CN115436446B - Preparation method and application of benzenediol isomer detection chip - Google Patents
Preparation method and application of benzenediol isomer detection chip Download PDFInfo
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- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
- G01N27/327—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
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to the technical field of detection of benzenediol pollutants, and relates to a preparation method and application of a benzenediol isomer detection chip. Preparing a nitrogen-doped carbon tube for packaging metal particles through a cracking reaction of a transition metal salt and a carbon source composite precursor, wherein the nitrogen-doped carbon tube is used for improving electrochemical sensing performance; and the high-performance nano material is mixed with the conductive ink, and the detection chip is prepared by adopting a screen printing method, so that the detection chip has excellent electrocatalytic capacity. The preparation process of the detection chip is simple and controllable, large-scale and production-based production is easy to realize, the biosensor based on the chip can realize identification and quick response of the benzenediol isomer in a real water sample, accurately distinguish the concentration information of different benzenediols, fill the blank of the existing monophenol substance detection products in the market, and greatly improve the detection efficiency of benzenediol pollutants in water.
Description
Technical Field
The invention belongs to the technical field of detection of benzenediol pollutants, and relates to a preparation method and application of a benzenediol isomer detection chip.
Background
With the rapid development of socioeconomic performance, a large amount of pollutants are widely discharged into water and soil due to the industrial activities of human beings. Among them, benzene diphenol is a non-degradable highly toxic phenol compound, which has three isomers of hydroquinone, catechol and resorcinol, and can cause serious harm to the environment and human health even at a low concentration. In the Chinese wastewater comprehensive emission standard, the total phenol value is used for measuring the content of phenols in the water body, and the maximum allowable concentration of the phenols in the water body is specified to be 0.4 mg/L. In general, the benzenediol pollutants mainly originate from the phenolic production section, and the discharge and leakage conditions of the benzenediol product line are difficult to accurately monitor only by detecting the total phenols in the water body, so that the pollution sources can not be controlled and managed in time under serious accidents and emergency situations. Therefore, developing in-situ real-time various benzenediol detection technologies has great significance for the leakage early warning of benzenediol isomers and the diffusion inhibition of pollutants.
At present, the detection means of the benzenediol mainly comprise High Performance Liquid Chromatography (HPLC), gas chromatography/mass spectrometry (GC/MS) and the like, however, the detection methods have long detection period, complicated pretreatment steps and large-scale equipment support, and cannot meet the requirement of rapid in-situ benzenediol detection. Compared with the detection technology, the electrochemical biological sensing technology has the characteristics of high response speed, convenient operation and real-time monitoring, and therefore, the electrochemical biological sensing technology is widely focused in the fields of environmental detection, food safety, fermentation industry and clinical medical treatment. For the detection of benzenediol, laccase is generally used as a biological recognition element, and Cu ions which mainly depend on the enzyme activity center of the laccase have excellent oxidation-reduction capability and can oxidize benzenediol substances into corresponding benzenediol quinone. However, laccase is a broad-spectrum phenol oxidase, so that the laccase-based phenol sensor is difficult to distinguish detection signals of three benzenediol isomers, and the anti-interference performance of the prepared biosensor is not ideal. In addition, in a real detection system, the benzenediol is usually co-present with various substances, so that the detection accuracy and stability thereof are susceptible to signal interference from oxidation of other compounds. In order to ensure that the sensor can realize high-sensitivity and specific identification of the benzenediol isomer in a complex detection environment, the electrocatalytic activity of the sensing film needs to be enhanced to meet the actual application requirements.
Disclosure of Invention
Aiming at the problems existing in the traditional benzenediol pollutant detection process, the invention provides a preparation method and application of a novel benzenediol isomer detection chip.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
A preparation method of a benzenediol isomer detection chip comprises the following specific steps:
(1) Preparation of nitrogen-doped carbon tube precursor encapsulating transition metal particles: fully dissolving transition metal salt serving as a metal source in deionized water to prepare a solution A; and dissolving or dispersing carbon-nitrogen organic matters serving as a carbon source in deionized water to obtain a solution or suspension B. Mixing the equal volumes A and B, fully stirring to be uniform, and fully dehydrating at 80 ℃ until the mixture is completely dried to obtain the transition metal salt-carbon nitrogen organic compound precursor powder.
