CN1584578A - Heavy metal ionic detecting method and apparatus in blood based on electrochemical stripping method - Google Patents
Heavy metal ionic detecting method and apparatus in blood based on electrochemical stripping method Download PDFInfo
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- CN1584578A CN1584578A CN200410014978.XA CN200410014978A CN1584578A CN 1584578 A CN1584578 A CN 1584578A CN 200410014978 A CN200410014978 A CN 200410014978A CN 1584578 A CN1584578 A CN 1584578A
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- electrode
- heavy metal
- blood
- metal ion
- dissolving
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- 239000008280 blood Substances 0.000 title claims abstract description 49
- 210000004369 blood Anatomy 0.000 title claims abstract description 49
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 13
- 238000010586 diagram Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000005331 crown glasses (windows) Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010241 blood sampling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 208000008127 lead poisoning Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
A method for detecting heavy metal ion in blood based on electrochemical dissolving method includes diluting blood sample with reagent placing it in electrolyzer and controlling electrolytic potential and time, enriching heavy metal ion on electrode surface then dissolving it out as heavy metal ion content being diret ratio to output peak and signal. A device for realizing the method is also disclosed by the present invention.
Description
Technical field
The present invention relates to a kind ofly, especially a kind ofly be used for the electro-chemical systems that heavy metal ion contents such as whole blood lead, copper, cadmium detect: comprise the heavy metal ion measuring instrument of blood sample reagent treatment (kit), blood, small-sized combination electrode based on heavy metal ion detection method and device thereof in the blood of galvanochemistry dissolving-out method.
Background technology
Along with the high speed development of modern industry and traffic, the lead contamination in the environment is on the rise, and it is human to have become influence, especially children's health important social concern.Studies show that, the every rising 100 μ g/l of lead levels, height can reduce 1.3cm, and IQ can be lost the 6-7 branch.U.S. CDC is recommended lead levels boundary 100ppb.Be lower than this value and be normal level.But recent research shows, even when lead levels is lower than 100ppb, also can cause harmful effect to health.China's health ministry is also paid much attention to saturnism and detection, and classifies the children blood lead detection as test item in 1999.Heavy metal ion in the blood is measured by clinical labororatory at present, comprise GFAAS (graphite furnace atomic absorption spectrometry) (GFAAS) and Electrothermal Atomic Absorption method (ETAAS) are generally adopted in the detection of blood lead, its cost is higher relatively, needs operating personnel that higher professional technique is arranged in addition.Electrochemical measuring technique is highly sensitive, easy and simple to handle, cost is low, can become the technology that is widely adopted.But present domestic electrochemical analysis is loaded down with trivial details to the blood sample treatment step during to the mensuration of heavy metal ion content in the blood, Hg in the reagent
2+Consumption is big, and environmental pollution is serious, and the instrument performance instability can not satisfy the requirement of automatic detection, efficient fast detecting.
Therefore, be necessary to seek the electrochemical analysis method of heavy metal ion in a kind of fast and convenient detection blood.The requirement instrumentation is easy, the automaticity height, and cost is low, and environment is not polluted, and is applicable to (particularly blood lead) level generaI investigation of heavy metal ion in state's inner blood and hospital, breadboard mensuration to heavy metal ion in the blood.
Summary of the invention
The objective of the invention is: provide a kind of, also comprise low cost, automaticity height, easy and simple to handle, heavy metal ion detection system or devices such as sampling amount is little, free of contamination substantially electrochemical analysis blood lead based on heavy metal ion detection method in the blood of galvanochemistry dissolving-out method.
A kind of based on heavy metal ion measuring method in the blood of galvanochemistry dissolving-out method, the treated reagent dilution of blood sample places electrolytic cell, the rotation of control electrolytic cell, control electrolytic potential and electrolysis time simultaneously, heavy metal ion enrichments such as lead are to electrode surface, stripping then.Heavy metal ion content is proportional to the peak area signal of output in the blood, and the instrument of making is the instrument of robotization, one-shot measurement about 5min consuming time, and reagent dosage can be controlled at 250 μ l.Especially with working electrode, contrast electrode, electrode made in the electrolytic cell that combination electrode immerses rotation detects, thereby both guaranteed the abundant enrichment of the quilt of heavy metal ion in the sample, guarantee the amount of few sample again, carrying out to use blood sampling volume still less to detect when children blood lead detects like this, thereby also can guarantee environment is not polluted.
Reagent treatment is an acidic electrolysis bath, and whole blood sample can directly be measured with apparatus of the present invention after this reagent dilution.Acidic electrolysis bath is generally selected mineral acid and strong organic acid, example hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid.
