CN101851586A - Fungus for efficiently decomposing synthetic dye and application thereof - Google Patents
Fungus for efficiently decomposing synthetic dye and application thereof Download PDFInfo
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- CN101851586A CN101851586A CN201010167953A CN201010167953A CN101851586A CN 101851586 A CN101851586 A CN 101851586A CN 201010167953 A CN201010167953 A CN 201010167953A CN 201010167953 A CN201010167953 A CN 201010167953A CN 101851586 A CN101851586 A CN 101851586A
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Abstract
The invention provides a whole set of engineering technology for preventing dyes from polluting the environment by a microbiological method for aiming at the deficiencies of a traditional related dye pollution and poisoning control technology, thereby effectively reducing the environmental pollution of the dyes such as anthraquinone dyes, azo dyes, triarylmethane dyes, phthalocyanine and the like and effectively protecting the environment. The invention is a cleaning engineering technology.
Description
Technical field
The invention belongs to environment protection, the technical field of preventing and remedying pollution, be specifically related to use microbial method efficiently to fall synthetic dyestuff method and uses thereof.
Background technology
1, the characteristics of dye discoloration
Synthetic dyestuff are water pollutants common in the printing and dyeing industrial waste water, component complexity, concentration height (COD is 1000～100,000 mg/L), colourity dark (500～500,000 times).Organic constituent in the waste water is a parent with aromatic hydrocarbons and heterogeneous ring compound mostly, and have the colour developing group (as-N=N-,-N=O) and polar group (as-SO
3Na ,-OH ,-NH
2).Also contain more raw material and byproduct in the waste water, as halogenide, nitro thing, aniline, phenols etc., and inorganic salt such as NaCl, Na
2SO4, Na
2S, also just like anthraquinone dye, azoic dyestuff, triarylmethane dye, phthalocyanine pigment etc., these dyestuff great majority have toxicity, mutagenesis, carcinogenic.
2, the decoloring method of waste water from dyestuff
Physico-chemical process and biological method may be used to the decolouring of waste water from dyestuff and handle, as flocculation sediment, absorption, ion-exchange, ultrafiltration, dialysis, chemical oxidation, photoxidation, electrolysis and bioremediation.Industrial method commonly used has methods such as flocculation sediment (air supporting), electrolysis, absorption, biological degradation, ion-exchange, membrane filtration ozonize, the difficulty in treatment of waste water from dyestuff at present: the one, and the COD height, and the BOD/COD value is less, biodegradability is poor; The 2nd, colourity height, and component complexity.Removal and the decolouring of COD have dependency, but the decolouring problem hard is bigger.Yet, be not widely used because there are problems such as cost height, length consuming time in these method great majority.At present, many researchs begin to focus on the microorganism aspect that has efficient decolorizing and decompose dyestuff.
This strain separating hangs tropical rain forest area, Luoshan in Hainan Province, we have studied the decoloring ability of Cladosporium cladosporioidesTXJ13021 to different chemical synthetic dyes such as orange G, tropeolin-D, sodium alizarinsulfonate, malachite green etc.At present also not about can the degrade report of above-mentioned dyestuff of Cladosporium cladosporioides TXJ13021, we utilize fungi Cladosporium cladosporioides TXJ13021 emphasis that sodium alizarinsulfonate and the orange two kinds of dyestuffs of methyl have been carried out degradation analysis, research pH value, carbon source, the influence of nitrogenous source to decolouring, find out the optimum decolorization condition of this bacterium, this fungi of expectation use is degraded and contains the trade effluent of sodium alizarinsulfonate or the relevant structure dyestuff with other of tropeolin-D.
Summary of the invention
Deficiency at existing relevant dye discoloration and murder by poisoning Prevention Technique of the present invention adopts microbial method to handle the pollution of degraded chemical synthetic dye, effectively protects environment, is a cleaning project.Can provide reference for environment protection correlative study person in addition.
1, the present invention obtains the microbial strains of strain energy efficient degradation dyestuff, and this microorganism is
Branch spore sample branch spore is mould,Latin name Cladosporium cladosporioides TXJ13021, be located away from Hainan Province and hang tropical rain forest area, Luoshan, be preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center, preservation date is in March, 2007, and preserving number is CGMCC No.1987.
