CN105241944A - Method for electrochemical detection of antibiotics in milk based on vertical and ordered micelle enrichment - Google Patents
Method for electrochemical detection of antibiotics in milk based on vertical and ordered micelle enrichment Download PDFInfo
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Abstract
The present invention discloses a method for electrochemical detection of antibiotics in milk based on vertical and ordered micelle enrichment. The method is characterized by comprising: diluting milk with an electrolyte solution so as to be adopted as a detected solution, adopting vertical and ordered CTAB micelle modified electrode as a working electrode, using an electrochemical voltammetry method, enriching antibiotics in the milk solution, and then detecting. According to the present invention, the vertical and ordered micelle modified electrode is adopted as the working electrode, the hydrophobic and electrically neutral antibiotics in the aqueous solution are extracted/enriched into the hydrophobic nanometer chambers of the surfactant micelles through the hydrophobic effect, and the reduction peak current of the antibiotics is adopted as the detection signal so as to achieve the quantitative detection in the complex milk background; and the constructed sensor integrated the pre-enrichment and the electrochemical detection, has characteristics of high sensitivity, wide linear detection range and low detection limit, and has great application potential in the food safety monitoring field.
Description
Technical field
The invention belongs to electrochemical sensing field, particularly relate to antibiotic detection method in a kind of milk.
Background technology
Current social food security causes the extensive concern of people, and wherein dairy safety problem is a large focal spot, and exploring quick, accurate, convenient, sensitive analytical approach becomes one of emphasis direction of quality of dairy products security study.Microbiotic is that a class has bacteria growing inhibiting or kills the material of bacterium, by the widespread use as animal pharmaceuticals and feed addictive.Research shows, antibiotic in milk residual have serious harm to human body, as produced allergic reaction, produce endurance strain, the flora imbalance etc. caused in human body intestinal canal.At present, the U.S., European Union and Japan and other countries have made clear and definite regulation to maximum residue limit antibiotic in raw material milk, and maximum residue limit is 4 μ g/kg.Therefore, in milk, antibiotic quick, highly sensitive detection is the strict important process controlling to prevent illegally adding microbiotic in food, ensure consumer health's rights and interests, has expanded the research to physiology and pathology simultaneously.
Up to now, researcher utilizes the microbiotic in various technical Analysis detection milk, as microbiological method, vapor-phase chromatography, liquid phase chromatography, immunoassay, electrochemical process etc.Wherein, electrochemical process owing to having highly sensitive, cheap, simple operation and other advantages, and is subject to the favor of researchers.The nano materials such as molecularly imprinted polymer, nano particle, carbon nano-tube can be modified on electrode, for enrichment microbiotic, improve detection perform.
In addition, the method for patent literature mainly contains: application number is that the Chinese patent literature of 200410013741.X reports antibiotic method in one pH meter detection milk.It adopts and lactobacillus inoculum utilization pH meter in milk sample is measured the pH value in milk sample in a certain time interval, by the change of pH value, determines whether containing microbiotic.It is a kind of based on antibiotic method in the visual quick detection milk of nm of gold that application number has been the patent literature of 201310069037.5, and it utilizes pyrocatechol violet to reduce gold chloride to prepare nm of gold.In the process of nm of gold synthesis, add because of antibiotic the synthesis that have impact on nm of gold, its color is changed, utilizes naked eyes and ultraviolet-visible absorption spectroscopy instrument quantitatively can detect microbiotic.These methods above-mentioned, are determine whether that, containing microbiotic, accuracy in detection is low by detecting indirect parameter, and easily affect by extraneous adjustment.
