CN1837809A - Sensor for detecting phenolic substance in compost and detection method thereof - Google Patents
Sensor for detecting phenolic substance in compost and detection method thereof Download PDFInfo
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- CN1837809A CN1837809A CNA2006100315064A CN200610031506A CN1837809A CN 1837809 A CN1837809 A CN 1837809A CN A2006100315064 A CNA2006100315064 A CN A2006100315064A CN 200610031506 A CN200610031506 A CN 200610031506A CN 1837809 A CN1837809 A CN 1837809A
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Abstract
This invention relates to a sensor for detecting phenolic substance in compost and detection method thereof. With the carbon paste electrode modified with laccase-Fe3O4 magnetic nano grain as the work electrode to detect the response current variation of compost leachate in tri-electrode electrolytic bath; with given regression equation that is linear for hydroquinone of 1*10-7~1.375*10-4M and pyrocatechin of 5*10-8~2.75*10-4M, and computing the phenol content in compost. This invention is faster than HPLC and overcomes the defects in spectrophotometry, and has wide application for domestic garbage compost control system.
Description
Technical field
The present invention relates to the phenol content detecting method, be specifically related to the biosensor assay of aldehydes matter in the compost complication system.
Background technology
Aldehydes matter is extensive organic chemical industry's very important base stock of industry and accessory substance, extensively exists in environment, is difficult to be had high toxicity by biology or non-biodegradation.As the objectionable impurities of generally acknowledging, phenol has very big influence to health and environment.In the producing fertilizer from refuse in daily life system, have multiple phenolic comp ' ds pollution, plurality of enzymes such as the oozy lignin peroxidase of natural microorganisms flora, manganese peroxidase, laccase and polyphenol oxidase all can the catalysis aldehydes matter in the compost detoxifcation and oxidation.Therefore, to the detection of the aldehydes matter in the composting process, can implement Monitoring and Controlling to environmental pollutants.
At present, adopt the more methods such as spectrophotometric method, high performance liquid chromatography (HPLC), vapor-phase chromatography that have to detect for the phenol Determination on content.Detect with spectrophotometric method, owing to, limited its accuracy and usable range the requirement of substrate turbidity and the influence of light interfering material; Adopt the liquid and gas chromatography to detect, need before the detection sample separation, detachment process needs pre-service usually, and is more loaded down with trivial details and consuming time, and detecting instrument costliness relatively, and inconvenience is in addition carried, and can not detect in real time.Therefore studying a kind of phenol assay that is adapted in the composting process control is the problem of needing solution badly.
Summary of the invention
The present invention is intended to use electrochemical principle, a kind of amperometric biosensor of measuring phenol content is provided, to improve sensitivity and the antijamming capability that aldehydes matter is measured, so that be applied to better in the producing fertilizer from refuse in daily life processing, solve the real time on-line monitoring problem in the composting process control system.
The present invention is achieved through the following technical solutions the foregoing invention purpose.
A kind of sensor that detects aldehydes matter in the compost, be in the carbon paste 1 at 8mm place, distance carbon paste electrode surface, to imbed magnet 2, electrode is after polishing, cleaning, 3 of the crosslinked bodies of laccase-magnetic nanoparticle getting capacity are coated in electrode surface, make the laccase sensor rinse out not the crosslinked body of absorption with phosphate buffered solution after.
The crosslinked body 3 of laccase-magnetic nanoparticle is at preparation Fe
3O
4Adding ethyl orthosilicate and aminopropyl trimethoxysilane are finished amino silaneization behind the gelatinous precipitate, be suspended in again to stir in the glutaraldehyde and make aldehyde radical core/shell type magnetic nanoparticle, then laccase and magnetic nanoparticle are joined by 1: 50 mass ratio in the phosphate buffered solution of pH7.0,1/15M and stirred 12 hours, clean several times suction filtration drying with phosphate buffered solution again.
