CN102260663A - Method for preparing magnetic immobilized particles for BOD (Biochemical Oxygen Demand) biological sensor - Google Patents
Method for preparing magnetic immobilized particles for BOD (Biochemical Oxygen Demand) biological sensor Download PDFInfo
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- CN102260663A CN102260663A CN 201110195464 CN201110195464A CN102260663A CN 102260663 A CN102260663 A CN 102260663A CN 201110195464 CN201110195464 CN 201110195464 CN 201110195464 A CN201110195464 A CN 201110195464A CN 102260663 A CN102260663 A CN 102260663A
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- sodium alginate
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 58
- 239000002245 particle Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 3
- 229910052760 oxygen Inorganic materials 0.000 title description 3
- 239000001301 oxygen Substances 0.000 title description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- 244000005700 microbiome Species 0.000 claims abstract description 19
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 16
- 239000000661 sodium alginate Substances 0.000 claims abstract description 16
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract 1
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 238000001514 detection method Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- 239000013598 vector Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 230000004071 biological effect Effects 0.000 description 8
- 239000011324 bead Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- 238000005842 biochemical reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses a method for preparing magnetic immobilized particles for BOD biological sensor, belonging to the technical field of environmental monitoring. The method comprises the steps of: using poval and sodium alginate as vectors of immobilized particles, mixing and embedding microorganisms and magnetic Fe3O4, then cross-linking by using boric acid solution and CaCl2 as a cross-linking agent and then reinforcing the cross-linking process with Na2SO4. The method of the invention can obviously improve the activity of the immobilized particles and enhance the stability of the BOD biological sensor and the accuracy of the detection result.
Description
Technical field
The invention belongs to the environmental monitoring technology field, be specifically related to a kind of preparation method of magnetic immobilization particle of the BOD of being used for biosensor.
Background technology
Biological identification element is the core component of BOD biosensor, has wherein comprised the needed microorganism of biochemical reaction.After being separated to suitable microorganism, adopt the means of various immobilized microorganisms, just can make the required recognition component of BOD biosensor.Its quality has determined the performance of BOD biosensor and the accuracy of mensuration to a great extent.Now, the investigator has done a large amount of research on BOD biosensor recognition component both at home and abroad, mainly concentrates on the biological activity aspect that improves biological identification element.
Any biology all has magnetic, so externally-applied magnetic field, and environmental magnetic field and biological intravital magnetic field all can exert an influence to the tissue and the vital movement of biology, are called biological effect of magnetic field.The character of this biological effect of magnetic field with strong and weak both with the character in magnetic field and strong and weak relevant, also relevant with the kind of biology and the tissue that is subjected to magnetic field etc.
The effect in magnetic field generally comprises physical action and chemical action.Physical action mainly is to utilize the effect of magnetic field force to carry out physical sepn, physical adsorption, and utilize the heat effect in magnetic field to eliminate dust, impurity, the application of aspects such as sterilization.And chemical action mechanism mainly is meant the speed of magnetic field acceleration chemical reaction, and then reaches the raising speed of reaction, the effect of efficient scrubbing.
In decades, mangneto physical chemistry biological effect is in biomedicine, environmental protection, and fields such as metallurgy obtain application more and more widely.Can improve biochemical reaction rate with magnetic field to the positive magnetic biological effect of microorganisms, thereby reach treatment effect preferably.Developing rapidly of biological magnetic technology is a important feature in the current biomagnetism.The metabolism of microorganism under magnetic field or the magnetic effect is the major cause that biodegradable organic is removed in the sewage.Since magnetic action, feasible microorganism of decomposing toxic substance, nitrobacterias etc. are enrichment gradually, and simultaneously, the katalysis in magnetic and magnetic field has improved microbic activity.Because magnetic Fe
3O
4The key attitude on surface, electronic state and surface atom coordination not congruent meeting different with granule interior cause its surfactivity increase, make it to become biological catalyst.And the existence of low-intensity magnetic field can promote Growth of Biologic Cell and metabolism, and the raising of the synthetic and enzymic activity of inducible enzyme, accelerates enzyme reaction.
In recent years, magnetization and magnetic biological effect are applied in the sewage disposal as a kind of enhancements.Many discovering adds magnetic in sewage treatment process, can increase substantially dissolved oxygen and improve microbic activity, improves the biological degradation efficient of waste water greatly.But magnetic technique combined with immobilization technology is used for the preparation of BOD biosensor biological identification element, does not also have relevant report at present.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of magnetic immobilization particle of the BOD of being used for biosensor.
