CN106525948B - A kind of preparation method and application of molecular engram detection 2,4-d sensor - Google Patents

A kind of preparation method and application of molecular engram detection 2,4-d sensor Download PDF

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CN106525948B
CN106525948B CN201610928894.XA CN201610928894A CN106525948B CN 106525948 B CN106525948 B CN 106525948B CN 201610928894 A CN201610928894 A CN 201610928894A CN 106525948 B CN106525948 B CN 106525948B
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concentration
porous silica
sensor
classifying porous
acid
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CN106525948A (en
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徐琴
王红梅
胡效亚
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Tihe (Hangzhou) Pharmaceutical Technology Service Co.,Ltd.
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Yangzhou University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

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Abstract

A kind of preparation method and application of molecular engram detection 2,4-d sensor, is related to preparation and the applied technical field of molecular engram sensor.It disperses classifying porous silica spheres in deionized water under ultrasound condition, then drop coating is in clean glassy carbon electrode surface, after drying drop coating naphthols again, obtains the classifying porous silica ball electrode of naphthols protection;The classifying porous silica ball electrode that naphthols is protected is placed in by 2; it is placed in the mixed solution being made of methanol and acetic acid again after carrying out deposition processes in the deposition liquid of 4-d and o-phenylenediamine composition, elutes 2,4- dichlorphenoxyacetic acid; it obtains molecular engram and detects 2,4-d sensor.The present invention can more 2, the 4-d molecular locus of trace, to improve the sensitivity of detection, in addition, classifying porous silica spheres have preferable biocompatibility, raw material is easy to get, it is low in cost the features such as.

