CN102937608B - Novel microbial sensor for detecting cadmium ions - Google Patents
Novel microbial sensor for detecting cadmium ions Download PDFInfo
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- CN102937608B CN102937608B CN201210473579.4A CN201210473579A CN102937608B CN 102937608 B CN102937608 B CN 102937608B CN 201210473579 A CN201210473579 A CN 201210473579A CN 102937608 B CN102937608 B CN 102937608B
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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 heavy metal that a kind of toxicity is very large, and its compound also mostly belongs to toxicant, is therefore considered to a kind of environmental contaminants of danger.The cadmium of denier just can damage human body, and it has feature stable, that accumulate and be difficult for elimination by food chain enrichment.In recent years no matter every studies have shown that, be 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 is all 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 discharges such as phosphate fertilizer such as the waste water (the about 0.065mg/L of cadmium content) of electroplating industry, war production discharge 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 paddy field, because cadmium pollution causes, is called as " global ten overall situation contamination accidents ".Cadmium has caused the attention of countries in the world to the harm of human body, various countries have all formulated corresponding national standard.China specifies that the maximal emission of cadmium in industrial wastewater is 0.1mg/L (being limited to 0.005mg/L in potable water on cadmium content), so cadmium wastewater must be processed before discharge, to reach the requirement of discharge, avoid 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 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 laboratory after spot sampling to analyze, expend height, efficiency is low, and owing to not detecting in time, water sample may change in censorship way, or polluted in water sample transmitting procedure, this all can have influence on the objectivity of testing result.And most of Modern Heavy metal analysis system, as atomic absorption spectrum, inductively coupled plasma atomic emission spectrum etc., although testing result accurately can be provided, but instrument is expensive, bulky, complex structure and sample pretreatment and analytic process that need to be longer, can not make Site Detection, cause early-warning and predicting effect seriously to lag behind.As everyone knows, sensor technology be a kind of simple, without the detection method of loaded down with trivial details sample preprocessing, and potential method detects heavy metal ion sensor low cost, high sensitivity and rapid-action instrument especially, its light portable, can carry out scene and detect in real time, thereby improve accuracy of measurement.
Summary of the invention:
The object of this invention is to provide one 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 there is an alloy coat conduction pathway, alloy coat conduction pathway one end is connected with lead-in wire, one end is for detecting coating in addition, above detecting coating, be coated with one deck PC cover plate, on 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 made up of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss, after three is mixed, is laid in 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, to avoid electric signal loss, can keep again its good sensitivity, and save space.
Described alloy coat conduction pathway is preferably electroplated and is formed with synthetic gold, platinum or silver, and it plays electric signal conduction.
Described PC detects base plate and PC cover plate, and to refer to its material be PC(polycarbonate) material detection base plate and the cover plate made.
Be preferably≤the 1mm of thickness of described cadmium ion inductive layer.
The microbiological sensor of novel detection cadmium ion of the present invention can be connected with multi-Channels Data Acquisition by lead-in wire, realizes quick, the effective analyzing and testing to cadmium ion in sample.
The present invention prepares electrode with freeze-drying Chlorella green alga, and learns cadmium ion content in 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 of in the past preparing sensor with active bio, retain biology sensor to detecting optionally advantage of object height, made up the shortcoming of the low stability of active bio sensor simultaneously, extend the serviceable life of sensor, also for biology sensor is laid a good foundation to on-the-spot, real-time, the easy detection method of structure of whole solid state development and foundation.
The present invention has realized the features such as sample requirement is few, detection time is short, highly sensitive, 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 to relevant measuring technology and data processing software, can further realize original position, online micro-analysis system, detect and bring basic change to traditional environment.
Bead of the present invention belongs to green alga (Chlorella Vulgaris) and derives from Chinese Academy of Sciences typical case culture collection council's algae kind storehouse (address: hydrobiont research institute of Chinese Academy of Sciences algae kind storehouse, No. 7, South Road, East Lake, Luo Jia Shan, Wuhan City, Hubei Province), its deposit number is: FACHB-1227, this algae kind is for sale, and anyone can be from buying this algae kind here.
Brief description of the 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 the response curve of the microbiological sensor (freeze-drying green alga adhesive electrodes) of the novel detection cadmium ion cadmium-ion solution to 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 the response curve of the cadmium-ion solution of freeze-drying green alga adhesive electrodes to 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 the response curve containing 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 illustrate of the present invention, instead of limitation of the present invention.
Embodiment 1:
One, the preparation of the microbiological sensor of novel detection cadmium ion:
1. the cultivation of Chlorella green alga and the preparation method of freeze-dried powder:
1) get 30mL and receive 3000mL in the formulated OECD fresh water algae nutrient culture media (pH 6 ~ 9) of sterilizing deionized water in the Chlorella green alga algae kind of exponential phase, the illumination box that is placed in intensity of illumination and is 4440lx ~ 8880lx is cultivated 144h ~ 168h, 23 DEG C ± 2 DEG C of temperature;
2) 3000mL nutrient solution is sub-packed in 1000mL centrifuge tube, the centrifugal 1h of 8000rpm, abandons supernatant, gets green alga precipitation;
3) green alga is precipitated to freezing draining, obtained Chlorella green alga freeze-dried powder.
