CN108181361A - Method that is a kind of while detecting a variety of environmental hormones - Google Patents
Method that is a kind of while detecting a variety of environmental hormones Download PDFInfo
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- CN108181361A CN108181361A CN201711408018.5A CN201711408018A CN108181361A CN 108181361 A CN108181361 A CN 108181361A CN 201711408018 A CN201711408018 A CN 201711408018A CN 108181361 A CN108181361 A CN 108181361A
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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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
The present invention relates to methods that is a kind of while detecting a variety of environmental hormones, belong to environmental hormone detection technique field.The preparation of the detection method including standard solution the CdS solution that compound concentration is 0.1M, builds three-electrode system, establishes standard working curve and quantitative detection, the method of the present invention is simple, it is easy to operate, detection range is wide, at low cost, and analysis time is short, high sensitivity, it is detected while not needing to using expensive precision instrument, and can realize a variety of environmental hormones, there is good promotion prospect.
Description
Technical field
The present invention relates to methods that is a kind of while detecting a variety of environmental hormones, belong to environmental hormone detection technique field.
Background technology
In recent years, " dairy products hormone " disturbance causes environmental hormone problem to receive people's concern.Environmental hormone is a kind of biology
Hormonal substance other than body, into human body in after, the endocrine function of human body can be influenced when serious or even causes certain cancers
Disease drastically influences the health of people, and therefore, the detection of environmental hormone just seems extremely important.
The traditional detection method of environmental hormone is mainly the physical chemistry instrumental method carried out in laboratory, including liquid chromatogram
Method, ultra-performance liquid chromatography, gas chromatography-mass spectrometry, capillary electrophoresis and biology detection etc..These points
The expensive large-scale precision instrument of analysis method generally existing needs is supported, complicated for operation, analysis time is longer, analysis cost is higher,
The problems such as can not carrying out Site Detection.Therefore, in face of environmental hormone detection new situations, there is an urgent need to develop and develop it is sensitive,
Quickly, accurately, low cost, can scene detect the new methods of a variety of environmental hormones simultaneously.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide method that is a kind of while detecting a variety of environmental hormones,
This method is easy to operate, at low cost, and analysis time is short, does not need to using expensive precision instrument, and can detect simultaneously a variety of
Environmental hormone.
Technical solution
The present inventor makes working electrode, using cadmium system quantum dot as luminescent material, drop coating to working electrode with ito glass
On, paper substrate with Electrochemical Detection research is combined and achievees the purpose that quickly to detect, the excellent separating property that paper substrate has is again
It is detected while realizing bi-component environmental hormone.Concrete scheme is as follows：
Method that is a kind of while detecting a variety of environmental hormones, includes the following steps：
(1) preparation of standard solution：
The standard sample of various varying environment hormones is prepared with the phosphate buffer solution that a concentration of 0.1mol/L, pH are 7.4
Product storing solution, concentration are 10mg/L, then dilute the one-component standard for preparing various concentration with phosphate buffer solution respectively
Solution, it is spare；
(2) compound concentration is the CdS solution of 0.1M：
CdS quantum dot is first prepared, adds water the CdS solution for being configured to a concentration of 0.1M；
(3) three-electrode system is built：
Using ITO electro-conductive glass as working electrode, the CdS solution of the 0.1M of 80 μ L of drop coating on the conducting surface of working electrode；Ginseng
It is fixed on the chassis of optical glass than electrode, to electrode and working electrode, chassis is horizontal by 30 ° of angles, chassis upper berth
Equipped with a rectangle filter paper, one end of filter paper is contacted with the conducting surface of working electrode；
(4) standard working curve is established：
One-component detects：The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats electricity
Chemical signal is stablized, and the standard solution of one-component environmental hormone made from 10 μ L steps (1), observation electricity are added in the filter paper other end
The quenching signal of chemiluminescence (ECL), calculates the difference of ECL and to measure the other concentration standards of one-component environmental hormone successively molten
The quenching difference of liquid draws standard working curve, and carries out polynomial curve fitting, obtains the side of the one-component regression curve
Journey；Measure the standard working curve of other environmental hormones and the equation of one-component regression curve successively again；
Multicomponent detects simultaneously：The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3),
It treats that electrochemical signals are stablized, one-component environmental hormone standard solution made from 10 μ L plurality of step (1) is added in the filter paper other end
Mixed liquor, different environmental hormones detached on filter paper, observes the quenching signal of ECL, calculates the difference and successively of ECL
The quenching difference of the other concentration standard solution of multigroup part of environmental hormone is measured, draws standard working curve, and carry out multinomial
Curve matching obtains the equation of the multigroup part of regression curve.
