CN106256902A - A kind of LBL self-assembly process for fixation of microorganism - Google Patents
A kind of LBL self-assembly process for fixation of microorganism Download PDFInfo
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Abstract
The present invention relates to chemical wastewater treatment technical field, particularly relating to the LBL self-assembly process for fixation of a kind of microorganism, the LBL self-assembly process for fixation of described microorganism comprises the following steps: the LBL self-assembly immobilization of the dilution of hyperbranched diazonium salt solution, the grafting of carrier, microbial immobilization and microorganism.The LBL self-assembly process for fixation of the microorganism of the present invention utilize hyperbranched diazol as cross-linking agent by Microorganism incubation on polyurethane surface, need not carrier surface and microorganism are carried out pretreatment, and the activity of microorganism is had no significant effect, have that method is simple to operate, be swift in response, microbial treatments efficiency high after immobilization, and the degree of self assembly can be controlled flexibly, it is advantageously implemented industrialization.
Description
Technical field
The present invention relates to chemical wastewater treatment technical field, particularly relate to a kind of microorganism layer by layer
Self-assembled monolayer method.
Background technology
Along with the industrial fast development of China, wastewater from chemical industry accounts in China's sewage composition
Ratio is increasing, and the industry such as petrochemical industry, process hides, papermaking, iron and steel can produce a large amount of wastewater from chemical industry,
Wastewater from chemical industry is high containing pollutant levels, complicated component, and major part is containing eutrophy units such as nitrogen phosphorus
Element, is directly discharged into water body and can cause serious water pollution.By traditional activated sludge process,
Not good enough to the treatment effect of wastewater from chemical industry, effluent quality is difficult to up to standard.
Phase early 1980s, immobilized microorganism technique starts to be applied to sewage disposal
Cheng Zhong, the concentration of microorganism, immobilized microorganism in this technology beneficially raising bioreactor
Can resist the impact of adverse environment, and the most reacted solid-liquid separation, shortening processes
The required time.
Common microorganism immobilization method has absorption method, investment, cross-linking method etc..Absorption method
The Van der Waals force, hydrogen bond, covalent bond and the ionic bond that are dependent between microorganism and carrier etc. act on
Being attached together, the method is simple to operate, but microorganism combines instability, easily comes off.
Investment utilizes the effect such as polymerization or ion network that microorganism is trapped in carrier
In porous network, thus realizing the fixing of microorganism, the microbial immobilized degree of the method is high,
Materialization is stable, and can resist the murder by poisoning of harmful substance, and shortcoming is the diffusion between microorganism and substrate
Resistance is big, and technique is more complicated, is not suitable for the decomposition of macromolecule contaminant matter.Cross-linking method is profit
With the multi-functional group such as aldehydes, amine as the knot forming covalent bond between cross-linking agent and microorganism
Close, by the flocculation granulating of microorganism self, thus a kind of immobilization technology realized, it lacks
Point is that medicament selection is more difficult, and cross-linking agent is costly.
Chinese invention patent application number 201410137361.0 discloses a kind of microbial immobilized
Method, prepares cation type polyurethane carrier, is the Polyurethane carrier of 30-60PPI by aperture
Material is placed in 3%-10% hydrochloric acid solution process 15-24 hour；Use absorption method, will inoculation
The reactor crossed is incubated 6-12 hour in 25-35 DEG C, and lactic acid bacteria raised growth also adsorbs poly-
Urethane surface.Its introduce utilize polyurethane as the method for carrier fixation of microbe, but immobilization
Microorganism easily come off, and it is microbial immobilized inefficient.
Summary of the invention
The technical problem to be solved is to overcome the deficiency of above-mentioned prior art, it is provided that
The LBL self-assembly process for fixation of a kind of microorganism, it is with the hyperbranched diazonium of high reaction activity
Salt, as cross-linking agent, utilizes the active function groups of hyperbranched diazol to make polyurethane surface with weight
The active function groups of nitrogen salt, then microorganism is by the diazol activity official's energy with polyurethane surface
Group forms covalent bond, thus microorganism is firmly fixed on polyurethane surface, more than repetition
Step, it is achieved microorganism is controlled the surface immobilized amount of Polyurethane carrier, thus realizes micro-life
Nitride layer layer self-assembled monolayer.
