CN107843637A - For detecting the block polymer decorated electrode and preparation method of lead ion - Google Patents
For detecting the block polymer decorated electrode and preparation method of lead ion Download PDFInfo
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- CN107843637A CN107843637A CN201710948075.6A CN201710948075A CN107843637A CN 107843637 A CN107843637 A CN 107843637A CN 201710948075 A CN201710948075 A CN 201710948075A CN 107843637 A CN107843637 A CN 107843637A
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The present invention discloses the block polymer decorated electrode for being used to detect lead ion prepared by a kind of visible light-initiated, without transition-metal catalyst ATRP, it is characterized in that again with block polymer decorated on bromine-containing compound modified electrode, the structure of the block copolymer is as follows：。
Description
Technical field
The present invention relates to a kind of modified electrode and preparation method that can be used for detection lead ion, especially a kind of visible ray draws
The block polymer decorated electrode and the preparation side that are used to detect lead ion prepared by hair, the ATRP without transition-metal catalyst
Method.
Background technology
Lead is that one kind is widely present and nondegradable heavy metal contaminants, many approach can cause lead content exceeded, give
The mankind cause much to endanger, therefore it is extremely important to detect lead ion content in solution.
The method of detection lead ion mainly had AAS, atomic absorption spectrography (AAS), chromatography, inductive etc. in the past
Ion mass spectrometry etc., although existing method, to the assay high sensitivity of lead ion, as a result also relatively more accurate, needs are high
Expensive instrument, complicated Sample Preparation Procedure, and skilled operator is needed, it is not suitable for live detection in real time.In recent years
Come, chemically modified electrode has obtained larger application in terms of detection of heavy metal ion, and various chemically modified electrodes are reported extensively
Road, wherein polymer modified electrode are subject to greater attention because its stability is good, detection site is more, preparation method is easy.Each
In the polymer of kind of structure, block copolymer is that the different polymer segment of two or more property connects together preparation
A kind of particular polymer formed, it has unique Microphase Separation behavior, in polymer blending solubilising, surfactant, glues
The fields such as mixture, coating, have a wide range of applications.
The preparation method of block copolymer has a variety of, ATRP（ATRP）Be maximally efficient means it
One.It is using organohalogen compounds as initiator, and transition metal complex is halogen atom carrier, by redox reaction, in activity
Dynamic equilibrium is established between kind and dormancy kind, it is possible to achieve the control to polymerisation.Including the molecular weight to polymer, molecule
Amount distribution, molecular structure are designed, therefore most pregnancy and had in macromolecule research field well with forming etc.
One of research work of challenge.But conventional ATRP has some shortcomings, for example lower valency transition metal is quicker to air
The aftertreatment technologys such as sense, Removal of catalyst are complicated.
The content of the invention
The present invention is to solve the above-mentioned technical problem present in prior art, there is provided it is a kind of it is visible it is light-initiated, need not
The block polymer decorated electrode and preparation method that are used to detect lead ion prepared by the ATRP of transition-metal catalyst.
The present invention technical solution be：A kind of block polymer decorated electrode for being used to detect lead ion, its feature
It is that, again with block polymer decorated on bromine-containing compound modified electrode, the structure of the block copolymer is as follows：
。
A kind of above-mentioned preparation method for being used to detect the block polymer decorated electrode of lead ion, it is characterised in that press successively
Carried out according to following steps：
A. take bromine-containing compound to be dissolved in wiring solution-forming in ethanol, gold electrode be placed in solution, at room temperature the h of self assembly 24,
Obtain bromine-containing compound modified electrode；
B. bromine-containing compound modified electrode is put into by methyl acrylamide monomer or acrylamide monomer, triethylamine and fluorescence
In the solution of element composition, vacuumize, LED lamplight shines 1 ~ 10 h, obtains polymer modified electrode；The methyl acrylamide monomer
Or the amount ratio of acrylamide monomer, triethylamine and fluorescein is 0.1 ~ 0.9 mol：12.5~125ml：0.5×10-4~4×10-4 mol；
C. obtained polymer modified electrode is put into by methacrylic acid monomer or acrylic monomers, triethylamine and fluorescence again
In the solution of element composition, vacuumize, LED lamplight shines 1 ~ 10 h, obtains block polymer decorated electrode；The methacrylic acid list
Body or acrylic monomers, the amount ratio of triethylamine and fluorescein are 0.1 ~ 0.9 mol：12.5~125ml：0.5×10-4~4×10-4 mol。
The present invention prepares block polymer decorated electrode using visible light-initiated ATRP reactions, easy to operate, required instrument
Device equipment is simple, without addition transition metal in addition as catalyst, solves the lower valency gold present in existing ATRP technologies
The problems such as metal catalyst pollution on the environment, residual in block copolymer.Block copolymer prepared by the present invention
Modified electrode has preferable identity, and preferably detection is realized to lead ion using electrochemical method.