(2) Precursor powder is cracked to prepare a nitrogen doped carbon tube encapsulating transition metal particles: weighing a metal source-carbon source precursor in a certain mass step (1), paving the metal source-carbon source precursor in a ceramic square boat, placing the ceramic square boat in a tubular atmosphere furnace, setting a proper heating rate and an inert gas flow rate, and carrying out cracking reaction at a high temperature for a proper reaction time. And after the reaction is finished, collecting the obtained powder, dispersing the powder in a hydrochloric acid solution with a certain concentration to remove redundant carbon sources and excessive unbound metal simple substances, continuously stirring for a certain time, adding NaOH to adjust the pH of the mixed solution to be neutral, extracting the residual substances in a suction filtration mode, namely the nitrogen-doped carbon tubes for encapsulating the transition metal particles, and placing the nitrogen-doped carbon tubes in a vacuum drying box for dehydration and drying.
(3) Preparation of a printed chip based on nitrogen-doped carbon tubes encapsulating transition metal particles: mixing the nitrogen-doped carbon tubes encapsulating the transition metal particles in the step (2) with conductive ink according to a certain proportion to obtain uniformly dispersed sensing slurry, and adding a solvent to achieve optimal printing ink viscosity; the method comprises the steps of taking mixed conductive ink as working electrode ink, taking carbon ink as counter electrode ink and Ag/AgCl as reference electrode ink, printing specific electrode patterns on a base plate in batches, splitting the base plate into a plurality of complete printing chips after drying, and sequentially putting the printing chips into ethanol and deionized water for soaking and flushing to remove interfering substances attached to the surface.
(4) Preparation of a benzenediol isomer sensing electrode: preparing laccase solution with a certain concentration and enzyme crosslinking solution; and (3) uniformly mixing the two components in equal volume, uniformly coating a proper amount of mixture on the working electrode area of the printed chip obtained in the step (3), and drying at 4 ℃ to obtain the biosensor for detecting the isomer of the benzenediol.
Preferably, the transition metal salt in the step (1) is any one of CoCl 2、NiCl2、Cu(NO3)2、MnCl2; the concentration of the solution A is 0.05-0.5g/mL; the carbon source is any one of melamine, dicyandiamide and urea, and the concentration of the solution B is 0.15-1g/mL.
Preferably, in the step (2), the mass of the metal source-carbon source precursor is 0.2-5g; the temperature of the cracking process is 600-900 ℃, the heating rate is 1-5 ℃/min, and the cracking reaction time is 2-6h; the inert gas is any one of nitrogen, argon and helium, and the gas flow rate is 0.5-15mL/min; the hydrochloric acid concentration of the treated cracking reaction product is 0.5-5M, and the reaction time is 2-8h.
Preferably, the conductive ink in the step (3) is any one of carbon ink, silver paste and gold paste, and the mass ratio of the nitrogen-doped carbon tube for packaging the transition metal particles to the conductive ink is 1:15-1:1; the screen printing base plate is made of conductive glass PET, ceramic; the solvent for adjusting the viscosity of the sensing slurry is any one of methanol, ethanol and water.
Preferably, the concentration of laccase solution in step (4) is 0.1-5mg/mL; the enzyme cross-linking agent is any one of glutaraldehyde, chitosan and carboxymethyl cellulose, and the concentration is 1-10mg/mL; the amount of the laccase solution and the enzyme crosslinking solution mixture on a single chip is 2-20 mu L; the low-temperature drying time is 5-24h.
