CN108251409A - A kind of complex microorganism guided missile material of absorption degradation greasy dirt and preparation method thereof - Google Patents
A kind of complex microorganism guided missile material of absorption degradation greasy dirt and preparation method thereof Download PDFInfo
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Abstract
Present invention firstly provides a kind of degradable stephanoporate nano materials, it is by modified aliphatic polyester porous nano particle, and internal layer is polar group, and outermost surface is nonpolar lipophilic group；The hole of the porous nano particle is in three-dimensional network-like structure.Also a kind of adsorbable, degradation grease complex microorganism targeting material of the present invention, referred to as " microorganism guided missile ", it is fixed with compound thermophilic oily bacterium using the degradable multiporous nano material as carrier on the carrier.Complex microorganism of the present invention targets material and can not only solve to apply free degradation bacteria with indigenous microbes there are antagonism, also with the ability for tracking greasy dirt.The present invention also provides the methods for preparing the complex microorganism targeting material.
Description
Technical field
The invention belongs to target the preparation field of material, and in particular to a kind of composite microbial for absorption degradation oil residues
Object guided missile carrier material and preparation method thereof.
Background technology
In recent years, oil spill accident caused by offshore oil exploitation, ship fortune oil is more frequent so that oil spill becomes
Global disaster, oil spill accident often bring the ecocatastrophe for being difficult to repair to marine environment, are brought to various countries huge
Economic loss.So the method that oil spilling greasy dirt is efficiently removed in research, restores contaminated ecological environment, is each maritime state, political affairs
The responsibility that mansion and scientific research department extremely pay close attention to.
At present, the main stream approach for clearing up oil spill is Physical and chemical method, and the two can quickly clear up major part
Oil spilling, but the Residual oil and chemicals at the thin oil film in sea, oil emulsion and sandy beach that can not be removed for machinery are prohibited from using
Inshore, safe and reliable bioanalysis just embodies the important function that can not be substituted.In fact, according to existing accident oil spilling
Amount calculates, and carries out the ocean alkane degradation bacterial of 5000 tons of the biological prosthetic needs in pollution marine site or more, and simple drops by nature
The solution preocess time is very long, and environment is aggrieved wide and deep.So artificially culture microbial augmentation degradation, by many scientific research departments
Concern.Although Biochemical method oil spilling has many advantages, such as safe and environment-friendly, reliable, still had in terms of practical application at present
Many problems demands solve.Using free degradation bacteria and indigenous microbes there are antagonism, but also be easy to run off there are thalline,
The shortcomings of sensitive to changes in environmental conditions.The immobilization technology of oil degradation bacterial strain can tentatively solve the problems, such as this, overcome
The antagonism of free state bacterial strain and indigenous microbes has certain effect, but still there are carrier material oil absorbency is low, machine
The shortcomings of tool intensity is weak, degradability is poor limits the large-scale promotion of Biochemical method oil spilling.
It is the key that realize industrialization to select suitable fixed microorganism carrier, and the quality of carrier depends on material
Adsorption rate, mechanical strength, the activity of service life and imbedded microbe cell.Ideal carrier material has oil absorbency height, can give birth to
The features such as object degradation, cheap, abundant hole.Carrier material should also have suspension, and the carrier material of suspension is conducive to micro-
Biology is bred in oil-water interfaces, and microorganism is made to be easier to contact with oil spilling.Many carrier materials have been reported for repairing oil spilling, so
And find the high material not a duck soup with floatability again of oil absorbency.Activated carbon is most widely used fixation support, such as public
Rice straw base, corncob base, the peanut shell base of the number of opening CN103923905A, CN103923904A, CN103923903A preparation
Activity carbon carrier, renovation agent obtained have floatability, but low to the adsorption rate of oil spilling；Publication number CN103194437A uses poly-
Vinyl alcohol-boric acid secondary cross-linking completes bacteria adhensionization for sewage disposal, and occlusion vehicle has high mechanical strength, cheap etc.
Advantage, but product does not have floatability, it is impossible to be used in handle the oil film on sea.The polyurethane of publication number CN103951039A inventions
The immobilized biological activated filler of nitrobacteria of carrier has floatability, but polyurethane foam is not degradable, easily causes secondary dirt
Dye.