Brief description of the drawings
Fig. 1 is the Different electrodes of the embodiment of the present invention 1 in the [Fe (CN) containing 0.1mmol/L6]3-/4-Phosphate-buffered
Cyclic voltammogram in liquid.
Fig. 2 is the block polymer decorated electrode of polyacrylamide-b- polymethylacrylic acid of the embodiment of the present invention 1（A）With
And detect the surface topography of electrode after lead ion（B）.
Fig. 3 is the differential pulse Anodic Stripping of the block polymer decorated electrode pair lead ion detection of the embodiment of the present invention 1
Voltammogram（A）And working curve（B）.
Fig. 4 is the selective schematic diagram that the block polymer decorated electrode pair lead ion of the embodiment of the present invention 1 detects.
Embodiment
Embodiment 1：
Follow the steps below：
A. according to the method for prior art, a certain amount of bromine-containing compound solid dissolving wiring solution-forming in ethanol is taken, will be clean
Gold electrode is placed in solution, at room temperature the h of self assembly 24, obtains bromine-containing compound modified electrode；
B. bromine-containing compound modified electrode is put into the acrylamide monomer containing 0.9 mol/L, 5 mL triethylamines, 4 × 10-4
In the solution of mol/L fluoresceins composition, vacuumize, using the commercially available h of common LED desk lamp illumination 10, obtain acrylamide polymerization
Thing；
C. above-mentioned electrode is put into containing 0.9 mol/L methacrylic acid monomers, 2 mL triethylamines, 2 × 10 again-4 Mol/L fluorescence
In the solution that element is configured to, vacuumize, the commercially available h of common LED desk lamp illumination 7, obtain polyacrylamide-b- polymethylacrylic acid
Block polymer decorated electrode, i.e., again with block polymer decorated on bromine-containing compound modified electrode, the block copolymer
Structure it is as follows：
。
The Different electrodes of the embodiment of the present invention 1 are in [the Fe (CN) containing 0.1mmol/L6]3-/4-PH=7.0 phosphate
Cyclic voltammogram in buffer solution is as shown in figure 1, it is 100mV/s to sweep speed.Curve 1 is naked gold electrode, and 2 be bromide modification gold electricity
Pole, 3 be Polyacrylamide-modified gold electrode, and 4 be the block polymer decorated electrode of polyacrylamide-b- polymethylacrylic acid.From
It can be seen that a pair of more symmetrical redox peaks occur in the CV curves of naked gold electrode in Fig. 1（Curve 1）, illustrate [Fe
(CN)6]3-/4-Reaction on electrode will definitely be inverse；After naked gold electrode surface is brominated thing modification, its redox peak current
There is obvious reduction（Curve 2）, illustrate that bromide is successfully assembled on electrode surface；After polymerization of acrylamide, oxidation is also
Parent peak electric current further reduces（Curve 3）, because the polymer of electrode surface increases resistance of the electronics by modified electrode
Power；After further polymerized methacrylic acid, reduce before redox peak current ratio more（Curve 4）, illustrate block copolymer
After modified electrode, the electron transmission ability of electrode more weakens.The result of cyclic voltammetry curve shows, is successfully made in electrode surface
For polyacrylamide-b- polymethylacrylic acid block copolymers.
The block polymer decorated electrode of polyacrylamide-b- polymethylacrylic acid and detection lead of the embodiment of the present invention 1
The surface topography of electrode is as shown in Figure 2 after ion.From figure 2 it can be seen that block polymer decorated electrode surface is in larger
It is laminar structured（Fig. 2A）, after detecting lead ion, electrode surface pattern is there occurs larger change, in the presence of lead ion,
Some lamellar structures coalesce together to form coarse club shaped structure（Fig. 2 B）.