Description

A kind of preparation method and application of molecular engram detection 2,4-d sensor
Technical field
The present invention relates to the preparation of molecular engram sensor and applied technical fields.
Background technique
2,4-d(2,4- dichlorphenoxyacetic acid) it is a kind of pesticide wide using region, application time is long, once as grinding Study carefully the model compound of microbial degradation chlorinated aromatic compound, and a kind of artificial synthesized plant hormone.2,4-d is similar to Auxin or other plant growth regulator, can be absorbable with stimulating growth, rejuvenation cell, the root of plant, leaf, passes through stimulation Nucleic acid and protein synthesis etc. influence plant metabolism.But 2,4-d be environment incretion interferent, thanks to intermediate production containing chloro Object is easy to accumulate in vivo, and residual minim medicament will cause certain harm, so the safety in order to determine food, leads to Often need to test and analyze the 2,4-d content in plant.
Mainly there are gas-chromatography, high performance liquid chromatography, an immunization to the method for the detection of 2,4-d at present, gas chromatography mass spectrometry, this A little methods are pre-processed using organic solvent extracting and enriching, so should must have the sample pre-treatments of complexity, using toxic solvent, And need the instrument of valuableness and the talent Jing Guo special training that can operate.
Summary of the invention
Object of the present invention is to propose a kind of preparation method of the sensor of molecular engram that can be used for facilitating detection 2,4-d.
The present invention the following steps are included:
1) it under ultrasound condition, disperses classifying porous silica spheres in deionized water, obtains classifying porous titanium dioxide Silicon ball water dispersant;
2) by classifying porous silica spheres water dispersant drop coating in clean glassy carbon electrode surface, drop coating again after drying Naphthols obtains the classifying porous silica ball electrode of naphthols protection;
3) the classifying porous silica ball electrode that naphthols is protected is placed in by 2,4-d (2,4 dichlorophenoxyacetic acid) and It is placed in the mixed solution being made of methanol and acetic acid again after carrying out deposition processes in the deposition liquid of o-phenylenediamine composition, elution 2, 4- dichlorphenoxyacetic acid obtains molecular engram and detects 2,4-d sensor.
The present invention wraps up naphthalene in classifying porous silica ball surface using classifying porous silica spheres as matrix Phenol can prevent classifying porous silica spheres from falling off from the surface of electrode.
The classifying porous silica spheres of the present invention have high specific surface area, can more 2, the 4-d molecular locus of trace, To improve the sensitivity of detection, in addition, classifying porous silica spheres have preferable biocompatibility, raw material is easy to get, at The features such as this is cheap.
Molecular engram sensor is due to easy to operate, the features such as pre-treatment that sample should not be complicated is quick, and stability is good, It is receive more and more attention, study (Xie C, Gao S, Guo Q, et al. Electrochemical sensor for 2,4-dichlorophenoxy acetic acid using molecularly imprinted polypyrrole Membrane as recognition element. Microchimica Acta, 2010,169 (1): 145-152.) table Bright, molecular engram can be used for detecting 2,4-d, and classifying porous silica spheres binding molecule trace is detected 2,4-d can be very Detection limit is improved in big degree, therefore is of great significance.
Further, the partial size of classifying porous silica spheres of the present invention is 150~200nm.Replant the institute of type There is silicon ball to have the 3D porous structure of interconnection, the presence in a large amount of nanometer sites provides big surface to the absorption of object Product, this kind of design feature are conducive to raising 2, the sensitivity of 4-d measurement.
The concentration of classifying porous silica spheres is 8mg/mL in the classifying porous silica spheres water dispersant.Selection The silicon ball of the concentration can provide enough areas for molecular engram site, while will not hinder the transmitting of electronics, to improve Detection sensitivity.The concentration too low energy of classifying porous silica spheres enough prints such as in classifying porous silica spheres water dispersant The molecule of mark is with regard to fewer, but excessive concentration can then hinder the transmitting of electronics.Therefore, classifying porous titanium dioxide of the present invention The concentration of classifying porous silica spheres is 8mg/mL in silicon ball water dispersant.
In addition, 2,4-d amount determine molecular engram site amount, such as selection concentration cross urine cannot be formed it is enough Site brings unnecessary waste if the excessive concentration selected.Therefore, the present invention in the deposition liquid 2,4-d it is dense Degree is 10 mmol/L.
In addition, the application the invention also provides the above sensor in 2,4- dichlorphenoxyacetic acid concentration determination, that is, examine Survey method.
Detection method includes the following steps:
1) sensor is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride, utilizes differential Pulse voltammetry measures initial peak point current (I when no 2,4-d0);
2) sensor is respectively placed in again at least five groups of 2,4-d (2,4 dichlorophenoxyacetic acid) solution of various concentration It takes out, then is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride after impregnating 4min, utilize differential Pulse voltammetry measures the initial peak point current (I) corresponding to different 2,4-d (2,4 dichlorophenoxyacetic acid) concentration;
3) current differential (I is made0- I) and corresponding 2,4 dichlorophenoxyacetic acid log concentration linear relationship chart;
4) sensor is placed in concentration to be measured 2, is taken out after impregnating 4min in 4-d solution, then be placed in the iron by potassium chloride In the mixed solution of potassium cyanide and potassium ferrocyanide composition, concentration 2,4-d solution to be measured is measured using Differential Pulse Voltammetry Initial peak point current;
5) it is conducive to current differential (I0- I) and the linear relationship chart of corresponding 2,4 dichlorophenoxyacetic acid log concentration check in The concentration value of 2,4-d in concentration 2,4-d solution to be measured corresponding to the initial peak point current of concentration 2,4-d solution to be measured.
Electrode made of above method of the present invention is placed on after being impregnated in 2,4-d solution, since imprinted sites are occupied, It is that peak current reduces, as 2,4-d concentration increases, site is occupied more, and electric current is smaller, utilizes current differential and 2,4-d The linear relationship of log concentration is, it can be achieved that 2, the detection of 4-d.The present invention is detected more convenient using electrochemical method.
Carrying out the detection of 2,4- dichlorphenoxyacetic acid using the present invention can be improved detection limit, and instrument price is cheap, no Complicated sample pre-treatments are needed, testing cost can be largely reduced, save detection time.
Detailed description of the invention
Fig. 1 is the linear relationship chart of the current differential and 2,4-d log concentration that are made of inventive sensor.
Specific embodiment
Below with reference to the embodiments and with reference to the accompanying drawing the technical solutions of the present invention will be further described.
One, sensor is prepared:
1, it under ultrasound condition, disperses the classifying porous silica spheres of 8mg that partial size is 150~200nm in 1 mL water, The water dispersant of classifying porous silica spheres is obtained, wherein the concentration of classifying porous silica spheres is 8mg/mL.
2, take the water dispersant drop coating of the 5 classifying porous silica spheres of μ L in clean glassy carbon electrode surface, natural airing One layer of naphthols of drop coating again afterwards obtains the classifying porous silica ball electrode of naphthols protection.
3, the classifying porous silica ball electrode that naphthols is protected is placed in by 2,4-d (2,4 dichlorophenoxyacetic acid) and It is placed in the mixed solution being made of methanol and acetic acid again after carrying out deposition processes in the deposition liquid of o-phenylenediamine composition, elution 2, 4- dichlorphenoxyacetic acid obtains molecular engram and detects 2,4-d sensor.
The concentration of 2,4-d is 10mol/L in the above deposition liquid.
Methanol and the acetic acid mixing that the mixed solution being made of above methanol and acetic acid is 8: 1 by volume ratio form.Similarly hereinafter.
Two, the linear relationship chart of current differential and 2,4-d log concentration is made:
1, the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride is prepared:
Potassium chloride, the potassium ferricyanide and potassium ferrocyanide are mixed with the ratio that volume ratio is 2: 1: 1.
2, different 2,4-d concentration liquids are configured:
Not same amount 2 are taken, 4-d is dissolved in deionized water, and being respectively formed concentration is 1.0 × 10-10, 2.5 × 10-10, 5.0 × 10-10, 7.5 × 10-10, 1.0 × 10-9, 2.5 × 10-9, 5.0 × 10-9, 7.5 × 10-9, 1.0 × 10-8, 2.5 × 10-8With 5.0 ×10-8The 2,4-d solution of mol/L.
3, sensor obtained is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride, benefit Initial peak point current I when 2,4-d concentration is 0 is measured with Differential Pulse Voltammetry0
4, by sensor obtained in a kind of above ten 2,4-d of various concentration (2,4 dichlorophenoxyacetic acid) solution It takes out, then is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride after impregnating 4min, utilize differential Pulse voltammetry measures the initial peak point current I corresponding to different 2,4-d (2,4 dichlorophenoxyacetic acid) concentration1、I2、I3、I4、 I5、I6、I7、I8、I9、I10、I11
5, each current differential: I is acquired respectively0- I1、I0- I2、I0- I3、I0- I4、I0- I5、I0- I6、I0- I7、I0? I8、I0- I9、I0- I10、I0- I11.And by each current differential and corresponding 2,4-d (2,4 dichlorophenoxyacetic acid) log concentration Linear relationship chart is made in value, as shown in Figure 1.
Three, sample detects:
In order to investigate the achieved reliability of this method, the detection of tall scrawny person's sample is carried out, due to through in detection tall scrawny person Without 2,4-d, so being detected using standard samples recovery.
Adding 2,4-d respectively in tall scrawny person and being formed containing concentration is 1 × 10-9mol/L、5×10-9Mol/L and 1 × 10-8Three groups of samples containing 2,4-d of mol/L.
By sensor obtained respectively in three above 2, the sample of 4-d concentration impregnate 4min after take out, then be placed in by In the mixed solution of the potassium ferricyanide and the potassium ferrocyanide composition of potassium chloride, initial peak current is measured using Differential Pulse Voltammetry Value.
By the linear relationship chart of Fig. 1,2, the 4-d concentration value for obtaining sample to be tested, 2,4-d, mono- concentration of three samples are searched Detected value is respectively 9.44 × 10-10mol/L、5.39×10-9Mol/L and 9.53 × 10-9Mol/L, as a result as shown in the table:
As seen from the above table: it can be convenient using inventive sensor, rapidly and accurately measure, 2,4-d concentration.
The present invention can overcome traditional detection 2,4-d thus have complex sample pre-treatment, toxic solvent, and need The disadvantages of instrument of valuableness, testing cost is greatly reduced, the efficiency of detection is improved.

