CN102320589A - Preparation of ordered mesoporous carbon doped with nitrogen atom and preparation and application in immobilized laccase sensor thereof - Google Patents
Preparation of ordered mesoporous carbon doped with nitrogen atom and preparation and application in immobilized laccase sensor thereof Download PDFInfo
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Abstract
The invention relates to preparation of ordered mesoporous carbon doped with nitrogen atoms and preparation and an application in an immobilized laccase sensor thereof. SBA-15 and pure aniline are dissolved in hydrochloric acid with dissolved ammonium persulfate, and vacuum drying is performed; ammonium persulfate is dissolved in hydrochloric acid, and is added into the dried mixture, and vacuum drying is performed; the prepared mixture is carbonized with the protection of nitrogen atmosphere; the obtained product is soaked with 40 wt% hydrofluoric acid, filtered, washed, and dried to obtain a constant weight. The preparation of an N-OMC modified gold electrode comprises the following steps: buffing and polishing an Au electrode, flushing with distilled water, performing ultrasonic cleaning, performing activation for 10 cycles by cyclic voltammetry scan in a PBS solution with a pH of 5.0, adding the acidified N-OMC into a prepared 1.0-2.0 mg/mL laccase solution, stirring, performing centrifugation separation, and removing the supernatant. The N-OMC modified immobilized laccase gold electrode has good electrocatalytic activity, a wide linear response range, and high sensitivity and selectivity for catechol.
Description
Technical field
The present invention relates to mix nitrogen-atoms ordered mesopore carbon preparation and in the preparation and the application of immobilization laccase transmitter.
Background technology
The laccase transmitter can detect the toxic substances such as phenols, aromatic amine, organo phosphorous compounds and Dioxins in the waste water quickly and easily, has broad application prospects.Therefore, the laccase transmitter of studying high sensing capabilities (like highly sensitive, fast response, wide detection line and low detection line etc.) has crucial meaning in environmental monitoring and context of detection.
The Direct Electrochemistry enzyme electrodes is the enzyme molecule directly to be adsorbed be fixed to electrode surface, is the redox active center and the electrode direct " interchange " of enzyme, can carry out electron transport quickly.But enzyme has bigger molecular weight usually, and the electric activity center of enzyme molecule is buried in the inside of molecule, and after electrode surface absorption, is prone to deform even inactivation, so be difficult to directly carry out transfer transport between enzyme and electrode.The enzyme Direct Electrochemistry that appears as of meso-porous carbon material provides new opportunity; Owing to itself have good mechanical property, chemicalstability and biocompatibility; And the surface effects that its good electroactive and nano-scale produces; Make its surface atom have very high reactive behavior, can provide one can keep its bioactive good microenvironment, prevent the loss of biomolecules for enzyme; Can orderly nanochannel be provided for effective transmission of electronics again, thereby wide prospect be provided for preparing a series of high performance transmitters.
Summary of the invention
The purpose of this invention is to provide the application of biosensor of preparation and immobilization laccase thereof of the ordered mesopore carbon (N-OMC) of doping nitrogen-atoms.
The present invention has the extensive studies prospect in fields such as actual monitoring.
The present invention's step that the preparation method of ordered mesopore carbon (N-OMC) laccase biosensor of nitrogen-atoms comprises of mixing:
Synthesizing of the ordered mesopore carbon of doping nitrogen-atoms (N-OMC):
1) 0.3-0.8g SBA-15 and purified petroleum benzin amine are joined in the 500mL 0.5-1.2M hydrochloric acid that ammonium persulphate content is 0.5-0.8wt.%; Abundant stirring and dissolving; Purified petroleum benzin amine is well-dispersed in the mesoporous silicon; And make it in the duct of SBA-15, polymerization take place, 80-120 ℃ of following vacuum-drying 10-15h then;
2) with the ammonium persulphate of 2.0-4.0g join stir in the 40-60mL 1M hydrochloric acid to dissolving evenly, then it is added in the first step dry mixture, make aniline polymerization complete, then 35 ℃ of-50 ℃ of following vacuum-drying 20-25h;
3) with above-mentioned 2) mixture of preparation is under the nitrogen atmosphere protection of 90-110mL/min at flow, rises to 900-1000 ℃ of carbonization 6-10h with the temperature rise rate of 3-10 ℃/min;
4) product that obtains is spent the night removing the silicon template with the hydrofluoric acid dips of 35wt%-45wt%, and then filter, use ethanol, deionized water wash respectively, 80-120 ℃ is dried to constant weight and promptly obtains N-OMC.