Fig. 3 is the differential pulse Anodic Stripping of the block polymer decorated electrode pair lead ion detection of the embodiment of the present invention 1
Voltammogram（A）And working curve（B）.In Fig. 3 A figures, plumbum ion concentration corresponding to 1 to 7 is respectively 1.0 × 10-11、1.0×10-10、1.0×10-9、1.0×10-8、1.0×10-7、1.0×10-6、1.0×10-5、1.0×10-4 Mol/L, Fig. 3 B are thus to obtain
The working curve arrived.From figure 3, it can be seen that plumbum ion concentration increases, peak current increase（A schemes）, and peak current and lead ion
Log concentration is directly proportional（B schemes）, visible through analyzing, imprinted polymer modified electrode prepared by the present invention can exist to lead ion
1.0×10-11~1.0 × 10-4Detected in the range of mol/L, linearly dependent coefficient isR 2=0.984。
Fig. 4 is the selection implementations that the block polymer decorated electrode pair lead ion of embodiment 1 detects.Can be with from Fig. 4
Find out, as 10 nmol/L Pb of detection2+When, 100 times of K+、Cu2+、Ni2+、Cd2+、Ca2+、Zn2+、Na+It is all not bright to lead ion
Aobvious interference, show that block polymer decorated electrode pair lead ion detection has good identification selection.
Embodiment 2：
Follow the steps below：
A. the method for pressing prior art, takes a certain amount of bromine-containing compound solid dissolving wiring solution-forming in ethanol, by clean gold
Electrode is placed in bromine-containing compound solution, at room temperature the h of self assembly 24, obtains bromine-containing compound modified electrode；
B. by bromine-containing compound modified electrode be put into the acrylamide monomer containing 0.1 mol/L, 0.5 mL triethylamines, 0.5 ×
10-4 In the solution of mol/L fluoresceins composition, vacuumize, using the commercially available h of common LED desk lamp illumination 1, obtain acrylamide and gather
Compound；
C. above-mentioned electrode is put into containing 0.1 mol/L acrylic monomers, 0.5 mL triethylamines, 4 × 10 again-4 Mol/L fluoresceins
In the solution being configured to, vacuumize, the commercially available h of common LED desk lamp illumination 10, obtain polyacrylamide-b- polyacrylic acid blocks and be total to
Polymers modified electrode, its structure is the same as embodiment 1.
Embodiment 3：
Follow the steps below：
A. the method for pressing prior art, takes a certain amount of bromine-containing compound solid dissolving wiring solution-forming in ethanol, by clean gold
Electrode is placed in bromine-containing compound solution, at room temperature the h of self assembly 24, obtains bromine-containing compound modified electrode；
B. bromine-containing compound modified electrode is put into the methyl acrylamide monomer containing 0.1 mol/L, 5 mL triethylamines, 0.5
×10-4 In the solution of mol/L fluoresceins composition, vacuumize, using the commercially available h of common LED desk lamp illumination 8, obtain metering system
Amide polymer；
C. above-mentioned electrode is put into containing 0.9 mol/L methacrylic acid monomers, 0.5 mL triethylamines, 2 × 10 again-4 Mol/L is glimmering
In the solution that light element is configured to, vacuumize, the commercially available h of common LED desk lamp illumination 2, obtain the poly- methyl of polymethacrylamide-b-
Acrylic block copolymers modified electrode, electrode structure is the same as embodiment 1.
Embodiment 4：
Follow the steps below：
A. according to the method for prior art, a certain amount of bromine-containing compound solid dissolving wiring solution-forming in ethanol is taken, will be clean
Gold electrode be placed in bromine-containing compound solution, the h of self assembly 24, obtains bromine-containing compound modified electrode at room temperature；
B. by bromine-containing compound modified electrode be put into the methyl acrylamide monomer containing 0.6 mol/L, 3 mL triethylamines, 3 ×
10-4 In the solution of mol/L fluoresceins composition, vacuumize, using the commercially available h of common LED desk lamp illumination 8, obtain methacryl
Amine polymer；
C. above-mentioned electrode is put into containing 0.7 mol/L acrylic monomers, 4 mL triethylamines, 0.5 × 10 again-4 Mol/L fluoresceins
In the solution being configured to, vacuumize, the commercially available h of common LED desk lamp illumination 7, it is embedding to obtain polymethacrylamide-b- polyacrylic acid
Section copolymer modified electrode, electrode structure is the same as embodiment 1.