(5) quantitative detection：
The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats that electrochemical signals are steady
It is fixed, the sample prepare liquid contained there are many environmental hormone of the 10 unknown contents of μ L is added in the filter paper other end, observes the quenching letter of ECL
Number, then substitute into the standard working curve for the multi-analyte immunoassay that step (4) obtains and the work of corresponding one-component examination criteria
Curve calculates the concentration value of each environmental hormone.
In step (2), the preparation method of CdS quantum dot can be microemulsion method, template and sol-gel method etc.,
The preparation method of preferred CdS quantum dot：Weigh 0.1971 gram of CdCl2·2.5H2O, in 100mL volumetric flasks, constant volume shakes up,
Obtain CdCl2Solution；Weigh 0.9598 gram of Na2S·9H2O dissolves in 4mL water, obtains Na2S solution；Add into three-necked flask
Enter the CdCl prepared2Solution under quick magnetic agitation, adds in 0.669 gram of HSCH2COOH, solution become cloudy, with NaOH solution tune
PH10, solution become clarification, Na are added dropwise2There is yellow in S solution, solution, are heated to 96 DEG C and flow back 12 hours, are subsequently cooled to
Room temperature stands the rear absolute ethyl alcohol for filtering, equivalent being added in smoke filtrate overnight, after standing is overnight, the rotating speed of 10000r/min
Lower centrifugation 3min after precipitation drying, obtains CdS quantum dot.
In step (3), the size of working electrode is 5.5cm × 1.0cm, drop coating 0.1M on the conducting surface of working electrode
The drop coating area of CdS solution is 12mm × 10mm.
In step (3), the size of filter paper is 25mm × 10mm.
In step (4), the base fluid is by 5mL phosphate buffer solutions and the H of 10 μ L2O2It mixes.
Advantageous effect：The present invention detaches a variety of environmental hormones using the method for paper substrate combination electrochemistry and is realized same
When detect, method is simple, easy to operate, and detection range is wide, at low cost, and analysis time is short, high sensitivity, do not need to using costliness
Precision instrument, and can realize a variety of environmental hormones while detect, there is good promotion prospect.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
In order to which the present invention will be described in detail, below with two kinds of representative environmental hormone (two fourths of bisphenol-A and phthalic acid
Ester) for describe in detail.
Embodiment 1
(1) preparation of standard solution：
The preparation of bisphenol-A standard solution：With the phosphate buffer solution compound concentration that a concentration of 0.1mol/L, pH are 7.4
It for the bisphenol-A standard sample storing solution of 10mg/L, then dilutes, prepares a concentration of 1mg/L, 100 μ g/L, 10 μ g/L, 1 μ respectively
The bisphenol-A standard solution of g/L, it is spare；
The preparation of dibutyl phthalate standard solution：It is molten with the phosphate-buffered that a concentration of 0.1mol/L, pH are 7.4
Liquid compound concentration is the dibutyl phthalate standard sample storing solution of 10mg/L, then dilutes, prepares respectively a concentration of
1mg/L, 100 μ g/L, 10 μ g/L, the dibutyl phthalate standard solution of 1 μ g/L are spare；
(2) compound concentration is the CdS solution of 0.1M：
Weigh 0.1971 gram of CdCl2·2.5H2O, in 100mL volumetric flasks, constant volume shakes up, and obtains CdCl2Solution；It weighs
0.9598 gram of Na2S·9H2O dissolves in 4mL water, obtains Na2S solution；Toward three mouthfuls
The CdCl prepared is added in flask2Solution under quick magnetic agitation, adds in 0.669 gram of HSCH2COOH, solution become muddy
