CN102495055A - Method and kit for detecting mercury ions - Google Patents
Method and kit for detecting mercury ions Download PDFInfo
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- CN102495055A CN102495055A CN2011104135502A CN201110413550A CN102495055A CN 102495055 A CN102495055 A CN 102495055A CN 2011104135502 A CN2011104135502 A CN 2011104135502A CN 201110413550 A CN201110413550 A CN 201110413550A CN 102495055 A CN102495055 A CN 102495055A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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Abstract
The invention relates to a method for detecting heavy metals, in particular to a method for detecting mercury ions, in particular to a method for quickly detecting the mercury ions in water and foods. Aiming at the problems of high detection cost, complicated operation and low detection accuracy in the conventional method for detecting the mercury ions, the invention provides a quick and low-cost method for detecting the mercury ions, and the detection result can be observed by eyes; and the invention also discloses a kit for detecting the mercury ions based on the method. A terpyridyl ruthenium complex solution is used as a color-developing agent; whether the mercury ions exit is judged according to the color change before and after the color-developing agent is added into a sample to be detected, so that the operation complexity is reduced, and common operators can finish high-accuracy and high-speed detection on the mercury ions.
Description
Technical field
The present invention relates to the heavy metal detection method, particularly relate to the detection method of mercury ion, relate to the method for quick of mercury ion in water and the food more specifically.
Background technology
Since nearly half a century, along with the quickening of process of industrialization, the discharging of mercury is increasing; Mercury constantly shifts in animal and plant body, accumulates, and finally runs up in people's the health through food chain, when the content of mercury in people's the body reaches certain value; To cause canceration; Distortion, or other sudden change, especially the central nervous system to the people has the greatest impact.Therefore, the mercury pollution that is caused by industrialization and the inspecting force of coherent detection superintendent office have received increasing concern.
The detection method of heavy metal is mainly to be instrumental method at present, like atomic absorption spectrography (AAS) (AAS), and atomic fluorescence spectrometry (AFS), inductively coupled plasma mass spectroscopy (ICP-MS), inductively coupled plasma emission spectrography (ICP-AES) etc.These methods need the operating personnel of expensive large-scale instrument and specialty, therefore detect the cost height, can not carry out on-site measurement fast.Also having a series of in addition is the AAS of representative with the dithizone, but the dithizone less stable, and all chromogenic reaction can take place with multiple metallic ion, disturbs morely, and the testing result accuracy is lower, usually produces false-positive result.
Therefore, find that a kind of convenience is quick, with low cost, the method for good stability, highly sensitive detection mercury ion becomes present problem demanding prompt solution.
Summary of the invention
The present invention is directed to the detection cost height, complicated operation, the low problem of testing result accuracy that exist in the present mercury ion detecting; Provide a kind of fast, can obtain testing result through naked-eye observation; Mercury ion detecting method with low cost; And further disclose the mercury ion detection kit that relies on this method, thereby reduced the complicacy of operation, common operating personnel gets final product the detection of the completion mercury ion of pin-point accuracy, two-forty.
In order to realize the foregoing invention purpose, the invention discloses a kind of detection method of mercury ion, said detection method is to be developer with the tris (bipyridine) ruthenium complex solution, judges the method for mercury ion through adding change color before and after the developer in the testing sample; The structural formula of said terpyridyl ruthenium complex is suc as formula shown in (I),
L in the formula
1Independently be selected from-NO
2,-OCH
3,-Cl ,-Br ,-I ,-CN ,-OH ,-SO
3H, CHO ,-among the OR one or more; L
2Respectively independently selection-Cl ,-Br ,-I ,-OH ,-SO
3H ,-H ,-OCH
3Among the ,-OR one or more; M independently is selected from-Cl ,-a kind of among the SCN.
Further, the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-5~ 1 mol/L.
More preferred, the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-4~ 0.1 mol/L.
The present invention further discloses said detection method and be with the tris (bipyridine) ruthenium complex solution is developer, judges the method for mercury ion through adding change color before and after the developer in the testing sample; The structural formula of said terpyridyl ruthenium complex is suc as formula shown in (II),
。
The concentration of terpyridyl ruthenium complex is 1 * 10 in the wherein said developer
-5~ 1 mol/L.
The concentration of terpyridyl ruthenium complex is 1 * 10 in the more preferably said developer
-4~ 0.1 mol/L.