Mesoporous silicon oxide (SiO
2, aperture 2-50nm) by the nano pore of aperture height all in the lump in periodic arrangement and around unbodied silicon dioxide form.In recent years, researcher adopt galvanochemistry assisted self assembling (Nat.Mater.2007,6,602-608) and
solution growth (Angew.Chem.Int.Ed.2012,51, the method such as 2173-2177), the collaborative generation of the self assembly of induced surface active agent molecule and the reaction of organosilane molecules hydrolysis/condensation, solid surface successfully prepared high-sequential arrangement and channel vertical in the SiO on surface
2nanochannel film.This film has very excellent performance: ultra-thin and thickness is adjustable (20-200nm), pore size and pore distribution high uniformity, and porosity is high (can reach 7.5 × 10
12cm
-2), excellent machinery, chemistry, thermal stability and biocompatibility, and cost is low, can larger area batch preparation, be a kind of desirable molecular recognition and the nanochannel film be separated, in fields such as catalysis, absorption, analysis, sensings, there is huge application potential.In this method, while the vertical ordered mesoporous silica dioxide of synthesis, the duct that template molecule and surfactant cetyl trimethyl ammonium bromide (CTAB) are evenly arranged in mesoporous silicon oxide is inner, forms vertical micella in order.In each micella, outwardly, and alkyl chain to be flocked together formation dewatering nano chamber by hydrophobic effect the charged polar group of CTAB.By hydrophobic effect, hydrophobic in aqueous solution, electroneutral electrochemical activity organic molecule can be extracted/be enriched in the nano-cavity of surfactant micella, and in micella/electrode interface generation electrochemical oxidation or reduction.
Summary of the invention
The invention provides a kind of based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, the method detection sensitivity is high.Vertical CTAB micella in order has suction-operated to the microbiotic in milk, can improve the concentration of microbiotic in micella, thus improve antibiotic Electrochemical Detection performance.
In milk proposed by the invention, the concrete steps of antibiotic electrochemical detection method are as follows:
First using milk with electrolyte solution dilution as detection solution, then using the vertical in order electrode that CTAB (cetyl trimethyl ammonium bromide) is micelle modified as working electrode, adopt galvanochemistry voltammetry, the laggard row of the first enrichment of the aromatic nitro microbiotic in milk soln is detected.
The present invention adopts galvanochemistry voltammetry, and with vertical electrode micelle modified in order for working electrode, platinum electrode and silver/silver chloride are respectively electrode and contrast electrode, detect fast microbiotic in milk.
As preferably, described electrolyte solution is selected from the one in sodium-chloride water solution, aqueous sodium persulfate solution, potassium chloride solution, phosphate buffer solution, NaAc_HAc buffer solution; More preferably sodium-chloride water solution or phosphate buffer solution.Described concentration of electrolyte solutions is 0.02 ~ 0.5mol/L, more preferably 0.08 ~ 0.2mol/L; The pH value of described electrolyte solution is 6 ~ 8; More preferably 6 ~ 7.As preferably, before testing, inert gas, nitrogen etc. can be passed in electrolyte solution, to get rid of Oxygen in Electrolytical Solution gas to the interference detected; Pass into inert gas, nitrogen equal time can be determined according to actual needs, general 3 ~ 30 minutes.As preferably, the extension rate of milk is 1 ~ 100 times, more preferably 5 ~ 10 times.
As preferably, described working electrode is selected from the one in tin indium oxide (ITO) electrode, fluorine-doped tin oxide (FTO) electrode, gold electrode, glass-carbon electrode (GCE) or screen printing electrode; More preferably tin indium oxide (ITO) electrode.
As preferably, the described vertical in order electrode that CTAB is micelle modified can adopt existing method to prepare, and such as, can be prepared by following two kinds of methods:
First method,
solution growth method: the solution that concrete steps form for working electrode being put into CTAB, water, ethanol, ammoniacal liquor and TEOS, leaves standstill growth 3 – 48 hours at 40 ~ 70 DEG C.
In the first preparation method, calculate with 1gCTAB, the volume of the water that needs add, ethanol, ammoniacal liquor, TEOS is respectively 400 ~ 550ml, 150 ~ 200ml, 50 ~ 80 μ L, 450 ~ 550 μ L.
