CN102306803B - Immune modification treatment method for anode of microbial fuel cell - Google Patents
Immune modification treatment method for anode of microbial fuel cell Download PDFInfo
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- CN102306803B CN102306803B CN2011102279824A CN201110227982A CN102306803B CN 102306803 B CN102306803 B CN 102306803B CN 2011102279824 A CN2011102279824 A CN 2011102279824A CN 201110227982 A CN201110227982 A CN 201110227982A CN 102306803 B CN102306803 B CN 102306803B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention discloses an immune modification treatment method for an anode of a microbial fuel cell. The method is characterized in that: the anode of the microbial fuel cell is treated through the following ways: firstly modifying chemical molecule groups on the anode surface of the microbial fuel cell; adopting the chemical molecule groups to fix the colloidal gold particle-modified anti-electricigen antibody to form the anode of the immune modification treated microbial fuel cell. According to the method, the contact chance of the microbial and the anode surface is improved, and the electrical conduction efficiency between the microbial and the anode is improved.
Description
Technical field
The invention belongs to the research and development technology field of microbiological fuel cell, be specifically related to a kind of anode of microbial fuel cell and immune modification processing method thereof.
Background technology
(Microbial Fuel Cells MFC) is a kind of device that utilizes microbe the chemical energy in the organic substance directly to be changed into electric energy to microbiological fuel cell.Microbiological fuel cell is as a kind of power technology of direct electrogenesis, for the application in fields such as biomass power generation, sewage disposal and space flight and aviation provides new principle and new method.Because microbial metabolism consumes the organic substance environmental pollution and plays catharsis in electrogenesis, receive much concern at present.
The basic functional principle of microbiological fuel cell is: under anode chamber's anaerobic environment, organic substance decomposes under microbial action and discharges electronics and proton, electronics relies on suitable electron transfer mediator effectively to transmit between biological components and anode, and is the electronics transmission production capacity process of unique electron acceptor with negative electrode.Electronics is delivered to negative electrode by external circuit and forms electric current, and proton is delivered to negative electrode by proton exchange membrane, and oxidant (being generally oxygen) obtains electronics at negative electrode and is reduced with proton and is combined into water.
Wherein microbe mainly contains 3 kinds to the mode of electrodes transfer electronics: 1) directly contact; 2) shift by transmitting the media implementation electronics; 3) utilize nano wire to transmit electronics at a distance.Because it is to shift by transmitting the media implementation electronics that quite a few microbe is arranged, the electron mediator that is applied at present among the MFC mainly contains methyl viologen, methyl blue (MB), 2-hydroxy-1,4-napthoquinone (HNQ), dimethyl diaminophenazine chloride (NR), thionine, Fe (III) EDTA etc.Though these electronic media amboceptors are the electrogenesis efficient that has improved MFC, because amboceptor is used input environment is just caused secondary pollution again.The present invention therefore.
Summary of the invention
The object of the invention is to provide a kind of anode of microbial fuel cell, has solved to have secondary pollution when the anode of microbial fuel cell microbe is to electrodes transfer electronics employing electron mediator in the prior art; The problem and other modes are difficult to prove effective etc.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
The anode of microbial fuel cell that a kind of immune modification is handled, it is characterized in that described anode of microbial fuel cell handles in the following manner: modify the chemical molecular group earlier on the anode of microbial fuel cell surface, the anti-electrogenesis microbe antibody that fixedly is modified with colloid gold particle by the chemical molecular group forms the anode of microbial fuel cell of immune modification processing then.
Preferably, described chemical molecular group is selected from amino, aldehyde radical, carboxyl or hydroxyl.
Preferably, described antibody is anti-electrogenesis microbe flagellum/cilium antibody.
Preferably, described anti-electrogenesis microbe flagellum/cilium/antibody is that the polyclonal antibody of electrogenesis microbe mixed immunity animal preparation, polyclonal antibody that the electrogenesis microbe prepares respectively are mixed into the antibody of anti-multidigit point in the anti-a plurality of sites of monoclonal antibody that prepare respectively of antibody admixed together or electrogenesis microbe again.
Preferably, the particle diameter of described colloid gold particle is between 1～1000nm.
Another object of the present invention is to provide a kind of anode of microbial fuel cell immune modification processing method, it is characterized in that said method comprising the steps of:
(1) chemical modification is carried out on the anode of microbial fuel cell surface and handled, make the anode of microbial fuel cell surface form a plurality of chemical molecular groups;
(2) the colloid gold particle labelled antibody is combined with the chemical molecular group on anode of microbial fuel cell surface and forms the anode of microbial fuel cell that immune modification is handled.
Preferably, the chemical molecular group is selected from amino, aldehyde radical, carboxyl, hydroxyl in the described method.