Based on heavy metal ion measurement mechanism in the blood of galvanochemistry dissolving-out method, comprise blood heavy metal ion measuring instrument, electrolytic cell and working electrode, contrast electrode, electrode is constituted, it is characterized in that working electrode, contrast electrode, electrode is made combination electrode, working electrode is the glass-carbon electrode of diameter 3-10mm, for guaranteeing to insert littler electrolytic cell, the glass-carbon electrode of 3-5mm is better, and contrast electrode is the Ag/AgCl electrode, is the Ag electrode to electrode.Electrode and contrast electrode are placed internal-filling liquid, and internal-filling liquid is conventional HCl solution, potassium sulfate solution etc., and concentration without limits.
During measurement, control electrolytic potential and electrolysis time, heavy metal ion to be measured in the stripping sample then in the time of the electrolytic cell rotation.Different electrolytic potential, time are set in the rotation of control sample when different heavy metal ion species detection, the peak area signal of the size of concentration and output relevant, thus by being provided with of instrument itself result is calculated demonstration (being finished automatically by instrument).
Characteristics of the present invention are: provide a kind of based on heavy metal ion detection method and device in the blood of galvanochemistry dissolving-out method, detect that cost is low, automaticity is high, easy and simple to handle, sampling amount is little.Be particularly useful for the detection of blood lead, also can be used for the detection of other metallic ion of blood.Test of the present invention can obtain realistic result, and the inventive method and device have following advantage:
1, sample preparation simple possible only needs to get final product with the matched reagent dilution, need not digest.
2, instrument performance is stable, reliable results.
3, easy and simple to handle, the automaticity height, the result directly shows, does not need the professional.
4, weak point consuming time, 5min can obtain analysis result.
5, cost is low.
Description of drawings
Fig. 1 is a reagent pipe sectional view, in the blood sample reagent treatment of certain volume is arranged.
Fig. 2 is the small-sized combined electrode structure synoptic diagram of this system.Left side figure is an electrode longitudinal profile synoptic diagram, and right figure is an electrode lower end cross sectional representation.1 is glass carbon working electrode, and diameter is 3-5mm; 2 is porous mass, guarantees conduction between electrode internal-filling liquid and the external solution and internal-filling liquid does not ooze out; 3 is silver-colored lead, connects glass-carbon electrode; 4 is the Ag/AgCl contrast electrode; 5 be Ag to electrode, 6 add inlet for internal-filling liquid; 7 is contact conductor.Crown glass 16, epoxy resin 14, be enclosed within the solution pool 15 of silver-colored lead outside.
Fig. 3 is the panel structure chart of heavy metal ion measuring instrument in the blood of the present invention, and 8 be the electrolytic cell interface, and 9 be electrode interface, simultaneously can fixed electorde, and 10 is the concentration display screen, and 11 is the measurement key, and 12 is check key, and 13 is the electrode cancel key.
Fig. 4 is a heavy metal ion analyzer circuit diagram in the blood, and it comprises the constant potential device, measures amplifying circuit and integrating circuit etc., and G1-2 is an integrating circuit among the figure, and K1 is an on-off circuit, and G3-4 is an amplifying circuit, and this circuit is existing custom circuit.
Fig. 5 is the calibration curve of concentration of heavy metal ion in measuring-signal and the blood.Abscissa is the content (ppb) of heavy metal ion, and ordinate is the area of detected peaks.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing and example:
Get 20 μ l whole blood samples and place the reagent pipe that the blood sample reagent treatment is housed shown in Figure 1, leave standstill 5min after shake well is even.Get the electrolytic cell that blood sample that 250 μ l handled places Fig. 1 then.
The middle-size and small-size combination electrode of Fig. 2 is inserted among Fig. 1, after fixing the electrode bottom is inserted in the solution.Open correcting button on the instrument control device, after proofreading and correct, press the measurement button and begin to measure, can read the heavy metal ion amount in the blood sample behind the 5min, unit is ppb.Measure and finish.
The heavy metal ion analyzer comprises the electrolytic cell interface in the blood, and electrode interface simultaneously can fixed electorde, is provided with the concentration display screen, measures key, check key, electrode cancel key.Also as shown in Figure 3, be mainly conventional electrochemical electronic detecting instrument, in MCU control is arranged, mainly be provided with the electrolytic cell interface, drive the rotation of electrolytic cell.Electrode interface inserts combination electrode, and 10 for the concentration display screen provides the result, and 11 measure key, 12 check keys.When electrode cleaned: electrolytic solution in the reagent pipe is added in the electrolytic cell, press the instrument cancel key, begin to clean, cleaning finished behind the 1min.
Acidic electrolysis bath is generally selected mineral acid and strong organic acid, hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid.
