CN102320589B - 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 preparation and the application of immobilization laccase sensor.
Background technology
The laccase sensor 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 sensor of studying high sensing capabilities (such as highly sensitive, fast response, wide detection line and low detection line etc.) is of great significance in environmental monitoring and context of detection tool.
The Direct Electrochemistry enzyme electrodes is the enzyme molecule directly to be adsorbed be fixed to electrode surface, is redox active center and the electrode direct " interchange " of enzyme, can carry out quickly the electronics transmission.But enzyme has larger molecular weight usually, and the electric activity center of enzyme molecule is buried in the inside of molecule, and easily deforms even inactivation after electrode surface absorption, so be difficult to directly carry out transfer transport between enzyme and electrode.The Direct electrochemistry of enzyme that appears as of meso-porous carbon material provides new opportunity, owing to itself have good mechanical property, chemical stability 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 for enzyme, prevent the loss of biomolecules, can provide for the effective communication of electronics orderly nanochannel again, thereby provide wide prospect for preparing a series of high performance sensors.
Summary of the invention
The purpose of this invention is to provide the application of the biosensor of the preparation of ordered mesopore carbon (N-OMC) of doping nitrogen-atoms and immobilization laccase thereof.
The present invention has widely Research Prospects 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 occur, 80-120 ℃ of lower vacuum-drying 10-15h then;
2) ammonium persulphate of 2.0-4.0g is joined 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 lower 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 to remove the silicon template with the hydrofluoric acid dips of 35wt%-45wt%, and then filter, use respectively ethanol, deionized water wash, 80-120 ℃ is dried to constant weight and namely 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, adopt the filtering with microporous membrane of 0.22 μ m, remove acid solution, to slightly acidic, at last 50-70 ℃ of lower vacuum-drying, obtain the N-OMC of acidifying with deionized water wash;
2) pre-treatment of electrode
Be the aluminum oxide (Al of 0.5～2.0 μ m with particle diameter
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
Dimethyl formamide (DMF) solution of preparation 0.2-1.5mg/ml N-OMC is got 10 μ L solution and is added drop-wise to the Au electrode surface that the diameter of handling well is 2mm, namely gets N-OMC after the drying at room temperature and modifies Au electrode, i.e. N-OMC/Au electrode;
4) N-OMC immobilization laccase
The N-OMC that gets the 2-5mg acidifying joins laccase (Lac) solution of the 0.5-1.5mg/mL that 2-5mL prepared, and 3-6 ℃ of lower stirring 20-25h fully being fixed on the solid support material with the assurance enzyme, centrifugation just obtains the immobilized laccase of N-OMC behind the removal supernatant liquid.
The gold electrode that the N-OMC immobilization laccase of preparation is modified is used for the electronics that the environment protection aspect detected/monitored 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, operating voltage 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 K_m
Be 6.4293 μ M, the time is about 23s, detects to be limited to 0.159 μ M (S/N=3); In addition, this laccase sensor 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 widely Research Prospects 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 N-OMC (a) of the acidifying of Fig. 2 embodiment 2 preparations and the scanning electron microscope (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
Embodiment 1
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 occur, then 100 ℃ of lower 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 lower vacuum-drying 24h; Be under the nitrogen atmosphere protection of 100mL/min at flow with the mixture of above-mentioned preparation, rise 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%, then filter, use respectively ethanol, deionized water wash, 100 ℃ are dried to constant weight and namely 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 preferably replica of SBA-15 structure.
Embodiment 2
800mg N-OMC is joined in the nitric acid mixing solutions of the vitriol oil of 90mL 98wt% and 30mL 68wt%, behind ultrasonication 20min, heated and stirred 1h in 60 ℃ of water-baths, adopt the filtering with microporous membrane of 0.22 μ m, remove acid solution, to slightly acidic, at last 60 ℃ of lower vacuum-dryings, obtain the N-OMC of acidifying with deionized water wash.The N-OMC that gets the 4mg acidifying joins in the Lac solution of the 1.0mg/mL that 4mL prepared, and at 4 ℃ of lower 24h of stirring guaranteeing fully being fixed on the solid support material of enzyme, centrifugation just obtains the immobilized laccase of N-OMC after removing supernatant liquid.The acidifying N-OMC and the immobilized laccase of N-OMC that make are done scanning electronic microscope (SEM) analysis, as shown in Figure 2, can find out and add before the enzyme, the surface of the N-OMC of acidifying is very loose, after adding laccase, the surface of material becomes tightr, 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% polyvinyl alcohol (PVA) solution that the mixture of the immobilized laccase of N-OMC of preparation among the embodiment 2 and 4mL are equipped with in advance mixes, the Lac+N-OMC/PVA solution of preparation 1.0mg/ml, then get this mixed solution 10 μ L with micropipet and cover equably the Au electrode of anticipating, leave standstill 2h under the room temperature, namely 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) is to electrode, saturated calomel electrode is reference electrode, take the N-OMC+Lac/PVA/Au electrode as working electrode, set operating voltage and carry out cyclic voltammetry scan for-0.2-0.9V.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, obvious redox reaction does not occur on the laccase electrode; And after adding pyrocatechol, near 0.3V, can see a pair of obvious redox peak, illustrate that namely 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 at the N-OMC carrier.