The ordered mesopore carbon of doping nitrogen-atoms is in the preparation method of the biosensor of immobilization laccase:
1) acidification of N-OMC
The N-OMC of 700-900mg is joined in the 80-100mL vitriol oil (98wt.%) and 20-40mL nitric acid (68wt.%) mixing solutions; Behind ultrasonication 15-30min, heated and stirred 1h in 50-70 ℃ of water-bath adopts the filtering with microporous membrane of 0.22 μ m; Remove acid solution; To slightly acidic, 50-70 ℃ of following vacuum-drying, obtain acidifying N-OMC with deionized water wash at last;
2) pre-treatment of electrode
Using particle diameter is the aluminum oxide (Al of 0.5～2.0 μ m
2O
3) powder is gold (Au) electrode sanding and polishing on chamois leather, through the redistilled water flushing, ultrasonic after, placing pH is that 5.0 phosphate buffered saline buffer (PBS solution) is through cyclic voltammetry scan activation 10 circles;
3) preparation of N-OMC modified gold electrode
N (DMF) solution of preparation 0.2-1.5mg/ml N-OMC is got 10 μ L drips of solution and is added to the Au electrode surface that the diameter of handling well is 2mm, promptly gets N-OMC after the drying at room temperature and modifies Au electrode, i.e. N-OMC/Au electrode;
4) N-OMC immobilization laccase
Get laccase (Lac) solution that 2-5mg acidifying N-OMC joins the 0.5-1.5mg/mL that 2-5mL prepared; And 3-6 ℃ of following stirring 20-25h fully being fixed on the solid support material with the assurance enzyme; Spinning just obtains the immobilized laccase of N-OMC behind the removal supernatant liquid.
The electronics that the gold electrode of the N-OMC immobilization laccase modification for preparing is used for environment protection aspect detection/monitoring toxic substance.
The gold electrode that N-OMC immobilization laccase of the present invention is modified can demonstrate good Direct Electrochemistry behavior; 25 ± 2 ℃ of room temperatures; The phosphate buffer soln of pH=5.0; WV is+experiment condition of 0.45V vs SCE under, the gold electrode (N-OMC+Lac/PVA/Au electrode) that the N-OMC immobilization laccase is modified shows good sensing capabilities, its linear detection range to the substrate pyrocatechol is 0.39～9.35 μ M; Selection sensitivity is 0.09659A/M (n=26); Apparent Michaelis-Menton constant
is 6.4293 μ M, and the time is about 23s, detects to be limited to 0.159 μ M (S/N=3); In addition, this laccase transmitter also has good repeatability and stable.Therefore, the ordered mesopore carbon N-OMC of doping nitrogen-atoms is expected to become a kind of material of novel immobilized enzyme, has the extensive studies prospect in fields such as actual monitoring.
Description of drawings
The transmission electron microscope photo of the ordered mesopore carbon (N-OMC) of the doping nitrogen-atoms of Fig. 1 embodiment 1 preparation (a) is parallel to the hole direction of principal axis, (b) perpendicular to the hole direction of principal axis.
The acidifying N-OMC (a) of Fig. 2 embodiment 2 preparations and the sem photograph of N-OMC+Lac (b).
The CV curve of the N-OMC+Lac/PVA/Au electrode of Fig. 3 embodiment 3 preparation in not containing pyrocatechol (a) and the pH=5.0PBS damping fluid that contains 0.05mM pyrocatechol (b): sweep speed and be 50mV/s.
