CN102937608A - Novel microbial sensor for detecting cadmium ions - Google Patents
Novel microbial sensor for detecting cadmium ions Download PDFInfo
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- CN102937608A CN102937608A CN2012104735794A CN201210473579A CN102937608A CN 102937608 A CN102937608 A CN 102937608A CN 2012104735794 A CN2012104735794 A CN 2012104735794A CN 201210473579 A CN201210473579 A CN 201210473579A CN 102937608 A CN102937608 A CN 102937608A
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Abstract
The invention discloses a novel microbial sensor for detecting cadmium ions. The microbial sensor comprises a PC detection base plate, the surface of the PC detection base plate is provided with an alloy coating conducting channel, one end of the alloy coating conducting channel is connected with a lead, the other end of the alloy coating conducting channel is a detection coating, a layer of PC cover plate is covered on the detection coating, a detection tank is arranged at a position corresponding to the detection coating on the PC cover plate, the detection coating serves as the bottom of the detection tank, and a cadmium ion induction layer is coated on the surface of the detection coating of the detection tank; and the cadmium ion induction layer is formed by graphite power, chlorella green algae freeze-dried powder and liquid paraffin with a mass ratio of 45:45:10 through even mixing and laid on the surface of the detection coating. The microbial sensor has the advantages of being few in requirements for samples, short in detection time, high in sensitivity, low in detection limit, easy to carry, convenient to monitor in real time, above all, low in manufacturing cost, capable of mass production and the like.
Description
Technical field
The invention belongs to microorganism microelectrode field, be specifically related to a kind of microbiological sensor of novel detection cadmium ion.
Background technology:
Cadmium is the very large heavy metal of a kind of toxicity, and its compound also mostly belongs to toxicant, therefore is considered to a kind of environmental contaminants of danger.The cadmium of denier just can damage human body, and it has characteristics stable, that accumulate and be difficult for eliminating by the food chain enrichment.In recent years no matter every studies have shown that is from toxicity or cumulative effect, and cadmium all will be the third heavy metal element that pollutes human environment, threat human health after mercury, lead.Cadmium all is widely used in industries such as plating, automobile and aviation, pigment, paint, printings, and the cadmium wastewater that factory discharges is the primary pollution source of water Cd pollution.The waste water (cadmium content is up to 0.089mg/L) etc. of producing the technique discharge such as phosphate fertilizer such as the waste water (cadmium content is 0.065mg/L approximately) of electroplating industry, war production discharging and sulfuric acid ore extracting sulfuric acid, rock phosphate in powder is particularly serious to water pollution.World-shaking Japan " itai-itai " is exactly the typical example that pollute in the paddy field,, is called as " global ten overall situation contamination accidents " because cadmium pollution causes.Cadmium has caused the attention of countries in the world to the harm of human body, various countries have all formulated corresponding national standard.The maximal emission of China's regulation cadmium in industrial wastewater is 0.1mg/L (being limited to 0.005mg/L in the potable water on the cadmium content), so cadmium wastewater must be processed before discharging, to reach the requirement of discharging, avoids polluting the generation of poisoning.Therefore, effective processing of cadmium wastewater is very urgent, and it is to prevent and stop the matter of utmost importance of cadmium pollution that cadmium ion in the water is carried out detecting in real time fast.
The method of the heavy metals such as traditional detection cadmium ion is to need to deliver to the laboratory behind the spot sampling to analyze, expend height, efficient is low, and owing in time not detecting, water sample may change in the censorship way, or polluted in the water sample transmission course, this all can have influence on the objectivity of testing result.And most of Modern Heavy metal analysis system, such as atomic absorption spectrum, inductively coupled plasma atomic emission spectrum etc., although accurately testing result can be provided, but instrument is expensive, bulky, complex structure and need long sample pretreatment and analytic process, can not make Site Detection, cause the early-warning and predicting effect seriously to lag behind.As everyone knows, sensor technology is a kind of simple, detection method of need not loaded down with trivial details sample preprocessing, and potential method detects heavy metal ion sensor especially low cost, high sensitivity and rapid-action instrument, its light portable, can carry out the scene and detect in real time, thereby improve accuracy of measurement.
Summary of the invention:
The purpose of this invention is to provide a kind of be simple and easy to, with low cost, be easy to carry, probe response is fast, highly sensitive, detects lower limit low, the microbiological sensor of the novel detection cadmium ion of long service life.
The microbiological sensor of novel detection cadmium ion of the present invention, it is characterized in that, comprise that PC detects base plate, detect backplate surface at PC and have an alloy coat conduction pathway, alloy coat conduction pathway one end links to each other with lead-in wire, an other end is for detecting coating, above detecting coating, be coated with one deck PC cover plate, on the PC cover plate, the position corresponding with detecting coating is provided with detection cell, detecting coating becomes the bottom surface of detection cell, is covered with one deck cadmium ion inductive layer at the detection coating surface of detection cell;
Described cadmium ion inductive layer is comprised of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss, after the three is mixed, is tiled in the detection coating surface.