With the thinking of biological missile drug, manufacture can be oriented, exactly prepares different oil product ingredients of degrading as needed
Sorbing material.Based on these features, we are made " microorganism guided missile " and transport at microorganism to suspension oil droplet, so as to reach absorption
The effect of degradation.The functional polymer carrier for coordination principle synthesis that specific biological molecules or group with targeting are affine,
It is attracted each other between lipophile strong material and oil droplet by targeting group, the preferable load for removing the pollution of oil spilling Residual oil can be become
Body.Its surface can be chemically modified to assign its surface various active by preparing this carrier with high absorption property
Feature capability group (such as-OH ,-COOH ,-CHO ,-NH2,-SH etc.).Biological missile carrier is in biomedicine, immobilized microorganism etc.
Many fields show powerful vitality.If publication number CN101045067A " nanometer biological missile " is to the spy of cancer cell identification
It is different in nature high, cancer cell is thoroughly killed by the physical action of explosion." one kind is introduced directly into formula and is mostly used publication number CN104689339A
Guidance device, gatherer and killing device applied chemistry coupling method are coupled by way biological missile " using molecule coupling labeled agent,
There is remarkable result for treating disease.Publication number CN1526450A " anticancer biological missile of internal radiating radium nuclein " is carried using ore
It is pure to produce radium nuclide, biochemical drug carrier is equipped with by combination reaction.
Invention content
The present invention primary and foremost purpose be：A kind of degradable stephanoporate nano material is provided, is had with grease good affine
Power has the ability of tracking sump oil.
It is another object of the present invention to：It is proposed a kind of composite microbial that can be used for the degradation remaining Residual oil of marine oil overflow
Object targets material, can not only solve to apply free degradation bacteria with indigenous microbes there are antagonism, also with tracking greasy dirt
Ability.
Another object of the present invention is：The method for preparing the complex microorganism targeting material is provided.
In order to achieve the above objectives, the technical solution that uses of the present invention is：
First, the first aspect of the present invention provides a kind of degradable stephanoporate nano material, it is by modified fat
Adoption ester porous nano particle, internal layer are polar group, and outermost surface is nonpolar lipophilic group；The porous nano
The hole of particle is in three-dimensional network-like structure.
In currently preferred porous nanometer material, the aliphatic polyester can be selected from polylactic acid, polyglycolic acid
Or any one in polycaprolactone or its copolymer；Most preferably polylactic acid.
In currently preferred porous nanometer material, the polar group of the internal layer can be hydroxyl, carboxyl, amino or carbonyl
Any one in base；Most preferably hydroxyl.
In currently preferred porous nanometer material, the nonpolar lipophilic group of the outermost surface can be selected from hydrocarbon
Base, including any one in methyl, aliphatic group, aryl, halogen or ester group etc.；Most preferable.
Currently preferred porous nanometer material, the modification include：First aliphatic polyester porous nano particle is passed through
Surface modified crosslinking polar functional group, then further it is crosslinked nonpolarity in the porous nano particle surface for being crosslinked with polar functional group
Lipophilic group.Thus form the aliphatic polyester porous nano that outer layer is nonpolar lipophilic group, internal layer is polar group
Grain.
The porous nanometer material of the present invention is aliphatic polyester porous nano particle on the whole, and ectonexine has respectively
Functional group of different nature；Wherein, aliphatic polyester has good degradability in itself so that porous nano material of the invention
Material also natively has excellent degradability；In addition, its outer layer lipophilic group has good grease affinity, it is in addition fatty
Adoption ester possessed lipophilicity in itself so that porous nanometer material entirety lipophile of the invention has reached more satisfactory water
It is flat, there is good tracking effect for oil substances.
The most preferred degradable stephanoporate nano material of the invention, it is by modified polylactic acid porous nanometer
Grain, internal layer are the polar group layer rich in hydroxyl, and outer layer is rich methylic silicone layer, the outer layer and internal layer it
Between connected by ehter bond；The hole of the porous nano particle is in three-dimensional network-like structure, and average pore size is 20-150 μm, hole
Gap rate is more than 80%.