Claims (3)

1. a kind of preparation method of molecular engram detection 2,4- dichlorphenoxyacetic acid sensor, it is characterised in that including following step It is rapid:
1) it under ultrasound condition, disperses classifying porous silica spheres in deionized water, obtains classifying porous silica spheres Water dispersant;The concentration of classifying porous silica spheres is 8mg/mL in the classifying porous silica spheres water dispersant;
2) by classifying porous silica spheres water dispersant drop coating in clean glassy carbon electrode surface, drop coating naphthalene again after drying Phenol obtains the classifying porous silica ball electrode of naphthols protection;
3) the classifying porous silica ball electrode that naphthols is protected is placed in and is made of 2,4 dichlorophenoxyacetic acid and o-phenylenediamine Deposition liquid in carry out deposition processes after be placed in the mixed solution being made of methanol and acetic acid again, elute 2,4- Dichlorophenoxy second Acid obtains molecular engram and detects 2,4- dichlorphenoxyacetic acid sensor;2,4 dichlorophenoxyacetic acid is dense in the deposition liquid Degree is 10 mmol/L.
2. the preparation method of molecular engram detection 2,4- dichlorphenoxyacetic acid sensor according to claim 1, feature The partial size for being the classifying porous silica spheres is 150~200 nm.
3. the sensor of method preparation as described in claim 1 is used for the detection method of 2,4- dichlorphenoxyacetic acid concentration, special Sign be the following steps are included:
1) sensor is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride, utilizes differentiated pulse Voltammetry measures initial peak point current when no 2,4 dichlorophenoxyacetic acid;
2) sensor is respectively placed in after impregnating 4min at least five groups of 2,4 dichlorophenoxyacetic acid solution of various concentration again and is taken Out, it then is placed in the mixed solution being made of the potassium ferricyanide and potassium ferrocyanide of potassium chloride, is surveyed using Differential Pulse Voltammetry Obtain the initial peak point current corresponding to different 2,4 dichlorophenoxyacetic acid concentration;
3) linear relationship chart of current differential and corresponding 2,4 dichlorophenoxyacetic acid log concentration is made;
4) sensor is placed in concentration to be measured 2, is taken out after impregnating 4min in 4- dichlorphenoxyacetic acid solution, then be placed in by chlorination In the mixed solution of the potassium ferricyanide and the potassium ferrocyanide composition of potassium, concentration to be measured 2,4- is measured using Differential Pulse Voltammetry The initial peak point current of dichlorphenoxyacetic acid solution;
5) it is to be measured to check in concentration for the linear relationship chart conducive to current differential and corresponding 2,4 dichlorophenoxyacetic acid log concentration 2 in the 2,4 dichlorophenoxyacetic acid solution to be measured of concentration corresponding to the initial peak point current of 2,4 dichlorophenoxyacetic acid solution, The concentration value of 4- dichlorphenoxyacetic acid.
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CN105688935A (en) * 2016-01-13 2016-06-22 安徽师范大学 Preparation method of Pt/Cu-Ni catalyst and method and application of catalyst for catalyzing and oxidizing alcohols
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