Described detection coating is preferably in the form of annular discs, and its diameter is 10 ~ 15mm.The discoid detection coating of this diameter can make above green alga is attached to effectively, avoids the electric signal loss, can keep again its good sensitivity, and save the space.
Described alloy coat conduction pathway is preferably electroplated with synthetic gold, platinum or silver and is formed, and it plays the electric signal conduction.
Described PC detects base plate and PC cover plate, and to refer to its material be the PC(polycarbonate) material detection base plate and the cover plate made.
The thickness of described cadmium ion inductive layer is preferably≤1mm.
The microbiological sensor of novel detection cadmium ion of the present invention can link to each other with multi-Channels Data Acquisition by lead-in wire, realize to cadmium ion in the sample fast, effective analyzing and testing.
The present invention prepares electrode with freeze-drying Chlorella green alga, and learns cadmium ion content in the solution by the potential difference values of analyzing electrode, thereby reaches the effect that detects cadmium ion.Preparation method of the present invention has not only broken the classic method that in the past prepares sensor with active bio, kept biology sensor to detecting optionally advantage of object height, remedied simultaneously the shortcoming of the low stability of active bio sensor, prolonged the serviceable life of sensor, also laid a good foundation to on-the-spot, real-time, the easy detection method of structure of whole solid state development and foundation for biology sensor.
The present invention has realized the characteristics such as the sample requirement is few, detection time is short, highly sensitive, the detection lower limit is low in addition, very easily carries, and is convenient to Real-Time Monitoring; The most important thing is that cost of manufacture is cheap, can be mass-produced.And the present invention combines with relevant measuring technology and data processing software, can further realize original position, online micro-analysis system, detects to traditional environment and brings basic change.
Bead of the present invention belongs to green alga (Chlorella Vulgaris) and derives from (address: No. 7 hydrobiont research institute of Chinese Academy of Sciences algae kind storehouses of Lopa Nationality an ancient woman's ornament Shandong, Wuhan City, Hubei Province Hunan Road), Chinese Academy of Sciences typical case culture collection council algae kind storehouse, its deposit number is: FACHB-1227, this algae kind is for sale, and anyone can be from buying this algae kind here.
Description of drawings:
Fig. 1 is the structural representation of the microbiological sensor of novel detection cadmium ion of the present invention;
Fig. 2 is the use schematic diagram of the microbiological sensor of novel detection cadmium ion of the present invention;
Fig. 3 is that the microbiological sensor (freeze-drying green alga adhesive electrodes) of novel detection cadmium ion is to the response curve of the cadmium-ion solution of variable concentrations;
Fig. 4 is freeze-drying green alga adhesive electrodes sensitivity test (concentration/voltage) typical curve;
Fig. 5 is freeze-drying green alga adhesive electrodes long term stability tests curve;
Fig. 6 is that freeze-drying green alga adhesive electrodes is to the response curve of the cadmium-ion solution of variable concentrations;
Fig. 7 is freeze-drying green alga adhesive electrodes concentration/voltage standard curve;
Fig. 8 is that freeze-drying green alga adhesive electrodes is to containing the response curve of cadmium water quality standard sample.
Wherein 1, PC detects base plate; 11, cadmium ion alloy coat conduction pathway; 111, cadmium ion detects coating; 112, silver wire; 2, PC cover plate; 3, cadmium ion detection cell; 4, multi-Channels Data Acquisition; 5, silver-silver chloride reference electrode.
Embodiment:
Following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1:
One, the preparation of the microbiological sensor of novel detection cadmium ion:
1. the preparation method of the cultivation of Chlorella green alga and freeze-dried powder:
1) getting Chlorella green alga algae kind that 30mL is in exponential phase receives 3000mL and has sterilized in the formulated OECD fresh water algae nutrient culture media (pH 6 ~ 9) of deionized water, placing intensity of illumination is that the illumination box of 4440lx ~ 8880lx is cultivated 144h ~ 168h, 23 ℃ ± 2 ℃ of temperature;
2) the 3000mL nutrient solution is sub-packed in the 1000mL centrifuge tube, the centrifugal 1h of 8000rpm abandons supernatant, gets the green alga precipitation;
3) green alga is precipitated freezing draining, obtained Chlorella green alga freeze-dried powder.