2, optimization of the present invention is cultivated
Branch spore sample branch spore is mould,Cladosporium cladosporioides TXJ13021 optimal conditions and method.Wherein condition comprises:
(1) optimum culture medium prescription, carbon-nitrogen ratio are 5: 1～25: 1; Carbon source the best is a sucrose, is glucose secondly, starch, and concentration is 1～10%; Nitrogenous source can be ammonium nitrate, ammonium chloride, ammonium sulfate, urea 1～10%.
(2) optimum culture temperature is 28 ℃-32 ℃.
(3) the yeast culture optimum pH is pH4.0-pH6.0.
(4) cultivating cultural method is " two-stage thalline fermentation culture ".One-level thalline fermentation culture " seed " can be carried out pigment degraded viable bacteria body in a large number by above-mentioned culture medium prescription production; Secondary thalline fermentation culture, essence are the further enlarged culturing of thalline, take into account the dyestuff degradation and decolorization simultaneously.
In a specific embodiment, with murphy juice liquid of glucose substratum (every 1000mL substratum contains leach liquor, the 20g glucose of 200g potato), obtain the thalline (mycoderm) of one grade fermemtation, mycoderm is being handled chemosynthesis pigment sodium alizarinsulfonate and tropeolin-D, the two with this understanding percent of decolourization all reach more than 90%.
3, the invention provides a series of
Branch spore sample branch spore is mouldThe condition and the method for Cladosporium cladosporioides TXJ13021 degraded different dyes pigment.I.e. " thalline fermentation, dyestuff degraded two-step approach ".Wherein the first step is thalline fermentation pure culture, produces by above-mentioned cultivation thalline method and can carry out pigment degraded viable bacteria body in a large number; Second step was taken into account the thalline enlarged culturing simultaneously for thalline dyestuff degradation and decolorization.
In a specific embodiment, at first should
Branch spore sample branch spore is mouldCladosporium cladosporioidesTXJ13021 is inoculated in the flat board that murphy juice liquid of glucose substratum is housed, turn out mycoderm, utilize mycoderm to carry out single factor experiment at pH value, carbon source and concentration thereof, nitrogenous source and the concentration thereof of this bacterium, measure its optimum culture condition, the result shows, cultivation through 96h, for sodium alizarinsulfonate, when the pH value is 3, with sucrose is carbon source (5g/L), when ammonium nitrate was nitrogenous source (0.2g/L), decolorizing effect reached optimum regime, and percent of decolourization reaches more than 90%.
In another concrete scheme, when the pH value is 9, with sucrose carbon source (7g/L), when urea is nitrogenous source (0.8g/L), reach best for the tropeolin-D decolorizing effect, percent of decolourization reaches more than 90%.
Technique effect
Advantage of the present invention and effect: fungi of the present invention has good degradation effect to anthraquinone, triphenyl methane and azo dyes, especially can be issued to good decolorizing effect at alkaline condition to azoic dyestuff tropeolin-D, and this is that a lot of fungies are not available.Because it much all is alkaline containing the trade effluent of azoic dyestuff, so use this kind fungus degrading tool to have an enormous advantage, not only can be the industrial production saving reduction spent time of waste water ph, and can reduce industrial cost, have very high using value.
Concrete embodiment
Embodiment 1: the mould screening of branch spore sample branch spore
Gather pedotheque from various places, adopt different substratum to screen, screen a plurality of bacterial strains, carry out the degradation of dye experiment one by one, obtain the degradation of dye bacterial strain, carry out the bacterial classification signing.
Embodiment 2: the mould preservation of branch spore sample branch spore
Be preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center, preservation date is in March, 2007, and preserving number is CGMCC No.1987.
Embodiment 3: the cultivation that branch spore sample branch spore is mould and the condition optimizing of degradation of dye
Spawn culture: in the ratio obtaining liq potato substratum of 200g/L potato leach liquor, 20g/L glucose, and the 25min that under 121 ℃, 0.1MPa condition, sterilizes.Get the sterilization culture dish, aseptic technique adds liquid potato substratum 10mL in each culture dish.Treat the substratum cool to room temperature, isolating Cladosporium cladosporioides TXJ13021 bacterial classification inoculation is cultivated 6～7d in culture dish, use in order to experiment subsequently behind the formation mycoderm.