On this basis, the second aspect of the present invention further provides for a kind of adsorbable, degradation grease complex microorganism
Material is targeted, it is fixed with compound thermophilic oil using degradable multiporous nano material of the present invention as carrier on the carrier
Bacterium.
In the complex microorganism targeting material of the present invention, described compound thermophilic oily bacterium is a variety of in the prior art can effectively to drop
Solve the combination of the bacterial strains of greases such as oil；Preferred compound thermophilic oily bacterium is selected from diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, waxy gemma
The combination of arbitrary two or more bacterial strains in bacillus, bacillus licheniformis or Lactobacillus rhamnosus；Most preferred compound thermophilic oily bacterium
It is collectively constituted by diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis and Lactobacillus rhamnosus
Bacterial strain combines.
In complex microorganism targeting material of the present invention, the compound thermophilic oily bacterium can be considered as sump oil of degrading
Multi-cultur es symbiosis microecosystem, which is fixed on the present invention using existing immobilized microorganism technology
On the porous nanometer material carrier that there is tracking greasy dirt ability, complex microorganism targeting material is formed, in view of it goes out
The sump oil Targeting Performance of color, the present inventor are visually referred to as " complex microorganism guided missile ".The present invention " complex microorganism is led
Bullet " can be widely applied to various water bodys, sandy beach, sandstone etc. varying environments.With conventional microbiological reparation of the prior art
Agent is different, and complex microorganism of the invention targeting material has the affinity of stronger sump oil, is scattered in and remains on seawater surface
Thin oil film on then firmly affine oil film, become scattered about in seawater that then drift looks for oil droplet and oil emulsion in the water surface, fall on sandy beach,
Then go down the affine Residual oil stayed in sandy beach and porous sandstone in the promotion of rainwater, tide, sea wind, not only solve bacterial strain and easily flow
The problem of mistake, is also provided with the ability of tracking sump oil.
The third aspect of the present invention provides the method for preparing the complex microorganism targeting material, includes the following steps：
1) aliphatic polyester porous nano particle is prepared, it is in three-dimensional network-like structure to make the particle Hole；
2) the aliphatic polyester porous nano particle that step 1) obtains is passed through into surface modified crosslinking polar group；
3) co-incubation is carried out to two or more thermophilic oily bacterium and obtains compound thermophilic oily bacterium, compound thermophilic oily bacterium is fixed on step
2) on the modified aliphatic polyester porous nano particle in surface；
4) the aliphatic polyester porous nano particle surface that step 3) is secured to compound thermophilic oily bacterium is further crosslinked lipophilic
Group obtains complex microorganism targeting material of the present invention.
In method of the present invention, the method for preparing aliphatic polyester porous nano particle described in step 1) can be
Existing various methods；Preferably method is：Aliphatic polyester presses (25~40) after being melted with pore-foaming agent:The quality of (60~80)
Than being mixed and made into mixture nano particle, the pore-foaming agent is then removed；The particle average pore size that this method obtains is in 20-150 μ
M, porosity are more than 80%.
In currently preferred method, the aliphatic polyester porous nano particle that step 1) is prepared is further roughened
Processing, so that porous nano particle surface obtains the structure of micro-rough, surface coarsening rate is to determine that porous nano particle is handed over
Join the key of polar group binding force quality；Most preferred method of roughening of the invention is by porous nano described made from step 1)
Particle is put into 1%~5% H2O230min is handled in solution；Thus it can obtain and the crosslinked best combination power of polar group.
In method of the present invention, the aliphatic polyester described in step 1) can be it is existing it is various satisfaction prepare it is porous
The aliphatic polyester of nano particle requirement；It may be selected from arbitrary in polylactic acid, polyglycolic acid or polycaprolactone or its copolymer
It is a kind of；Most preferably polylactic acid.
In method of the present invention, described in step 2) by surface modified crosslinking polar group, can be by existing
The various polar groups for being conducive to fixed thermophilic oily bacterium of a variety of methods crosslinking；It is preferred that in crosslinking hydroxyl, carboxyl, amino or carbonyl
Any one；Most preferably it is crosslinked hydroxyl.