The method of aldehydes matter is in being connected to the electrolytic cell of three-electrode system in the sensor compost, is contrast electrode with the saturated calomel electrode, and the platinized platinum electrode is to electrode, to have modified laccase-Fe
3O
4The carbon paste electrode of the crosslinked body of magnetic nanoparticle is a working electrode, measure with chronoamperometry, regulate the pH value to 5.5 of the compost leaching solution that contains phenol earlier with the phosphate buffered solution of 1/15M, measuring the response current of sensor under reduction potential-0.232V changes, equation of linear regression according to p-dihydroxy-benzene and catechol content and electric current variation foundation calculates phenol content in the compost leaching solution, and the equation of linear regression that p-dihydroxy-benzene content and electric current change is:
y＝(0.2118±0.0045)x+(0.9834±0.2496)
Y is the value (μ A) that electric current changes, and x adds p-dihydroxy-benzene concentration (μ M).The range of linearity of p-dihydroxy-benzene is 1 * 10
-7～1.375 * 10
-4M detects lower limit and reaches 3 * 10
-10M, r
2Be 0.9933.
The equation of linear regression that catechol content and electric current change is:
y＝(0.1581±0.0025)x+(0.7702±0.2764)
Y is the value (μ A) that electric current changes, and x adds catechol concentration (μ M).The range of linearity of catechol is 5 * 10
-8～2.75 * 10
-4M detects lower limit and reaches 5 * 10
-8M, r
2Be 0.9953.
Be described in further detail the present invention below in conjunction with accompanying drawing:
Description of drawings
The carbon paste electrode structure that Fig. 1 modifies with the crosslinked body of laccase-magnetic nanoparticle;
1, carbon paste 2, magnet
3, the crosslinked body 4 of laccase-magnetic nanoparticle, pvc pipe
5, promotion plug 6, electric wire
The mechanism of Fig. 2 laccase redox phenol; QH wherein
2Represent phenol, Q
OxRepresent the oxidation product of phenol;
Fig. 3 measures the grading current response that adds p-dihydroxy-benzene in the compost leaching solution with chronoamperometry;
The linear regression graph that Fig. 4 p-dihydroxy-benzene content and electric current change;
The linear regression graph that Fig. 5 catechol content and electric current change;
Laccase (laccase, EC1.10.3.2) be the polyphenol oxidase that contains copper ion, contain four copper ions in each laccase protein molecular, comprise an I type copper atom, be the single electron acceptor, and amino acid residue is combined into the monokaryon center, an II type copper atom, also be the single electron acceptor, consist of three nuclear centers with two III type copper atoms; Two III type copper atoms are double electron acceptors, form the ion pair of coupling. Copper ion is the catalytic active center of laccase, is the decisive factor of laccase performance catalytic activity. Laccase is the one-electron oxidation reductase, but more than 250 kind of substrate of catalytic oxidation, wherein phenol and derivative thereof account for the over half of sum, and along with the substituent kind of phenols substrate, number are different with the position on aromatic ring, the catalytic activity of laccase is also variant. Catalytic oxidation is mainly manifested in the synergy of four copper ions in the generation of substrate free radical and the laccase molecule. In Laccase Catalyzed phenols substrate reactions, phenol is transferred to I type copper atom with electronics, by amino acid ligand electronics is passed to three nuclear sites, and the enzyme molecule of reduction-state shifts by the quadrielectron and passes to O2, the phenol that loses electronics becomes the quinone free radical, forms oxidation product, O by radical reaction again2Then be reduced to water. Whole course of reaction needs continuous one-electron oxidation to be used for satisfying the abundant reduction of laccase.
Laccase is mainly produced by fungus secretions such as some higher plants such as lacquer tree and whiterot fungis, and some bacterium also can produce laccase. In compositing system, also there are the many dominant bacterias that can secrete laccase, such as Phanerochaete chrysosporium (Phanerochaete chrysosporium), simple mould (Penicillium simplicissimum) etc. Laccase is ectoenzyme, oxidation to substrate has nonspecific characteristics, have quite widely Substratspezifitaet and preferably stability, oxygen to directly oxidize in can catalytic air decomposes compound and their derivatives such as phenols, arylamine class and carboxylic acids, also has in addition steroid hormone, biochrome, metallorganic and some non-phenolic compounds. Therefore, utilize laccase can prepare sensitive stable phenol sensor to the catalytic action of aldehydes matter, realize the real-time online of aldehydes matter in the compositing system is measured.
