CN108562632B - Soil bio-availability heavy metal enrichment electrode and preparation method and application thereof - Google Patents
Soil bio-availability heavy metal enrichment electrode and preparation method and application thereof Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 84
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- 239000004917 carbon fiber Substances 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- 238000001514 detection method Methods 0.000 claims abstract description 33
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- 238000000576 coating method Methods 0.000 claims abstract description 11
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- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
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- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical compound N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 108091023037 Aptamer Proteins 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052793 cadmium Inorganic materials 0.000 abstract description 23
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052785 arsenic Inorganic materials 0.000 abstract description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052804 chromium Inorganic materials 0.000 abstract description 16
- 239000011651 chromium Substances 0.000 abstract description 16
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 239000010949 copper Substances 0.000 abstract description 16
- 239000011133 lead Substances 0.000 abstract description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052753 mercury Inorganic materials 0.000 abstract description 16
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 108700008625 Reporter Genes Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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Abstract
The invention belongs to the technical field of soil sensing detection, and particularly relates to a soil biological effectiveness heavy metal enrichment electrode and a preparation method and application thereof. The method provided by the invention comprises the steps of modifying the surface of carbon fiber, activating the surface, coating a silver layer, and compounding the carbon fiber with cyclodextrin, starch, chitin and a nucleic acid aptamer to prepare the soil bioavailability heavy metal enrichment electrode. The electrode has multi-channel detection capability, can simultaneously detect the biological effectiveness of 8 heavy metals such as cadmium, mercury, arsenic, lead, chromium, copper, nickel, zinc and the like and inorganic substances in soil, and the detection limit of the electrode meets the soil environment quality standard GB 15618-2008.
Description
Technical Field
The invention belongs to the technical field of soil sensing detection, and particularly relates to a soil biological effectiveness heavy metal enrichment electrode and a preparation method and application thereof.
Background
The heavy metals in the soil have toxic action on plants and threaten the health of human bodies through a food chain; the existing soil heavy metal detection method is used for determining the total amount (unit is mg/kg, namely the content of heavy metal in 1kg of soil) of soil heavy metal, the detection process is complex, and a large part of soil heavy metal in the determination result has no biological effectiveness. The soil active heavy metal detected by the soil active heavy metal detection method can reflect the relationship between the soil heavy metal and the plant root system absorption to the maximum extent, and represents the soil heavy metal pollution state. The soil environment quality standard GB15618-2008 stipulates that heavy metals to be measured include 16 kinds of cadmium, mercury, arsenic, lead, chromium, copper, nickel, zinc, and the like (wherein arsenic is not a heavy metal element, but is generally classified as a heavy metal in soil quality).
Benzhofu et al (Acta Sci circle, 2005,25(12): 1661-1668.) define soil heavy metal availability as the ratio of crop heavy metal uptake to total soil heavy metal uptake. The higher the availability of soil heavy metals, the more readily the metals are absorbed by the crop. Therefore, only by accurately judging the effectiveness of the heavy metal, the risk assessment of the heavy metal can be better carried out. However, the effectiveness of heavy metals is influenced by various factors, wherein pH and organic matters are factors which have larger influence, and in addition, soil oxidation-reduction potential, soil organisms and the like also have certain influence on the effectiveness of the heavy metals in the soil (J Zhejiang Agric Sci 2012, (5): 729-.
The inventor discloses a series of detection methods (CN 106153587A, CN106124281A and CN 105866093A) for soil active heavy metals, and adopts an ultra-large amount of soil analysis sample volume, diethylenetriamine pentaacetic acid as a chelating agent, calcium ions in calcium chloride as a chelating and leaching balancing agent, triethanolamine as a buffering agent, and chelating and leaching to extract the soil active heavy metals; and (3) ensuring the detection of the ultra-micro soil active heavy metal in the soil by using an atomic fluorescence spectroscopy and adopting a low mass fraction standard curve.