Simultaneously, the present invention also further discloses described detection method and may further comprise the steps:
(1) sample pre-treatments, said sample pre-treatments is for adopting microwave digestion technology, with the water white transparency sample solution of taking next sample preparation to become to can be used for detecting;
(2) in sample solution, splash into developer;
(3) leave standstill;
(4) observe; Be always blue if be mixed with the sample solution color of developer; Then qualitatively judge and do not contain mercury ion in the sample solution, if the color of mixed liquor becomes pink colour, redness, aubergine, purple ie in solution absorbing wavelength blue shift by blueness then contains mercury ion in the judgement sample solution.
Simultaneously, in order to simplify the mercury ion detecting step, improve the accuracy and the depth of parallelism that detect, the invention also discloses a kind of kit that detects mercury ion, comprise reagent bottle and sample hose in the said kit, it is 1 * 10 that concentration is housed in the said reagent bottle
-5~ 1 mol/L, optium concentration is 1 * 10
-4~ 0.1 mol/L suc as formula the developer shown in (I),
L in the formula
1Independently be selected from-NO
2,-OCH
3,-Cl ,-Br ,-I ,-CN ,-OH ,-SO
3H, CHO ,-among the OR one or more; L
2Respectively independently selection-Cl ,-Br ,-I ,-OH ,-SO
3H ,-H ,-OCH
3Among the ,-OR one or more; M independently is selected from-Cl ,-a kind of among the SCN.
Simultaneously, further disclose a kind of kit that detects mercury ion, it is characterized in that: comprise reagent bottle and sample hose in the said kit, it is 1 * 10 that concentration is housed in the said reagent bottle
-5~ 1 mol/L, optium concentration is 1 * 10
-4~ 0.1 mol/L suc as formula the developer shown in (II),
Because terpyridyl ruthenium complex and mercury ion can form complex compound; And then change original electron distributions state, thus cause the change of compound absorbing wavelength, demonstrate redness or its phase advancing coloud nearside; Other metallic ion does not then react with the terpyridyl ruthenium complex; And then do not produce new complex compound, thus there is not change in color, the existence that can judge mercury ion in the testing sample through visual inspection mixed liquor change in color in view of the above is whether.
Compare with existing detection technique, the disclosed detection method of the present invention has the following advantages:
⑴ simple to operate, do not need Specialty Experiment technician operation.
⑵ good stability.The many bipyridyl complexes that the present invention relates to contain ruthenium have good stability, and the normal temperature sealing was preserved the term of validity greater than 12 months.But the complex compound after the colour developing is stable existence also, and the tester can operate calmly.
⑶ fast convenient.The present invention operates little, the light weight of used material volume, is easy to carry.One-time detection only needs 10 to 20 seconds.
⑷ selectivity is good.Complex provided by the present invention only with the mercury complexing, and not can with Cd
2+, Cu
2+, Zn
2+, Pb
2+, Fe
2+Deng combination, avoid the interference of other metallic ion in the sample, result's reliability is stronger.Allow coexisting ion amount: Pb
2+(30000 times), Al3+ (50000 times), Fe
3+, Mg
2+, Cr
6+, Mn
2+, Cd
2+, Ba
2+Do not disturb Deng 1000 times.
Embodiment
The narrow spectrum checking of embodiment 1 detection method
Take by weighing the compound shown in the 0.2 g formula (II) and fully be dissolved among 2 mlDMF, be made into the developer of 2.1 mmol/L.Measure distilled water respectively, contain 0.1 mg/l mercury ion solution, contain 30 g/l Al
3+, contain 30 g/l Pb
2+Solution, contain 1 g/l Fe
3+Solution, contain 1 g/l Mg
2+, contain 1 g/l Cr
6+, contain 1 g/l Mn
2+Solution and contain 1 g/l Cd
2+Each 1 ml of solution put into sample hose, be labeled as in order respectively 1~No. 9, in 1~No. 9 sample hose, drip the developer of 0.30~0.35 ml respectively; Be about 6~7, left standstill 10~20 seconds, treat that color no longer changes after; Observe the interior solution colour of sample hose 1~No. 9, wherein No. 1 pipe, 3~No. 9 pipes are blueness, and mixed solution is an aubergine in No. 2 pipes; Show complex provided by the present invention only with the mercury complexing, and not can with Cd
2+, Cu
2+, Zn
2+, Pb
2+, Fe
2+Deng combination, avoid the interference of other metallic ion in the sample, result's reliability is stronger.Allow coexisting ion amount: Pb
2+(30000 times), Al
3+(50000 times), Fe
3+, Mg
2+, Cr
6+, Mn
2+, Cd
2+, Ba
2+Do not disturb Deng 1000 times.