A kind of preparation method of polyvinyl alcohol immobilized microorganism particles, carry out according to following steps:
(1) place water to mix polyvinyl alcohol and sodium alginate, heating in water bath also slowly is stirred to and dissolves, and makes the mixing solutions of polyvinyl alcohol and sodium alginate, leaves standstill and reduces to normal temperature;
(2) with microbial suspension and magnetic Fe
3O
4Mix mutually, make magnetic microbe suspension;
(3) mixing solutions with polyvinyl alcohol and sodium alginate mixes with magnetic microbe suspension;
(4) in boric acid solution, add CaCl
2, obtain cross-linking agent solution;
(5) drips of solution that step (3) is made with syringe or dropper is added in 30～45 ℃ the cross-linking agent solution, produces white spherical granules, and soaks therein 1～2 hour;
(6) leave standstill and leach white spherical granules behind 1～2h and be transposed to Na
2SO
4In the solution, soak about 2h after, the moisture that blots particle surface with filter paper makes the magnetic immobilization particle.
Step (1) adds the per-cent that polyvinyl alcohol, sodium alginate and water accounts for polyvinyl alcohol, sodium alginate and water gross weight and is respectively 8～12.5%, 0.5～1%, 87～91%; The mass concentration of microorganism is 10～30% in step (2) microbial suspension, magnetic Fe
3O
4Mass concentration be 1～10%; The volume ratio that step (3) adds the mixing solutions of magnetic microbe suspension and polyvinyl alcohol and sodium alginate is 1: 2; The mass concentration of step (4) boric acid solution mesoboric acid is 3-7%, CaCl in the cross-linking agent solution
2Mass concentration be 2-5%; Step (6) Na
2SO
4Na in the solution
2SO
4Mass concentration be 5-20%.
Beneficial effect of the present invention: (1) the inventive method can significantly improve the activity of immobilized microorganism, improves the performance of BOD biosensor and the accuracy of mensuration.(2) magnetic immobilization microorganism particles long service life of the present invention is as reaching more than three months the work-ing life with the magnetic immobilized active mud of the inventive method preparation.
Embodiment
The present invention will be further described with specific embodiment below.
The preparation of embodiment 1 magnetic immobilized active mud
Preparation process is as follows:
(1) be 10% polyvinyl alcohol (PVA) with massfraction and massfraction is the mixed solution thermosol of 1% sodium alginate, as embedded material; Heating in water bath leaves standstill and reduces to normal temperature to dissolving;
(2) get sewage disposal plant aeration tank water, leave standstill, treat the pond water stratification, pour out supernatant liquor to another container, remaining denseer mud mixture is fully shaken up, get 300ml, be diluted to 1000ml with supernatant liquid, add 1g glucose, in shaking bath in 30 ℃, cultivated 3 days down for 150 rev/mins, centrifugation obtains wet thallus.
(3) in the wet thallus that step (2) obtains, add 2wt% magnetic Nano Fe
3O
4Particulate, the mixture that obtains mix with step (1) solution according to 1: 2 embedding of volume ratio ratio;
(4) add 2g CaCl in the saturated boric acid solution of 100ml
2, prepare cross-linking agent solution;
(5) syringe with 0.40mm ID is added drop-wise to the mixed solution in the step (3) in the refrigerative cross-linking agent solution, forms the white spherical bead of 4mm diameter, and soaks 1～2h therein;
(6) leave standstill and leach particle behind 1～2h to be transposed to massfraction be 10%Na
2SO
4In the solution, soak about 2h after, wash white spherical bead with physiological saline, the moisture that blots particle surface with filter paper makes the magnetic immobilization particle.
The preparation of embodiment 2 magnetic immobilized active mud
Preparation process is as follows:
(1) be 8% polyvinyl alcohol (PVA) with massfraction and massfraction is the mixed solution thermosol of 0.5% sodium alginate, as embedded material; Heating in water bath leaves standstill and reduces to normal temperature to dissolving;
(2) get sewage disposal plant aeration tank water, leave standstill, treat the pond water stratification, pour out supernatant liquor to another container, remaining denseer mud mixture is fully shaken up, get 300ml, be diluted to 1000ml with supernatant liquid, add 1g glucose, in shaking bath in 30 ℃, cultivated 3 days down for 150 rev/mins, centrifugation obtains wet thallus.
(3) in the wet thallus that step (2) obtains, add 5wt% magnetic Nano Fe
3O
4Particulate, the mixture that obtains mix with step (1) solution according to 1: 2 embedding of volume ratio ratio;
(4) add 4g CaCl in the saturated boric acid solution of 100ml
2, prepare cross-linking agent solution;
(5) syringe with 0.40mm ID is added drop-wise to the mixed solution in the step (3) in the refrigerative cross-linking agent solution, forms the white spherical bead of 4mm diameter, and soaks 1～2h therein;
(6) leave standstill and leach particle behind 1～2h to be transposed to massfraction be 8%Na
2SO
4In the solution, soak about 2h after, wash white spherical bead with physiological saline, the moisture that blots particle surface with filter paper makes the magnetic immobilization particle.