The Wenzhou medical university invents a microbiological method (CN 104946681A) for detecting heavy metal cadmium, and particularly relates to a construction method for detecting a cadmium escherichia coli engineering strain and establishment of a method for detecting cadmium in water. The construction of the engineering strain is obtained by firstly knocking out the cadmium resistance znTA and znTR genes of the Escherichia coli by adopting a Red recombination system, and then replacing the pmerrR-MerR (M) -pmerrR-gfp mut2 reporter gene to the znTR coding gene position by adopting a gene knock-in technology. The minimum detection range of the engineering strain for cadmium meets the Integrated wastewater discharge Standard GB8978-1996, and the defects that the engineering strain based on the plasmid vector has high fluorescence background value, poor detection signal and the like are overcome. The engineering strain disclosed by the invention can be used for complementarily analyzing the biological effectiveness and the total amount of cadmium with physical and chemical analysis methods such as AAS (anaerobic-anoxic-oxic) and the like, and provides a basis for objectively evaluating the biological toxicity of cadmium.
Zhaiming et al studied "soil heavy metal pollution detection mechanism and technology based on a nano-electrode array sensor" (Master thesis of the university of south and central province, 2014), studied the electrochemical characteristics of the nano-electrode array, electrode modification method and the nonlinear diffusion effect, small time constant effect, transfer rate and signal-to-noise ratio of the nano-electrode sensor. The design method and the notice of the nano electrode array and the manufacturing method of the nano electrode array are obtained. A heavy metal detection system model is provided and designed, internal parameters of circuits such as solution resistance, double electric layer capacitance and the like are researched aiming at a three-electrode detection system, and soil heavy metal diffusion and dispersion effects are researched. Starting from the diffusion law and the mass conservation law, a set of soil heavy metal propagation model based on the diffusion law and the mass conservation is established. And the application range of the model is analyzed, and theoretical support is provided for early warning of heavy metals.
In summary, the following methods are mainly used for detecting the soil bio-effective heavy metals: (1) plant adsorption method; the method is most accurate by enriching the heavy metals in the soil by utilizing roots, stems, leaves and the like of plants, but has long time consumption, wide occupied area and low efficiency; (2) chemical extraction; the method is high in speed and efficiency, but a scientific relation between biological effectiveness and extraction is not established, namely a theoretical basis is lacked. (3) Biosensing chelation; the method can overcome the defects of the two methods, and establishes an in-situ real-time detection method for the soil bioavailability heavy metal, but the sensitivity is poor, and the detection limit is not satisfactory. If the heavy metal enrichment technology is fused with the biosensing technology, the problems are expected to be solved.
Disclosure of Invention
The invention aims to provide a soil biological effectiveness heavy metal enrichment electrode and a preparation method and application thereof.
The invention provides a preparation method of a soil bioavailability heavy metal enrichment electrode, which comprises the following specific steps:
(1) surface modification: fixing carbon fiber cloth with the length of 4-6 cm and the width of 1-3 cm on a rotary disc of a spin coater, controlling the temperature of the rotary disc to be 110-130 ℃ and the rotating speed to be 900-1100 r/min, dropwise adding 9-11 ml of 3-aminopropyl trimethoxysilane solution with the mass fraction of 0.5-1.5%, reducing the temperature of the rotary disc to 20-30 ℃ after dropwise adding, and stopping rotating the rotary disc to obtain a modified carbon fiber electrode; wherein the solute of the 3-aminopropyl trimethoxy silane solution is 3-aminopropyl trimethoxy silane, and the solvent is acetone;
(2) surface activation: immersing the modified carbon fiber electrode in the step (1) into a chloroauric acid aqueous solution with the mass fraction of 0.5-1.5%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.05-0.15%, standing for 4-6 minutes, taking out, washing with deionized water for 3-4 times (each time can be 100 ml), and obtaining an activated carbon fiber electrode;
(3) silver coating: immersing the activated carbon fiber electrode in the step (2) into 40-60 ml of silver ammonium solution, then dropwise adding 9-11 ml of glucose aqueous solution with the mass fraction of 9-11%, standing for 4-6 minutes after dropwise adding, taking out, washing for 3-4 times (each time can be 100 ml) by using deionized water, and obtaining a silver-coated carbon fiber electrode; wherein, the solute of the silver ammonium solution is silver nitrate and ammonia water, the solvent is deionized water, the mass fraction of the silver nitrate is 3-4%, and the mass fraction of the ammonia water is 0.5-1.5%;
(4) preparing an electrode: mixing 1-2 g of cyclodextrin, 2-4 g of starch, 1.5-4.5 g of chitin and 1-3 g of aptamer with 15-25 ml of deionized water, stirring to form paste, coating the paste on the silver-coated carbon fiber electrode in the step (3), placing the silver-coated carbon fiber electrode in a drying oven, baking for 2-4 hours at 50-70 ℃, and taking out to obtain the soil bioavailability heavy metal enriched electrode.