In preferred method of the invention, the surface modifying method described in step 2) is as follows：The fat that step 1) is obtained
Adoption ester porous nano particle obtains hydroxylated aliphatic polyester porous nano particle using polyhydroxy compound modified.
In method of the present invention, the two or more thermophilic oily bacterium described in step 3) can degrade selected from existing
The arbitrary two or more thermophilic oily bacterium of sump oil；In preferred method, thermophilic oil bacterium is selected from：It is diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, waxy
The combination of arbitrary two or more bacterial strains in bacillus, bacillus licheniformis or Lactobacillus rhamnosus；It is most preferred compound thermophilic
Oily bacterium is by diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis and common group of Lactobacillus rhamnosus
Into bacterial strain combination.
In currently preferred method, the surface-crosslinked lipophilic group described in step 4) is using silane coupling agent hydrolysis production
What the polar group of the object aliphatic polyester porous nano particle surface modified with step 3) was reacted and was completed；At the same time silicon
Polycondensation also occurs between each other for alkane coupling agent hydrolysate, generates crosslinked action, finally poly- in the generation of porous nano particle surface
Siloxane layer.The further preferred trim,ethylchlorosilane of the silane coupling agent or methyl trichlorosilane (MTS).
A kind of most preferred method for preparing the complex microorganism targeting material of the invention, includes the following steps：
1. polylactic acid (PLA) is with starch pore-foaming agent according to (25~40):It is mixed to carry out heating melting for (60~80) mass ratio
It closes, the particle that PLA is mixed with starch is made；
2. step 1 gained particle is added in starch enzyme buffer liquid, it is more to obtain PLA for 30~40 DEG C of shaken cultivations 2~3 days
Porous materials；Gained PLA porous materials are put into 1%~5% H2O2Roughening treatment 30min in solution, is washed with deionized into
Property, the PLA porous materials being roughened；
3. the PLA porous materials after the roughening that 2~10 parts of steps 2 obtain is taken to use 1~5 part of beta-cyclodextrin (β-CD) solution
It is modified, make its beta-cyclodextrin of the crosslinking rich in hydroxyl, the reaction equation is as follows：
4. with diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis and Lactobacillus rhamnosus group
Into hybrid bacterial strain as thermophilic oily bacterium, carry out Zengjing Granule jointly, 1~3d of constant temperature incubation in 24 DEG C obtains composite microbial thing liquid
Body；
5. weighing 2~10 parts of the material that step 3 obtains, add in the complex microorganism liquid that step 4 obtains, shake culture
1-3d filters off culture solution, obtains the complex microorganism carrier of immobilization；
6. step 5 gained complex microorganism carrier and 0.1~5 part of methyl trichlorosilane are impregnated 3 in organic solvent~
8min makes the hydrolysate of methyl trichlorosilane be reacted with the hydroxyl condensation of step 5 gained complex microorganism carrier surface, completes
Methyl is in the crosslinking of complex microorganism carrier surface, while polycondensation also occurs between each other for the hydrolysate of methyl trichlorosilane,
Crosslinking is formed, in silicone layer of the complex microorganism carrier outmost surface generation rich in lipophilic methyl；The reaction
Equation is as follows：
Compared with prior art, preparation method of the invention is with the thinking of biological missile drug, in nano material preparation side
On the basis of method, by regulating and controlling parameter, degradable stephanoporate nano material is obtained, by carrying out surface modification to nano material,
Its surface is made to take particular functional group, then is grafted lipophilic group afterwards after further treatment, the internal layer of gained " microorganism guided missile " is
Polar group, outer layer are nonpolar lipophilic group, and the ability that material is made to have tracking sump oil shows the effect of guided missile.Not only
It can solve to apply free degradation bacteria with indigenous microbes there are antagonism, also with the ability for tracking greasy dirt.Due to molecule
Coupling, the material after grafting show the sump oils such as absorption diesel oil more higher than PLA monomer as targeting " bullet "
Identification and selection binding ability, and the presence of lipophile aliphatic polyester can enhance its lipophile on PLA molecules, this is just material
Automatic-searching absorption Residual oil opened up a new way, and embody the function of microorganism guided missile.Microorganism guided missile can be in stormy waves stream
The lower automatic tracing of effect and the diesel oil for adsorbing 50-80 times of own wt, degradation rate reach more than 80% in 3 days.