In the process of preparation laccase and magnetic nanoparticle crosslinked, at first adopt the method for chemical coprecipitation to prepare Fe3O
4Colloid, its particle diameter are about 10nm. Then use the reagent such as ethyl orthosilicate and polyethylene glycol at Fe3O
4Pan coating one deck SiO2Shell, the magnetic nano-particle of formation core/shell type, it is shaped as sphere, and particle diameter is about 120nm. Again with aminopropyl trimethoxysilane with the nanoparticle surface amino silane, then with the amino reaction of glutaraldehyde with particle surface, the formation schiff base structure, thereby make the crosslinked magnetic particle surface that is fixed on of laccase. The magnetic nano-particle specific area is very large, and the adsorptive enzyme amount is higher, and make immobilized enzyme in solution with the abundant haptoreaction of substrate, electrochemical response is very sensitive.
Fill carbon paste in pvc pipe, and imbed the high energy Nd-Fe-B magnet steel, this kind magnet has the characteristics such as magnetic force is large, and volume is little. After making magnetic carbon paste electrode, get laccase and the Fe of capacity3O
4The magnetic nanoparticle crosslinked drips and is coated in electrode surface, forms magnetic absorption, thereby prepares the laccase sensor, and its structure is seen Fig. 1. With laccase and Fe3O
4Magnetic nanoparticle is crosslinked, reaches the effect of immobilised enzymes, strengthens Enzymic stability, the extending enzyme electrode life, and in 20 days, response current remains unchanged substantially; About 40 days, drop to 70% of initial communication electric current. Utilize paramagnetism, laccase-magnetic nanoparticle is adsorbed onto on the carbon paste electrode surface, be convenient to separate and regeneration, and simple to operate. When the response signal of enzyme sensor significantly reduces, can by upgrading electrode surface, again adsorb the activated laccase of tool and Fe3O
4The magnetic nanoparticle crosslinked reaches the purpose of regeneration. Be about to the promotion plug forward impelling of the rear end of electrode, extrude the mixed layer of the laccase of inactivation-magnetic-particle crosslinked and carbon paste, with 0.5 μ m Al2O
3It is bright and clean that powder is polished to electrode surface, forms new electrode surface, and then water flushing electrode surface is used 38%HNO more successively3, acetone, water cleans in ultrasonic wave, uses at last PBS (pH7.0) flushing again, naturally dries for subsequent use. The activated laccase of electrode adsorption tool and Fe through again processing3O
4The magnetic nanoparticle crosslinked is finished regeneration. Also can use the wash bottle purge sensor surface that distilled water is housed, the particle purge of magnetic field absorption is clean, again adsorb again the activated laccase of tool and Fe after naturally drying3O
4The magnetic nanoparticle crosslinked reaches the purpose of regeneration. Rear a kind of method is more simple and easy to do.
Aldehydes matter is seen Fig. 2 in the redox mechanism of sensor surface, and laccase is with O2With phenol be substrate, with the phenol catalytic oxidation. The oxide of phenol becomes phenol in the electrode reduction, and the generation current signal, thereby can detect specifically the concentration of phenol in the sample.
Take hydroquinones as substrate, the catalytic reaction equation is:
Take catechol as substrate, the catalytic reaction equation is:
The CHI660B electro-chemical systems that electrochemical gaging employing of the present invention Shanghai, Shanghai occasion China instrument company produces is connected with the three-electrode system in the 50ml electrolytic cell, controls and monitors. This three-electrode system is to have modified laccase-Fe3O
4The carbon paste electrode of magnetic nanoparticle crosslinked (diameter 8mm) is as working electrode (being basal electrode), and saturated calomel electrode is as reference electrode, and platinum plate electrode carries out stable measurement as to electrode. All working is all finished under room temperature (25 ℃).
The present invention has tested the content of aldehydes matter in the compost leaching solution take hydroquinones, catechol as substrate, has set up the linear relationship between curent change and hydroquinones, the catechol content. Fig. 3 is illustrated in the compost leaching solution take hydroquinones as example, under reduction potential-0.232V condition, adds the resulting curent change curve of 10 μ M hydroquinones at every turn.
