrocene
The oxidizing potential and peak current that segment generates increase, and spike potential difference increases.Therefore, with the increase of grafting ferrocene chain length, though
Right redox current increases, but the electrochemical reversibility of modified electrode is deteriorated.Therefore, comprehensive electrochemical is excellent in order to obtain
The mass content of good MWCNTs@Au-g-PMAEFc, controllable Au are that 73.4%, PMAEFc grafting rate is about 38%.Thus may be used
Preparation has apparent redox peak current, and the MWCNTs Au-g-PMAEFc of good redox electrochemical reversibility is used
In electrode modification.
In order to detect the residual of the metrifonate in authentic sample, three kinds of 1.5g apple, tomato, cucumber samples are cut into respectively
Strip is put into 50mL beaker, and adding containing metrifonate concentration is respectively 0.5 × 10-10、1.0×10-10, 2.0 × 10-10
With 4.0 × 10-10mol l-1PBS buffer solution, impregnate 6h.Then sample is surpassed in the PBS buffer solution of 30mL pH=7
Then sound 1h obtains extracting solution by 0.45 μm of membrane filtration.Extracting solution is transferred in 50mL volumetric flask, then slow with PBS
It rushes standardization of solution and is diluted to graduation mark, obtained required solution, and save backup at 4 DEG C.
It is examined as electrode modified material in metrifonate residual quantity to assess the nano combined electrochemical sensing material of preparation
Application in survey is determined metrifonate residual quantity using DPV method.Before measurement, first using DPV method to the school of metrifonate
Directrix curve is demarcated, calibration method are as follows: is used MWCNTs@Au-g-PMAEFc/GCE modified electrode sensor, is passed through DPV method
The linear equation between anode (oxidation) peak current and metrifonate concentration is obtained, the calibration curve of metrifonate is obtained.All realities
It tests all in 10mL 0.2mol l-1Containing metrifonate solution concentration range from 1.0 × 10-7To 1.0 × 10-13mol l-1PBS
It is carried out in electrolyte, measurement result is as shown in figure 13.It is obvious that 1.0 × 10-7To 1.0 × 10-13mol l-1Wide metrifonate
In concentration range, anodic peak current (Ip,a) linearly improved with the raising of metrifonate log concentration logC, as shown in figure 14,
Linear gauging equation are as follows:
Ip,a(μ A)=0.5834 (- logC) -0.0153 (R2=0.9982)
And the present invention is thus calculated, (LOD) value is limited down to 7.6 × 10 to the detection of metrifonate-9mol l-1。
Similarly, we also use DPV method to detect food additives content of melamine, and it is good to obtain linear relationship
Good peak current and content of melamine correction equation is as follows:
Ip,a(μ A)=0.0664 (- lgC) -0.0417 (R2=0.9973)
Thus the present invention is obtained to the detection limit about 6.7 × 10 of melamine measurement-9mol l-1(1.7×10-3mg l-1)。
Then, DPV measurement has been carried out to three apple, mushroom and cucumber samples using calibration curve and correction equation, often
A sample measures 5 times, is averaged, passes through the I measuredp,aEstimate that drug residue of food concentration, the rate of recovery and relative standard are inclined
Difference, measurement result are as shown in table 1.
The measurement result of metrifonate content in 1 authentic sample of table
Note: a represents the average value of 5 measurements in table.
Seen from table 1, MWCNTs@Au-g-PAMEFc of the present invention is certain density in apple, mushroom and cucumber for measuring
When pesticide metrifonate content, measured value and additional amount have the value being almost similar, and have low standard deviation (apple
0.6%~3.6%；Mushroom 0.5%~6.1%；Cucumber 0.6%~5.8%) and the high rate of recovery (apple 89.0%~
102.3%；Mushroom 85.0%~112.5%；Cucumber 82.0%~99.0%).Therefore, MWCNTs@Au-g-PMAEFc of the present invention
Modified electrode sensor is a kind of promising reliable tool, can quickly, easily and effectively detect authentic sample (such as food
And fruit) in metrifonate residual quantity.