In the measurement mechanism of the present invention, working electrode, contrast electrode, the combination electrode that electrode is constituted are inserted in the electrolytic cell.Electrolytic cell 8 adopts crown glass, and working electrode is located on the megohmite insulant, as epoxy resin 9.One circle porous mass is located at the outer ring of megohmite insulant, and as spongy material, the sponge porous mass guarantees conduction between electrode internal-filling liquid and the external solution and internal-filling liquid does not ooze out; When the working electrode diameter is big, need more sample and bigger electrolytic cell, but the present invention can be controlled at 250 μ l as reagent dosage with less reagent when adopting the glass-carbon electrode of 3-5mm.Described reagent is that sample is quantitatively inserted electrolytic cell after acidic electrolysis bath is handled well.3 is silver-colored lead, connects glass-carbon electrode; 4 is the Ag/AgCl contrast electrode; 5 be Ag to electrode, 6 add inlet for internal-filling liquid; 7 is contact conductor.
Claims (7)
1, a kind of based on heavy metal ion measuring method in the blood of galvanochemistry dissolving-out method, it is characterized in that the treated reagent dilution of blood sample, place electrolytic cell, control electrolytic potential and electrolysis time in the time of the electrolytic cell rotation, heavy metal ion enrichment is to electrode surface in the blood, stripping then, heavy metal ion content is proportional to the peak area signal of output in the blood.
2, described by claim 1 based on heavy metal ion measuring method in the blood of galvanochemistry dissolving-out method, it is characterized in that reagent treatment is an acidic electrolysis bath, generally selects mineral acid and strong organic acid, hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid.
3, described by claim 1 based on heavy metal ion measuring method in the blood of galvanochemistry dissolving-out method, when it is characterized in that measuring, make in the electrolytic cell that combination electrode immerses rotation with working electrode, contrast electrode, to electrode and to detect.
4, based on heavy metal ion measurement mechanism in the blood of galvanochemistry dissolving-out method, comprise blood heavy metal ion measuring instrument, electrolytic cell and working electrode, contrast electrode, electrode is constituted, it is characterized in that working electrode, contrast electrode, electrode made combination electrode.
5, described by claim 4 based on heavy metal ion measurement mechanism in the blood of galvanochemistry dissolving-out method, it is characterized in that working electrode is the glass-carbon electrode of diameter 3-10mm.
6, described by claim 4 based on heavy metal ion measurement mechanism in the blood of galvanochemistry dissolving-out method, it is characterized in that working electrode is the glass-carbon electrode of 3-5mm, contrast electrode is the Ag/AgCl electrode, is the Ag electrode to electrode.
7, described by claim 4 based on heavy metal ion measurement mechanism in the blood of galvanochemistry dissolving-out method, it is characterized in that working electrode is located on the megohmite insulant, one circle porous mass is located at the outer ring of megohmite insulant, guarantees conduction between electrode internal-filling liquid and the external solution and internal-filling liquid does not ooze out.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410014978.XA CN1282871C (en) | 2004-05-24 | 2004-05-24 | Heavy metal ionic detecting method and apparatus in blood based on electrochemical stripping method |
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| CN200410014978.XA CN1282871C (en) | 2004-05-24 | 2004-05-24 | Heavy metal ionic detecting method and apparatus in blood based on electrochemical stripping method |
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| CN1584578A true CN1584578A (en) | 2005-02-23 |
| CN1282871C CN1282871C (en) | 2006-11-01 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101839851A (en) * | 2010-04-27 | 2010-09-22 | 华东理工大学 | Field fast detection method for heavy metal ions in water |
| CN105675379A (en) * | 2015-12-30 | 2016-06-15 | 南京工业大学 | Blood synchronously separating and detecting device |
| CN105699466A (en) * | 2016-01-15 | 2016-06-22 | 刘文涛 | High-concentration organic matter sample pretreatment method and heavy metal content measuring method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101256167B (en) * | 2008-04-17 | 2011-11-23 | 重庆大学 | Reading circuit of micro-array biosensor |
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2004
- 2004-05-24 CN CN200410014978.XA patent/CN1282871C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101839851A (en) * | 2010-04-27 | 2010-09-22 | 华东理工大学 | Field fast detection method for heavy metal ions in water |
| CN101839851B (en) * | 2010-04-27 | 2011-10-05 | 华东理工大学 | Field fast detection method for heavy metal ions in water |
| CN105675379A (en) * | 2015-12-30 | 2016-06-15 | 南京工业大学 | Blood synchronously separating and detecting device |
| CN105675379B (en) * | 2015-12-30 | 2018-11-13 | 南京工业大学 | A kind of blood separated in synchronization verifying attachment |
| CN105699466A (en) * | 2016-01-15 | 2016-06-22 | 刘文涛 | High-concentration organic matter sample pretreatment method and heavy metal content measuring method |
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| CN1282871C (en) | 2006-11-01 |
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