It is main that the LBL self-assembly process for fixation of a kind of microorganism that the present invention provides uses
Technical scheme is: comprise the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 50～100 times；
(2) grafting of carrier: at a certain temperature, is immersed in the over-expense after dilution by carrier
Change certain time in diazonium salt solution；
(3) microbial immobilization: take out described carrier, utilizes water to clean up, with one
The cold wind of fixed temperature dries up rapidly；At a certain temperature, then by described carrier invade not micro-in activity
Certain time in biological solution；
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 to
The most once, whole self-assembled monolayer process is completed.
The LBL self-assembly process for fixation of a kind of microorganism that the present invention provides uses the most attached
Genus technical scheme:
In described step 1, the structural formula of hyperbranched diazol is
The number of iterations of chemical group in wherein m is above-mentioned molecular formula brace.
In described step 1, the preparation method of hyperbranched diazol comprises the steps:
(1) it is that the N of 1: 2, N-(2-ethoxy) aniline reacts with oxychloride by mol ratio
Generate N, N-(2-chloroethyl) aniline；
(2) by PABA that mol ratio is 2: 1 and N, N-(2-chloroethyl) aniline
React and replace N, N-(2-chloroethyl) aniline chlorine therein atom；
(3) then under the catalysis of sodium nitrite, sulphuric acid, acetic acid and dimethylformamide,
There is the hyperbranched diazol described in polyreaction generation in the product self that generates of above-mentioned steps 2.
Carrier Immersion time in hyperbranched diazonium salt solution described in described step 2 is
0.5-2h。
The Immersion time in described active microorganism solution of the carrier described in described step 3 is
4-6h。
The submergence crosslinking in described hyperbranched diazonium salt solution of the carrier described in described step 2
Temperature be 2-4 DEG C.
The temperature of submergence absorption in described active microorganism of carrier described in described step 3 is
4-8℃。
The storage temperature of the hyperbranched diazonium salt solution after described dilution is 2-4 DEG C.
Described carrier is polyurethane.
Described polyurethane be shaped as length and width a height of 10-20mm square or cuboid.
LBL self-assembly is the method utilizing successively alternating deposit, by the intermolecular weak phase of each layer
Interaction (such as electrostatic attraction, hydrogen bond, coordinate bond etc.), makes layer and layer spontaneously associate formation
Structural integrity, stable performance, the molecule aggregate with certain specific function and supramolecular structure
Process.It is the one table simple, multi-functional that the nineties in 20th century, fast development was got up
Surface modification method, it mainly utilizes charged substrate alternating deposit preparation in oppositely charged poly-
Electrolyte self-assembled multilayer film.
Diazol is containing diazo salt, soluble in water, ionizes, and aqueous solution has
The strongest conductive capability, is a kind of important initiator of material surface chemical modification.Hyperbranched
Diazol is due to its hyperbranched polymer architecture and polyfunctional group character so that it is in microorganism
Immobilization field has potential use.
Polyurethane is a kind of high-molecular organic material, and it is big that it has specific surface area, and foam pores is many,
The features such as enabling capabilities is strong, stable in properties, the application in terms of immobilized microorganism is by extensively
Pay close attention to.
Having the beneficial effects that of the LBL self-assembly process for fixation of the microorganism of the present invention:
1) the LBL self-assembly process for fixation of the microorganism of the present invention utilizes hyperbranched diazol
As cross-linking agent by Microorganism incubation on polyurethane surface, it is not necessary to carrier surface and micro-life
Thing carries out pretreatment, and has no significant effect the activity of microorganism, have method simple to operate,
Be swift in response, microbial treatments efficiency high after immobilization, and can control from group flexibly
The degree of dress, is advantageously implemented industrialization.
2) in the LBL self-assembly process for fixation of the microorganism of the present invention in hyperbranched diazol
Containing a large amount of double bonds and phenyl ring, there is rigid structure, formed certain sterically hindered, as friendship
Connection agent can keep a part of active group inwardly to react with carrier, another part active group
Outwards and microbial reaction.
3) the LBL self-assembly process for fixation of the microorganism of the present invention is by the most layer by layer from group
Dress, can be cross-linked with each other into three-dimensional netted knot between dissaving polymer and its fixing microorganism
Structure, can fixation of microbe further, improve microbial immobilization efficiency.