Specific embodiment
The technical solution and effect further illustrated the present invention below by way of the mode for enumerating specific embodiment.But the present invention
Range be not limited to cited specific embodiment.
By weight, the raw material and reagent that various embodiments of the present invention are used are as follows：
Embodiment 1.
Prepare it is a kind of it is traceable, adsorb and sea Residual oil of degrading " complex microorganism guided missile ", specific method is following (wherein
Described " part " refers both to parts by weight unless otherwise specified)：
1.35 parts of polylactic acid are mixed with 65 parts of starch by heating melting is carried out, and obtain polylactic acid and starch hybrid particles, are marked
It is denoted as PLAS.
2. the PLAS particles that step 1 obtains are added in the triangular flask equipped with starch enzyme buffer liquid, 40 DEG C, 180r/min
Shaken cultivation, pore-foaming agent ingredient therein of degrading, pore-foaming agent ingredient degradation rate reaches 100% within 3 days.The porous materials of PLA after degradation
Material is put into 2% H2O2Roughening treatment 30min in solution is washed with deionized to neutrality, the PLA porous materials being roughened,
Hole is in three-dimensional network-like structure, and a diameter of 20-150 μm of average pore size, porosity is more than 80%.
3. 2 parts of beta-cyclodextrins of materials'use (β-CD) solution modification that 2 parts of steps 2 is taken to obtain, operating condition are：At 80 DEG C
Under thermostatic ultrasonic oscillating condition, β-CD solution is added dropwise in PLA solution, 4h is vibrated, then makes in 30 DEG C of constant temperature distilled water
It is dialysed 36 hours with bag filter, removes solvent and free β-CD, obtain the product of crosslinking hydroxyl；
4. immobilized thallus：With the preferable hybrid bacterial strain of degraded oil effect (including diesel oil alkane eating bacteria, Bo Ku islands food alkane
Bacterium, bacillus cereus, bacillus licheniformis, Lactobacillus rhamnosus) as thermophilic oily bacterium, it is used for using 2216E sea water mediums
The Zengjing Granule of the raw thermophilic oily bacterium in sea, constant temperature incubation 3d in 24 DEG C, obtains complex microorganism.
5. weighing 2 parts of the crosslinking hydroxylcontaining materials that step 3 obtains, add in step 4 and cultivated in the complex microorganism liquid of 3d,
The shake culture 1d on shaking table filters off culture solution, obtains the complex microorganism carrier of immobilization；
6. 2 parts of complex microorganism carriers obtained by step 5 are put into the hexane solution containing 0.5% (v/v) MTS, soak
5min is steeped, taking-up is dried, and obtains the complex microorganism carrier of 0.5 part of methyl trichlorosilane of grafting.
Since molecules act on, the material after grafting shows absorption diesel oil more mono- than PLA as targeting bullet
The higher identification of body and selection binding ability, and the presence of lipophile aliphatic polyester can enhance its lipophile on PLA molecules, this
Just Residual oil is adsorbed for material Automatic-searching opened up a new way, embody the function of microorganism guided missile.Microorganism guided missile can be
Automatic tracing and the diesel oil of 80 times of own wt is adsorbed under the action of stormy waves stream, degradation rate reaches 85% in 3 days.
Embodiment 2.
Prepare it is a kind of it is traceable, adsorb and sea surface oil stain of degrading " complex microorganism guided missile ", specific method is following (wherein
Described " part " refers both to parts by weight unless otherwise specified)：
1.25 parts of polylactic acid carry out heating melting with 80 parts of starch and mix, and obtain polylactic acid and starch hybrid particles, mark
For PLAS.
2. the PLAS particles that step 1 obtains are added in the triangular flask equipped with starch enzyme buffer liquid, 30 DEG C, 180r/min
Shaken cultivation, pore-foaming agent ingredient therein of degrading, pore-foaming agent ingredient degradation rate reaches 100% within 3 days.The porous materials of PLA after degradation
Material is put into 4% H2O2Roughening treatment 30min in solution is washed with deionized to neutrality, the PLA porous materials being roughened,
Hole is in three-dimensional network-like structure, and a diameter of 20-150 μm of average pore size, porosity is more than 80%.