The timing current-responsive curve (a) of the N-OMC+Lac/PVA/Au electrode of Fig. 4 embodiment 4 and steady state current response curve (b).
The catalytic response electric current of the N-OMC+Lac/PVA/Au electrode of Fig. 5 embodiment 4-concentration relationship curve (a) and Lineweave-Burk curve (b) :+0.45V vs SCE.
Embodiment
0.5g SBA-15 and 2.5g purified petroleum benzin amine are joined in the 500mL 1M hydrochloric acid that ammonium persulphate content is 0.6wt.%; Abundant stirring and dissolving; Purified petroleum benzin amine is well-dispersed in the mesoporous silicon, and makes it in the duct of SBA-15, polymerization take place, then 100 ℃ of following vacuum-drying 12h; With the ammonium persulphate of 3.0g join stir in the 50mL 1M hydrochloric acid to dissolving evenly, then it is added in the dry mixture of front, make aniline polymerization complete, then at 40 ℃ of following vacuum-drying 24h; With the mixture of above-mentioned preparation is under the nitrogen atmosphere protection of 100mL/min at flow, rises to 950 ℃ of carbonization 6h with the temperature rise rate of 5 ℃/min; At last, the product that obtains is spent the night to remove the silicon template with the hydrofluoric acid dips of 40wt%, filter then, use ethanol, deionized water wash respectively, 100 ℃ are dried to constant weight and promptly obtain N-OMC.The N-OMC that makes is done transmission electron microscope (TEM) analysis, as shown in Figure 1, in the direction that is parallel to the hole axle; Can see that the hole is the hexagonal structure of rule; The aperture is approximately 4.2nm, in the direction perpendicular to the hole axle, can see that the orderly linearity in duct arranges; Form the sequential 2 D hexagonal meso-hole structure of uniform and ordered, N-OMC is a SBA-15 structure replica preferably.
800mg N-OMC is joined in the nitric acid mixing solutions of the vitriol oil and 30mL 68wt% of 90mL 98wt%; Behind ultrasonication 20min, heated and stirred 1h in 60 ℃ of water-baths adopts the filtering with microporous membrane of 0.22 μ m; Remove acid solution; To slightly acidic, 60 ℃ of following vacuum-dryings, obtain acidifying N-OMC with deionized water wash at last.Get in the Lac solution that 4mg acidifying N-OMC joins the 1.0mg/mL that 4mL prepared, and stir 24h down guaranteeing fully being fixed on the solid support material of enzyme at 4 ℃, spinning just obtains the immobilized laccase of N-OMC after removing supernatant liquid.Acidifying N-OMC that makes and the immobilized laccase of N-OMC are done sem (SEM) analysis, as shown in Figure 2, can find out to add before the enzyme; The surface of acidifying N-OMC is very loose; After adding laccase, it is tightr that the surface of material becomes, and proves that laccase loads in the duct of N-OMC.
With the uniform Al of particle diameter
2O
3Powder is Au electrode sanding and polishing on chamois leather, through the redistilled water flushing, ultrasonic after, placing pH is that 5.0 PBS solution is through cyclic voltammetry scan activation 10 circles.0.1% Z 150PH (PVA) solution that mixture and the 4mL of the immobilized laccase of N-OMC of preparation among the embodiment 2 is equipped with in advance mixes; The Lac+N-OMC/PVA solution of preparation 1.0mg/ml; Get this mixed solution 10 μ L with micropipet then and cover the Au electrode of anticipating equably; Leave standstill 2h under the room temperature, promptly obtain the Lac+NOMC/PVA/Au electrode.