4) the hyperbranched diazonium used by the LBL self-assembly process for fixation of the microorganism of the present invention
Diazonium groups contained in salt, has high reaction activity, adsorption efficiency height and effect stability；And
This method can apply on the carrier of multiple unlike material, and universality is good.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the LBL self-assembly process for fixation of the microorganism of the present invention.
1-polyurethane, the hyperbranched diazol of 2-,
3-microorganism.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
As it is shown in figure 1, the LBL self-assembly process for fixation of microorganism of the present invention, bag
Include following steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 50～100 times, is then stored at a temperature of 2-4 DEG C, to protect
Demonstrate,prove the stability of hyperbranched diazol；In the hyperbranched diazol of the present invention containing a large amount of double bonds and
Phenyl ring, has rigid structure, is formed certain sterically hindered, can keep one as cross-linking agent
Amount of activated group inwardly reacts with carrier, and another part active group is the most anti-with microorganism
Should.
(2) grafting of carrier: at 2-4 DEG C, is immersed in the over-expense after dilution by polyurethane
Change 0.5-2h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
The cold wind of uniform temperature dries up rapidly；At a temperature of 4-8 DEG C, more described polyurethane is invaded bubble
4-6h in active microorganism solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 to
The most once, whole self-assembled monolayer process is completed；The LBL self-assembly of the microorganism of the present invention
Process for fixation by repeatedly LBL self-assembly, dissaving polymer and its fixing microorganism it
Between can be cross-linked with each other into tridimensional network, can fixation of microbe further, improve microorganism
Immobilization efficiency.
The LBL self-assembly process for fixation of the microorganism of the present invention utilizes hyperbranched diazol to make
For cross-linking agent by Microorganism incubation on polyurethane surface, it is not necessary to polyurethane surface and micro-life
Thing carries out pretreatment, and has no significant effect the activity of microorganism, have method simple to operate,
Be swift in response, microbial treatments efficiency high after immobilization, and can control from group flexibly
The degree of dress, is advantageously implemented industrialization.
Above-mentioned polyurethane be shaped as length and width a height of 10-20mm square or cuboid.
Embodiment 1
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 50 times, is then stored at a temperature of 2 DEG C, hyperbranched to ensure
The stability of diazol；
(2) grafting of carrier: at 4 DEG C, be immersed in by polyurethane after dilution is hyperbranched
0.5h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
1 DEG C of cold wind dries up rapidly；At a temperature of 4 DEG C, more described polyurethane is invaded steep in activity micro-
6h in biological solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 five
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 3.5g/L, it is only necessary to 2d can complete polyurethane surface
Face and the biofilm of inside, take the change that certain COD (hereinafter referred to as COD) is 850mg/L
Work waste water, as water inlet, can reach more than 93% to the clearance of COD, and water outlet COD is less than
80mg/L.By the polyurethane to LBL self-assembly immobilized microorganism with without immobilized poly-
Urethane finds after being analyzed contrast, after hyperbranched diazol crosslinking LBL self-assembly is fixing
Polyurethane, its fixing Biomass can improve 40%.
Embodiment 2
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 100 times, is then stored at a temperature of 4 DEG C, to ensure over-expense
Change the stability of diazol；
(2) grafting of carrier: at 2 DEG C, be immersed in by polyurethane after dilution is hyperbranched
2h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
4 DEG C of cold wind dry up rapidly；At a temperature of 8 DEG C, more described polyurethane is invaded steep in activity micro-
4h in biological solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 eight
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 4g/L, it is only necessary to 3d can complete polyurethane surface
And the biofilm of inside, take wastewater from chemical industry that certain COD is 800mg/L as water inlet, to COD's
Clearance can reach more than 90%, and water outlet COD is less than 80mg/L.By to LBL self-assembly
The polyurethane of immobilized microorganism and finding after being analyzed contrast without immobilized polyurethane,
Polyurethane after hyperbranched diazol crosslinking LBL self-assembly is fixing, its fixing Biomass can
To improve 35%.