Preferably, the colloid gold particle labelled antibody produces by polyclonal antibody or monoclonal antibody absorption colloid gold particle in the described method.
Preferably, described method also comprises and forming behind the anode of microbial fuel cell that immune modification handles by different pH or/and different ions concentration is handled the step that anode is changed microbe.
Preferably, the anode of microbial fuel cell that immune modification is handled in the described method cleans the anode of microbial fuel cell surface in pH value in 1～7 scope, in ion concentration 0.1～4.5M/L, place replacing electrogenesis microbe in the microbiological fuel cell then.
Technical solution of the present invention is modified at the MFC anode surface by the anode of microbial fuel cell immune modification and is made microbe can directly contact the MFC anode surface, so just can guarantee that microbe just can directly will pass to anode to improve electrogenesis efficient at the electronics of metabolism.
Modify chemical groups such as amino or aldehyde radical in the technical scheme at the MFC anode surface, so just can be on these groups in conjunction with the polyclonal antibody of relevant decorrelation electrogenesis microbe flagellum/cilium, can make the electrogenesis microbe directly be attached to the MFC anode surface like this, guarantee that electronics that the growth of microorganism metabolism discharges just can be directly passed to anode and not need to walk again and cause damage between the biological components in anode pond, and be delivered to negative electrode by external circuit and form electric current and improve the production by biological electrical efficiency.Reduce resistivity in order to improve the electrogenesis rate, the present invention adopts at these antibody finishing colloid gold particles, utilizes colloid gold particle to improve its electric conductivity.
Concrete anode of microbial fuel cell immune modification processing method is that chemical groups such as amino, aldehyde radical, carboxyl, hydroxyl are beneficial to antibody and are attached to anode surface on anode surface is modified, prepare anti-electrogenesis microbe antibody, the colloid gold particle of preparation 1nm～1000nm, the antibody of preparation colloid gold particle is to improve its conductivity.Simultaneously also can be according to being combined in anode surface microbe what and vitality (being the metabolism active degree) cleaning the anode of microbial fuel cell surface and make death or metabolism not purchase vigorous microbe to come off and change the energetic microbe of another batch and paste clothes and keep higher electrogenesis efficient to guarantee MFC by regulating pH value 1～7 or ion concentration 0.1～4.5M/L, also avoided simultaneously in the past making its resistance increase influence electrogenesis efficient and have to change the waste that anode brings when the microbial death of anode surface., put into microbiological fuel cell after the cleaning again and just can change the energetic electrogenesis microbes of another batch and be combined in anode surface to guarantee the higher electrogenesis efficient of MFC maintenance or/and ion concentration 0.1～4.5M/L cleans the anode of microbial fuel cell surface makes death or metabolism not purchase vigorous microbe it is come off by regulating pH1～7.
The anode of microbial fuel cell of a kind of immune modification that the present invention obtains is modified the antibody that has colloid gold particle at anode of microbial fuel cell.It is amino, aldehyde radical, carboxyl, hydroxyl equimolecular group on anode surface is modified earlier, and then fixedly has the antibody of colloid gold particle.The colloid gold particle diameter is between 1～1000nm in the antibody of colloid gold particle.Described antibody should be anti-electrogenesis microbe flagellum (cilium) antibody.Described anti-electrogenesis microbe flagellum (cilium) antibody can be many particles antibody of various electrogenesis microbe mixed immunity animal preparations, also can be the polyclonal antibody for preparing respectively of various electrogenesis microbes antibody admixed together again, can also be the antibody that anti-a plurality of sites of monoclonal antibody that various electrogenesis microbes prepare respectively are mixed into anti-multidigit point.
The antibody that has colloid gold particle is colloid gold particle in combination on the antibody.Colloid gold particle applied chemistry reducing process prepares the colloid gold particle of 1～1000nm.By buying or make by oneself the polyclonal antibody of decorrelation electrogenesis microbe flagellum (cilium).According to the good pH of colloid gold particle size adjustment, preparation colloid gold particle labelled antibody behind ion concentration and colloid gold particle and the AC.Associated antibodies obtains antiserum by separate cultivating relevant electrogenesis microbe immune animal, with the immunization method separation and Extraction go out polyclonal antibody or screen isolate each relevant electrogenesis microbe respectively immune animal to prepare various monoclonal antibodies standby.