The detection of embodiment 2 water sample mercury ions
Take by weighing the compound shown in the 0.2 g formula (II) and fully be dissolved among 2 mlDMF, be made into the developer of 2.1 mmol/L.With parallel absorption 1 ml of the water sample that collects, put into sample hose, be labeled as respectively 1~No. 3; In 1~No. 3 sample hose, drip the developer of 0.30~0.35 ml respectively, be about 6~7, left standstill 10~20 seconds; After treating that color no longer changes; Observe the interior solution colour of sample hose 1~No. 3,, show in the water sample to be measured and contain mercury ion if all become pink.If still be blue, then show and do not contain mercury ion in the water sample to be measured.
The detection of embodiment 3 water sample mercury ions
Take by weighing the compound shown in the 0.2 g formula (III) and fully be dissolved among 2 mlDMF, be made into the developer of 2.1 mmol/L.With parallel absorption 1 ml of the water sample that collects, put into sample hose, be labeled as respectively 1~No. 3; In 1~No. 3 sample hose, drip the developer of 0.30~0.35 ml respectively, be about 6~7, left standstill 10~20 seconds; After treating that color no longer changes; Observe the interior solution colour of sample hose 1~No. 3,, show in the water sample to be measured and contain mercury ion if all become pink.If still be blue, then show and do not contain mercury ion in the water sample to be measured.
The detection of mercury in the food such as embodiment 4 animal tissues, vegetables, fruit
1. pre-treatment
Adopt microwave digestion technology that sample is carried out pre-treatment.In taking by weighing in 0.10-0.50 g sample and the digestion jar, add nitric acid 2.0-3.0 ml, hydrogen peroxide 1.0-2.0 ml, jar is put into the outer jar of digestion in will digest, and it is 0.5 MPa-1.0 MPa, times 480 s that the condition of micro-wave oven digestion system is made as.Clear up the back and take out, open jar after the cooling, solution in the jar is transferred in the 10.0 ml volumetric flasks, with deionized water rinsing for several times, merge washing lotion, it is subsequent use to be settled to 10.0 ml.Establish the reagent blank contrast simultaneously.Sample solution is answered water white transparency.
2. the detection method of mercury.
Take by weighing the compound shown in the 0.2 g formula (IV) and fully be dissolved among the 2ml DMF, be made into the chromogenic reagent solution of 2.1mmol/L, get that each 1 ml of solution and distilled water puts into sample hose in the above-mentioned 10 ml volumetric flasks; Drip 6-7 and drip developer, leave standstill several seconds after, color contrast; If the food treating fluid becomes pink, redness or purple; Contain mercury ion in the then former food, blue if food treating fluid color is always, there is not mercury ion in the then former food.
Claims (9)
1. the detection method of a mercury ion is characterized in that: said method is to be developer with the tris (bipyridine) ruthenium complex solution, judges the method for mercury ion through adding change color before and after the developer in the testing sample; The structural formula of said terpyridyl ruthenium complex is suc as formula shown in (I),
L in the formula
1Independently be selected from-NO
2,-OCH
3,-Cl ,-Br ,-I ,-CN ,-OH ,-SO
3H ,-CHO ,-among the OR one or more; L
2Respectively independently selection-Cl ,-Br ,-I ,-OH ,-SO
3H ,-H ,-OCH
3Among the ,-OR one or more; M independently is selected from-Cl ,-a kind of among the SCN.
2. the detection method of mercury ion as claimed in claim 1, it is characterized in that: the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-5~ 1 mol/L.
3. the detection method of mercury ion as claimed in claim 2, it is characterized in that: the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-4~ 0.1 mol/L.
4. the detection method of mercury ion as claimed in claim 1 is characterized in that: said detection method is to be developer with the tris (bipyridine) ruthenium complex solution, judges the method for mercury ion through adding change color before and after the developer in the testing sample; The structural formula of said terpyridyl ruthenium complex is suc as formula shown in (II),
。
5. the detection method of mercury ion as claimed in claim 4, it is characterized in that: the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-5~ 1 mol/L.
6. the detection method of mercury ion as claimed in claim 5, it is characterized in that: the concentration of terpyridyl ruthenium complex is 1 * 10 in the said developer
-4~ 0.1 mol/L.
7. like the detection method of any described mercury ion in the claim 1 to 6, it is characterized in that: described detection method may further comprise the steps:
(1) sample pre-treatments, said sample pre-treatments is for adopting microwave digestion technology, with the water white transparency sample solution of taking next sample preparation to become to can be used for detecting;
(2) in sample solution, splash into developer;
(3) leave standstill;
(4) observe; Be always blue if be mixed with the sample solution color of developer; Then qualitatively judge and do not contain mercury ion in the sample solution, if the color of mixed liquor becomes pink colour, redness, aubergine, purple ie in solution absorbing wavelength blue shift by blueness then contains mercury ion in the judgement sample solution.