Embodiment 3
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 80 times, is then stored at a temperature of 3 DEG C, hyperbranched to ensure
The stability of diazol；
(2) grafting of carrier: at 3 DEG C, be immersed in by polyurethane after dilution is hyperbranched
1h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
3 DEG C of cold wind dry up rapidly；At a temperature of 6 DEG C, more described polyurethane is invaded steep in activity micro-
5h in biological solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 seven
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 3.8g/L, it is only necessary to 3d can complete polyurethane surface
Face and the biofilm of inside, take wastewater from chemical industry that certain COD is 900mg/L as water inlet, to COD
Clearance can reach more than 95%, water outlet COD be less than 80mg/L.By to layer by layer from group
Dress immobilized microorganism polyurethane and without immobilized polyurethane be analyzed contrast after send out
Existing, after hyperbranched diazol crosslinking LBL self-assembly is fixing polyurethane, its fixing biology
Amount can improve 38%.
Embodiment 4
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 70 times, is then stored at a temperature of 3.5 DEG C, to ensure over-expense
Change the stability of diazol；
(2) grafting of carrier: at 3 DEG C, be immersed in by polyurethane after dilution is hyperbranched
1.5h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
2 DEG C of cold wind dry up rapidly；At a temperature of 7 DEG C, more described polyurethane is invaded steep in activity micro-
4.5h in biological solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 30
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 3g/L, it is only necessary to 2d can complete polyurethane surface
And the biofilm of inside, take wastewater from chemical industry that certain COD is 750mg/L as water inlet, to COD's
Clearance can reach more than 95%, and water outlet COD is less than 80mg/L.By to LBL self-assembly
The polyurethane of immobilized microorganism and finding after being analyzed contrast without immobilized polyurethane,
Polyurethane after hyperbranched diazol crosslinking LBL self-assembly is fixing, its fixing Biomass can
To improve 36%.
Embodiment 5
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 60 times, is then stored at a temperature of 4 DEG C, hyperbranched to ensure
The stability of diazol；
(2) grafting of carrier: at 4 DEG C, be immersed in by polyurethane after dilution is hyperbranched
0.5h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
Cold wind dries up rapidly；At a temperature of 6 DEG C, more described polyurethane is invaded steep in active microorganism
5.5h in solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 six
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 4g/L, it is only necessary to 3d can complete polyurethane surface
And the biofilm of inside, take wastewater from chemical industry that certain COD is 950mg/L as water inlet, to COD's
Clearance can reach more than 95%, and water outlet COD is less than 80mg/L.By to LBL self-assembly
The polyurethane of immobilized microorganism and finding after being analyzed contrast without immobilized polyurethane,
Polyurethane after hyperbranched diazol crosslinking LBL self-assembly is fixing, its fixing Biomass can
To improve 38%.
Embodiment 6
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 80 times, is then stored at a temperature of 4 DEG C, hyperbranched to ensure
The stability of diazol；
(2) grafting of carrier: at 3 DEG C, be immersed in by polyurethane after dilution is hyperbranched
1h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
Cold wind dries up rapidly；At a temperature of 6 DEG C, more described polyurethane is invaded steep in active microorganism
5h in solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 30
Five times, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 3.8g/L, it is only necessary to 3d can complete polyurethane surface
Face and the biofilm of inside, take wastewater from chemical industry that certain COD is 900mg/L as water inlet, to COD
Clearance can reach more than 95%, water outlet COD be less than 80mg/L.By to layer by layer from group
Dress immobilized microorganism polyurethane and without immobilized polyurethane be analyzed contrast after send out
Existing, after hyperbranched diazol crosslinking LBL self-assembly is fixing polyurethane, its fixing biology
Amount can improve 37%.
Embodiment 7
The LBL self-assembly process for fixation of the microorganism of the present invention, comprises the steps:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 90 times, is then stored at a temperature of 3.5 DEG C, to ensure over-expense
Change the stability of diazol；
(2) grafting of carrier: at 3 DEG C, be immersed in by polyurethane after dilution is hyperbranched
1h in diazonium salt solution；
(3) microbial immobilization: take out described polyurethane, utilizes water to clean up, and uses
Cold wind dries up rapidly；At a temperature of 7 DEG C, more described polyurethane is invaded steep in active microorganism
4h in solution, to reach saturated absorption.
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 30
Secondary, complete whole self-assembled monolayer process.