Wherein, the sequence of the aptamer is as follows:
AAAAAAAATACTCAGGGCACTTGCAAGCAATTGTGGTCCCAATGGGCTGAGTAT（SEQ ID NO.1）。
the soil bioavailability heavy metal enrichment electrode prepared by the method is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with the calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively lower than 0.20mg/kg, 10mg/kg, 40mg/kg, 100mg/kg, 20mg/kg and 50 mg/kg.
If cyclodextrin is not used as a raw material in the step (4), the invention also provides the following technical scheme as a comparison:
and mixing 2g of starch, 1.5g of chitin and 1g of the aptamer with 20ml of deionized water, and performing the same operation to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 20mg/kg, 25mg/kg, 150mg/kg, 420mg/kg, 550mg/kg, 280mg/kg, 240mg/kg and 530 mg/kg.
If starch is not used as a raw material in the step (4), the invention also provides the following technical scheme as a comparison:
and mixing 2g of cyclodextrin, 4.5g of chitin and 3g of the aptamer with 20ml of deionized water, and performing the same operation to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 25mg/kg, 20mg/kg, 180mg/kg, 480mg/kg, 510mg/kg, 210mg/kg, 200mg/kg and 560 mg/kg.
If the chitin is not used as the raw material in the step (4), the invention also provides the following technical scheme as a comparison:
and mixing 1g of cyclodextrin, 4g of starch and 1g of the aptamer with 20ml of deionized water, and performing the same operation to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 30mg/kg, 35mg/kg, 110mg/kg, 310mg/kg, 450mg/kg, 380mg/kg, 440mg/kg and 450 mg/kg.
It can be seen from the above comparative technical solutions that the technical effect of the present invention, that is, "detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel, and zinc" measured by a soil bio-availability heavy metal enrichment electrode is a result of the combined action of the components in the electrode material, and once a certain component is changed, the detection limit values of cadmium, mercury, arsenic, lead, chromium, copper, nickel, and zinc are sharply increased, i.e., have a synergistic effect of "1 +1> 2", which is a phenomenon not reported in other documents.
Therefore, the soil bioavailability heavy metal enrichment electrode prepared by the invention can be used for detecting soil bioavailability heavy metal elements. The device has multi-channel detection capability, can simultaneously detect 8 heavy metals such as cadmium, mercury, arsenic, lead, chromium, copper, nickel, zinc and the like and inorganic substances, and has detection limits meeting the soil environment quality standard GB 15618-2008.
The invention has the beneficial effects that:
(1) the detection limits of the soil biological effectiveness heavy metal enrichment electrode on cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively lower than 0.20mg/kg, 10mg/kg, 40mg/kg, 100mg/kg, 20mg/kg and 50mg/kg, and the soil environment quality standard GB15618-2008 is met;
(2) the soil bioavailability heavy metal enrichment electrode can simultaneously detect 8 heavy metals and inorganic matters, has multi-channel detection capability, and can greatly improve the detection efficiency.
Detailed Description
The invention is further described below by way of example.
Example 1
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotary disc of a spin coater, controlling the temperature of the rotary disc at 120 ℃ and the rotating speed at 1000 r/min, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotary disc to 25 ℃ after finishing dripping, and stopping rotating the rotary disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 1g of cyclodextrin, 2g of starch, 1.5g of chitin, 1g of the aptamer and 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into a drying oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enriched electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 0.18mg/kg, 0.16mg/kg, 8mg/kg, 20mg/kg, 60mg/kg, 12mg/kg, 16mg/kg and 32 mg/kg.