Investigated the assaying reaction condition of hydroquinones, catechol, find to be 5～6 in PBS pH value scope under reduction potential-0.232V, hydroquinones concentration is 1 * 10-7～1.375×10
-4M, catechol concentration is 5 * 10-8～2.75×10
-4During M, electric current is more remarkable to the response ratio of hydroquinones, catechol. Optimum condition is in PBS (pH5.5), measures respectively the content of hydroquinones, catechol by curent change. The equation of linear regression of hydroquinones is:
y＝(0.2118±0.0045)x+(0.9834±0.2496)
Y is the value (μ A) that electric current changes, and x adds p-dihydroxy-benzene concentration (μ M).The range of linearity of p-dihydroxy-benzene is 1 * 10
-7～1.375 * 10
-4M detects lower limit and reaches 3 * 10
-10M.The linear regression curve is seen Fig. 4.
The equation of linear regression of catechol is:
y＝(0.1581±0.0025)x+(0.7702±0.2764)
Y is the value (μ A) that electric current changes, and x adds catechol concentration (μ M).The range of linearity of catechol is 5 * 10
-8～2.75 * 10
-4M detects lower limit and reaches 5 * 10
-8M.The linear regression curve is seen Fig. 5.
Be the contrast experiment with p-dihydroxy-benzene and catechol respectively.3 groups of compost leaching solution samples that contain phenol are measured with high performance liquid chromatography and laccase biosensor respectively.Under top condition, adopt chronoamperometry to measure the phenol concentration value that obtains through sensor, very approaching with the corresponding value that records with high performance liquid chromatography.
This assay method is applied in the middle of the compost treatment, not only measurement result and high performance liquid chromatography are very close but also operate quick, easy, highly sensitive, selectivity is good, renovation process is simple and easy to do, and can also overcome spectrophotometric method the interference problem of turbidity and light interfering material in the unvanquishable complication system, in the producing fertilizer from refuse in daily life control system fast, the online detection of phenol content cheaply provides technical support.
Embodiment
1, laccase-Fe
3O
4The preparation of the crosslinked body of magnetic nanoparticle
Under the nitrogen protection, with a certain amount of Fe that presses
2+: Fe
3+The FeCl of=1: 2 proportionings
2, FeCl
3After adding in the 38mL 0.4M hydrochloric acid dissolving, pour in the 375mL 0.7M ammoniacal liquor, strong agitation generates Fe
3O
4Gelatinous precipitate.Get 0.232g precipitation then, join in the 200mL n-propanol, add 5.36g PEG (polyglycol), 20mL H more successively after ultrasonic
2O, 10mL ammoniacal liquor and 1.2mL TEOS (ethyl orthosilicate), stir 24h, after separation, cleaning, the freeze drying, getting 0.5g is suspended in the 10mL methyl alcohol, add 0.5mL APTMS (aminopropyl trimethoxysilane), stirring at room 12h finishes silanization, is suspended in afterwards in 5mL 2.5% glutaraldehyde to stir, and promptly obtains aldehyde radical core/shell type magnetic nanoparticle.At 4 ℃, 0.01g laccase and 0.5g magnetic nanoparticle are joined 5mL by 1/15M Na then
2HPO
4And 1/15MKH
2PO
4Stir 12h in the phosphate buffered solution that is made into (pH7.0), finish crosslinked, clean 3 times with phosphate buffered solution (pH7.0) after the suction filtration drying, be suspended in the 1mL phosphate buffered solution (pH7.0).
2, the preparation of laccase sensor
At first in pvc pipe, fill carbon paste, its component is that mass ratio is 1.25: 1 graphite and a paraffin, apart from surperficial 8mm place, put into the high energy Nd-Fe-B magnet steel of 6.5mm * 1.5mm, form magnetic regions, and continue to fill carbon paste, make electrode surface have excellent conducting performance, and leave the carbon paste layer that upgrades regeneration usefulness.With 0.5 μ m Al
2O
3It is bright and clean that powder is polished to electrode surface, and water flushing electrode surface is used 38%HNO more successively then
3, acetone, water cleans in ultrasound wave, uses phosphate buffered solution (pH7.0) flushing at last again, dries standby naturally.The crosslinked liquid suspension of laccase-magnetic-particle of getting 60 μ L drips and is coated in electrode surface, and air drying 1 hour with phosphate buffered solution (pH7.0) flushing, removes the crosslinked body of loose laccase-magnetic-particle, places 4 ℃ of storages standby.