The sensing chip obtained by the preparation method can show excellent stability and signal distinguishing capability in the detection of the benzenediol isomer.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention obtains the high-stability biosensing chip based on the electrochemical biosensing technology through doping the nitrogen doped carbon tube of the high-performance nano material-encapsulated metal particles, and the biosensing chip has excellent electrochemical biosensing performance.
2. The detection chip based on the high-performance nano material and the biological enzyme composite structure can simultaneously realize concentration response and detection signal distinction of three benzenediol isomers, fills the blank of the existing monophenol substance detection products on the market, and greatly improves the detection efficiency of benzenediol pollutants in water bodies.
3. The benzenediol isomer detection chip can still have excellent selectivity of hydroquinone in a water sample with complex components in a real environment, has high sensitivity, low detection limit, strong anti-interference capability and excellent long-term stability, and can realize in-situ real-time benzenediol isomer monitoring.
Drawings
FIG. 1 is a scanning electron microscope image of various nitrogen doped carbon tubes encapsulating metal particles.
FIG. 2 is an independent signal response of the hydroquinone isomer of the sensor chip.
Detailed Description
In order that the above objects, features and advantages of the application will be more clearly understood, a further description of the application will be provided with reference to specific examples. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the present invention is not limited to the specific embodiments of the disclosure that follow.
Example 1
The example provides a process for preparing a benzenediol isomer detection chip, comprising the following steps.
(1) Taking CoCl 2 as a metal source, weighing 1g, fully dissolving in 20mL of deionized water, and obtaining 0.05g/mL of clear solution A; with urea as a carbon source, 3g was weighed and dissolved in 20mL of deionized water to obtain 0.15g/mL of clear solution B. Mixing the A and the B, fully stirring to be uniform, and fully dehydrating at 80 ℃ until the mixture is completely dried to obtain Co-urea composite precursor powder.
(2) Weighing 0.2g of the Co-urea precursor in the step (1), paving the precursor in a ceramic square boat, placing the ceramic square boat in a tubular atmosphere furnace, introducing argon, and controlling the gas flow rate to be 0.5mL/min; setting the heating rate to be 1 ℃/min, raising the temperature to 900 ℃ and keeping the temperature, carrying out high-temperature cracking reaction, collecting the obtained powder after 2 hours reaction, dispersing the obtained powder in 5M hydrochloric acid solution to remove redundant carbon sources and excessive uncombined metal simple substances, continuously stirring the mixture for 2 hours, adding NaOH to adjust the pH of the mixture to be neutral, extracting the residual substances in a suction filtration mode, namely the nitrogen-doped carbon tube for encapsulating Co metal particles, and placing the nitrogen-doped carbon tube in a vacuum drying oven at 100 ℃ for dehydration drying for 12 hours, as shown in figure 1.
(3) Mixing the nitrogen-doped carbon tube encapsulating the Co metal particles in the step (2) with conductive silver paste according to a ratio of 1:1 to obtain uniformly dispersed sensing paste, and adding methanol to achieve proper printing ink viscosity (printing can be achieved); the method comprises the steps of taking mixed conductive ink as working electrode ink, taking carbon ink as counter electrode ink, taking Ag/AgCl as reference electrode ink, uniformly filling and covering mesh holes of a screen printing plate, printing a specific electrode pattern on a conductive glass base plate, and sequentially putting the conductive glass base plate into ethanol and deionized water for soaking and flushing after drying to remove interfering substances attached to the surface.
(4) Preparing laccase solution a with the concentration of 0.1mg/mL and glutaraldehyde solution b with the concentration of 1 mg/mL; and (3) uniformly coating 2 mu L of mixed enzyme solution on the working electrode area of the printed chip obtained in the step (3) after mixing the two in equal volumes, and drying at 4 ℃ for 5 hours to obtain the biosensor for detecting the benzenediol isomer.