The preparation of embodiment 3 magnetic immobilized active mud
Preparation process is as follows:
(1) be 12.5% polyvinyl alcohol (PVA) with massfraction and massfraction is the mixed solution thermosol of 0.8% sodium alginate, as embedded material; Heating in water bath leaves standstill and reduces to normal temperature to dissolving;
(2) get sewage disposal plant aeration tank water, leave standstill, treat the pond water stratification, pour out supernatant liquor to another container, remaining denseer mud mixture is fully shaken up, get 300ml, be diluted to 1000ml with supernatant liquid, add 1g glucose, in shaking bath in 30 ℃, cultivated 3 days down for 150 rev/mins, centrifugation obtains wet thallus.
(3) in the wet thallus that step (2) obtains, add 4wt% magnetic Nano Fe
3O
4Particulate, the mixture that obtains mix with step (1) solution according to 1: 2 embedding of volume ratio ratio;
(4) add 5g CaCl in the saturated boric acid solution of 100ml
2, prepare cross-linking agent solution;
(5) syringe with 0.40mm ID is added drop-wise to the mixed solution in the step (3) in the refrigerative cross-linking agent solution, forms the white spherical bead of 4mm diameter, and soaks 1～2h therein;
(6) leave standstill and leach particle behind 1～2h to be transposed to massfraction be 12%Na
2SO
4In the solution, soak about 2h after, wash white spherical bead with physiological saline, the moisture that blots particle surface with filter paper makes the magnetic immobilization particle.
The proof test of embodiment 4 magnetic immobilized microorganism effects
Carry out according to following steps:
(1) in the 250ml triangular flask, adds the immobilization microorganism particles that 5g embodiment 1 prepares, mix with the GGA standardized solution of 100ml different concns;
(2) (Thermo electron corporation USA) as the detector of DO change in concentration in the reactor, realizes DO data in real time record to adopt Orion 850A type dissolved oxygen instrument.
(3) take out immobilization microorganism particles, clean up, carry out the next batch experiment with distilled water;
(4) repeated experiments step (2)～(4).
As a result, the magnetic immobilization microorganism particles that utilizes present method to make is as shown in table 1 to the solution response of different GGA concentration.Compare with traditional method, the magnetic immobilized active mud granule biological activity of the embodiment of the invention 1 preparation is significantly strengthened, the relative biological activity of particulate has improved about 30%, and the GGA standardized solution to different concns has good linear dependence, improves the performance of BOD biosensor and the accuracy of mensuration.Simultaneously, the water-soluble coefficient of expansion of particle among the present invention (grain diameter per-cent before and after cultivating) is lower, and granule strength is significantly strengthened, and has prolonged work-ing life greatly.
Table 1 magnetic immobilization microorganism particles is to the response of different concns GGA standardized solution
Claims (2)
1. the preparation method of a polyvinyl alcohol immobilized microorganism particles is characterized in that, carries out according to following steps:
(1) place water to mix polyvinyl alcohol and sodium alginate, heating in water bath also slowly is stirred to and dissolves, and makes the mixing solutions of polyvinyl alcohol and sodium alginate, leaves standstill and reduces to normal temperature;
(2) with microbial suspension and magnetic Fe
3O
4Mix mutually, make magnetic microbe suspension;
(3) mixing solutions with polyvinyl alcohol and sodium alginate mixes with magnetic microbe suspension;
(4) in boric acid solution, add CaCl
2, obtain cross-linking agent solution;
(5) drips of solution that step (3) is made with syringe or dropper is added in 30～45 ℃ the cross-linking agent solution, produces white spherical granules, and soaks therein 1～2 hour;
(6) leave standstill and leach white spherical granules behind 1～2h and be transposed to Na
2SO
4In the solution, soak about 2h after, the moisture that blots particle surface with filter paper makes the magnetic immobilization particle.
2. according to the preparation method of the described a kind of polyvinyl alcohol immobilized microorganism particles of claim 1, it is characterized in that step (1) adds the per-cent that polyvinyl alcohol, sodium alginate and water accounts for polyvinyl alcohol, sodium alginate and water gross weight and is respectively 8～12.5%, 0.5～1%, 87～91%; The mass concentration of microorganism is 10～30% in step (2) microbial suspension, magnetic Fe
3O
4Mass concentration be 1～10%; The volume ratio that step (3) adds the mixing solutions of magnetic microbe suspension and polyvinyl alcohol and sodium alginate is 1: 2; The mass concentration of step (4) boric acid solution mesoboric acid is 3-7%, CaCl in the cross-linking agent solution
2Mass concentration be 2-5%; Step (6) Na
2SO
4Na in the solution
2SO
4Mass concentration be 5-20%.
