CN105241944B - The method of antibiotic in Electrochemical Detection milk based on the vertical enrichment of micella in order - Google Patents
The method of antibiotic in Electrochemical Detection milk based on the vertical enrichment of micella in order Download PDFInfo
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- CN105241944B CN105241944B CN201510624367.5A CN201510624367A CN105241944B CN 105241944 B CN105241944 B CN 105241944B CN 201510624367 A CN201510624367 A CN 201510624367A CN 105241944 B CN105241944 B CN 105241944B
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Abstract
The invention discloses a kind of method of antibiotic in Electrochemical Detection milk based on the vertical enrichment of micella in order, it is characterised in that including：Milk is diluted as detection solution with electrolyte solution first, then using vertical orderly electrode micelle modified CTAB as working electrode, using electrochemistry voltammetry, the antibiotic in milk soln is first enriched with and detected afterwards.The present invention is using vertical orderly micelle modified electrode as working electrode, pass through hydrophobic effect, hydrophobic in the aqueous solution, electroneutral antibiotic is extracted/is enriched in the dewatering nano chamber of surfactant micellar, using the reduction peak current of antibiotic as detection signal, so as to realize the quantitative detection under the complex background of milk.The sensor that the present invention is built is by preenrichment and Electrochemical Detection in one, and sensitivity is high, the detection range of linearity is wide, test limit is low, has larger application potential in food safety monitoring field.
Description
Technical field
The invention belongs to a kind of detection method of antibiotic in electrochemical sensing field, more particularly to milk.
Background technology
Current social food security causes the extensive concern of people, and wherein dairy safety problem is a large focal spot, explores
Quickly, accurate, convenient, sensitive analysis method turns into one of emphasis direction of quality of dairy products security study.Antibiotic is one
Class has bacteria growing inhibiting or kills the material of bacterium, by the extensive use as animal pharmaceuticals and feed addictive.Research
Show, the residual of antibiotic has serious harm to human body in milk, such as produce allergic reaction, produce endurance strain, cause
Flora imbalance in human body intestinal canal etc..At present, the U.S., European Union and Japan and other countries are remained to the maximum of antibiotic in raw material milk
Amount has made clear and definite regulation, and maximum residue limit is 4 μ g/kg.Therefore, quick, the highly sensitive detection of antibiotic is strict in milk
Control prevents in food illegal addition antibiotic, ensures the important process of consumer health's rights and interests, at the same expanded to physiology and
The research of pathology.
So far, researcher detects the antibiotic in milk, such as microbiological method, gas phase using various technical Analysis
Chromatography, liquid chromatography, immunoassay, electrochemical process etc..Wherein, electrochemical process is due to low with sensitivity height, price
Honest and clean, simple operation and other advantages, and favored by researchers.The nanometers such as molecularly imprinted polymer, nano-particle, CNT
Material can be modified on electrode, for being enriched with antibiotic, improve detection performance.
In addition, the method for patent literature mainly has：Application No. 200410013741.X Chinese patent literature report
A kind of method that antibiotic in milk is detected with pH meter in road.It is used utilizes lactobacillus inoculum with pH meter one in milk sample
PH value in the interior measure milk sample in interval of fixing time, by the change of pH value, to determine whether containing antibiotic.Application No.
The side of antibiotic in a kind of visualization quick detection milk based on nanogold of 201310069037.5 patent literature
Method, it reduces gold chloride to prepare nanogold using pyrocatechol violet.Because of the addition of antibiotic during nanogold is synthesized
The synthesis of nanogold is have impact on, its color is changed, can be to antibiotic using naked eyes and ultraviolet-visible absorption spectroscopy instrument
Quantitatively detected.These above-mentioned methods, be by detecting that indirect parameter determines whether that, containing antibiotic, accuracy in detection is low,
And easily influenceed by extraneous regulation.