The performance test of the chip hydroquinone isomer is carried out by adopting the differential pulse method function of the Shanghai Chenhua CHI660E electrochemical workstation, the voltage variation range is 0-0.8V, the amplification is 0.005V, and the three electrode contacts of the printed chip are respectively connected with the corresponding electrode wires on the electrochemical workstation. The detection sensitivity of the obtained sensing printing chip hydroquinone isomer is very high, and the detection sensitivity is respectively as follows: hydroquinone-23.76 muA.mM -1, catechol-37.93 muA.mM -1, resorcinol-31.35 muA.mM -1, detection limits as low as 30 nM, and linear ranges of 100 nM-500 muM. After the standard curve test is completed, the printed chip based on the encapsulated Co nitrogen doped carbon tube is stored in PBS buffer solution at 4 ℃ for 30 days, and the response signal is 97% of the initial signal, which indicates that the benzenediol isomer detection chip has excellent stability. The reliability of the detection of the print chip prepared in this example in a real lake water system was examined by a standard addition method, and the recovery rate of the print chip was 98.69% -103.54% and the relative standard deviation of the detection was 3.83% (n=3) for a system in which the concentrations of all three benzenediol isomers were 50 μm. The result shows that the chip can realize the accurate detection of the benzenediol isomer in complex real water, and has excellent anti-interference capability and wide application prospect.
Example 2
A preparation method of a benzenediol isomer detection chip comprises the following steps.
(1) Taking NiCl 2 as a metal source, weighing 10g, fully dissolving in 20mL of deionized water, and obtaining 0.5g/mL of clear solution A; dicyandiamide is used as a carbon source, 20g is weighed and dissolved in 20mL of deionized water to obtain 1g/mL of solution B. Mixing the A and the B, fully stirring to be uniform, and fully dehydrating at 80 ℃ until the mixture is completely dried to obtain Ni-dicyandiamide composite precursor powder.
(2) Weighing 5g of the Ni-dicyandiamide precursor in the step (1), paving the Ni-dicyandiamide precursor in a ceramic square boat, and placing the ceramic square boat in a tubular atmosphere furnace, wherein the inert atmosphere is nitrogen, and the gas flow rate is 15mL/min; setting the heating rate to 5 ℃/min, and carrying out cracking reaction for 6 hours at 600 ℃. After the reaction, collecting the obtained powder, dispersing the powder in 0.5M hydrochloric acid solution to remove redundant carbon sources and excessive unbound metal simple substances, continuously stirring for 8 hours, adding NaOH to adjust the pH of the mixed solution to be neutral, extracting the residual substances by a suction filtration mode, namely the nitrogen-doped carbon tubes for encapsulating Ni metal particles, and placing the carbon tubes in a vacuum drying oven at 100 ℃ for dehydration and drying for 12 hours, as shown in figure 1.
(3) Mixing the nitrogen-doped carbon tubes encapsulating the Ni metal particles in the step (2) with conductive carbon ink according to a ratio of 1:15 to obtain uniformly dispersed sensing slurry, and adding methanol to achieve optimal printing ink viscosity; the method comprises the steps of taking mixed conductive ink as working electrode ink, taking carbon ink as counter electrode ink, taking Ag/AgCl as reference electrode ink, uniformly filling and covering mesh holes of a screen printing plate, printing a specific electrode pattern on a PET bottom plate, and sequentially putting the PET bottom plate into ethanol and deionized water for soaking and flushing after drying to remove interfering substances attached to the surface.
(4) Preparing 5mg/mL laccase solution a and 10mg/mL carboxymethyl cellulose solution b; and (3) uniformly coating 20 mu L of mixed enzyme solution on the working electrode area of the printed chip obtained in the step (3) after mixing the two in equal volumes, and drying at 4 ℃ for 24 hours to obtain the biosensor for detecting the benzenediol isomer.