3. 5 parts of beta-cyclodextrins of materials'use (β-CD) solution modification that 10 parts of steps 2 is taken to obtain, operating condition are：80
Under DEG C thermostatic ultrasonic oscillating condition, β-CD solution is added dropwise in PLA solution, 4h is vibrated, then in 30 DEG C of constant temperature distilled water
It is dialysed 36 hours using bag filter, removes solvent and free β-CD, obtain the product of crosslinking hydroxyl.
4. immobilized thallus：With the preferable hybrid bacterial strain of degraded oil effect (including diesel oil alkane eating bacteria, Bo Ku islands food alkane
Bacterium, bacillus cereus, bacillus licheniformis, Lactobacillus rhamnosus) as thermophilic oily bacterium, it is used for using 2216E bacteria culture medias
The Zengjing Granule of the raw thermophilic oily bacterium in sea, constant temperature incubation 2d in 24 DEG C, obtains complex microorganism.
5. weighing 8 parts of the material that step 3 obtains, add in the complex microorganism liquid for having cultivated 2d, shaken on shaking table
2d is cultivated, filters off culture solution, obtains the complex microorganism carrier of immobilization；
6. 8 parts of complex microorganism carriers obtained by step 5 are put into the hexane solution containing 0.5% (v/v) MTS, soak
5min is steeped, taking-up is dried, and obtains the complex microorganism carrier of 2.5 parts of methyl trichlorosilanes of grafting.
Since molecules act on, the material after grafting shows absorption diesel oil more mono- than PLA as targeting bullet
The higher identification of body and selection binding ability, and the presence of lipophile aliphatic polyester can enhance its lipophile on PLA molecules, this
Just Residual oil is adsorbed for material Automatic-searching opened up a new way, embody the function of microorganism guided missile.Microorganism guided missile can be
Automatic tracing and the diesel oil of 80 times of own wt is adsorbed under the action of stormy waves stream, degradation rate reaches 85% in 3 days.
Embodiment 3.
Prepare it is a kind of it is traceable, adsorb and sea surface oil stain of degrading " complex microorganism guided missile ", specific method is following (wherein
Described " part " refers both to parts by weight unless otherwise specified)：
1.40 parts of polylactic acid carry out heating melting with 60 parts of starch and mix, and obtain polylactic acid and starch hybrid particles, mark
For PLAS.
2. the PLAS particles of step 1 are added in the triangular flask equipped with starch enzyme buffer liquid, 40 DEG C, 180r/min oscillations
Culture, pore-foaming agent ingredient therein of degrading, pore-foaming agent ingredient degradation rate reaches 100% within 2 days.PLA porous materials after degradation are put
Enter 1% H2O2Roughening treatment 30min in solution is washed with deionized to neutrality, the PLA porous materials being roughened, hole
In three-dimensional network-like structure, a diameter of 20-150 μm of average pore size, porosity is more than 80%.
3. 1 part of beta-cyclodextrin of materials'use (β-CD) solution modification that 2 parts of steps 2 is taken to obtain, operating condition are：At 80 DEG C
Under thermostatic ultrasonic oscillating condition, β-CD solution is added dropwise in PLA solution, 4h is vibrated, then makes in 30 DEG C of constant temperature distilled water
It is dialysed 36 hours with bag filter, removes solvent and free β-CD, obtain the product of crosslinking hydroxyl；
4. immobilized thallus：With the preferable hybrid bacterial strain of degraded oil effect (including diesel oil alkane eating bacteria, Bo Ku islands food alkane
Bacterium, bacillus cereus, bacillus licheniformis, Lactobacillus rhamnosus) as thermophilic oily bacterium, it is used for using 2216E bacteria culture medias
The Zengjing Granule of the raw thermophilic oily bacterium in sea, constant temperature incubation 3d in 24 DEG C, obtains complex microorganism.
5. weighing 2 parts of the material that step 3 obtains, add in the complex microorganism liquid for having cultivated 3d, shaken on shaking table
3d is cultivated, filters off culture solution, obtains the complex microorganism carrier of immobilization.