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|---|---|---|---|
| CN 201110195464 CN102260663B (en) | 2011-07-13 | 2011-07-13 | Method for preparing magnetic immobilized particles for BOD (Biochemical Oxygen Demand) biological sensor |
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|---|---|---|---|
| CN 201110195464 CN102260663B (en) | 2011-07-13 | 2011-07-13 | Method for preparing magnetic immobilized particles for BOD (Biochemical Oxygen Demand) biological sensor |
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|---|---|
| CN102260663A true CN102260663A (en) | 2011-11-30 |
| CN102260663B CN102260663B (en) | 2013-06-12 |
Family
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374560A (en) * | 2012-04-19 | 2013-10-30 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol immobilized microorganism gel |
| CN104894099A (en) * | 2015-06-12 | 2015-09-09 | 福建省农业科学院中心实验室 | Bacteria immobilization particles for water purification and preparation method of bacteria immobilization particles |
| CN105441418A (en) * | 2015-12-11 | 2016-03-30 | 华南理工大学 | Polyvinyl alcohol immobilized microorganism gel beads and preparation method and use thereof |
| CN109207465A (en) * | 2018-09-25 | 2019-01-15 | 青岛理工大学 | Embedding medium for BOD sensor, preparation method and determination method thereof |
| CN111470615A (en) * | 2020-05-06 | 2020-07-31 | 北京工业大学 | Preparation and application of sulfate-reducing-reinforced composite bacteria embedded bioactive filler |
| CN111518298A (en) * | 2020-05-29 | 2020-08-11 | 深圳硅基传感科技有限公司 | Polymer film for biosensor and method for preparing the same |
| CN115432811A (en) * | 2022-10-06 | 2022-12-06 | 北京工业大学 | Nitrifying embedded particles for sewage treatment and preparation method thereof |
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| CN101519675A (en) * | 2009-03-30 | 2009-09-02 | 中国科学院等离子体物理研究所 | L-lactic acid fermentation method by using polyvinyl alcohol to solidify rhizopus oryzae |
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Patent Citations (1)
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| CN101519675A (en) * | 2009-03-30 | 2009-09-02 | 中国科学院等离子体物理研究所 | L-lactic acid fermentation method by using polyvinyl alcohol to solidify rhizopus oryzae |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374560A (en) * | 2012-04-19 | 2013-10-30 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol immobilized microorganism gel |
| CN103374560B (en) * | 2012-04-19 | 2016-01-20 | 中国石油化工集团公司 | A kind of preparation method of polyvinyl alcohol immobilized microorganism gel |
| CN104894099A (en) * | 2015-06-12 | 2015-09-09 | 福建省农业科学院中心实验室 | Bacteria immobilization particles for water purification and preparation method of bacteria immobilization particles |
| CN105441418A (en) * | 2015-12-11 | 2016-03-30 | 华南理工大学 | Polyvinyl alcohol immobilized microorganism gel beads and preparation method and use thereof |
| CN109207465A (en) * | 2018-09-25 | 2019-01-15 | 青岛理工大学 | Embedding medium for BOD sensor, preparation method and determination method thereof |
| CN109207465B (en) * | 2018-09-25 | 2021-10-01 | 无锡虞衡环境科技有限公司 | Embedding medium for BOD sensor, preparation method and determination method thereof |
| CN111470615A (en) * | 2020-05-06 | 2020-07-31 | 北京工业大学 | Preparation and application of sulfate-reducing-reinforced composite bacteria embedded bioactive filler |
| CN111518298A (en) * | 2020-05-29 | 2020-08-11 | 深圳硅基传感科技有限公司 | Polymer film for biosensor and method for preparing the same |
| WO2021238577A1 (en) * | 2020-05-29 | 2021-12-02 | 深圳硅基传感科技有限公司 | Polymer film for biosensor and preparation method therefor |
| CN111518298B (en) * | 2020-05-29 | 2022-03-29 | 深圳硅基传感科技有限公司 | Polymer film for biosensor and method for preparing the same |
| CN115432811A (en) * | 2022-10-06 | 2022-12-06 | 北京工业大学 | Nitrifying embedded particles for sewage treatment and preparation method thereof |
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|---|---|
| CN102260663B (en) | 2013-06-12 |
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