3, composting conditions
Concrete windrow composition is seen as follows: soil 218g, take a sample in being following 1m place, side top layer, Yue Lu Shandong, straw 2600
G, dining room residue 988g, wheat bran 52g, water percentage 51%.Windrow is mixed the laggard oxygen compost of acting charitably, and environment temperature remains on 30 ℃ (constant temperature water baths), and ventilation is 0.033m
3/ h.
4, compost leaching solution preparation
Get compost sample 10g and place conical flask, add 200mL distilled water, at 37 ℃ of 120min that vibrate down, speed 200r/min, with the centrifugal 5min of filtrate, 10000r/min, supernatant liquid filtering promptly obtain compost leaching solution after the filtration.
5, the demarcation of phenol
The typical curve of p-dihydroxy-benzene is to demarcate under top condition.Top condition is that (1/15M, pH5.5), reduction potential-0.232V adds certain density p-dihydroxy-benzene respectively to phosphate buffered solution, changes the concentration that can calculate p-dihydroxy-benzene in the cell according to response current.
The demarcating steps of catechol is the same, under top condition, adds certain density catechol respectively, changes the concentration that can calculate catechol in the cell according to response current.
6, the mensuration of phenol in the compost leaching solution
Adopt the method for timing electric current, to have modified laccase-Fe
3O
4The carbon paste electrode of the crosslinked body of magnetic nanoparticle is a basal electrode, the pH value of regulating the compost leaching solution contain phenol with phosphate buffered solution (1/15M) is to pH5.5, changes with the response current of sensor under reduction potential-0.232V and measures phenol content in the compost leaching solution.Identical sample is measured with Agilent 1100 high performance liquid chromatography, adopted H
2O, acetonitrile and acetate (88: 10: 2) are as moving phase, and flow velocity is 0.7mL/min, and ultraviolet spectrophotometer detects at wavelength 280nm place.The phenol content results that obtains is compared with sensor result, see the following form.
| Sample | Determinand | The concentration of phenol (μ M) | Relative error % | |
| Laccase biosensor | High | |||
| 1 | The p-dihydroxy-benzene catechol | 7.13 20.76 | 6.70 21.17 | 6.42 1.94 |
| 2 | The p-dihydroxy-benzene catechol | 11.87 29.77 | 12.53 29.57 | 5.27 0.07 |
| 3 | The p-dihydroxy-benzene catechol | 22.56 53.27 | 22.31 52.40 | 1.12 1.66 |
7, enzyme sensor regeneration
When the response signal of enzyme sensor significantly reduces,, extrude the crosslinked body of laccase-magnetic-particle of inactivation and the mixolimnion of carbon paste, with 0.5 μ m Al with the promotion plug forward impelling of the rear end of electrode
2O
3It is bright and clean that powder is polished to electrode surface, forms new electrode surface, with the method for step 2 electrode handled again, adsorbed and have active laccase and Fe then
3O
4The crosslinked body of magnetic nanoparticle is finished regeneration.
Claims (3)
1, a kind of sensor that detects aldehydes matter in the compost, it is characterized in that in the carbon paste (1) at 8mm place, distance carbon paste electrode surface, imbedding magnet (2), electrode is after polishing, cleaning, the crosslinked body of laccase-magnetic nanoparticle (3) of getting capacity drips and to be coated in electrode surface, makes the laccase sensor rinse out the crosslinked body of not absorption with phosphate buffered solution after.
2, the sensor of aldehydes matter in the detection compost according to claim 1, the crosslinked body of laccase-magnetic nanoparticle (3) are at preparation Fe
3O
4Adding ethyl orthosilicate and aminopropyl trimethoxysilane are finished amino silaneization behind the gelatinous precipitate, are suspended in to stir in the glutaraldehyde to make aldehyde radical core/shell type magnetic nanoparticle again, it is characterized in that laccase and Fe
3O
4Magnetic nanoparticle joins by 1: 50 mass ratio in the phosphate buffered solution of pH7.0,1/15M and stirred 12 hours, cleans several times with phosphate buffered solution again, the suction filtration drying.