6. 2 parts of complex microorganism carriers obtained by step 5 are put into the hexane solution containing 0.5% (v/v) MTS, soak
5min is steeped, taking-up is dried, and obtains the complex microorganism carrier of 1 part of methyl trichlorosilane of grafting.
Since molecules act on, the material after grafting shows absorption diesel oil more mono- than PLA as targeting bullet
The higher identification of body and selection binding ability, and the presence of lipophile aliphatic polyester can enhance its lipophile on PLA molecules, this
Just Residual oil is adsorbed for material Automatic-searching opened up a new way, embody the function of microorganism guided missile.Microorganism guided missile can be
Automatic tracing and the diesel oil of 80 times of own wt is adsorbed under the action of stormy waves stream, degradation rate reaches 85% in 3 days.
Test example
With " the complex microorganism guided missile " prepared by the embodiment of the present invention 1 for sample, detected and calculated by routine test
It is for the oil absorption to heavy oil, crude oil and diesel oil.
Oil absorption is calculated according to formula (1), (2)：
In formula：K is oil absorbency, g/g；Q is protects oil cut rate, %；m1The quality before oil product is adsorbed for sample；m2It is soaked for sample
Not in solution, the quality after standing about 30s is taken out in adsorption saturation；m3It is taken out from oil for sample and continues to stand the matter after 15min
Amount.
Parallel test 3 times records experimental result, is averaged, obtains m1、m2And m3, corresponding oil absorbency k is calculated
With guarantor oil cut rate q, 1 the results are shown in Table.
Material prepared by 1 embodiment 1 of table is to the absorption property test result of different oil products
From the above it is found that the oil suction of " the complex microorganism guided missile " of the present invention to sump oils such as heavy oil, crude oil and diesel oil
Rate and retention rate are all very high, thus have the ability of tracking, absorption and sump oil of degrading.
Claims (10)
1. a kind of degradable stephanoporate nano material, it is by modified aliphatic polyester porous nano particle, and internal layer is
Polar group, outermost surface are nonpolar lipophilic group；The hole of the porous nano particle is in three-dimensional network-like structure.
2. porous nanometer material described in claim 1, it is characterised in that：The aliphatic polyester is selected from polylactic acid, poly- hydroxyl
Any one in guanidine-acetic acid or polycaprolactone or its copolymer；Most preferably polylactic acid；The polar group of the internal layer be hydroxyl,
Any one in carboxyl, amino or carbonyl；Most preferably hydroxyl；The nonpolar lipophilic group of the outermost surface is selected from hydrocarbon
Base, including any one in methyl, aliphatic group, aryl, halogen or ester group etc.；Most preferable.
3. porous nanometer material described in claim 1, which is characterized in that the modification includes：It is first that aliphatic polyester is more
The surface-modified crosslinking polar functional group of hole nano particle, then in the porous nano particle surface for being crosslinked with polar functional group into one
The nonpolar lipophilic group of step crosslinking.
4. porous nanometer material described in claim 1, which is characterized in that it is by modified polylactic acid porous nanometer
Grain, internal layer are the polar group layer rich in hydroxyl, and outer layer is rich methylic silicone layer, the outer layer and internal layer it
Between connected by ehter bond；The hole of the porous nano particle is in three-dimensional network-like structure, and average pore size is 20-150 μm, hole
Gap rate is more than 80%.
5. a kind of adsorbable, degradation grease complex microorganism targeting material, it degradable multiporous is received with described in claim 1
Rice material is carrier, and compound thermophilic oily bacterium is fixed on the carrier.
6. the complex microorganism targeting material described in claim 5, which is characterized in that the compound thermophilic oily bacterium eats selected from diesel oil
Arbitrary two or more bacterial strains in alkane bacterium, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis or Lactobacillus rhamnosus
Combination；Preferred compound thermophilic oily bacterium is by diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis
The bacterial strain combination collectively constituted with Lactobacillus rhamnosus.