The N-OMC+Lac/PVA/Au electrode that makes is not being contained pyrocatechol and containing the CV tracing analysis of doing respectively in the pH=5.0PBS damping fluid of 0.05mM pyrocatechol.Electro-chemical test adopts three electrode test systems to be: platinum (Pt) silk (diameter is 1mm) be a counter electrode, and SCE is a reference electrode, is working electrode with the N-OMC+Lac/PVA/Au electrode, set WV to be-0.2-0.9V carries out cyclic voltammetry scan.The result shows; The N-OMC+Lac/PVA/Au electrode has significantly different in not containing the PBS damping fluid of pyrocatechol and the pH=5.0 that contains the 0.05mM pyrocatechol; When not containing the pollution substance pyrocatechol in the solution to be measured, tangible redox reaction does not take place on the laccase electrode; And after adding pyrocatechol; Near 0.3V, can see a pair of tangible redox peak; Explain that promptly pyrocatechol carries out direct electrochemical reaction at the modified electrode surface energy; Prove that simultaneously immobilization material has good biocompatibility, laccase keeps good electro catalytic activity on the N-OMC carrier.
Embodiment 4
Electro-chemical test adopts three electrode test systems: Pt silk (diameter is 1mm) is a counter electrode, and SCE is a reference electrode, is working electrode with the N-OMC+Lac/PVA/Au electrode, sets WV+0.45V and carries out cyclic voltammetry scan.Response current at the bottom of relative saturation mercurous chloride electrode current potential (SCE) is measured the different concns pyrocatechol of modified electrode down in the liquid is done response current-concentration curve and Lineweave-Burk curve.Shown in Fig. 4 and 5.
The result shows; The linear response range of N-OMC+Lac/PVA/Au transmitter is 0.39～9.35 μ M; Selection sensitivity is 0.09659A/M (n=26), and the selection sensitivity of the laccase electrode that N-OMC modifies is very high, and this explains the electron transport speed that has improved N-OMC of mixing of nitrogen-atoms; And nitrogen-atoms improved combining of mesoporous carbon and laccase, improved the stability of transmitter.Can to obtain the apparent Michaelis-Menton constant
of N-OMC+Lac/PVA/Au electrode be 6.4430 μ M for gained collinear slope and intercept from 1/I-1/C figure.Detectability can be tried to achieve by formula 3 σ b/m; M refers to the inverse of 1/I-1/C figure cathetus slope; σ b refers to the standard deviation of blank signal under certain SNR; Therefore the N-OMC+Lac/PVA/Au laccase transmitter that calculates structure is respectively 0.159 μ M (S/N=3) to the detectability of pyrocatechol, and the time of response is 23s.
Claims (3)
1. the preparation of the ordered mesopore carbon of the nitrogen-atoms that mixes is characterized in that step is following:
1) 0.3-0.8g SBA-15 and purified petroleum benzin amine are joined in the 500mL 0.5-1.2M hydrochloric acid that ammonium persulphate content is 0.5-0.8wt.%; Abundant stirring and dissolving; Purified petroleum benzin amine is well-dispersed in the mesoporous silicon; And make it in the duct of SBA-15, polymerization take place, 80-120 ℃ of following vacuum-drying 10-15h then;
2) with the ammonium persulphate of 2.0-4.0g join stir in the 40-60mL 1M hydrochloric acid to dissolving evenly, then it is added in the first step dry mixture, make aniline polymerization complete, then 35 ℃ of-50 ℃ of following vacuum-drying 20-25h;
3) with above-mentioned 2) mixture of preparation is under the nitrogen atmosphere protection of 90-110mL/min at flow, rises to 900-1000 ℃ of carbonization 6-10h with the temperature rise rate of 3-10 ℃/min;
4) product that obtains is spent the night removing the silicon template with the hydrofluoric acid dips of 35wt%-45wt%, and then filter, use ethanol, deionized water wash respectively, 80-120 ℃ is dried to constant weight promptly obtain the mixing ordered mesopore carbon of nitrogen-atoms.