Turbid, with NaOH solution tune pH10, solution becomes clarification, Na is added dropwise2There is yellow in S solution, solution, are heated to 96 DEG C of reflux 12
Hour is subsequently cooled to room temperature, stands the rear absolute ethyl alcohol for filtering, equivalent being added in smoke filtrate overnight, after standing is overnight,
3min is centrifuged under the rotating speed of 10000r/min, after precipitation drying, obtains CdS quantum dot；
(3) three-electrode system is built：
Using Ag/AgCl electrodes as reference electrode, Pt is to electrode, using ITO electro-conductive glass as working electrode, working electrode
On conducting surface the 0.1M of 80 μ L of drop coating CdS solution (size of working electrode be 5.5cm × 1.0cm, the conducting surface of working electrode
The drop coating area of the CdS solution of upper drop coating 0.1M is 12mm × 10mm)；Reference electrode is fixed on light to electrode and working electrode
In the electrode mounting disc for learning glass system, electrode mounting disc is equipped with a rectangle filter paper horizontal by 30 ° of angles in electrode mounting disc
(filter paper size is 25mm × 10mm), one end of filter paper is contacted with the conducting surface of working electrode；
(4) standard working curve is established：
One-component detects：The base fluid of 95 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3) (by 5mL phosphorus
The H of hydrochlorate buffer solution and 10 μ L2O2Mix), it treats that electrochemical signals are stablized, 10 μ L steps (1) is added in the filter paper other end
The standard solution of 10mg/L bisphenol-As obtained observes the quenching signal of electrochemical luminescence, calculates the difference of ECL and surveys successively
The quenching difference of the other concentration standard solution of the bisphenol-A is measured, it is observed that the reduction of the concentration with bisphenol-A, quenching value are got over
Carry out lower, drafting standard working curve, and carry out polynomial curve fitting, obtain the equation of bisphenol-A regression curve；With such
It pushes away, draws the standard working curve of dibutyl phthalate, and obtain the equation of dibutyl phthalate regression curve；
It is detected while bi-component：The base fluid of 95 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats
Electrochemical signals are stablized, and add in the mixed liquor of 10 μ L bisphenol-As and dibutyl phthalate in the filter paper other end, utilize paper substrate
Excellent separating property, with reference to gravity, both environmental hormones detach on filter paper, observe two apparent quenching letters
Number, the molal weight of BPA is 228g/mol, and the molal weight of DBP is 278g/mo, and BPA detects that first is sudden before DBP
Go out appearance time to add in after environmental hormone 300 seconds, the quenching difference of BPA is 235, the time that second quenching occurs for plus
Enter 1200 seconds after environmental hormone, the quenching difference of DBP is 264；It is molten that the other concentration standards of both environmental hormones are measured successively
The quenching difference of liquid draws standard working curve, and carries out polynomial curve fitting, obtains the side of the two-component regression curve
Journey.
(5) quantitative detection：
The base fluid of 95 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats that electrochemical signals are stablized,
The filter paper other end adds in the bisphenol-A of the 10 unknown contents of μ L and the mixed liquor of dibutyl phthalate, observes the quenching letter of ECL
Number, then substitute into the standard working curve for the bi-component detection that step (4) obtains and the work of corresponding one-component examination criteria
Curve can calculate the concentration value of bisphenol-A and dibutyl phthalate.