Mesoporous silicon oxide (SiO2, aperture 2-50nm) and it is in the lump in the nano pore of periodic arrangement by aperture height
And its unbodied silica composition of surrounding.In recent years, researcher uses electrochemistry assisted self assembling
(Nat.Mater.2007,6,602-608) andSolution growth (Angew.Chem.Int.Ed.2012,51,2173-
2177) collaboration of the method such as, induction surfactant molecule self assembly and the reaction of organosilane molecules hydrolysis/condensation occurs,
The surface of solids be successfully prepared for high-sequential arrangement and passage perpendicular to surface SiO2Nanochannel film.The film has
Very excellent performance：Ultra-thin and thickness is adjustable (20-200nm), and pore size and pore distribution high uniformity, porosity are high
(up to 7.5 × 1012cm-2), excellent machinery, chemistry, heat endurance and biocompatibility, and cost it is low, can larger area
Prepared by batch, be the nanochannel film of a kind of preferable molecular recognition and separation, in fields such as catalysis, absorption, analysis, sensings
With huge application potential.In this method, while vertical ordered mesoporous silica dioxide is synthesized, template molecule is surface-active
Agent cetyl trimethylammonium bromide (CTAB) is evenly spaced in inside the duct of mesoporous silicon oxide, forms vertical glue in order
Beam.In each micella, outwardly, and alkyl chain flocks together to form one CTAB powered polar group by hydrophobic effect
Dewatering nano chamber.By hydrophobic effect, hydrophobic in the aqueous solution, electroneutral electro-chemical activity organic molecule can be extracted/
It is enriched in the nano-cavity of surfactant micellar, and occurs electrochemical oxidation or reduction in micella/electrode interface.
The content of the invention
, should the invention provides a kind of method of antibiotic in Electrochemical Detection milk based on the vertical enrichment of micella in order
Method detection sensitivity is high.Vertical CTAB micellas in order have suction-operated to the antibiotic in milk, can improve antibiotic
Concentration in micella, so as to improve the Electrochemical Detection performance of antibiotic.
The electrochemical detection method of antibiotic comprises the following steps that in milk proposed by the invention：
Milk is diluted as detection solution, then with vertical CTAB (cetyls three in order with electrolyte solution first
Methyl bromide ammonium) micelle modified electrode is as working electrode, using electrochemistry voltammetry, to the aromatic nitro in milk soln
Antibiotic is first enriched with and detected afterwards.
The present invention uses electrochemistry voltammetry, using vertical micelle modified electrode in order as working electrode, and platinum electrode and silver/
Silver chlorate is respectively, to electrode and reference electrode, antibiotic in milk to be used for quickly detecting.
Preferably, the electrolyte solution is selected from sodium-chloride water solution, aqueous sodium persulfate solution, potassium chloride solution, phosphorus
One kind in acid buffering solution, NaAc_HAc buffer solution；More preferably sodium-chloride water solution or phosphoric acid buffer is molten
Liquid.The concentration of electrolyte solutions is 0.02~0.5mol/L, more preferably 0.08~0.2mol/L；The electrolyte is molten
The pH value of liquid is 6~8；More preferably 6~7.Preferably, inertia can be passed through into electrolyte solution before testing
Gas, nitrogen etc., to exclude interference of the Oxygen in Electrolytical Solution gas to detection；Being passed through the times such as inert gas, nitrogen can basis
It is actually needed determination, general 3~30 minutes.Preferably, the extension rate of milk is 1~100 times, more preferably
5~10 times.
Preferably, the working electrode is selected from tin indium oxide (ITO) electrode, fluorine-doped tin oxide (FTO) electrode, gold electricity
One kind in pole, glass-carbon electrode (GCE) or screen printing electrode；More preferably tin indium oxide (ITO) electrode.
Preferably, the vertical orderly electrode micelle modified CTAB can be prepared using existing method, for example,
It can be prepared by following two methods：
First method,Solution growth method：Concretely comprise the following steps and working electrode is put into CTAB, water, ethanol, ammoniacal liquor
In the solution constituted with TEOS, growth 3-48 hours are stood at 40~70 DEG C.
In the first preparation method, with 1gCTAB calculating, it is necessary to which the water added, ethanol, ammoniacal liquor, TEOS volume are respectively
400~550ml, 150~200ml, 50~80 μ L, 450~550 μ L.
Second method, electrochemistry assisted self assembling method：Concretely comprise the following steps and working electrode is put into CTAB, TEOS, water, second
The solution (stirring 1~3 hour in advance) that alcohol, sodium nitrate and hydrochloric acid are constituted, applies constant current density -0.1mA cm-2~-1mA
cm-2Growth 3-30 seconds.
In second of preparation method, calculated with 1gCTAB, the TEOS of addition, water, ethanol, sodium nitrate, the amount difference of hydrochloric acid
For：1.5~2.0g, 10~15ml, 10~15ml, 0.08~0.15g, 2~3 μ L.