The performance test of the chip hydroquinone isomer is carried out by adopting the differential pulse method function of the Shanghai Chenhua CHI660E electrochemical workstation, the voltage variation range is 0-0.8V, the amplification is 0.005V, and the three electrode contacts of the printed chip are respectively connected with the corresponding electrode wires on the electrochemical workstation. The detection sensitivity of the obtained sensing printing chip hydroquinone isomer is very high, and the detection sensitivity is respectively as follows: hydroquinone-29.39 muA.mM -1, catechol-42.81 muA.mM -1, resorcinol-40.03 muA.mM -1, detection limits as low as 45 nM, and linear ranges of 100 nM-400 muM. After the standard curve test is completed, the printed chip based on the encapsulated Ni nitrogen-doped carbon tube is stored in PBS buffer solution at 4 ℃ for 30 days, and the response signal is 97% of the initial signal, which indicates that the benzenediol isomer detection chip has excellent stability. The reliability of the detection of the printing chip prepared in this example in a real lake water system was examined by a standard addition method, and the recovery rate of the printing chip was 99.21% -102.69% and the relative standard deviation of the detection was 4.55% (n=3) for a system in which the concentrations of all three benzenediol isomers were 50 μm. The result shows that the chip can realize the accurate detection of the benzenediol isomer in complex real water, and has excellent anti-interference capability and wide application prospect.
Example 3
A preparation method of a benzenediol isomer detection chip comprises the following steps.
(1) Cu (NO 3)2 is used as a metal source, 5g is weighed and fully dissolved in 20mL of deionized water to obtain a clear solution A of 0.25g/mL, melamine is used as a carbon source, 10g is weighed and dissolved in 20mL of deionized water to obtain a solution B of 0.5g/mL, the solution A and the solution B are mixed and fully stirred until being uniform, and the mixture is fully dehydrated at 80 ℃ until being fully dried to obtain the Cu-melamine composite precursor powder.
(2) Weighing 3g of the Cu-melamine precursor in the step (1), paving the precursor in a ceramic square boat, and placing the ceramic square boat in a tubular atmosphere furnace, wherein the inert atmosphere is helium, and the gas flow rate is 10mL/min; setting the heating rate to 3 ℃/min, and carrying out cracking reaction for 4 hours at 700 ℃. After the reaction, collecting the obtained powder, dispersing the powder in a 2M hydrochloric acid solution to remove redundant carbon sources and excessive unbound metal simple substances, continuously stirring for 5 hours, adding NaOH to adjust the pH of the mixed solution to be neutral, extracting the residual substances by a suction filtration mode, namely the nitrogen-doped carbon tubes for encapsulating Cu metal particles, and placing the carbon tubes in a vacuum drying oven at 100 ℃ for dehydration and drying for 12 hours, as shown in figure 1.
(3) Mixing the nitrogen-doped carbon tubes encapsulating the Cu metal particles in the step (2) with the conductive gold paste according to a ratio of 1:5 to obtain uniformly dispersed sensing paste, and adding methanol to achieve optimal printing ink viscosity; the method comprises the steps of taking mixed conductive ink as working electrode ink, taking carbon ink as counter electrode ink, taking Ag/AgCl as reference electrode ink, uniformly filling and covering mesh holes of a screen printing plate, printing a specific electrode pattern on a ceramic bottom plate, and sequentially putting the ceramic bottom plate into ethanol and deionized water for soaking and flushing after the ceramic bottom plate is dried to remove interfering substances attached to the surface.
(4) Preparing 2mg/mL laccase solution a and 5mg/mL chitosan solution b; and (3) uniformly coating 10 mu L of mixed enzyme solution on the working electrode area of the printed chip obtained in the step (3) after mixing the two in equal volumes, and drying at 4 ℃ for 16 hours to obtain the biosensor for detecting the benzenediol isomer.