8. kit that detects mercury ion, it is characterized in that: comprise reagent bottle and sample hose in the said kit, it is 1 * 10 that concentration is housed in the said reagent bottle
-5~ 1 mol/L, optium concentration is 1 * 10
-4~ 0.1 mol/L suc as formula the developer shown in (I),
L in the formula
1Independently be selected from-NO
2,-OCH
3,-Cl ,-Br ,-I ,-CN ,-OH ,-SO
3H ,-CHO ,-among the OR one or more; L
2Respectively independently selection-Cl ,-Br ,-I ,-OH ,-SO
3H ,-H ,-OCH
3Among the ,-OR one or more; M independently is selected from-Cl ,-a kind of among the SCN.
9. kit that detects mercury ion, it is characterized in that: comprise reagent bottle and sample hose in the said kit, it is 1 * 10 that concentration is housed in the said reagent bottle
-5~ 1 mol/L, optium concentration is 1 * 10
-4~ 0.1 mol/L suc as formula the developer shown in (II),
。
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CN2011104135502A CN102495055A (en) | 2011-12-13 | 2011-12-13 | Method and kit for detecting mercury ions |
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CN2011104135502A CN102495055A (en) | 2011-12-13 | 2011-12-13 | Method and kit for detecting mercury ions |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103145764A (en) * | 2013-03-05 | 2013-06-12 | 苏州太湖电工新材料股份有限公司 | Ruthenium comlex and mercury ion sensor as well as preparation methods thereof |
CN107286198A (en) * | 2017-06-12 | 2017-10-24 | 大连理工大学 | A kind of ruthenium (II) complex, ruthenium (II) complex TiO2 functional membranes and its application |
WO2019213894A1 (en) * | 2018-05-10 | 2019-11-14 | South University Of Science And Technology Of China | Alkynylplatinum (ii) terpyridine system coupled with rhodamine derivative: interplay of aggregation, de-aggregation and ring-opening processes for ratiometric luminescence sensing |
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WO2008025977A1 (en) * | 2006-08-31 | 2008-03-06 | Imperial Innovations Limited | Mercury scavenging |
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Non-Patent Citations (4)
Title |
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《高等学校化学学报》 20060331 李襄宏等 新型两亲性混配钌配合物的合成及其对Hg~(2+)的选择性"肉眼"识别 419-423页 1-9 第27卷, 第03期 * |
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X. –H. LI. ET AL.: "Synthesis of N,N,N-4,4"-Di-(4-methylphenyl)-2,2":6",2"- terpyridine-N,N,N-tris(isothiocyanato) Ruthenium(II) and Application to Colorimetric Hg2+ Sensor", 《CHINESE JOURNAL OF CHEMISTRY》 * |
李襄宏等: "新型两亲性混配钌配合物的合成及其对Hg~(2+)的选择性"肉眼"识别", 《高等学校化学学报》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103145764A (en) * | 2013-03-05 | 2013-06-12 | 苏州太湖电工新材料股份有限公司 | Ruthenium comlex and mercury ion sensor as well as preparation methods thereof |
CN103145764B (en) * | 2013-03-05 | 2015-11-11 | 苏州太湖电工新材料股份有限公司 | Ruthenium complexe, mercury ion sensor and their preparation method |
CN107286198A (en) * | 2017-06-12 | 2017-10-24 | 大连理工大学 | A kind of ruthenium (II) complex, ruthenium (II) complex TiO2 functional membranes and its application |
CN107286198B (en) * | 2017-06-12 | 2019-10-11 | 大连理工大学 | A kind of ruthenium (II) complex, ruthenium (II) complex-TiO2 functional membrane and its application |
WO2019213894A1 (en) * | 2018-05-10 | 2019-11-14 | South University Of Science And Technology Of China | Alkynylplatinum (ii) terpyridine system coupled with rhodamine derivative: interplay of aggregation, de-aggregation and ring-opening processes for ratiometric luminescence sensing |
US12006334B2 (en) | 2018-05-10 | 2024-06-11 | South University Of Science And Technology Of China | Alkynylplatinum (II) terpyridine system coupled with rhodamine derivative: interplay of aggregation, de-aggregation and ring-opening processes for ratiometric luminescence sensing |
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Application publication date: 20120613 |