The present invention also provides a kind of fixing means in anode of microbial fuel cell surface electrogenesis microbe, comprise: the antibody probe by the fixing anti-electrogenesis microbe of chemical group of amino or aldehyde radical is set on the anode of microbial fuel cell surface, and these antibody probes all are modified with colloid gold particle.Can make the electrogenesis microbe directly be attached to the MFC anode surface like this, guarantee that electronics that the growth of microorganism metabolism discharges just can be directly passed to anode and not need to walk again and cause damage between the biological components in anode pond, and be delivered to negative electrode by external circuit and form electric current and improve the production by biological electrical efficiency
The present invention can selectively be fixed on the electrogenesis microbe in the microbiological fuel cell anode surface to improve the production by biological electrical efficiency, simultaneously also can be according to being attached to anode surface microbe what and vital activity (metabolism active degree) making and be combined in the anode of microbial fuel cell surface microorganism and come off and change the energetic electrogenesis microbe of another batch and keep higher electrogenesis efficient to guarantee MFC by regulating pH or ion concentration, the microbial death of also having avoided simultaneously in the past working as anode surface makes its resistance increase and will change the waste that anode brings, and it is time saving and energy saving to improve microbiological fuel cell electrogenesis efficient and need not change the cleaning anode of microbial fuel cell.
With respect to scheme of the prior art, advantage of the present invention is:
The invention belongs to the cultivation of microbe immunofixation and conduction technical field, a kind of fixing means in anode of microbial fuel cell surface electrogenesis microbe is provided, improve microbe and anode surface touch opportunity, improved electrical efficiency between microbe and anode.Concrete, by the antibody probe by the fixing anti-electrogenesis microbe of chemical group of amino or aldehyde radical is set on the anode of microbial fuel cell surface, and these antibody probes all are modified with colloid gold particle, have the antibody of colloid gold particle at anode modification.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 carries out the schematic diagram of immune modification to anode of microbial fuel cell for the embodiment of the invention.
Wherein 1 is not modified anode of microbial fuel cell; 2 are modified with the anode of microbial fuel cell of aldehyde radical for bonding; 3 are modified with aldehyde radical and amino anode of microbial fuel cell for bonding; 4 are modified with aldehyde radical and adsorb the anode of microbial fuel cell of antibody for bonding.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment
The anode of microbial fuel cell immune modification of present embodiment is modified aminoly the anode of microbial fuel cell surface is modified amino or modified group such as aldehyde radical with chemical method after as shown in Figure 1 again, and the antibody that will be adsorbed with collaurum again is attached to anode surface.Experiment shows that above design parameter is suitable for various electrogenesis microbes and is fixed on the anode of microbial fuel cell film.
Concrete steps are as follows:
1) preparation of colloid gold particle: the applied chemistry reducing process prepares the colloid gold particle of 1～1000nm.
The preparation reducing process of collaurum is mainly reduced gold chloride (HAuCl4) with reducing agent.Reducing agent commonly used has natrium citricum, tannic acid, ascorbic acid, white phosphorus, sodium borohydride etc.Earlier HauC14 is mixed with 0.01% aqueous solution earlier during preparation, gets 100ml and be heated to and boil.Under stirring, accurately add a certain amount of 1% reducing agent aqueous solution, 0.1～20ml.Continuing heating boiled 15 minutes.Can be observed flaxen aqueous solution of chloraurate and gray very soon after reducing agent adds this moment, continuous and change into black, stablizes into till the redness gradually subsequently.Select required particle according to the experiment needs, power according to reducing agent type and reduction, control preparation colloid gold particle size by regulating reducing agent and addition, reducing agent adds, and to lack the colloid gold particle of preparing just big, and the colloid gold particle of many preparations that reducing agent adds is just little.
2) polyclonal antibody or the Monoclonal Antibody of decorrelation electrogenesis microbe flagellum (cilium).
Add adjuvant immunity rabbit inguinal lymph nodes after getting every milliliter of 107～1015 bacteria inactivations of compound electrogenesis bacterium that separate the back cultivation, booster immunization after 15～30 days, can take vein or heart extracting blood according to the situation of tiring after 10～15 days, extract with 40%, 35% and 33% saturated ammonium sulfate respectively behind the separation of serum, measure the adjustment protein concentration of tiring and carry that to add the freezing preservation of 0.02%NaN3 between 2～10mg/ml standby through extracting the back for three times.
Add the purebred mouse web portion of adjuvant immunity after getting every milliliter of 107～1015 bacteria inactivations of compound electrogenesis bacterium that separate the back cultivation, booster immunization once after 10～15 days, after 20～40 days booster immunizations for the second time, get mouse spleen cell and murine myeloma cell after survey is tired and merge the antibody that the anti-electrogenesis bacterium of generation is selected in cultivation, obtain monoclonal antibody, the antibody mixing that obtains the anti-multidigit point of many strains namely can be applicable to anode modification and uses.The monoclonal antibody that obtains can be adjusted protein concentration and carries that to add the freezing preservation of 0.02%NaN3 between 2～10mg standby.