3, the method for aldehydes matter is in being connected to the electrolytic cell of three-electrode system in a kind of sensor compost as claimed in claim 1, is contrast electrode with the saturated calomel electrode, and the platinized platinum electrode is to electrode, to have modified laccase-Fe
3O
4The carbon paste electrode of the crosslinked body of magnetic nanoparticle is a working electrode, measure with chronoamperometry, it is characterized in that regulating the pH value to 5.5 of the compost leaching solution that contains aldehydes matter with the phosphate buffered solution of 1/15M, measuring the response current of sensor under reduction potential-0.232V changes, equation of linear regression according to p-dihydroxy-benzene and catechol content and electric current variation foundation calculates phenol content in the compost leaching solution, and the equation of linear regression that p-dihydroxy-benzene content and electric current change is:
y＝(0.2118±0.0045)x+(0.9834±0.2496)
Y is the value (μ A) that electric current changes, and x adds p-dihydroxy-benzene concentration (μ M), and the range of linearity of p-dihydroxy-benzene is 1 * 10
-7～1.375 * 10
-4M detects lower limit and reaches 3 * 10
-10M, r
2Be 0.9933,
The equation of linear regression that catechol content and electric current change is:
y＝(0.1581±0.0025)x+(0.7702±0.2764)
Y is the value (μ A) that electric current changes, and x adds catechol concentration (μ M), and the range of linearity of catechol is 5 * 10
-8～2.75 * 10
-4M detects lower limit and reaches 5 * 10
-8M, r
2Be 0.9953.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101581694B (en) * | 2009-06-20 | 2012-05-09 | 西北师范大学 | Electrochemical detection method for quinhydrone |
| CN102632247A (en) * | 2012-04-20 | 2012-08-15 | 武汉大学 | Preparation method of load-type silver nano-composite material |
| CN101349700B (en) * | 2008-07-14 | 2012-12-26 | 湖南大学 | On-line detection method and detection system of hydroquinone in stockpile manure |
| CN103063728A (en) * | 2012-12-30 | 2013-04-24 | 南京师范大学 | Electrochemical method for simultaneous determination of tetrachlorocatechol and tetrachlorohydroquinone based on graphene/chitosan-modified electrode |
| CN104977339A (en) * | 2014-04-04 | 2015-10-14 | 浙江海洋学院 | Magnetic-nanoparticle-modification-based enzyme sensor used for detecting okadaic acid and preparation method of sensor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH559912A5 (en) * | 1971-09-09 | 1975-03-14 | Hoffmann La Roche | |
| US4145255A (en) * | 1977-02-25 | 1979-03-20 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method and device for the detection of phenol and related compounds |
| DE4342351A1 (en) * | 1993-12-11 | 1995-06-14 | Byk Gulden Italia Spa | Enzymatic amplification system for oxidn. and redn. of aminophenol |
| CN1156692C (en) * | 2001-10-12 | 2004-07-07 | 中国科学院长春应用化学研究所 | Process for preparing biologic sensor by embedding enzyme with composite titanium oxide sol-gel membrane |
| CN100335893C (en) * | 2004-12-23 | 2007-09-05 | 湖南大学 | Electrochemical determination method for peroxidase activity in compost |
| CN100393672C (en) * | 2005-06-15 | 2008-06-11 | 湖南大学 | Active additive for promoting agricultural waste material compost decomposition and its application |
-
2006
- 2006-04-18 CN CNB2006100315064A patent/CN100385234C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101349700B (en) * | 2008-07-14 | 2012-12-26 | 湖南大学 | On-line detection method and detection system of hydroquinone in stockpile manure |
| CN101581694B (en) * | 2009-06-20 | 2012-05-09 | 西北师范大学 | Electrochemical detection method for quinhydrone |
| CN102632247A (en) * | 2012-04-20 | 2012-08-15 | 武汉大学 | Preparation method of load-type silver nano-composite material |
| CN102632247B (en) * | 2012-04-20 | 2013-12-04 | 武汉大学 | Preparation method of load-type silver nano-composite material |
| CN103063728A (en) * | 2012-12-30 | 2013-04-24 | 南京师范大学 | Electrochemical method for simultaneous determination of tetrachlorocatechol and tetrachlorohydroquinone based on graphene/chitosan-modified electrode |
| CN104977339A (en) * | 2014-04-04 | 2015-10-14 | 浙江海洋学院 | Magnetic-nanoparticle-modification-based enzyme sensor used for detecting okadaic acid and preparation method of sensor |
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