7. preparing the method for the complex microorganism targeting material described in claim 5, include the following steps：
1) aliphatic polyester porous nano particle is prepared, it is in three-dimensional network-like structure to make the particle Hole；
2) the aliphatic polyester porous nano particle that step 1) obtains is passed through into surface modified crosslinking polar group；
3) co-incubation is carried out to two or more thermophilic oily bacterium and obtains compound thermophilic oily bacterium, compound thermophilic oily bacterium is fixed on step 2) table
On the modified aliphatic polyester porous nano particle in face；
4) the aliphatic polyester porous nano particle surface that step 3) is secured to compound thermophilic oily bacterium is further crosslinked lipophilic group,
Obtain the complex microorganism targeting material.
8. the method described in claim 7, it is characterised in that：Aliphatic polyester porous nano particle is prepared described in step 1)
Method is：Aliphatic polyester presses (25~40) after being melted with pore-foaming agent:The mass ratio of (60~80), preferably by 35:65 quality
Than being mixed and made into mixture nano particle, then removing the pore-foaming agent；Aliphatic polyester described in step 1) is selected from poly- breast
Any one in acid, polyglycolic acid or polycaprolactone or its copolymer；Most preferably polylactic acid；Pass through table described in step 2)
Face modified crosslinking polar group is any one being crosslinked in hydroxyl, carboxyl, amino or carbonyl；Most preferably hydroxyl；Step 2) institute
The surface modifying method stated is as follows：The aliphatic polyester porous nano particle that step 1) obtains is changed using polyol
Property, obtain hydroxylated aliphatic polyester porous nano particle；Two or more thermophilic oily bacterium described in step 3) are selected from：Diesel oil is eaten
Arbitrary two or more bacterial strains in alkane bacterium, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis or Lactobacillus rhamnosus
Combination, preferred compound thermophilic oily bacterium is by diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis
The bacterial strain combination collectively constituted with Lactobacillus rhamnosus.
9. the method described in claim 7, it is characterised in that：Surface-crosslinked lipophilic group described in step 4) is even using silane
What the polar group of the connection agent hydrolysate aliphatic polyester porous nano particle surface modified with step 3) was reacted and was completed；
At the same time polycondensation also occurs between each other for silane coupling agent hydrolysate, crosslinked action is generated, finally in porous nano particle
Surface Creation silicone layer；The preferred trim,ethylchlorosilane of the silane coupling agent or methyl trichlorosilane.
10. the method described in claim 7, which is characterized in that include the following steps：
1. polylactic acid (PLA) is with starch pore-foaming agent according to (25~40):(60~80) mass ratio carries out heating and melts mixing, system
The particle mixed into PLA and starch；
2. 1. gained particle is added in starch enzyme buffer liquid step, 30~40 DEG C of shaken cultivations 2~3 days obtain the porous materials of PLA
Material；Gained PLA porous materials are put into 1%~5% H2O2Roughening treatment 30min in solution is washed with deionized to neutrality,
The PLA porous materials being roughened；
3. the PLA porous materials after 2. roughening that 2~10 parts of steps obtain is taken to change using 1~5 part of beta-cyclodextrin (β-CD) solution
Property, make its beta-cyclodextrin of the crosslinking rich in hydroxyl, the reaction equation is as follows：
4. it is formed with diesel oil alkane eating bacteria, Bo Ku islands alkane eating bacteria, bacillus cereus, bacillus licheniformis, Lactobacillus rhamnosus
Hybrid bacterial strain carries out Zengjing Granule as thermophilic oily bacterium jointly, and 1~3d of constant temperature incubation in 24 DEG C obtains complex microorganism liquid；
5. weighing 3. 2~10 parts of material that step obtains, add in 4. complex microorganism liquid that step obtains, shake culture 1-
3d filters off culture solution, obtains the complex microorganism carrier of immobilization；
6. step 5 gained complex microorganism carrier and 0.1~5 part of methyl trichlorosilane are impregnated into 3~8min in organic solvent,
The hydroxyl condensation of the hydrolysate of methyl trichlorosilane and step 5. gained complex microorganism carrier surface is made react, completion methyl
Polycondensation also occurs between each other in the hydrolysate of the crosslinking of complex microorganism carrier surface, while methyl trichlorosilane, is formed
Crosslinking, in silicone layer of the complex microorganism carrier outmost surface generation rich in lipophilicity methyl；The reaction equation
It is as follows：
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