Second method, galvanochemistry assisted self assembling method: the solution (stirring 1 ~ 3 hour in advance) that concrete steps form for working electrode being put into CTAB, TEOS, water, ethanol, sodium nitrate and hydrochloric acid, applies constant current density-0.1mAcm
-2~-1mAcm
-2grow 3 – 30 seconds.
In the second preparation method, calculate with 1gCTAB, the amount of the TEOS added, water, ethanol, sodium nitrate, hydrochloric acid is respectively: 1.5 ~ 2.0g, 10 ~ 15ml, 10 ~ 15ml, 0.08 ~ 0.15g, 2 ~ 3 μ L.
In the described vertical in order electrode that CTAB is micelle modified, the aperture of mesoporous silicon oxide is 2 ~ 3nm; Comprise vertical meso-porous titanium dioxide silicon layer from top to bottom successively, electrode basement layer and glassy layer.The thickness of vertical meso-porous titanium dioxide silicon layer is 20 ~ 200nm, more preferably 80 ~ 120nm.
As preferably, described enrichment method is for stirring enrichment or constant potential enrichment.Stirring enrichment is mechanical raking 0 ~ 20min; More preferably 8 ~ 15 minutes; Described constant potential enrichment is enrichment 0 ~ 20min under-1.0 ~ 0.4V condition; Preferred constant potential enrichment condition is enrichment 25 ~ 35s under-0.5 ~ 0V current potential further.
As preferably, described aromatic nitro microbiotic is one in chloromycetin, furantoin or two kinds.The content of described aromatic nitro microbiotic in milk is 0.4 ~ 50ppm, in this content range, adopts the inventive method, all has higher degree of accuracy.
The present invention with vertical electrode micelle modified in order for working electrode, pass through hydrophobic effect, hydrophobic in aqueous solution, electroneutral microbiotic is extracted/is enriched in the dewatering nano chamber of surfactant micella, with antibiotic reduction peak current for detection signal, thus realize the quantitative detection under the complex background of milk.The sensor that the present invention builds by preenrichment and Electrochemical Detection in one, highly sensitive, detect linear wide ranges, detectability is low, has larger application potential in food safety monitoring field.
Relative to prior art, beneficial effect of the present invention is embodied in:
1, the present invention adopt galvanochemistry assisted self assembling and
vertical ordered mesoporous silica dioxide prepared by solution growth method is as hard template, at the cylindrical CTAB micella of electrode surface bearing height ordered arrangement, each micella all effectively contacts with basal electrode surface, is conducive to mass transfer, has expanded it and has analyzed the application space in sensing.
2, the aperture of the vertical hard template mesoporous silicon oxide of CTAB micella is in order at 2 ~ 3nm, has size selectivity, can enter into electrode surface by the exclusion size molecule that is greater than micelle diameters.Therefore, can realize antibiotic selective enrichment.
3, the method detects rapidly, as long as the several seconds can obtain testing result.
4, the method is without the need to carrying out pre-service to milk, electrode antipollution and anti-interference good, highly sensitive.
5, detection method of the present invention can be extended to the Sensitive Detection of hydrophobic to other, neutral electrochemical activity organic molecule, as environmental contaminants, agricultural chemicals, explosive, antioxidant etc.
Accompanying drawing explanation
Fig. 1 is the solution to be detected in the embodiment of the present invention 1 after milk dilution.
Fig. 2 is transmission electron microscope picture (vertical view (a), sectional view (b)) and the scanning electron microscope (SEM) photograph (c) of vertical mesoporous silicon oxide in the embodiment of the present invention 1.
The differential pulse volt-ampere curve of ITO electrode (c) in the milk soln containing 5ppm chloromycetin that Fig. 3 is naked ITO electrode (a) in the embodiment of the present invention 1, the vertical in order ITO electrode (b) that CTAB is micelle modified is modified with vertical ordered mesoporous silica dioxide.
Fig. 4 be in the embodiment of the present invention 1 cyclic voltammogram (a) of the vertical in order ITO electrode that CTAB is micelle modified under difference sweeps speed and peak current with sweep fast subduplicate linear relationship chart (b).Electrolyte solution is the milk soln containing 10ppm chloromycetin.Sweep speed is respectively 10,50,100,150,200mV/s.