2. the ordered mesopore carbon of the doping nitrogen-atoms of claim 1 is characterized in that in the preparation of immobilization laccase transmitter step is following:
1) acidification of the ordered mesopore carbon of doping nitrogen-atoms
The ordered mesopore carbon of the doping nitrogen-atoms of 700-900mg is joined in the 80-100mL vitriol oil (98wt.%) and 20-40mL nitric acid (68wt.%) mixing solutions; Behind ultrasonication 15-30min, heated and stirred 1h in 50-70 ℃ of water-bath adopts the filtering with microporous membrane of 0.22 μ m; Remove acid solution; To slightly acidic,, obtain the ordered mesopore carbon of acidifying doping nitrogen-atoms with deionized water wash at last 50-70 ℃ of following vacuum-drying;
2) pre-treatment of electrode
Use particle diameter be the aluminum oxide powder of 0.5～2.0 μ m with gold electrode sanding and polishing on chamois leather, through the redistilled water flushing, ultrasonic after, placing pH is that 5.0 phosphate buffered saline buffer is through cyclic voltammetry scan activation 10 circles;
3) preparation of the ordered mesopore carbon modified gold electrode of doping nitrogen-atoms
The dimethyl formamide solution of preparation 0.2-1.5mg/ml N-OMC is got 10 μ L drips of solution and is added to the Au electrode surface that the diameter of handling well is 2mm, promptly gets N-OMC after the drying at room temperature and modifies Au electrode, the ordered mesopore carbon of the nitrogen-atoms that promptly mixes/Au electrode;
4) the ordered mesopore carbon immobilization laccase of doping nitrogen-atoms
The ordered mesopore carbon of getting 2-5mg acidifying doping nitrogen-atoms joins the laccase solution of the 0.5-1.5mg/mL that 2-5mL prepared; And 3-6 ℃ of following stirring 20-25h fully being fixed on the solid support material with the assurance enzyme; The immobilized laccase of ordered mesopore carbon of the nitrogen-atoms that just obtains behind the supernatant liquid mixing is removed in spinning.
3. the ordered mesopore carbon of the doping nitrogen-atoms of claim 2 is characterized in that being used for the electronics of environment protection aspect detection/monitoring toxic substance in the immobilization laccase application of sensor.
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| CN102583319A (en) * | 2012-02-28 | 2012-07-18 | 中国科学院长春应用化学研究所 | Nitrogen-doped porous carbon material and preparation method thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
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| CN102583319B (en) * | 2012-02-28 | 2014-02-12 | 中国科学院长春应用化学研究所 | Nitrogen-doped porous carbon material and preparation method thereof |
| CN104003368B (en) * | 2014-05-06 | 2016-05-11 | 北京理工大学 | A kind of porous phosphorus-nitrogen co-doped material with carbon element and preparation method thereof |
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
| CN104003367B (en) * | 2014-05-06 | 2016-02-24 | 北京理工大学 | A kind of phosphorus-nitrogen exotic atom doped porous carbon material and synthetic method thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN105244510A (en) * | 2015-10-29 | 2016-01-13 | 南京理工大学 | Laccase catalyzed electrochemical assembly polyaniline / graphene oxide composite modified electrode and preparation method and application thereof |
| CN106083589A (en) * | 2016-06-14 | 2016-11-09 | 常州大学 | A kind of process for catalytic synthesis of senior β ketone ester |
| CN106083589B (en) * | 2016-06-14 | 2019-03-22 | 常州大学 | A kind of nitrogen-containing ordered mesopore carbon material catalyst synthesizes the application in advanced 'beta '-ketoester in transesterification |
| CN108493754A (en) * | 2018-04-13 | 2018-09-04 | 吉林大学 | A kind of application of mesoporous carbon spheres in making saturable absorber |
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| CN115436446A (en) * | 2022-10-26 | 2022-12-06 | 南京工业大学 | Preparation method and application of hydroquinone isomeride detection chip |
| CN115436446B (en) * | 2022-10-26 | 2024-08-02 | 南京工业大学 | Preparation method and application of benzenediol isomer detection chip |
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