The selected dyestuff of degrading: common dyes such as tropeolin-D (characteristic wavelength 476nm), methyl red (characteristic wavelength 430nm), malachite green (characteristic wavelength 617nm), Viola crystallina (characteristic wavelength 583nm), aniline blue (characteristic wavelength 585nm), sodium alizarinsulfonate (characteristic wavelength 420nm), orange G (characteristic wavelength 478nm) etc. are selected in experiment for use, carry out wide spectrum degraded test, used substratum is dyestuff-Kirk liquid nutrient medium (composition (g/L): glucose, 5; Ammonium tartrate, 0.22; KH
2PO
4, 0.2; MgSO
47H
2O, 0.05; CaCl
2, 0.01; VITMAIN B1,1mg/L; 10% tween 80 of 10mg/L; 10mL/L 100mM veratryl alcohol; 10mg/L trace element solution (g/L:CuSO
4, 0.08; H
2MoO
4, 0.05; MnSO
44H
2O, 0.07; ZnSO
47H
2O, 0.043; Fe
2(SO
4)
30.05)), dye strength is 100mg/L, mycoderm is inoculated in carries out 5 days observation by a definite date in this substratum, the result shows, this bacterium can the decomposition of methyl orange, methyl red, malachite green, sodium alizarinsulfonate, orange G, and 5 days degradation rate is all above 85%, and Viola crystallina, the more weak degraded of aniline blue tool are only reached about 30%.
Percent of decolourization (%)=[(A
0-A
t)/A
0] * 100%
A
tThe light absorption value of dyestuff during for time t, A
0Initial light absorption value before the dyestuff degraded.
The optimization of degradation condition: A-pH value, B-carbon source, C-nitrogenous source
The A-pH value is to the influence of decolorizing effect: get the Erlenmeyer flask of five 250mL, be labeled as respectively: A, B, C, D, E, F.Measuring 100mL concentration in five Erlenmeyer flasks respectively is sodium alizarinsulfonate-Kirk substratum of 0.1g/L, and regulates with 0.1mol/LHCl/NaOH, makes its pH value be followed successively by 1,3,5,7,9,11.Other gets the Erlenmeyer flask of five 250mL, is labeled as respectively: a, b, c, d, e.In five Erlenmeyer flasks, measure 0.1g/L tropeolin-D-Kirk substratum of 100mL respectively, and regulate, make its pH value be followed successively by 1,3,5,7,9,11 with 0.1mol/L HCl/NaOH.Cultured mycoderm is inoculated into respectively organizes in the Erlenmeyer flask, constant temperature culture 96h gets and respectively organizes solution and filter, and measures the light absorption value of respectively organizing filtrate; Draw under the situation of different pH values, respectively percent of decolourization of group is as shown in Table 1:
Table one pH is to the influence of sodium alizarinsulfonate and tropeolin-D decolouring
| ??pH | ??1 | ??3 | ??5 | ??7 | ??9 | ??11 |
| Percent of decolourization % (sodium alizarinsulfonate) | ??40 | ??92 | ??80 | ??68 | ??53 | ??61 |
| Percent of decolourization % (tropeolin-D) | ??41 | ??73 | ??66 | ??90 | ??90 | ??82 |
The different carbon sources of B-are to the influence of decolorizing effect: get the Erlenmeyer flask of 12 250mL respectively, be labeled as respectively: A
1A
2A
3, B
1B
2B
3, C
1C
2C
3, D
1D
2D
3With sucrose, fructose, maltose equivalent replaces the glucose preparation 0.1g/L sodium alizarinsulfonate-Kirk substratum in the Kirk substratum.Regulate substratum with 0.1mol/L HCl/NaOH, make it reach optimum pH 3.Other gets 12 250mL Erlenmeyer flasks, is labeled as respectively: E
1E
2E
3, F
1F
2F
3, G
1G
2G
3, H
1H
2H
3With sucrose, fructose, maltose equivalent replaces the glucose preparation 0.1g/L tropeolin-D-Kirk substratum in the Kirk substratum, and regulates substratum with 0.1mol/L HCL/NaOH, makes it reach optimum pH 9.To A
1～3, B
1～3, C
1～3, D
1～3Contain glucose, sucrose, fructose, the sodium alizarinsulfonate of maltose-Kirk substratum 100mL corresponding the adding in the Erlenmeyer flask; To E