In the vertical orderly electrode micelle modified CTAB, the aperture of mesoporous silicon oxide is 2~3nm；From top to bottom
Include vertical meso-porous titanium dioxide silicon layer, electrode basement layer and glassy layer successively.The thickness of vertical meso-porous titanium dioxide silicon layer for 20~
200nm, more preferably 80~120nm.
Preferably, the enrichment method is stirring enrichment or constant potential enrichment.Stirring enrichment for mechanical agitation 0~
20min；More preferably 8~15 minutes；The constant potential enrichment is 0~20min of enrichment under the conditions of -1.0~0.4V；Enter one
The preferred constant potential enrichment condition of step is 25~35s of enrichment under -0.5~0V current potentials.
Preferably, the aromatic nitro antibiotic is the one or two kinds of in chloramphenicol, furantoin.The fragrance
Content of the nitro antibiotic in milk is 0.4~50ppm, in the content range, using the inventive method, is respectively provided with higher
Accuracy.
The present invention is using vertical micelle modified electrode in order as working electrode, by hydrophobic effect, hydrophobic, electricity in the aqueous solution
Neutral antibiotic is extracted/is enriched in the dewatering nano chamber of surfactant micellar, using the reduction peak current of antibiotic as
Signal is detected, so as to realize the quantitative detection under the complex background of milk.The sensor that the present invention is built is by preenrichment and electricity
Chemical detection is in one, and sensitivity is high, the detection range of linearity is wide, test limit is low, has in food safety monitoring field larger
Application potential.
Relative to prior art, beneficial effects of the present invention are embodied in：
1st, the present invention using electrochemistry assisted self assembling andIt is vertical order mesoporous prepared by solution growth method
Silica is as hard template, in the cylindrical CTAB micellas of electrode surface bearing height ordered arrangement, and each micella is and base
Hearth electrode surface is effectively contacted, and is conducive to mass transfer, has expanded its application space in analysis sensing.
2nd, the aperture of the vertical hard template mesoporous silicon oxide of CTAB micellas in order is in 2~3nm, with size selectivity,
The molecule that micelle diameters can be more than with exclusion size enters electrode surface.It is thereby achieved that the selectivity to antibiotic is rich
Collection.
3rd, this method detection is rapid, as long as the several seconds is that can obtain testing result.
4th, this method to milk without pre-processing, and electrode antipollution and anti-interference are good, and sensitivity is high.
5th, detection method of the invention can be extended to the spirit of the electro-chemical activity organic molecule hydrophobic, neutral to other
Quick detection, such as environmental contaminants, agricultural chemicals, explosive, antioxidant.
Brief description of the drawings
Fig. 1 is the solution to be detected after milk dilution in the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture (top view (a), sectional view (b)) of vertical mesoporous silicon oxide in the embodiment of the present invention 1
With scanning electron microscope (SEM) photograph (c).
Fig. 3 is naked ITO electrode (a), vertical orderly ITO electrode (b) micelle modified CTAB in the embodiment of the present invention 1 and hangs down
Differential pulse volt-ampere of the ITO electrode (c) of straight ordered mesoporous silica dioxide modification in the milk soln containing 5ppm chloramphenicol
Curve.
Fig. 4 is vertical orderly ITO electrode micelle modified CTAB in the embodiment of the present invention 1 in the different circulations volts swept under speed
Antu (a) and peak current are with sweeping fast subduplicate linear relationship chart (b).Electrolyte solution is the milk containing 10ppm chloramphenicol
Solution.Sweep speed is respectively 10,50,100,150,200mV/s.
Fig. 5 is containing various concentrations chloramphenicol for vertical orderly ITO electrode micelle modified CTAB in the embodiment of the present invention 1
Milk in differential pulse volt-ampere curve.
Fig. 6 is the structural representation of vertical orderly ITO electrode micelle modified CTAB in the present invention.
Fig. 7 is the detection means figure of the electrochemistry voltammetry of the present invention.
Embodiment
Embodiment 1
Using vertical orderly ITO electrode micelle modified CTAB, the electrochemical process of chloramphenicol in milk is detected：
(1) milk for being bought direct supermarket with 0.1mol/L, the sodium-chloride water solution that pH value is 6 dilutes 10 times, as
Solution to be detected, as shown in Figure 1.Argon gas is passed through in the solution to be measured, to exclude the interference of the oxygen in solution.Using simple
Three-electrode system, as shown in fig. 7, ITO electrode, platinum electrode and the silver/silver chloride electrode of the vertical modifications of CTAB in order are made respectively
For working electrode, to electrode and reference electrode.