2. the preparation ionic conduction becomes gold plating:
As shown in Figure 1, with 50 * 75 * 1mm(long * wide * thick) polycarbonate base plate (PC plate) detect base plate 1 as PC, detect base plate 1 usefulness alloy material (main composition is copper and mickel) at PC and electroplate one for conducting electrical signals " match type " passage, i.e. cadmium ion alloy coat conduction pathway 11.Cadmium ion alloy coat conduction pathway 11 be by diameter be the circular coating of 10mm and 7 * 60mm(long * wide) the rectangle coating be formed by connecting, circular coating place is as detecting coating, be cadmium ion and detect coating 111, will be decided to be detection site herein, the rectangle coating plays the signal transmission effect; Then PC detect base plate 1 bottom, 50 * 55mm(long * wide) scope in be coated with equably the approximately epoxy resin of 400 μ m thickness of one deck, cadmium ion detects on the coating 111 and does not apply epoxy resin, then, with 50 * 55 * 1mm(long * wide * thick) PC cover plate 2 be covered in PC detect base plate 1 bottom above, it is sticked to above the epoxy resin, epoxy resin mainly plays a part to adhere to and insulation, and the circular opening that diameter is 10mm is left in the position of corresponding cadmium ion detection coating 111 on this PC cover plate 2, hole part and detection coating just form detection cell, be cadmium ion detection cell 3, detect the bottom surface that coating 111 is positioned at cadmium ion detection cell 3.
3. prepare the cadmium ion inductive layer
The compound method of cadmium ion inductive layer is: the raw material of cadmium ion inductive layer is comprised of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss.
According to above-mentioned mass ratio, take by weighing Chlorella green alga freeze-dried powder, dag and whiteruss, the three is mixed thoroughly stirring, get the green alga potpourri.With pure water rinsing cadmium ion detection cell 3, blow and spray to remove residual water droplet with nitrogen gun again; Then getting 0.5g green alga potpourri is applied on the cadmium ion detection coating 111 thinly, entirely, equably, the green alga potpourri that is applied on the cadmium ion detection coating 111 is the cadmium ion inductive layer, its thickness is approximately 1mm, and whole pick-up unit is called green alga graphite adhesive electrodes.Set up respectively simple plug and silver wire 112 in cadmium ion alloy coat conduction pathway 11 upper ends, obtain therefrom the microbiological sensor of novel detection cadmium ion of the present invention, be kept at last in the clean glassware.
Two. the Performance Detection of the microbiological sensor of novel detection cadmium ion:
Before experiment, pass into 50mL 10 with nitrogen
-1Remove oxygen in the mol/L Tris-HCl solution (pH=6.7); Then, drip 10 μ L 10
-1Mol/L CdCl
2Solution (pH=5) stirs evenly to Tris-HCl solution; Again the microbiological sensor of novel detection cadmium ion is immersed and contain the Trace Cadmium ion (concentration is about 10
-5Mol/L) in the Tris-HCl solution, soak 15 minutes (immersion process needs the magnetic force rotor to stir) with active electrode.Soak and thoroughly clean up the cadmium ion inductive layer with pure water later.As shown in Figure 2, the cadmium ion alloy coat conduction pathway 11 of electrode is by silver wire 112 and multi-Channels Data Acquisition 4(Keithly 2700 types) high-end electromotive force interface (H) be connected, silver-silver chloride reference electrode 5(Shanghai thunder magnetic 218 types) be connected with the low side electromotive force interface (L) of multi-Channels Data Acquisition 4 and together immerse at the bottom of the 100mL potassium nitrate in the liquid (concentration: 0.1mol/L, pH=6) with the microbiological sensor of novel detection cadmium ion.Subsequently, add successively 10 μ L, 100 μ L, 1000 μ L 10
-3Mol/L CdCl
2Solution and 100 μ L, 1000 μ L 10
-1Mol/L CdCl
2Solution; At last, the concentration range that draws cadmium ion is 10
-7Mol/L～10
-3Mol/L.The sensor basis of the detection cadmium ion that this is novel draws corresponding with it potential difference values to the detection of the cadmium-ion solution of variable concentrations.As shown in Figure 3, potential difference values raises along with the rising of concentration, and presents regular, stair-stepping ascendant trend; Fig. 4 then is the typical curve of concentration/voltage, the potential difference values that the reflection sensor is measured and the linear relationship of concentration of cadmium ions.10
-7Mol/L to 10
-5Mol/L Cd
2+Under the concentration range, transducer sensitivity is the 28mV/pCd(theoretical value: 30mV/dec); 10
-5Mol/L to 10
-3Mol/L Cd
2+Under the concentration range, transducer sensitivity is 13mV/pCd; Lowest detection to cadmium ion is limited to 0.08 μ mol/L, and the response time is less than 90s.And the present invention can reuse, and reaches 15 week or above (see figure 5)s during use.