1～3, F
1～3, G
1～3, H
1～ 3Contain glucose, sucrose, fructose, the tropeolin-D of maltose-Kirk substratum 100mL corresponding the adding in the Erlenmeyer flask.The substratum that branch is installed is at 121 ℃, and 12～15min sterilizes under the condition of 0.1MPA.Good substratum cool to room temperature subject to sterilization is inoculated into cultured mycoderm and respectively organizes in the Erlenmeyer flask, behind the constant temperature culture 96h, gets each bottle solution and filters, and records and respectively organizes percent of decolourization as shown in Table 2:
The different carbon sources of table two are to the influence of sodium alizarinsulfonate and tropeolin-D decolouring
| Carbon source (5g/L) | Glucose | Sucrose | Fructose | Maltose |
| Percent of decolourization % (sodium alizarinsulfonate) | ??89 | ??93 | ??89 | ??88 |
| Percent of decolourization % (tropeolin-D) | ??93 | ??95 | ??86 | ??92 |
B-carbon source (sucrose) concentration is to the influence of decolorizing effect
Get the Erlenmeyer flask of five 250mL, be labeled as respectively: T
1, T
3, T
5, T
7, T
9Preparation 0.1g/L sodium alizarinsulfonate, sucrose concentration is respectively the Kirk substratum of 1g/L, 3g/L, 5g/L, 7g/L, 9g/L, and regulates with 0.1mol/L HCl/NaOH, makes that the pH value of substratum is 3.6.2 get the Erlenmeyer flask of five 250mL in addition, be labeled as C respectively
1, C
3, C
5, C
7, C
9Preparation 0.1g/L tropeolin-D, sucrose concentration is respectively the Kirk substratum of 1g/L, 3g/L, 5g/L, 7g/L, 9g/L, and regulates with 0.1mol/L HCl/NaOH, makes that the pH value of substratum is 9.The substratum of respectively organizing of measuring 100mL respectively is added in the corresponding Erlenmeyer flask of each group, and at 121 ℃, 15min sterilizes under the 0.1MPa condition.After the cooling mycoderm is inoculated into and respectively organizes in the substratum, constant temperature culture 96h gets and respectively organizes solution and filter, and measures the light absorption value of each group, draw under the different carbon source concentrations percent of decolourization as shown in Table 3:
Under table three different sucrose to the influence of sodium alizarinsulfonate and tropeolin-D decolouring
| Sucrose concentration | ??0.1％ | ??0.3％ | ??0.5％ | ??0.7％ | ??0.9％ |
| Percent of decolourization % (sodium alizarinsulfonate) | ??88 | ??87 | ??92 | ??89 | ??90 |
| Percent of decolourization % (tropeolin-D) | ??83 | ??87 | ??91 | ??96 | ??91 |
The C-different nitrogen sources is to the influence of decolorizing effect: get the Erlenmeyer flask of 15 250mL, be labeled as respectively: a
1a
2a
3, b
1b
2b
3, c
1c
2c
3, d
1d
2d
3, e
1e
2e
3With sucrose is carbon source, and uses ammonium nitrate respectively, ammonium sulfate, and peptone, it is nitrogenous source preparation 0.1g/L sodium alizarinsulfonate-Kirk substratum that urea equivalent replaces ammonium tartrate, regulates substratum with 0.1mol/L HCl/NaOH, making its pH value is 3.Other gets the Erlenmeyer flask of 15 250mL, is labeled as f respectively
1f
2f
3, g
1g
2g
3, h
1h
2h
3, m
1m
2m
3, n
1n
2n
3With sucrose is carbon source, and uses ammonium nitrate respectively, ammonium sulfate, and peptone, it is nitrogenous source preparation 0.1g/L tropeolin-D-Kirk substratum that urea equivalent replaces ammonium tartrate, and regulates substratum with 0.1mol/L HCl/NaOH, making its pH value is 9.To a
1～3, b
1～3, c
1～3, d
1～3, e
1～3The corresponding respectively sodium alizarinsulfonate-Kirk substratum 100mL that contains ammonium tartrate, ammonium nitrate, ammonium sulfate, peptone, urea that adds; To f
1～3, g
1～3, h
1～3, m
1～3, n