Example 2
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotating disc of a spin coater, controlling the temperature of the rotating disc at 120 ℃ and the rotating speed at 1000 revolutions per minute, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotating disc to 25 ℃ after finishing dripping, and stopping rotating the rotating disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 2g of cyclodextrin, 4g of starch, 4.5g of chitin, 3g of the aptamer and 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into a baking oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enriched electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 0.12mg/kg, 0.19mg/kg, 9mg/kg, 35mg/kg, 55mg/kg, 14mg/kg, 12mg/kg and 45 mg/kg.
Example 3
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotating disc of a spin coater, controlling the temperature of the rotating disc at 120 ℃ and the rotating speed at 1000 revolutions per minute, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotating disc to 25 ℃ after finishing dripping, and stopping rotating the rotating disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 1.5g of cyclodextrin, 3g of starch, 3g of chitin and 2g of aptamer with 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into a drying oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enriched electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample of the calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 0.16mg/kg, 0.15mg/kg, 6mg/kg, 28mg/kg, 92mg/kg, 14mg/kg, 9mg/kg and 38 mg/kg.
Example 4
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotating disc of a spin coater, controlling the temperature of the rotating disc at 120 ℃ and the rotating speed at 1000 revolutions per minute, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotating disc to 25 ℃ after finishing dripping, and stopping rotating the rotating disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 2g of starch, 1.5g of chitin and 1g of the aptamer with 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into an oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 20mg/kg, 25mg/kg, 150mg/kg, 420mg/kg, 550mg/kg, 280mg/kg, 240mg/kg and 530 mg/kg.
Example 5
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotating disc of a spin coater, controlling the temperature of the rotating disc at 120 ℃ and the rotating speed at 1000 revolutions per minute, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotating disc to 25 ℃ after finishing dripping, and stopping rotating the rotating disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 2g of cyclodextrin, 4.5g of chitin and 3g of aptamer with 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into a baking oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 25mg/kg, 20mg/kg, 180mg/kg, 480mg/kg, 510mg/kg, 210mg/kg, 200mg/kg and 560 mg/kg.
Example 6
1g of 3-aminopropyltrimethoxysilane and 99g of acetone are mixed to obtain a 3-aminopropyltrimethoxysilane solution. Fixing carbon fiber cloth with the length of 5cm and the width of 2cm on a rotating disc of a spin coater, controlling the temperature of the rotating disc at 120 ℃ and the rotating speed at 1000 revolutions per minute, dropwise adding 10ml of 3-aminopropyl trimethoxy silane solution, reducing the temperature of the rotating disc to 25 ℃ after finishing dripping, and stopping rotating the rotating disc to obtain the modified carbon fiber electrode.
And (2) immersing the modified carbon fiber electrode into a chloroauric acid aqueous solution with the mass fraction of 1%, standing for 1 hour, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.1%, standing for 5 minutes, taking out, washing with deionized water for 3 times, and obtaining the activated carbon fiber electrode, wherein each time is 100 ml.
Mixing 3.5g of silver nitrate, 3.5ml of 28% ammonia water and 95.5g of deionized water to obtain a silver ammonium solution; and (3) immersing the activated carbon fiber electrode into 50ml of silver ammonium solution, then dropwise adding 10ml of glucose aqueous solution with the mass fraction of 10%, standing for 5 minutes after dropwise adding, taking out, washing for 3 times by deionized water, and obtaining the silver-coated carbon fiber electrode by 100ml each time.
Mixing 1g of cyclodextrin, 4g of starch, 1g of the aptamer and 20ml of deionized water, stirring into paste, coating the paste on a silver-coated carbon fiber electrode, putting the silver-coated carbon fiber electrode into an oven, baking the silver-coated carbon fiber electrode for 3 hours at 60 ℃, and taking out the silver-coated carbon fiber electrode to obtain the soil bioavailability heavy metal enrichment electrode. The soil bioavailability heavy metal enrichment electrode is used as a working electrode and assembled into a three-electrode system of an electrochemical workstation, the electrode is calibrated by utilizing a soil standard sample with calibrated bioavailability heavy metal, and the detection limits of cadmium, mercury, arsenic, lead, chromium, copper, nickel and zinc are respectively 30mg/kg, 35mg/kg, 110mg/kg, 310mg/kg, 450mg/kg, 380mg/kg, 440mg/kg and 450 mg/kg.