Claims (8)
1. a kind of carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer being inlaid with gold, it is characterised in that the electricity
The structure of chemical sensing material is as follows:
In formulaAu nanoparticle is represented,Carbon nanotube is represented, the partial size of Au nanoparticle is 5~20nm, and Au accounts for Au and receives
The 20%~80% of rice corpuscles and carbon nanotube gross mass；N represents the degree of polymerization of methacrylic acid ferrocene formyl 2-ethoxyethyl acetate, gathers
The nuclear-magnetism grafting rate of methacrylic acid ferrocene formyl 2-ethoxyethyl acetate is 4.5%~55%.
2. the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer according to claim 1 being inlaid with gold
Material, it is characterised in that: the Au accounts for the 65%~75% of Au nanoparticle and carbon nanotube gross mass, two cyclopentadienyl of polymethylacrylic acid
The nuclear-magnetism grafting rate of armor acyl-oxygen ethyl ester is 30%~40%.
3. the carbon nanotube grafting polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate being inlaid with gold described in a kind of claim 1 is nano combined
The preparation method of electrochemical sensing material, it is characterised in that it is made of following step:
(1) CNTs@Au nanocomposite is prepared
By in-situ chemical reducing process, carbon nano tube surface after modification inlays Au nanoparticle, obtains Au nanometers of CNTs@again
Condensation material, the partial size of Au nanoparticle is 5~20nm in the CNTs@Au nanocomposite, and the mass content of Au is 20%
~80%；
(2) atom transfer radical polymerization initiator is prepared
By molar ratio 1:4~7 of Au and mercaptoethanol, CNTs@Au nanocomposite is reacted with mercaptoethanol and generates CNTs@
Au-SCH2CH2OH；Then with CNTs@Au-SCH2CH2The meter of the substance of mercaptoethanol in OH, by CNTs@Au-SCH2CH2OH
In molar ratio it is 1:2~5:2~5 with 2- bromine isobutyl acylbromide, triethylamine, the carbon nanotube being inlaid with gold is prepared by acyl bromination reaction
Atom transfer radical polymerization initiator；
(3) the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer that preparation is inlaid with gold
Using CuBr as catalyst, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylene tetramines are ligand, by methacrylic acid ferrocene first
Acyl-oxygen ethyl ester reacts 12~36h in the case where the carbon nanotube atom transfer radical polymerization initiator being inlaid with gold causes at 80~90 DEG C,
The carbon nanotube grafting nano combined electrochemical sensing material of polymethylacrylic acid ferrocene formyl 2-ethoxyethyl acetate being inlaid with gold.
4. the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer according to claim 3 being inlaid with gold
Preparation method, it is characterised in that: in step (1), in the CNTs@Au nanocomposite mass content of Au be 65%
~75%.
5. the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer according to claim 3 being inlaid with gold
Preparation method, it is characterised in that: in step (3), in the carbon nanotube atom transfer radical polymerization initiator that is inlaid with gold
The meter of the substance of 2- bromine isobutyryl, carbon nanotube atom transfer radical polymerization initiator, the metering system being inlaid with gold
Sour ferrocene formyl 2-ethoxyethyl acetate, CuBr, 1,1,4,7,10,10- hexamethyl triethylene tetramine molar ratio be 1:50~400:6:
5。
6. the carbon nanotube grafting nano combined electrochemical sensing material of ferrocene polymer according to claim 5 being inlaid with gold
Preparation method, it is characterised in that: in step (3), in the carbon nanotube atom transfer radical polymerization initiator that is inlaid with gold
The meter of the substance of 2- bromine isobutyryl, carbon nanotube atom transfer radical polymerization initiator, the metering system being inlaid with gold
Sour ferrocene formyl 2-ethoxyethyl acetate, CuBr, 1,1,4,7,10,10- hexamethyl triethylene tetramine molar ratio be 1:100~200:6:
5。
7. the carbon nanotube grafting nano combined electrochemical sensing material conduct of ferrocene polymer described in claim 1 being inlaid with gold
Application of the electrode modified material in detection pesticide metrifonate residual quantity.
8. the carbon nanotube grafting nano combined electrochemical sensing material conduct of ferrocene polymer described in claim 1 being inlaid with gold
Application of the electrode modified material in detection food additives content of melamine.
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