1～3The corresponding respectively tropeolin-D-Kirk substratum 100mL that contains ammonium tartrate, ammonium nitrate, ammonium sulfate, peptone, urea that adds.The substratum that branch is installed is at 121 ℃, under the 0.1MPa condition, and sterilization 12～15min.Good substratum cool to room temperature subject to sterilization is inoculated into cultured mycoderm and respectively organizes in the Erlenmeyer flask, behind the constant temperature culture 96h, gets each bottle solution and filters, and records and respectively organizes percent of decolourization as shown in Table 4:
Table four different nitrogen sources is to the influence of sodium alizarinsulfonate and tropeolin-D decolouring
| Nitrogenous source (0.22g/L) | Ammonium tartrate | Ammonium nitrate | Ammonium sulfate | Peptone | Urea |
| Percent of decolourization % (sodium alizarinsulfonate) | ??90 | ??93 | ??92 | ??91 | ??82 |
| Nitrogenous source (0.22g/L) | Ammonium tartrate | Ammonium nitrate | Ammonium sulfate | Peptone | Urea |
| Percent of decolourization % (tropeolin-D) | ??86 | ??69 | ??85 | ??85 | ??93 |
C-nitrogenous source (urea) concentration is to the influence of decolorizing effect:
Get the Erlenmeyer flask of five 250mL, be labeled as respectively: N
0.05, N
0.1, N
0.2, N
0.4, N
0.8The preparation urea concentration is respectively 0.1g/L sodium alizarinsulfonate-Kirk substratum of 0.1g/L, 0.2g/L, 0.4g/L, 0.8g/L, and regulates with 0.1mol/L HCl/NaOH, makes that the pH value of substratum is 3.Other gets the Erlenmeyer flask of 7 250mL, is labeled as n respectively
0.1, n
0.2, n
0.4, n
0.8, n
1.2, n
1.6, n
2.0The preparation urea concentration is respectively 0.1g/L tropeolin-D-Kirk substratum of 0.1g/L, 0.2g/L, 0.4g/L, 0.8g/L, and regulates with 0.1mol/L HCl/NaOH, makes that the pH value of substratum is 9.The substratum of respectively organizing of measuring 100mL respectively is added in the corresponding Erlenmeyer flask of each group, seals; At 121 ℃, the 0.1MPa 25min that sterilizes.Mycoderm is inoculated into respectively organizes in the substratum, constant temperature culture 96h gets and respectively organizes solution and filter, and measures the light absorption value of each group, draw under the different nitrogen sources concentration percent of decolourization as shown in Table 5:
The different urea concentrations of table five are to the influence of sodium alizarinsulfonate and tropeolin-D decolouring
| Urea concentration | ??0.1g/L | ??0.2g/L | ??0.4g/L | ??0.8g/L |
| Percent of decolourization % (sodium alizarinsulfonate) | ??90 | ??92 | ??90 | ??89 |
| Percent of decolourization % (tropeolin-D) | ??79.5 | ??80 | ??89 | ??93.8 |
Embodiment 4:
(colourity is about 50000 times to get waste water from printing and dyeing mill, pH 9.5) 200 kilograms, directly cultured Cladosporiumcladosporioides TXJ13021 mycoderm " seed liquor " 20L (dry mycelium content 1%) pours into wherein in advance, handled 15 days under the natural condition, 20～35 ℃ of temperature, percent of decolourization is 67%, and colourity is reduced to 8100 times.And do not add the control group of Cladosporium cladosporioidesTXJ13021, and percent of decolourization only is about 5%, colourity is only reduced to 43000 times.
Embodiment 5:
(colourity is about 50000 times to get waste water from printing and dyeing mill, pH 9.5) 200 kilograms, directly cultured Cladosporiumcladosporioides TXJ13021 mycoderm " seed liquor " 80L (dry mycelium content 1%) pours into wherein in advance, handled 15 days under the natural condition, 20～35 ℃ of temperature, percent of decolourization is 67%, and colourity is reduced to 2100 times.And do not add the control group of Cladosporium cladosporioidesTXJ13021, and percent of decolourization only is about 5%, colourity is only reduced to 43000 times.