Three. the microbiological sensor of novel detection cadmium ion is to containing the detection of cadmium water quality standard sample:
At first, according to above-mentioned experimental technique, with the sensor of this invention respectively to 10
-7Mol/L, 10
-6Mol/L, 10
-5Mol/L, 10
-4Mol/L and 10
-3The cadmium-containing solution of mol/L concentration detects, and according to its magnitude of voltage of measuring, draws the typical curve (Fig. 6,7) of concentration/voltage.Then, sensor is immersed contain cadmium sample (lot number: 201422, standard value: 64.6 ± 5.3 μ g/L, relative concentration: 58 ± 5 μ mol/L), measuring magnitude of voltage is 63mV(Fig. 8).Shown in typical curve Fig. 7, the corresponding magnitude of voltage of 58 ± 5 μ mol/L concentration of cadmium ions is 55 ± 1mV, the magnitude of voltage very close (error is about 14%) of gained when containing the cadmium standard model with the sensor detection.The microbiological sensor that proves thus novel detection cadmium ion of the present invention is reliably, can be used for monitoring industrial cadmium wastewater (maximal emission of China's regulation cadmium in industrial wastewater is: 0.9 μ mol/L is equivalent to 0.1mg/L).And, according to concentration/voltage standard curve learn detect the gained potential difference values with it corresponding ion concentration whether meet or exceed the safety standard of national regulation industrial sewage, carry out effectively, targetedly necessary deeper safety analysis, and take adequate measures; Also can tentatively determine situation and the pollution source of sewage pollution according to testing result, avoid blindly dropping into, cause the waste of too much manpower and materials, this is the safety of water source assessment development trend that tallies with the national condition.
Claims (4)
1. the microbiological sensor of a novel detection cadmium ion, it is characterized in that, comprise that PC detects base plate, detect backplate surface at PC and have an alloy coat conduction pathway, alloy coat conduction pathway one end links to each other with lead-in wire, an other end is for detecting coating, be coated with one deck PC cover plate above detecting coating, on the PC cover plate, the position corresponding with detecting coating is provided with detection cell, detecting coating becomes the bottom surface of detection cell, is covered with one deck cadmium ion inductive layer at the detection coating surface of detection cell;
Described cadmium ion inductive layer is comprised of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss, after the three is mixed, is tiled in the detection coating surface.
2. the microbiological sensor of novel detection cadmium ion according to claim 1 is characterized in that, described detection coating is in the form of annular discs, and its diameter is 10 ~ 15mm.
3. the microbiological sensor of novel detection cadmium ion according to claim 1 is characterized in that, described alloy coat conduction pathway is to electroplate with synthetic gold, platinum or silver to form.
4. the microbiological sensor of novel detection cadmium ion according to claim 1 is characterized in that the thickness≤1mm of described cadmium ion inductive layer.
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|---|---|---|---|
| CN201210473579.4A CN102937608B (en) | 2012-11-20 | 2012-11-20 | Novel microbial sensor for detecting cadmium ions |
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| CN201210473579.4A CN102937608B (en) | 2012-11-20 | 2012-11-20 | Novel microbial sensor for detecting cadmium ions |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107561240A (en) * | 2017-08-23 | 2018-01-09 | 湖南城市学院 | A kind of evaluation method using turfgrass microbial association cadmium pollution soil repair |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262205A (en) * | 1990-07-20 | 1993-11-16 | Battelle-Institut E.V. | Process for producing the ion-sensitive probe electrode of a heavy-metal-ion sensor |
| CN102507698A (en) * | 2011-09-23 | 2012-06-20 | 广东省微生物研究所 | Novel sensor for synchronously detecting copper ions and lead ions |
-
2012
- 2012-11-20 CN CN201210473579.4A patent/CN102937608B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262205A (en) * | 1990-07-20 | 1993-11-16 | Battelle-Institut E.V. | Process for producing the ion-sensitive probe electrode of a heavy-metal-ion sensor |
| CN102507698A (en) * | 2011-09-23 | 2012-06-20 | 广东省微生物研究所 | Novel sensor for synchronously detecting copper ions and lead ions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107561240A (en) * | 2017-08-23 | 2018-01-09 | 湖南城市学院 | A kind of evaluation method using turfgrass microbial association cadmium pollution soil repair |
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Address after: 510070 No. 100 martyrs Middle Road, Guangdong, Guangzhou Co-patentee after: Foshan Environment Health and Safety Evaluation and Research Center Patentee after: Guangdong Institute of Microbiology (Guangdong province microbiological analysis and testing center) Address before: 510070 No. 100 martyrs Middle Road, Guangdong, Guangzhou Co-patentee before: Foshan Environment Health and Safety Evaluation and Research Center Patentee before: Guangdong Institute of Microbiology |