The performance test of the chip hydroquinone isomer is carried out by adopting the differential pulse method function of the Shanghai Chenhua CHI660E electrochemical workstation, the voltage variation range is 0-0.8V, the amplification is 0.005V, and the three electrode contacts of the printed chip are respectively connected with the corresponding electrode wires on the electrochemical workstation. The detection sensitivity of the obtained sensing printing chip hydroquinone isomer is very high, and the detection sensitivity is respectively as follows: hydroquinone-39.39 mu A. MM -1, catechol-42.81 mu A. MM -1, resorcinol-40.03 mu A. MM -1, detection limits as low as 45 nM, and linear ranges of 100 nM-400 mu M. After the standard curve test is completed, the printed chip based on the encapsulated Ni nitrogen-doped carbon tube is stored in PBS buffer solution at 4 ℃ for 30 days, and the response signal is 97% of the initial signal, which indicates that the benzenediol isomer detection chip has excellent stability. The reliability of the detection of the printing chip prepared in this example in a real lake water system was examined by a standard addition method, and the recovery rate of the printing chip was 99.21% -102.69% and the relative standard deviation of the detection was 4.55% (n=3) for a system in which the concentrations of all three benzenediol isomers were 50 μm. The result shows that the chip can realize the accurate detection of the benzenediol isomer in complex real water, and has excellent anti-interference capability and wide application prospect.
Example 4
This example differs from example 1 in that the precursor cleavage reaction time is changed from 900 ℃ to 500 ℃ with the remaining conditions remaining unchanged. Experiments prove that the obtained cracking product cannot form a nitrogen-doped carbon tube structure of the packaged Co, but has irregular morphology. The sensing printing chip prepared based on the cracking product has no obvious response to hydroquinone and resorcinol, and the detection sensitivity of the catechol is only 3.42 mu A.mM -1, which fully proves that the nitrogen-doped carbon tube configuration of the packaging metal plays a key role in the simultaneous detection of three diphenol isomers.
Example 5
The difference between this example and example 2 is that the gas flow rate of the precursor cracking process was increased from 15mL/min to 30mL/min, with the remaining conditions unchanged. The obtained cracking product cannot form a nitrogen-doped carbon tube configuration of the encapsulated Co, but has a random morphology. The gas flow rate has a great influence on the product performance. The sensing printing chip prepared based on the cracking product has no obvious response to hydroquinone and resorcinol, and the detection sensitivity of the catechol is only 4.07 mu A.mM -1, which again shows that the nitrogen-doped carbon tube configuration of the packaging metal plays a key role in the simultaneous detection of three diphenol isomers.
Example 6
The difference between this example and example 2 is that the ratio of the nitrogen doped carbon tube encapsulating Ni in the sensing paste to the conductive carbon ink is 1:25, the remaining conditions remain unchanged. The detection sensitivity of the sensing printing chip hydroquinone isomer prepared based on the mixed sensing slurry is respectively as follows: hydroquinone-8.53 mu A.mM -1, catechol-9.21 mu A.mM -1, resorcinol-6.74 mu A.mM -1, a detection limit of 200 nM, and a linear range of 500 nM-500 mu M, and the performance of the chip is obviously reduced compared with that of the chip in the example 2, which shows that the detection performance of the content hydroquinone isomer of the nitrogen-doped carbon tube of the packaging metal in the conductive ink is obviously influenced.
Example 7
The difference between this example and example 2 is that the ratio of the nitrogen doped carbon tube encapsulating Ni in the sensing paste to the conductive carbon ink is 3:1, the remaining conditions remain unchanged. The mixed sensing paste cannot be adjusted to a proper viscosity and chip printing cannot be performed.
Example 8
The difference between this example and example 3 is that the volume of the mixed enzyme solution added dropwise to the surface of the working electrode was 40. Mu.L, and the remaining conditions were kept unchanged. The detection performance of the obtained sensing printing chip hydroquinone isomer is similar to that of the chip in the example 5, which shows that the excessive enzyme loading can cause the attenuation of detection signals, mainly due to the poor electron transmission capability of an enzyme layer.
Example 9
The difference between this example and example 3 is that Cu (NO 3)2 metal source is replaced by MnCl 2 and the rest of the conditions are kept unchanged. The detection performance of the obtained sensor printing chip hydroquinone isomer is relatively similar to that of the chip in example 3.