Embodiment 6:
(colourity is about 50000 times to get waste water from printing and dyeing mill, pH 9.5) 200 kilograms, directly cultured Cladosporiumcladosporioides TXJ13021 mycoderm " seed liquor " 60L (dry mycelium content 1%) pours into wherein in advance, handled 15 days under the natural condition, 20～35 ℃ of temperature, percent of decolourization is 67%, and colourity is reduced to 3500 times.And do not add the control group of Cladosporium cladosporioidesTXJ13021, and percent of decolourization only is about 5%, colourity is only reduced to 43000 times.
Embodiment 7:
(colourity is about 50000 times to get waste water from printing and dyeing mill, pH 9.5) 200 kilograms, directly cultured Cladosporiumcladosporioides TXJ13021 mycoderm " seed liquor " 40L (dry mycelium content 1%) pours into wherein in advance, handled 15 days under the natural condition, 20～35 ℃ of temperature, percent of decolourization is 67%, and colourity is reduced to 4000 times.And do not add the control group of Cladosporium cladosporioidesTXJ13021, and percent of decolourization only is about 5%, colourity is only reduced to 43000 times.
Claims (5)
1. the present invention obtains the microbial strains of strain energy efficient degradation dyestuff, this microorganism is that branch spore sample branch spore is mould, latin name Cladosporium cladosporioides TXJ13021, be located away from Hainan Province and hang tropical rain forest area, Luoshan, be preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center, preservation date is in March, 2007, and preserving number is CGMCC No.1987.
2. one kind comprises the mould little ecological dyestuff degradation bacterial agent of described spore sample of claim 1 branch spore.
3. the described little ecological dyestuff degradation bacterial agent of claim 2 wherein also comprises: the metabolic product of this bacterial strain.
4. described genus bacillus of claim 1 or claim 2 or 3 described dyestuff degradation bacterial agents are used for the purposes of dyestuff degraded in process for processing.
5. the described purposes of claim 4 is wherein used little ecological dyestuff degradation bacterial agent and an amount of hybrid technique of dyeing waste water, handles under the natural condition, and the degradable dyestuff significantly descends its chroma in waste water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466805A (en) * | 2013-09-09 | 2013-12-25 | 江苏大学 | Technique for removing anthraquinone compounds in wastewater by using Ceriporiopsis subvermispora thallus |
| CN103466807A (en) * | 2013-09-09 | 2013-12-25 | 江苏大学 | Technique for degrading anthraquinone compounds by using Ceriporiopsis subvermispora |
| CN103614300A (en) * | 2013-11-08 | 2014-03-05 | 浙江大学 | Acrogenospora sphaerocephala and application thereof |
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| CN101050435A (en) * | 2007-03-16 | 2007-10-10 | 山东省科学院生物研究所 | Solid microbe agent for degrading petroleum pollution, and petroleum products, and preparation method |
| CN101054555A (en) * | 2007-03-30 | 2007-10-17 | 南京大学 | An epiphyte capable of digesting agar |
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| CN1423716A (en) * | 1999-12-23 | 2003-06-11 | 诺沃奇梅兹有限公司 | Process for removal of excess dispersedye from printed or dyed textile material |
| JP2003274929A (en) * | 2002-03-26 | 2003-09-30 | Takuma Co Ltd | Microorganism for decomposing persistent substance including colored component and method for treating sewage and wastewater by using the same |
| CN101050435A (en) * | 2007-03-16 | 2007-10-10 | 山东省科学院生物研究所 | Solid microbe agent for degrading petroleum pollution, and petroleum products, and preparation method |
| CN101054555A (en) * | 2007-03-30 | 2007-10-17 | 南京大学 | An epiphyte capable of digesting agar |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466805A (en) * | 2013-09-09 | 2013-12-25 | 江苏大学 | Technique for removing anthraquinone compounds in wastewater by using Ceriporiopsis subvermispora thallus |
| CN103466807A (en) * | 2013-09-09 | 2013-12-25 | 江苏大学 | Technique for degrading anthraquinone compounds by using Ceriporiopsis subvermispora |
| CN103614300A (en) * | 2013-11-08 | 2014-03-05 | 浙江大学 | Acrogenospora sphaerocephala and application thereof |
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