Fig. 5 is the vertical differential pulse volt-ampere curve of ITO electrode in the milk containing variable concentrations chloromycetin that CTAB is micelle modified in order in the embodiment of the present invention 1.
Fig. 6 be of the present invention in the structural representation of the vertical ITO electrode that CTAB is micelle modified in order.
Fig. 7 is the pick-up unit figure of galvanochemistry voltammetry of the present invention.
Embodiment
Embodiment 1
Use the vertical ITO electrode that CTAB is micelle modified in order, detect the electrochemical process of chloromycetin in milk:
(1) with the sodium-chloride water solution that 0.1mol/L, pH value are 6, the milk that direct supermarket is bought is diluted 10 times, as solution to be detected, as shown in Figure 1.Argon gas is passed into, to get rid of the interference of the oxygen in solution in this solution to be measured.Adopt simple three-electrode system, as shown in Figure 7, ITO electrode, platinum electrode and silver/silver chloride electrode that vertical CTAB in order modifies are respectively as working electrode, to electrode and contrast electrode.
(2) be dissolved in absolute ethyl alcohol by chloromycetin and be configured to storing solution, the chloromycetin storing solution adding different volumes in solution to be measured obtains a series of solution to be measured, and (concentration of chloromycetin is 0.4ppm, 0.7ppm respectively, 1ppm, 2ppm, 3ppm, 5ppm, 7ppm, 10ppm, 15ppm, 20ppm, 30ppm, 35ppm), carry out the test of differential pulse volt-ampere after stirring 10s.
The preparation method of the vertical ITO electrode that CTAB is micelle modified is in order
solution growth method, concrete steps are as follows:
ITO electrode is put into the solution that 0.16gCTAB, 70mL water, 30mL ethanol, 10 μ L ammoniacal liquor and 80 μ LTEOS form, at 60 DEG C, leave standstill growth 24 hours.
The Electronic Speculum figure of the vertical ITO electrode that CTAB is micelle modified in order prepared by said method is Fig. 2.
(what in fact detect is the vertical ITO electrode that CTAB is micelle modified in order to vertical ordered mesoporous silica dioxide shown in Fig. 2, the vertical in order ITO electrode that CTAB is micelle modified needs dispersion in ethanol when doing Electronic Speculum, CTAB can dissolve in ethanol in ethanol) transmission electron microscope picture vertical view, in Fig. 2 (a), white bright spot is hole, namely CTAB micella present position, can find out that the aperture of mesoporous silicon oxide is 2 ~ 3nm; The sectional view of transmission electron microscope shows the order (in Fig. 2 (b)) in duct, can clearly see three layers (in Fig. 2 (c)) from scanning electron microscope (SEM) photograph, be respectively vertical meso-porous titanium dioxide silicon layer from top to bottom, 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), the differential pulse volt-ampere curve of ITO electrode (c) in the milk containing 5ppm chloromycetin that the vertical in order ITO electrode (b) that CTAB is micelle modified is modified with vertical ordered mesoporous silica dioxide, can find out, vertical ordered mesoporous silica dioxide modifies reduction peak current ITO electrode and naked ITO electrode almost not observing chloromycetin, and reduction peak is obviously sharp-pointed in the vertical in order ITO electrode that CTAB is micelle modified, prove that the CTAB micella be present in mesoporous silicon oxide duct serves inrichment in the detection of chloromycetin, effective raising electrode surface analyte concentration, thus enhance the sensitivity of detection.
Fig. 4 be the vertical in order ITO electrode that CTAB is micelle modified difference sweep speed (sweep speed is respectively 10,50,100,150,200mV/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 the square root sweeping speed, shows that chloromycetin controls for diffusion in the electrochemical reaction of electrode surface, proves that chloromycetin can enter CTAB micella and arrive electrode surface smoothly further.