Embodiment 4
Electro-chemical test adopts three electrode test systems: Pt silk (diameter is 1mm) is that saturated calomel electrode is reference electrode to electrode, take the N-OMC+Lac/PVA/Au electrode as working electrode, sets operating voltage+0.45V and carries out cyclic voltammetry scan.Response current in liquid at the bottom of the different concns pyrocatechol of the lower mensuration of relative saturation mercurous chloride electrode current potential (SCE) modified electrode 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 sensor is 0.39～9.35 μ M, selection sensitivity is 0.09659A/M (n=26), the selection sensitivity of the laccase electrode that N-OMC modifies is very high, and this illustrates the electronics transfer rate that has improved N-OMC of mixing of nitrogen-atoms, and nitrogen-atoms improved the combination of mesoporous carbon and laccase, improved the stability of sensor.The slope of gained straight line and intercept can obtain the apparent K_m of N-OMC+Lac/PVA/Au electrode from 1/I-1/C figure
Be 6.4430 μ M.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 signal to noise ratio, therefore the N-OMC+Lac/PVA/Au laccase sensor 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 (1)
1. the ordered mesopore carbon of the nitrogen-atoms that mixes is characterized in that in the preparation method of immobilization laccase sensor:
(1) preparation method of the ordered mesopore carbon of doping nitrogen-atoms:
1) 0.3-0.8g SBA-15 and purified petroleum benzin amine are joined in the 500mL0.5-1.2M 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 occur, 80-120 ℃ of lower vacuum-drying 10-15h then;
2) ammonium persulphate of 2.0-4.0g is joined stir in the 40-60mL1M hydrochloric acid to dissolving evenly, then it is added in the first step dry mixture, make aniline polymerization complete, then vacuum-drying 20-25h under 35 ° of C-50 ° of C;
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 C carbonization 6-10h with the temperature rise rate of 3-10 ° of C/min;
4) product that obtains is spent the night to remove the silicon template with the hydrofluoric acid dips of 35wt%-45wt%, and then filter, use respectively ethanol, deionized water wash, 80-120 ℃ is dried to constant weight namely obtain the mixing ordered mesopore carbon of nitrogen-atoms;
(2) ordered mesopore carbon of doping nitrogen-atoms is in the preparation method of immobilization laccase sensor:
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 C water-bath, adopt the filtering with microporous membrane of 0.22 μ m, remove acid solution, to slightly acidic, at last vacuum-drying under 50-70 ° of C obtains the ordered mesopore carbon of the doping nitrogen-atoms of acidifying with deionized water wash;
2) pre-treatment of electrode
With 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 solution and is added drop-wise to the Au electrode surface that the diameter of handling well is 2mm, namely gets N-OMC after the drying at room temperature and modifies Au electrode, the ordered mesopore carbon of the nitrogen-atoms that namely mixes/Au electrode;
4) the ordered mesopore carbon immobilization laccase of doping nitrogen-atoms
The ordered mesopore carbon of getting the doping nitrogen-atoms of 2-5mg acidifying joins the laccase solution of the 0.5-1.5mg/mL that 2-5mL prepared, and under 3-6 ° of C, stir 20-25h to guarantee fully being fixed on the solid support material of enzyme, the immobilized laccase of ordered mesopore carbon of the nitrogen-atoms that just obtains behind the supernatant liquid mixing is removed in centrifugation;
5) the N-OMC immobilization laccase is modified on the N-OMC+Lac/PVA/Au electrode, preparation immobilization laccase sensor.
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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 |
| 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 |
| 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 |
| CN105244510B (en) * | 2015-10-29 | 2017-06-27 | 南京理工大学 | Laccase Catalyzed electrochemical assembling polyaniline/graphene oxide compound modified electrode and its preparation method and application |
| 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 |
| CN108493754B (en) * | 2018-04-13 | 2021-01-05 | 吉林大学 | Application of mesoporous carbon spheres in preparation of saturable absorber |
| CN109081325A (en) * | 2018-08-10 | 2018-12-25 | 湖南大学 | A kind of preparation method of carbon material |
| 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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