Claims (5)
1. method that is a kind of while detecting a variety of environmental hormones, which is characterized in that include the following steps：
(1) preparation of standard solution：
The standard sample that various varying environment hormones are prepared with the phosphate buffer solution that a concentration of 0.1mol/L, pH are 7.4 stores up
Standby liquid, concentration is 10mg/L, then dilutes the one-component standard solution for preparing various concentration with phosphate buffer solution respectively,
It is spare；
(2) compound concentration is the CdS quantum dot solution of 0.1M：
CdS quantum dot is first prepared, adds water the CdS quantum dot solution for being configured to a concentration of 0.1M；
(3) three-electrode system is built：
Using ITO electro-conductive glass as working electrode, the CdS solution of the 0.1M of 80 μ L of drop coating on the conducting surface of working electrode；Reference electricity
Pole is fixed on the chassis of optical glass electrode and working electrode, and chassis is equipped on chassis horizontal by 30 ° of angles
One rectangle filter paper, one end of filter paper are contacted with the conducting surface of working electrode；
(4) standard working curve is established：
One-component detects：The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats electrochemistry
Signal stabilization adds in the standard solution of one-component environmental hormone made from 10 μ L steps (1) in the filter paper other end, observes electrochemistry
The quenching signal of luminous (ECL), calculates the difference of ECL and measures the other concentration standard solution of the one-component environmental hormone successively
Difference is quenched, standard working curve is drawn, and carry out polynomial curve fitting, obtains the equation of the one-component regression curve；Again
The standard working curve of other environmental hormones and the equation of one-component regression curve are measured successively；
Multicomponent detects simultaneously：The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats electricity
Chemical signal is stablized, and the mixed of one-component environmental hormone standard solution made from 10 μ L plurality of step (1) is added in the filter paper other end
Liquid is closed, different environmental hormones is detached on filter paper, observes the quenching signal of ECL, calculate the difference of ECL and measure successively
The quenching difference of the other concentration standard solution of multigroup part of environmental hormone draws standard working curve, and carries out polynomial curve
Fitting obtains the equation of the multigroup part of regression curve；
(5) quantitative detection：
The base fluid of 50-100 μ L is added dropwise on rectangle filter paper in the three-electrode system of step (3), treats that electrochemical signals are stablized,
The filter paper other end adds in the sample prepare liquid contained there are many environmental hormone of the 10 unknown contents of μ L, observes the quenching signal of ECL, so
The standard work for substituting into the multi-analyte immunoassay that step (4) obtains afterwards is bent
Line and corresponding one-component examination criteria working curve calculate the concentration value of each environmental hormone.
2. the method as described in claim 1 for detecting a variety of environmental hormones simultaneously, which is characterized in that in step (2), CdS amounts
The preparation method of son point：Weigh 0.1971 gram of CdCl2·2.5H2O, in 100mL volumetric flasks, constant volume shakes up, and obtains CdCl2It is molten
Liquid；Weigh 0.9598 gram of Na2S·9H2O dissolves in 4mL water, obtains Na2S solution；Add in what is prepared into three-necked flask
CdCl2Solution under quick magnetic agitation, adds in 0.669 gram of HSCH2COOH, solution become cloudy, with NaOH solution tune pH10, solution
Become clarification, Na is added dropwise2There is yellow in S solution, solution, are heated to 96 DEG C and flow back 12 hours, be subsequently cooled to room temperature, stand
It is filtered after overnight, the absolute ethyl alcohol of equivalent is added in smoke filtrate, after standing is overnight, is centrifuged under the rotating speed of 10000r/min
3min after precipitation drying, obtains CdS quantum dot.
3. the method as described in claim 1 for detecting a variety of environmental hormones simultaneously, which is characterized in that in step (3), work electricity
The size of pole is 5.5cm × 1.0cm, on the conducting surface of working electrode the drop coating area of the CdS solution of drop coating 0.1M for 12mm ×
10mm。
4. the method as described in claim 1 for detecting a variety of environmental hormones simultaneously, which is characterized in that in step (3), filter paper
Size is 25mm × 10mm.
5. the method for a variety of environmental hormones is detected while as claimed in claim 1 or 2 or 3 or 4, which is characterized in that step (4)
In, the base fluid is by 5mL phosphate buffer solutions and the H of 10 μ L2O2It mixes.
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2017
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| CN101865843A (en) * | 2010-05-04 | 2010-10-20 | 中国科学院深圳先进技术研究院 | Detection equipment and method of multicomponent biological marker |
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| CN102095711A (en) * | 2010-12-17 | 2011-06-15 | 中国科学院合肥物质科学研究院 | Double colour fluorescent chemical sensor used for visually detecting explosive and manufacturing method thereof |
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