CN100385234C - 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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- CN100385234C CN100385234C CNB2006100315064A CN200610031506A CN100385234C CN 100385234 C CN100385234 C CN 100385234C CN B2006100315064 A CNB2006100315064 A CN B2006100315064A CN 200610031506 A CN200610031506 A CN 200610031506A CN 100385234 C CN100385234 C CN 100385234C
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Abstract
The present invention relates to a biosensor for detecting phenol content in a compost system. The present invention adopts a carbon paste electrode modified with laccase-Fe3O4 magnetic nanometer particles as a working electrode to detect the response current variation in compost extract in a tri-electrode electrolytic cell; the phenol content in compost extract can be calculated with an established equation of linear regression of the variation of hydroquinone, pyrocatechol and current. The range of linear relation of the phenol content and the variation of the current in the present invention is that the hydroquinone is 1*10<-7 > to 1.375*10<-4 > M, and the pyrocatechol is 5*10<-8 > to 2.75*10<-4 > M. Compared with high-efficiency liquid chromatography, the present invention for detecting phenol content in the compost not only has the advantages of rapid operation, convenience and sensitivity, but also the present invention can overcome the problems of interference by turbidity and light disturbance materials existed in spectrophotometry for detecting in a complex system. The present invention can become a set of rapid phenol content detection technology with low cost in an urban waste 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, EC 1.10.3.2) is the polyphenol oxidase that contains copper ion, contains in each laccase protein molecular Four copper ions comprise an I type copper atom, are that single electron acceptor and amino acid residue are combined into the monokaryon center, An II type copper atom also is the single electron acceptor, consists of three nuclear centers with two III type copper atoms; Two III type copper are former Son is double electron acceptor, forms the ion pair of coupling. Copper ion is the catalytic active center of laccase, is laccase performance catalysis Active decisive factor. Laccase is one-electron oxidation reduction enzyme, but more than 250 kind of substrate of catalytic oxidation, wherein phenol and spreading out Biology accounts for the over half of sum, along with kind, the number of phenols substrate substituting group are different with the position on aromatic ring, and lacquer The catalytic activity of enzyme is also variant. Catalytic oxidation is mainly manifested in the generation of substrate free radical and the laccase molecule four The synergy of copper ion. In laccase catalysis phenols substrate reactions, phenol is transferred to I type copper atom with electronics, passes through ammonia The sour part of base passes to three nuclear sites with electronics, 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 the free radical reaction again2Then be reduced to water. Whole course of reaction Need 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 lacquer Enzyme. In compositing system, also there are the many dominant bacterias that can secrete laccase, such as the flat lead fungi of yellow archespore hair (Phanerochaete chrysosporium), simple mould (Penicillium simplicissimum) etc. Laccase is ectoenzyme, Oxidation to substrate has nonspecific characteristics, has quite widely Substratspezifitaet and preferably stability, can Oxygen to directly oxidize in the catalytic air decomposes compound and their derivatives such as phenols, arylamine class and carboxylic acid class, this Outer in addition steroid hormone, biological pigment, metal organic matter and some non-phenolic compounds. Therefore, utilize laccase to phenol The catalytic action of class material can prepare sensitive stable phenol sensor, and realization is real-time to aldehydes matter in the compositing system On-line determination.
In the process of preparation laccase and the crosslinked body of magnetic nanoparticle, at first adopt the method for chemical coprecipitation to prepare Fe3O
4Colloid, its particle diameter are about 10nm. Use then the reagent such as positive silester and polyethylene glycol at Fe3O
4One layer of SiO of pan coating2Shell, the magnetic nano-particle of formation core/shell type, it is shaped as sphere, and particle diameter is about 120nm. Use again ammonia Propyl trimethoxy silicane is with the nanoparticle surface amino silane, and then the amino with glutaraldehyde and particle surface reacts, Form schiff base structure, thereby make the crosslinked magnetic particle surface that is fixed on of laccase. The magnetic nano-particle specific area is very big, Absorption enzyme amount is higher, and makes the enzyme of fixingization fully contact reaction with substrate in solution, and electrochemical response is very sensitive.