Embodiment 5：
Follow the steps below：
A. according to the method for prior art, a certain amount of bromine-containing compound solid dissolving wiring solution-forming in ethanol is taken, will be clean
Gold electrode be placed in bromine-containing compound solution, the h of self assembly 24, obtains bromine-containing compound modified electrode, electrode structure at room temperature
With embodiment 1；
B. bromine-containing compound modified electrode is put into the acrylamide monomer containing 0.3 mol/L, 2 mL triethylamines, 2 × 10-4
In the solution of mol/L fluoresceins composition, vacuumize, using the commercially available h of common LED desk lamp illumination 6, obtain acrylamide polymer；
C. above-mentioned electrode is put into containing 0.8 mol/L methacrylic acid monomers, 5 mL triethylamines, 1 × 10 again-4 Mol/L fluorescence
In the solution that element is configured to, vacuumize, the commercially available h of common LED desk lamp illumination 1, obtain polyacrylamide-b- polymethylacrylic acid
Block polymer decorated electrode.
Claims (2)
1. a kind of block polymer decorated electrode for being used to detect lead ion, it is characterised in that be in bromine-containing compound modified electrode
On again with block polymer decorated, the structure of the block copolymer is as follows：
。
2. a kind of preparation method for being used to detect the block polymer decorated electrode of lead ion as claimed in claim 1, its feature
It is to carry out in accordance with the following steps successively：
A. take bromine-containing compound to be dissolved in wiring solution-forming in ethanol, gold electrode be placed in solution, at room temperature the h of self assembly 24,
Obtain bromine-containing compound modified electrode；
B. bromine-containing compound modified electrode is put into by methyl acrylamide monomer or acrylamide monomer, triethylamine and fluorescence
In the solution of element composition, vacuumize, LED lamplight shines 1 ~ 10 h, obtains polymer modified electrode；The methyl acrylamide monomer
Or the amount ratio of acrylamide monomer, triethylamine and fluorescein is 0.1 ~ 0.9 mol：12.5~125ml：0.5×10-4~4×10-4 mol；
C. obtained polymer modified electrode is put into by methacrylic acid monomer or acrylic monomers, triethylamine and fluorescence again
In the solution of element composition, vacuumize, LED lamplight shines 1 ~ 10 h, obtains block polymer decorated electrode；The methacrylic acid list
Body or acrylic monomers, the amount ratio of triethylamine and fluorescein are 0.1 ~ 0.9 mol：12.5~125ml：0.5×10-4~4×10-4 mol。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108931564A (en) * | 2018-05-11 | 2018-12-04 | 辽宁师范大学 | 3D nickel billon nano-cluster Nanosilica electrode for highly sensitive detection erythromycin |
| CN109187688A (en) * | 2018-12-05 | 2019-01-11 | 中国科学院烟台海岸带研究所 | A kind of light-operated polymer sensitive membrane electrochemical detection method and its device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105017476A (en) * | 2015-07-14 | 2015-11-04 | 辽宁师范大学 | Preparation method for hemoglobin molecularly imprinted polymers through autocatalysis of ATRP |
| CN105891286A (en) * | 2016-05-31 | 2016-08-24 | 中华人民共和国南通出入境检验检疫局 | Lead ion direct electrochemical detection method for probe-integrated functional nucleic acid modified electrode |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017476A (en) * | 2015-07-14 | 2015-11-04 | 辽宁师范大学 | Preparation method for hemoglobin molecularly imprinted polymers through autocatalysis of ATRP |
| CN105891286A (en) * | 2016-05-31 | 2016-08-24 | 中华人民共和国南通出入境检验检疫局 | Lead ion direct electrochemical detection method for probe-integrated functional nucleic acid modified electrode |
Non-Patent Citations (3)
| Title |
|---|
| YUE SUN 等: "Preparation of block copolymers via metal-free visible-light-induced ATRP for the detection of lead ions", 《J. APPL. POLYM. SCI.》 * |
| 李亚平 等: "氧化石墨烯／聚丙烯酰胺／聚甲基丙烯酸复合水凝胶", 《高分子材料科学与工程》 * |
| 陈明清 等: "PAm-g-PMAA亲水性聚合物微球的合成", 《高分子学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108931564A (en) * | 2018-05-11 | 2018-12-04 | 辽宁师范大学 | 3D nickel billon nano-cluster Nanosilica electrode for highly sensitive detection erythromycin |
| CN108931564B (en) * | 2018-05-11 | 2020-10-30 | 辽宁师范大学 | 3D nickel-gold alloy nanocluster imprinting modified electrode for high-sensitivity detection of erythromycin |
| CN109187688A (en) * | 2018-12-05 | 2019-01-11 | 中国科学院烟台海岸带研究所 | A kind of light-operated polymer sensitive membrane electrochemical detection method and its device |
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Application publication date: 20180327 |