2. preparation ionic conduction becomes gold plating:
As shown in Figure 1, long × wide × thick using 50 × 75 × 1mm() polycarbonate base plate (PC plate) detect base plate 1 as PC, detect on base plate 1 and electroplate one for conducting electrical signals " match type " passage, i.e. cadmium ion alloy coat conduction pathway 11 with alloy material (main composition is copper and mickel) at PC.The circular coating that cadmium ion alloy coat conduction pathway 11 is is 10mm by diameter and 7 × 60mm(are long × wide) 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, rectangle coating plays signal transmission effect, then detect base plate 1 bottom 50 × 55mm(at PC long × wide) scope in be coated with equably the epoxy resin of one deck approximately 400 μ m thickness, cadmium ion detects in coating 111 and does not apply epoxy resin, then, 50 × 55 × 1mm(is long × wide × thick) PC cover plate 2 be covered in PC detect base plate 1 bottom above, it is sticked to above epoxy resin, epoxy resin mainly plays a part to adhere to and insulation, and the circular opening that diameter is 10mm is outputed 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 cadmium ion inductive layer
The compound method of cadmium ion inductive layer is: the raw material of cadmium ion inductive layer is made up of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss.
According to above-mentioned mass ratio, take Chlorella green alga freeze-dried powder, dag and whiteruss, three is mixed thoroughly and stirred, obtain green alga potpourri.With pure water rinsing cadmium ion detection cell 3, then blow and spray to remove residual water droplet by nitrogen gun; Then getting 0.5g green alga potpourri is applied in cadmium ion detection coating 111 thinly, entirely, equably, the green alga potpourri being applied in cadmium ion detection coating 111 is 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 finally kept in clean glassware.
Two. the Performance Detection of the microbiological sensor of novel detection cadmium ion:
Before experiment, pass into 50mL 10 with nitrogen
-1in mol/L Tris-HCl solution (pH=6.7), remove oxygen; Then, drip 10 μ L 10
-1mol/L CdCl
2solution (pH=5), to Tris-HCl solution, stirs evenly; (concentration is about 10 again the microbiological sensor immersion of novel detection cadmium ion to be contained to Trace Cadmium ion
-5mol/L), in Tris-HCl solution, soak 15 minutes (immersion process needs magnetic force rotor to stir) with active electrode.Soak later and thoroughly clean up cadmium ion inductive layer with pure water.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 100mL potassium nitrate in 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; Finally, the concentration range that draws cadmium ion is 10
-7mol/L～10
-3mol/L.The sensor of this novel detection cadmium ion, according to the detection of the cadmium-ion solution to variable concentrations, draws the potential difference values of answering in contrast.As shown in Figure 3, potential difference values raises along with the rising of concentration, and presents regular, stair-stepping ascendant trend; Fig. 4 is the typical curve of concentration/voltage, the potential difference values that reflection sensor is measured and the linear relationship of concentration of cadmium ions.10
-7mol/L to 10
-5mol/L Cd
2+under concentration range, transducer sensitivity is 28mV/pCd(theoretical value: 30mV/dec); 10
-5mol/L to 10
-3mol/L Cd
2+under concentration range, transducer sensitivity is 13mV/pCd; The lowest detection of cadmium ion is limited to 0.08 μ mol/L, and the response time is less than 90s.And the present invention can reuse, when use, reach 15 weeks or above (see figure 5).
Three. the microbiological sensor of novel detection cadmium ion is to containing the detection of cadmium water quality standard sample:
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 the magnitude of voltage of measuring according to it draws the typical curve (Fig. 6,7) of concentration/voltage.Then, sensor is immersed containing in 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 while detecting containing cadmium standard model with sensor.The microbiological sensor that proves thus novel detection cadmium ion of the present invention is reliably, can be used for monitoring industrial cadmium wastewater (China specifies that the maximal emission of 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 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, according to testing result, tentatively determine situation and the pollution source of sewage pollution, avoid blindly dropping into, cause the waste of too much manpower and materials, this is the safety of water source assessment development trend tallying 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 have an alloy coat conduction pathway at PC, alloy coat conduction pathway one end is connected with lead-in wire, one end is for detecting coating in addition, above detecting coating, be coated with one deck PC cover plate, on 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 made up of according to mass ratio 45:45:10 dag, Chlorella green alga freeze-dried powder and whiteruss, after three is mixed, is laid in 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 and form with synthetic gold, platinum or silver.
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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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 |
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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 |
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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 |
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