(2) chloramphenicol is dissolved in absolute ethyl alcohol and is configured to storing solution, the chlorine that different volumes are added in solution to be measured is mould
Plain storing solution obtain a series of solution to be measured (concentration of chloramphenicol is 0.4ppm, 0.7ppm, 1ppm, 2ppm, 3ppm respectively,
5ppm, 7ppm, 10ppm, 15ppm, 20ppm, 30ppm, 35ppm), stir and differential pulse volt-ampere test is carried out after 10s.
Vertically the preparation method of orderly ITO electrode micelle modified CTAB isSolution growth method, specific steps are such as
Under：
By ITO electrode be put into that 0.16g CTAB, 70mL water, 30mL ethanol, 10 μ L ammoniacal liquor and 80 μ L TEOS are constituted it is molten
In liquid, growth 24 hours are stood at 60 DEG C.
The electron microscope of the ITO electrode micelle modified vertical orderly CTAB that is prepared by the above method is Fig. 2.
Vertical ordered mesoporous silica dioxide (the ITO electricity micelle modified for vertical CTAB in order actually detected shown in Fig. 2
Pole, vertical orderly ITO electrode micelle modified CTAB is needed to disperse in ethanol when Electronic Speculum is done, and CTAB in ethanol can
Dissolving is in ethanol) transmission electron microscope picture top view, in Fig. 2 (a), white bright spot is hole, that is, position residing for CTAB micellas
Put, it can be seen that the aperture of mesoporous silicon oxide is 2~3nm；The sectional view of transmission electron microscope shows the order in duct (in Fig. 2
(b) three layers (in Fig. 2 (c))), are can be clearly seen that from scanning electron microscope (SEM) photograph, from top to bottom respectively vertical meso-porous titanium dioxide
Silicon layer, ITO layer and glassy layer, and the thickness of vertical meso-porous titanium dioxide silicon layer is 95nm.
Fig. 3 is naked ITO electrode (a), vertical ITO electrode (b) micelle modified CTAB and vertical order mesoporous dioxy in order
Differential pulse volt-ampere curve of the ITO electrode (c) of SiClx modification in the milk containing 5ppm chloramphenicol, it can be seen that vertical
Ordered mesoporous silica dioxide modifies the reduction peak current that chloramphenicol is barely perceivable in ITO electrode and naked ITO electrode, and vertical
Reduction peak is obvious and sharp in ITO electrode micelle modified CTAB in order, it was demonstrated that be present in mesoporous silicon oxide duct
CTAB micellas serve enrichment in the detection of chloramphenicol, effectively improve electrode surface analyte concentration, so as to enhance
The sensitivity of detection.
Fig. 4 for vertical micelle modified CTAB ITO electrode in order difference sweep speed (sweep speed is respectively 10,50,100,
150th, 200mV/s) under cyclic voltammogram (in Fig. 4 (a)) and peak current and sweep fast subduplicate linear relationship chart (in Fig. 4
(b)).Peak current has linear relationship with sweeping the square root of speed, and it is diffusion in the electrochemical reaction of electrode surface to show chloramphenicol
Control, further proves that chloramphenicol can enter CTAB micellas and smoothly reach electrode surface.
Differentials of the Fig. 5 for vertical orderly ITO electrode micelle modified CTAB in the milk containing various concentrations chloramphenicol
Pulse Voltammetry curve, it can be seen that reduction peak current increases with the increase of chloramphenicol concentration.
Fig. 6 is the structural representation of vertical orderly ITO electrode micelle modified CTAB.
The electrode that result above analysis result demonstrates the vertical modifications of CTAB in order can successfully be used for detecting in milk
Chloromycetin content.
Embodiment 2
Using vertical orderly ITO electrode micelle modified CTAB, the electrochemical process of furantoin in milk is detected：
(1) 5 times are diluted for the 7 phosphate buffer solution milk of buying direct supermarket with 0.1mol/L, pH value, as treating
Detect solution.Nitrogen is passed through in the solution to be measured, to exclude the interference of the oxygen in solution.Using simple three electrode system
System, FTO electrodes, platinum electrode and the silver/silver chloride electrode of the vertical modifications of CTAB in order are respectively as working electrode, to electrode and ginseng
Compare electrode.
(2) furantoin is dissolved in absolute ethyl alcohol and is configured to storing solution, the furan of different volumes is added in solution to be measured
Mutter appropriate because storing solution obtains being enriched with progress differential pulse volt-ampere test after 30s under a series of solution to be measured, -0.4V current potentials.