3) antibody colloidal gold preparation
Collaurum and protein bound are got albumen quality slightly more than the collaurum amount, and at less salt solution reaction 5～30 minutes, the albumen that centrifugal removal is not combined with collaurum, precipitation suspends with the buffer solution that contains PEG or BSA, recover centrifugal again behind the original volume.So washing is 2～4 times.Thoroughly remove unconjugated protein.Being mixed with working concentration with PBS or Tris preserves standby.
4) the anode surface antibody colloidal gold is modified
With 0.05mol/L pH9.6CBS oneself is known that antibody dilution to protein concentration is 0.01～3.0mg with measuring the antibody of tiring, cover the anode be modified with amino group put 37～45 ℃ 20～60 minutes, wash 3 times with 0.01M pH7.4PBS, again with 1～5mg/L bSA or 5～15% calf serums cover anode put 35～45 ℃ 20～60 minutes, dry up the anode postlyophilization with nitrogen stream after washing 3 times with 0.01M/LpH7.4PBS and preserve standby or directly apply to microbiological fuel cell.
Also can be according to being combined in anode surface electrogenesis microbe what and vital activity (metabolism active degree) after a period of time cleaning the anode of microbial fuel cell surface and make death or metabolism not purchase vigorous microbe it is come off by regulating pH1～7 or ion concentration 0.1～4.5M/L in battery applications, put into microbiological fuel cell after the cleaning again and just can change the energetic electrogenesis microbes of another batch and be combined in anode surface and can guarantee the higher electrogenesis efficient of MFC maintenance like this.
Experiment shows, is suitable for various electrogenesis microbes with upper type and is fixed on the anode of microbial fuel cell film.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All spirit essence is done according to the present invention equivalent transformation or modification all should be encompassed within protection scope of the present invention.
Claims (2)
1. the anode of microbial fuel cell handled of an immune modification, it is characterized in that described anode of microbial fuel cell handles in the following manner: modify the chemical molecular group earlier on the anode of microbial fuel cell surface, the anti-electrogenesis microbe antibody that fixedly is modified with colloid gold particle by the chemical molecular group forms the anode of microbial fuel cell of immune modification processing then; Described chemical molecular group is selected from amino, aldehyde radical, carboxyl or hydroxyl; Described anti-electrogenesis microbe antibody is anti-electrogenesis microbe flagellar antibody or cilium antibody; Described anti-electrogenesis microbe flagellar antibody or cilium antibody is the polyclonal antibody of electrogenesis microbe mixed immunity animal preparation, with the polyclonal antibody antibody admixed together that the electrogenesis microbe prepares respectively, the monoclonal antibody that maybe will resist the electrogenesis microbe in a plurality of sites to prepare is respectively mixed the antibody that forms anti-multidigit point; The particle diameter of described colloid gold particle is between 1～1000nm.
2. anode of microbial fuel cell immune modification processing method is characterized in that said method comprising the steps of:
(1) chemical modification is carried out on the anode of microbial fuel cell surface and handled, make the anode of microbial fuel cell surface form a plurality of chemical molecular groups;
(2) the colloid gold particle labelled antibody is combined with the chemical molecular group on anode of microbial fuel cell surface and forms the anode of microbial fuel cell that immune modification is handled; The chemical molecular group is selected from An Ji ﹑ Quan Ji ﹑ Suo Ji ﹑ hydroxyl in the described method; The colloid gold particle labelled antibody produces by polyclonal antibody or monoclonal antibody absorption colloid gold particle in the described method; Described method also comprises and forming behind the anode of microbial fuel cell that immune modification handles by different pH or/and different ions concentration is handled the step that anode is changed microbe; The anode of microbial fuel cell that immune modification is handled in the described method cleans the anode of microbial fuel cell surface in pH value in 1～7 scope, in ion concentration 0.1～4.5M/L, place replacing electrogenesis microbe in the microbiological fuel cell then.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0827229A2 (en) * | 1996-08-29 | 1998-03-04 | Korea Institute Of Science And Technology | Biofuel cell without electron transfer mediator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0827229A2 (en) * | 1996-08-29 | 1998-03-04 | Korea Institute Of Science And Technology | Biofuel cell without electron transfer mediator |
Non-Patent Citations (2)
| Title |
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| Nanograss array boron-doped diamond electrode for enhanced electron transfer from Shewanella loihica PV-4;Wenguo Wu, et al;《Electrochemistry Communications》;20110527;第13卷(第8期);872-874 * |
| Wenguo Wu, et al.Nanograss array boron-doped diamond electrode for enhanced electron transfer from Shewanella loihica PV-4.《Electrochemistry Communications》.2011,第13卷(第8期),872-874. |
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