Fig. 5 is the vertical differential pulse volt-ampere curve of ITO electrode in the milk containing variable concentrations chloromycetin that CTAB is micelle modified in order, and can find out, reduction peak current increases along with the increase of chloramphenicol concentration.
Fig. 6 is the structural representation of the vertical ITO electrode that CTAB is micelle modified in order.
Above interpretation of result result demonstrates the vertical in order electrode that CTAB modifies and can successfully be used for detecting the chloromycetin content in milk.
Embodiment 2
Use the vertical ITO electrode that CTAB is micelle modified in order, detect the electrochemical process of furantoin in milk:
(1) milk that direct supermarket is bought is diluted 5 times, as solution to be detected with the phosphate buffer solution that 0.1mol/L, pH value are 7.Nitrogen is passed into, to get rid of the interference of the oxygen in solution in this solution to be measured.Adopt simple three-electrode system, FTO electrode, platinum electrode and silver/silver chloride electrode that vertical CTAB in order modifies are respectively as working electrode, to electrode and contrast electrode.
(2) be dissolved in absolute ethyl alcohol by furantoin and be configured to storing solution, the furantoin storing solution adding different volumes in solution to be measured obtains a series of solution to be measured, carries out the test of differential pulse volt-ampere under-0.4V current potential after enrichment 30s.
The preparation method of the vertical FTO electrode that CTAB is micelle modified is in order galvanochemistry assisted self assembling method, and concrete steps are as follows:
FTO electrode is put into the solution (stirring 2.5 hours in advance) that 1.585gCTAB, 2.833gTEOS, 20mL water, 20mL ethanol, 0.17g sodium nitrate and 4.18 μ L hydrochloric acid form, apply constant current density-0.5mAcm
-2grow 10 seconds.Prove after tested, embodiment 2 detection method has good Detection results equally to the furantoin in milk.
Claims (9)
1., based on an antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, comprising:
First using milk with electrolyte solution dilution as detection solution, then using the vertical in order electrode that CTAB is micelle modified as working electrode, adopt galvanochemistry voltammetry, the laggard row of the first enrichment of the microbiotic in milk soln detected.
2. according to claim 1 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, described electrolyte solution is the one in sodium-chloride water solution, aqueous sodium persulfate solution, potassium chloride solution, phosphate buffer solution, NaAc_HAc buffer solution, concentration is 0.02 ~ 0.5mol/L, and pH value is 6 ~ 8.
3. according to claim 1 and 2 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, before detection, in electrolyte solution, pass into inert gas or nitrogen, get rid of the oxygen in electrolyte solution.
4. according to claim 1 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, described working electrode is one of vertical in order cycle unit that CTAB is micelle modified: the one in indium-tin oxide electrode, fluorine-doped tin oxide electrode, gold electrode, glass-carbon electrode or screen printing electrode.
5. according to claim 1 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, described working electrode is prepared by following method:
solution growth method or galvanochemistry assisted self assembling method.
6. according to claim 1 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, enrichment method is for stirring enrichment or constant potential enrichment.
7. according to claim 6 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, described stirring enrichment is mechanical raking 0 ~ 20min.
8. according to claim 6 based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, it is characterized in that, described constant potential enrichment is enrichment 0 ~ 20min under-1.0 ~ 0.4V condition.
9. according to claim 1ly it is characterized in that based on antibiotic method in the Electrochemical Detection milk of vertical micella enrichment in order, described microbiotic is one or both in chloromycetin, furantoin.
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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 |
| CN106501243A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | A kind of method of use molecular engram test strips quick detection tripolycyanamide |
| 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 |
| CN110940715A (en) * | 2019-11-26 | 2020-03-31 | 广西医科大学附属肿瘤医院 | Silicon dioxide nano-pore 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106501243A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | A kind of method of use molecular engram test strips quick detection tripolycyanamide |
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| 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 |
| CN110940715A (en) * | 2019-11-26 | 2020-03-31 | 广西医科大学附属肿瘤医院 | Silicon dioxide nano-pore membrane modified glassy carbon electrode and preparation method and application thereof |
| 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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