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Claims (3)
1. A preparation method of a soil biological effectiveness heavy metal enrichment electrode is characterized by comprising the following specific steps:
(1) surface modification: fixing carbon fiber cloth with the length of 4-6 cm and the width of 1-3 cm on a rotary disc of a spin coater, controlling the temperature of the rotary disc to be 110-130 ℃ and the rotating speed to be 900-1100 r/min, dropwise adding 9-11 ml of 3-aminopropyl trimethoxysilane solution with the mass fraction of 0.5-1.5%, reducing the temperature of the rotary disc to 20-30 ℃ after dropwise adding, and stopping rotating the rotary disc to obtain a modified carbon fiber electrode; wherein the solute of the 3-aminopropyl trimethoxy silane solution is 3-aminopropyl trimethoxy silane, and the solvent is acetone;
(2) surface activation: immersing the modified carbon fiber electrode in the step (1) into a chloroauric acid aqueous solution with the mass fraction of 0.5-1.5%, standing for 0.5-1.5 hours, taking out, immersing into a sodium borohydride aqueous solution with the mass fraction of 0.05-0.15%, standing for 4-6 minutes, taking out, and washing for 3-4 times by using deionized water to obtain an activated carbon fiber electrode;
(3) silver coating: immersing the activated carbon fiber electrode in the step (2) into 40-60 ml of silver ammonium solution, then dropwise adding 9-11 ml of glucose aqueous solution with the mass fraction of 9-11%, standing for 4-6 minutes after dropwise adding, taking out, and washing for 3-4 times by using deionized water to obtain a silver-coated carbon fiber electrode; wherein, the solute of the silver ammonium solution is silver nitrate and ammonia water, the solvent is deionized water, the mass fraction of the silver nitrate is 3-4%, and the mass fraction of the ammonia water is 0.5-1.5%;
(4) preparing an electrode: mixing 1-2 g of cyclodextrin, 2-4 g of starch, 1.5-4.5 g of chitin and 1-3 g of aptamer with 15-25 ml of deionized water, stirring into paste, coating the paste on the silver-coated carbon fiber electrode in the step (3), putting the silver-coated carbon fiber electrode into a drying oven, baking the silver-coated carbon fiber electrode for 2-4 hours at 50-70 ℃, and taking out the silver-coated carbon fiber electrode to obtain a soil bioavailability heavy metal enriched electrode;
wherein, the sequence of the aptamer is SEQ ID NO. 1.
2. The soil bio-effective heavy metal enrichment electrode prepared by the preparation method of claim 1.
3. The use of the soil bio-effective heavy metal enrichment electrode of claim 2 in the detection of heavy metal elements in soil.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931570A (en) * | 2015-06-08 | 2015-09-23 | 济南大学 | Preparation method and application of electrochemical sensor for heavy metal ions based on aptamers |
| CN105606675A (en) * | 2015-12-30 | 2016-05-25 | 湖南大学 | Aptamer sensor used for detecting lead and preparation method and application thereof |
| CN105866093A (en) * | 2016-06-21 | 2016-08-17 | 何文 | Detection method of soil active-state lead |
| CN106153587A (en) * | 2016-06-21 | 2016-11-23 | 何文 | A kind of detection method of soil activation state cadmium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104931570A (en) * | 2015-06-08 | 2015-09-23 | 济南大学 | Preparation method and application of electrochemical sensor for heavy metal ions based on aptamers |
| CN105606675A (en) * | 2015-12-30 | 2016-05-25 | 湖南大学 | Aptamer sensor used for detecting lead and preparation method and application thereof |
| CN105866093A (en) * | 2016-06-21 | 2016-08-17 | 何文 | Detection method of soil active-state lead |
| CN106153587A (en) * | 2016-06-21 | 2016-11-23 | 何文 | A kind of detection method of soil activation state cadmium |
Non-Patent Citations (1)
| Title |
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| A mini-review on functional nucleic acids-based heavy metal ion detection;Shenshan Zhan et al;《Biosensors and Bioelectronics》;20160625;353-368 * |
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