From the comparison of the detection performance of the sensor chip obtained in the above embodiment, it can be found that the nitrogen-doped carbon tube configuration of the packaging metal, the content of the packaging metal in the conductive printing ink and the loading amount of the active enzyme layer all have important influence on the detection result. Compared with the traditional carbon nano tube and metal nano particles, the novel nano material of the nitrogen doped carbon tube for encapsulating the metal can promote electrocatalytic activity due to the synergistic catalytic effect of the metal coated on the inner layer and the carbon nano tube coated on the outer layer, and is favorable for generating and transmitting catalytic electrons, so that obvious benzenediol isomeride response is shown in the electrochemical sensing process. Based on the above, the simulation calculation can also find that the adsorption rate and adsorption energy of the hydroquinone isomer of the nitrogen-doped carbon tube material for packaging the metal are obviously different from big to small, namely hydroquinone > catechol > resorcinol, so that the response signals of three benzenediol isomers can be distinguished, and the detection potentials are respectively hydroquinone, catechol and resorcinol from low to high, as shown in figure 2. Meanwhile, the intermediate state substances of the nitrogen doped carbon tube of the packaging metal and the three benzenediol isomers passing through the adsorption performance are compared, the intermediate state substances can be found to have the smallest energy with hydroquinone, the intermediate state substances formed with resorcinol have the largest energy, the difficulty degree of the material in identifying the three benzenediol isomers can be illustrated, and the material is also related to the detection potential and the signal peak position sequence.
In addition, the ratio of the conductive ink to the nitrogen-doped carbon tube in the sensor chip is also an important factor affecting the detection performance. The commercialized conductive ink not only plays a role in conducting electricity in a chip, but also provides bonding and adhesive force for the stable existence of the nano material on the chip, and the bonding and adhesive force is a compound formed by micron-sized particles, compared with a nitrogen-doped carbon tube of nano-sized packaging metal, the electrical conductivity and the electrocatalytic activity of the composite are obviously inferior, so that the improvement of the proportion of the nitrogen-doped carbon tube of the packaging metal is an important method for improving the detection performance. In example 6, the detection performance of hydroquinone isomer is obviously reduced compared with the chip of example 2 doped with normal proportion due to the excessive content of conductive carbon paste in the mixed ink. However, when the ratio of the nitrogen-doped carbon tube of the encapsulation metal to the conductive ink is greater than 1, the bonding effect of the conductive carbon paste is greatly weakened, resulting in the obtained chip and its non-uniformity, even failure to be molded.
In addition, the loading of the active enzyme layer is also an important factor affecting the detection performance. Although the excessive enzyme load can still maintain the signal resolving capability of the chip to three benzenediol isomers, the catalytic signal generated by the contact of the surface enzyme molecules and the object to be detected is not easy to be transmitted to the surface of the sensing slurry, so that the signal transmission and amplification effect of the sensing slurry cannot be exerted. Thus, an appropriate amount of enzyme loading can be ensured to produce an excellent signal response to the benzenediol.