The preparation method of vertical orderly FTO electrodes micelle modified CTAB is electrochemistry assisted self assembling method, specific steps
It is as follows：
By FTO electrodes be put into 1.585g CTAB, 2.833g TEOS, 20mL water, 20mL ethanol, 0.17g sodium nitrate and
The solution (stirring 2.5 hours in advance) that 4.18 μ L hydrochloric acid are constituted, applies constant current density -0.5mA cm-2Growth 10 seconds.Through surveying
Examination proves that the detection method of embodiment 2 equally has good Detection results to the furantoin in milk.
Claims (8)
1. a kind of method of antibiotic in Electrochemical Detection milk based on the vertical enrichment of micella in order, it is characterised in that including：
Milk is diluted as detection solution, then with electrode work micelle modified vertical CTAB in order with electrolyte solution first
For working electrode, using electrochemistry voltammetry, the antibiotic in milk soln is first enriched with and detected afterwards, the antibiotic is
One or both of chloramphenicol, furantoin.
2. the method for antibiotic in the Electrochemical Detection milk according to claim 1 based on the vertical enrichment of micella in order,
Characterized in that, the electrolyte solution is that sodium-chloride water solution, aqueous sodium persulfate solution, potassium chloride solution, phosphoric acid buffer are molten
One kind in liquid, NaAc_HAc buffer solution, concentration is 0.02~0.5mol/L, and pH value is 6~8.
3. the side of antibiotic in the Electrochemical Detection milk according to claim 1 or 2 based on the vertical enrichment of micella in order
Method, it is characterised in that before detection, inert gas or nitrogen are passed through into electrolyte solution, exclude the oxygen in electrolyte solution
Gas.
4. the method for antibiotic in the Electrochemical Detection milk according to claim 1 based on the vertical enrichment of micella in order,
Characterized in that, the working electrode is one of vertical orderly cycle unit micelle modified CTAB：Indium-tin oxide electrode, fluorine are mixed
One kind in miscellaneous tin oxide electrode, gold electrode, glass-carbon electrode or screen printing electrode.
5. the method for antibiotic in the Electrochemical Detection milk according to claim 1 based on the vertical enrichment of micella in order,
Characterized in that, the working electrode is prepared by following methods：Solution growth method or electrochemistry assisted self assembling
Method.
6. the method for antibiotic in the Electrochemical Detection milk according to claim 1 based on the vertical enrichment of micella in order,
Characterized in that, enrichment method is stirring enrichment or constant potential enrichment.
7. the method for antibiotic in the Electrochemical Detection milk according to claim 6 based on the vertical enrichment of micella in order,
Characterized in that, the stirring enrichment is 0~20min of mechanical agitation.
8. the method for antibiotic in the Electrochemical Detection milk according to claim 6 based on the vertical enrichment of micella in order,
Characterized in that, the constant potential enrichment is 0~20min of enrichment under the conditions of -1.0~0.4V.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106093172A (en) * | 2016-06-12 | 2016-11-09 | 浙江大学 | The electrochemical detection method of antibiotic content in a kind of human blood |
| CN106501243B (en) * | 2016-10-01 | 2019-10-11 | 桂林理工大学 | A method of melamine is quickly detected with molecular engram test strips |
| CN107219284A (en) * | 2017-06-09 | 2017-09-29 | 沧州医学高等专科学校 | A kind of adulterated method of fluoride ion electrode detection milk |
| CN110940715B (en) * | 2019-11-26 | 2022-06-10 | 广西医科大学附属肿瘤医院 | Silicon dioxide nanopore membrane modified glassy carbon electrode and preparation method and application thereof |
| CN114324523A (en) * | 2022-01-12 | 2022-04-12 | 中国药科大学 | In-vitro drug metabolism real-time detection method |
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| CN104311852A (en) * | 2014-10-27 | 2015-01-28 | 上海理工大学 | Method and device for preparing vertical orderly carbon nano tube/polyaniline composite membrane |
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| WO2010120193A1 (en) * | 2009-04-12 | 2010-10-21 | Lely Patent N.V. | Sensing techniques for on-farm analysis of milk components |
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| CN104311852A (en) * | 2014-10-27 | 2015-01-28 | 上海理工大学 | Method and device for preparing vertical orderly carbon nano tube/polyaniline composite membrane |
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