Fill carbon paste in pvc pipe, and imbed the high energy Nd-Fe-B magnet steel, it is big that this kind magnet has magnetic force, volume is little wait special The point. After making magnetic carbon paste electrode, get laccase and the Fe of capacity3O
4The crosslinked body of magnetic nanoparticle drips and is coated in electrode The surface forms magnetic absorption, thereby prepares the laccase sensor, and its structure is seen Fig. 1. With laccase and Fe3O
4Magnetic Nano Particle is crosslinked, reaches the effect of immobilised enzymes, strengthens Enzymic stability, prolongs enzyme electrode service life, in 20 days, rings Induced current remains unchanged substantially; About 40 days, drop to 70% of initial communication electric current. Utilize paramagnetism, with laccase-Magnetic nanoparticle is adsorbed onto on the carbon paste electrode surface, is convenient to separate and regeneration, and also simple to operate. When enzyme sensor When the response signal significantly reduces, can be by upgrading electrode surface, absorption has active laccase and Fe again3O
4Magnetic The crosslinked body of nanometer particle reaches the purpose of regeneration. Be about to the promotion plug forward impelling of the rear end of electrode, extrude the laccase of inactivation-The mixing layer of the crosslinked body of magnetic-particle and carbon paste is with 0.5 μ m Al2O
3It is bright and clean that powder is polished to electrode surface, forms new electrode surface, and water flushing electrode surface is used 38%HNO more successively then3, acetone, water cleans in ultrasonic wave, Use again at last phosphate buffered solution (pH 7.0) flushing, naturally dry for subsequent use. Electrode adsorption through again processing has activity Laccase and Fe3O
4The crosslinked body of magnetic nanoparticle is finished regeneration. Also can use the wash bottle purge that distilled water is housed to pass Sensor surfaces, the particle purge of magnetic field absorption is clean, again adsorb again laccase and the Fe with activity after naturally drying3O
4The crosslinked body of magnetic nanoparticle 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 Oxygen Change. The oxide of phenol becomes phenol in the electrode reduction, and the generation current signal, thereby can detect out sample specifically The concentration of middle phenol.
Take hydroquinones as substrate, the catalytic reaction equation is:
Take catechol as substrate, the catalytic reaction equation is:
CHI660B electro-chemical systems and 50ml that electrochemical gaging of the present invention adopts Shanghai, Shanghai occasion China instrument company to produce Three-electrode system in the electrolytic cell is connected, and controls and monitors. This three-electrode system is to have modified laccase-Fe3O
4Magnetic The carbon paste electrode of the crosslinked body of nanometer particle (diameter 8mm) is as work electrode (being the substrate electrode), saturated calomel electrode conduct Reference electrode, 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, sets up Linearity relation between curent change and hydroquinones, the catechol content. Fig. 3 is illustrated in take hydroquinones as example In the compost leaching solution, under reduction current potential-0.232V condition, add the resulting curent change of 10 μ M hydroquinones at every turn Curve.
Investigated the assaying reaction condition of hydroquinones, catechol, find to be 5～6 in phosphate buffered pH value of solution value scope under reduction current 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 of hydroquinones, catechol. Best condition is at phosphoric acid In the salt buffer solution (pH 5.5), measure respectively the content of hydroquinones, catechol by curent change. Hydroquinones Equation of linear regression be:
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 1.2mLTEOS (ethyl orthosilicate), stir 24h, after separation, cleaning, the freeze drying, getting 0.5g is suspended in the 10mL methyl alcohol, add 0.5mLAPTMS (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 (pH 7.0), finish crosslinked, clean 3 times with phosphate buffered solution (pH 7.0) after the suction filtration drying, be suspended in the 1mL phosphate buffered solution (pH 7.0).
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 (pH 7.0) 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 (pH 7.0) 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 2600g, 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 pH 5.5, 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.
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. 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 is coated in electrode surface, make the laccase sensor rinse out not the crosslinked body of absorption with phosphate buffered solution after, wherein magnetic nanoparticle is 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 crosslinking chemical glutaraldehyde to make aldehyde radical core/shell type magnetic nanoparticle again.
2. the sensor of aldehydes matter in the detection compost according to claim 1 is characterized in that the crosslinked body of laccase-magnetic nanoparticle (3) is with 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 the 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 that electric current changes, and its unit is μ A, and x adds p-dihydroxy-benzene concentration, and its unit is 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 that electric current changes, and its unit is μ A, and x adds catechol concentration, and its unit is 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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Families Citing this family (5)
| 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 |
| 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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