Polyurethane after above-mentioned immobilization is put into aerobic reaction pond carries out bio-film colonization experiment,
In the case of Aerobic Pond sludge concentration is 3.3g/L, it is only necessary to 2.5d can complete polyurethane
Surface and the biofilm of inside, take wastewater from chemical industry that certain COD is 800mg/L as water inlet, right
The clearance of COD can reach more than 90%, and water outlet COD is less than 80mg/L.By to layer by layer
The polyurethane of self-assembled monolayer microorganism and be analyzed contrast without immobilized polyurethane
Rear discovery, the polyurethane after hyperbranched diazol crosslinking LBL self-assembly is fixing, it is fixed
Biomass can improve 36%.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not to this
The restriction of invention protection domain, one of ordinary skill in the art should be understood that in technical scheme
On the basis of, those skilled in the art need not to pay various amendments that creative work can make or
Deformation is still within protection scope of the present invention.
Claims (10)
1. the LBL self-assembly process for fixation of a microorganism, it is characterised in that include as
Lower step:
(1) dilution of hyperbranched diazonium salt solution: the hyperbranched diazonium of measured amounts volume
Saline solution, is diluted with water to 50～100 times；
(2) grafting of carrier: at a certain temperature, is immersed in the over-expense after dilution by carrier
Change certain time in diazonium salt solution；
(3) microbial immobilization: take out described carrier, utilizes water to clean up, with one
The cold wind of fixed temperature dries up rapidly；At a certain temperature, then by described carrier invade not micro-in activity
Certain time in biological solution；
(4) the LBL self-assembly immobilization of microorganism: be repeated in step 2 and step 3 to
The most once, whole self-assembled monolayer process is completed.
2. the LBL self-assembly process for fixation of microorganism as claimed in claim 1, it is special
Levy and be: in described step 1, the structural formula of hyperbranched diazol is
The number of iterations of chemical group in wherein m is above-mentioned molecular formula brace.
3. the LBL self-assembly process for fixation of microorganism as claimed in claim 2, it is special
Levying and be, in described step 1, the preparation method of hyperbranched diazol comprises the steps:
(1) it is that the N of 1: 2, N-(2-ethoxy) aniline reacts with oxychloride by mol ratio
Generate N, N-(2-chloroethyl) aniline；
(2) by PABA that mol ratio is 2: 1 and N, N-(2-chloroethyl) aniline
React and replace N, N-(2-chloroethyl) aniline chlorine therein atom；
(3) then under the catalysis of sodium nitrite, sulphuric acid, acetic acid and dimethylformamide,
There is the hyperbranched diazol described in polyreaction generation in the product self that generates of above-mentioned steps 2.
4. the LBL self-assembly process for fixation of microorganism as claimed in claim 1, it is special
Levy and be: carrier Immersion time in hyperbranched diazonium salt solution described in described step 2 is
0.5-2h。
5. the LBL self-assembly process for fixation of microorganism as claimed in claim 1, it is special
Levy and be: the Immersion time in described active microorganism solution of the carrier described in described step 3
For 4-6h.
6. the LBL self-assembly process for fixation of microorganism as claimed in claim 1, it is special
Levy and be: the submergence in described hyperbranched diazonium salt solution of the carrier described in described step 2 is handed over
The temperature of connection is 2-4 DEG C.
7. the LBL self-assembly process for fixation of microorganism as claimed in claim 1, it is special
Levy and be: carrier described in described step 3 is the temperature of submergence absorption in described active microorganism
For 4-8 DEG C.
8. the LBL self-assembly immobilization of the microorganism as according to any one of claim 1-7
Method, it is characterised in that: the storage temperature of the hyperbranched diazonium salt solution after described dilution is
2-4℃。
9. the LBL self-assembly immobilization of the microorganism as according to any one of claim 1-7
Method, it is characterised in that: described carrier is polyurethane.
10. the LBL self-assembly process for fixation of microorganism as claimed in claim 9, it is special
Levy and be: described polyurethane be shaped as length and width a height of 10-20mm square or cuboid.
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| LOMBA MIGUEL等: "《Cell adhesion on surface patterns generated by the photocrosslinking of hyperbranched polyesters with a trisdiazonium salt》", 《REACTIVE AND FUNCTIONAL POLYMERS》 * |
| PENGCHAO CHE等: "《Synthesizing hyperbranched Azo polymer through Azo-coupling reaction》", 《CHEMISTRY LETTERS》 * |
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| 王玉晓等: "《以亲水化改性聚氨酯为多孔载体的生物膜移动床反应器处理污水中试研究》", 《环境科学》 * |
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| CN106256902B (en) | 2019-08-20 |
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