In conclusion, the detection chip based on the encapsulated metal nitrogen-doped carbon tube prepared by the invention has excellent electrocatalytic activity and electron transfer efficiency, and can distinguish response signals of three benzenediol isomers. Under the optimal preparation condition, the detection performance of the sensing chip on three benzenediol isomers can be achieved: hydroquinone-39.39 mu A.mM-1, catechol-42.81 mu A.mM-1 and resorcinol-40.03 mu A.mM-1, the detection limit is as low as 45 nM, the linear range is 100 nM-400 mu M, and the accurate detection of the extremely low concentration of the benzenediol isomer can be realized. On the basis, the prepared sensing chip can be stored in PBS buffer solution at the temperature of 4 ℃ for 30 days, the response signal can still reach 97% of the initial signal, and meanwhile, the sensing chip also shows excellent reliability and pollution resistance in real water sample detection. In addition, the chip can ensure the stability of a detection signal and the sensitive response of hydroquinone isomer in continuous monitoring for up to 1000 hours, can maintain the signal response strength under the condition of large-angle bending, and shows excellent long-term stability.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the detection chip capable of simultaneously detecting three isomers of the benzenediol is characterized by comprising the following specific steps of:
(1) Preparation of nitrogen-doped carbon tube precursor
Dissolving soluble transition metal salt in deionized water to prepare A; dissolving or dispersing carbon-nitrogen organic matters in deionized water to prepare B; fully mixing and uniformly stirring the equal volumes A and B, and fully dehydrating at 80 ℃ until the equal volumes A and B are completely dried to obtain transition metal salt-carbon nitrogen organic compound precursor powder;
(2) Preparation of nitrogen doped carbon tubes
Placing transition metal salt-carbon nitrogen organic compound precursor powder in a calciner, carrying out high-temperature pyrolysis under an inert gas atmosphere, collecting the obtained powder after the reaction is finished, dispersing the obtained powder in a hydrochloric acid solution for continuous stirring, adding NaOH to adjust the pH value to be neutral, carrying out suction filtration, and then placing the obtained product in a vacuum drying oven for dehydration and drying to obtain the nitrogen-doped carbon tube for encapsulating the transition metal particles;
(3) Preparation of printed chips
Uniformly mixing nitrogen-doped carbon tubes encapsulating transition metal particles with conductive ink to obtain sensing slurry, adding a solvent to achieve printing viscosity to serve as working electrode ink, carbon ink serves as counter electrode ink, ag/AgCl serves as reference electrode ink, uniformly filling and covering mesh holes of a screen printing plate, printing on a substrate plate to obtain chips, drying, sequentially soaking and flushing in ethanol and deionized water, and removing interfering substances attached to the surface;
(4) Preparation of benzenediol isomer sensing electrode
Preparing laccase solution and enzyme crosslinking solution, uniformly coating the laccase solution and the enzyme crosslinking solution on the working electrode area of the chip in the step (3) after mixing in equal volume, and drying at 4 ℃ to obtain the biosensor for detecting the benzenediol isomer;
the three isomers of the benzenediol are hydroquinone, catechol and resorcinol.
2. The method for preparing a chip for simultaneously detecting three isomers of benzenediol according to claim 1, wherein the soluble transition metal salt in the step (1) is any one of CoCl 2、NiCl2、Cu(NO3)2、MnCl2; the concentration of A is 0.05-0.5g/mL; the carbon nitrogen organic matter is any one of melamine, dicyandiamide and urea, and the concentration of B is 0.15-1g/mL.
3. The method for preparing the chip for simultaneously detecting three isomers of benzenediol according to claim 1, wherein the cracking temperature in the step (2) is 600-900 ℃, the heating rate is 1-5 ℃/min, and the cracking time is 2-6h; the inert gas is any one of nitrogen, argon and helium, and the gas flow rate is 0.5-15mL/min; the concentration of the hydrochloric acid solution is 0.5-5M, and the dispersion time is 2-8h; the vacuum drying temperature was 100℃and the drying time was 12 hours.
4. The method for preparing the detection chip capable of simultaneously detecting three isomers of benzenediol according to claim 1, wherein the conductive ink in the step (3) is any one of carbon ink, silver paste and gold paste, and the mass ratio of the nitrogen-doped carbon tube for encapsulating the transition metal particles to the conductive ink is 1:15-1:1; the substrate plate is made of any one of conductive glass, PET and ceramic; the solvent is any one of methanol, ethanol and water.
5. The method for preparing a chip for simultaneously detecting three isomers of benzenediol according to claim 1, wherein the concentration of the laccase solution in the step (4) is 0.1-5mg/mL; the enzyme cross-linking agent is any one of glutaraldehyde, chitosan and carboxymethyl cellulose, and the concentration is 1-10mg/mL; the coating amount of each working electrode is 2-20 mu L; the drying time is 5-24h.
6. Use of a chip prepared by the method of any one of claims 1-5 in simultaneous detection of three isomers of benzenediol.
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