CN103411962A - Kit and method for detecting cobalt ions through colorimetric method - Google Patents

Kit and method for detecting cobalt ions through colorimetric method Download PDF

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CN103411962A
CN103411962A CN2013101796305A CN201310179630A CN103411962A CN 103411962 A CN103411962 A CN 103411962A CN 2013101796305 A CN2013101796305 A CN 2013101796305A CN 201310179630 A CN201310179630 A CN 201310179630A CN 103411962 A CN103411962 A CN 103411962A
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solution
concentration
cobalt ions
ctab
kit
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CN103411962B (en
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陈兆鹏
张志阳
陈令新
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Yantai Institute of Coastal Zone Research of CAS
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Abstract

The invention relates to the technical field of environmental and biological analysis, and particularly relates to a kit and method for detecting cobalt ions through a colorimetric method. The kit comprises a CTAB (Cetyltrimethyl Ammonium Bromide)-containing borate buffer solution, a sodium bicarbonate solution, a hydrogen peroxide solution, a potassium thiocyanate solution, a gold nanorod solution, a standard colorimetric card F and a colorimetric tube, wherein the pH of the CTAB-containing borate buffer solution is 7.4-9.6, and the concentration of the CTAB-containing borate buffer solution is 10-200 mM; the concentration of the sodium bicarbonate solution is 0.01-1 M; the concentration of the H2O2 solution is 0.01-1 M; the concentration of the potassium thiocyanate solution is 0.01-1 M. The kit and the method disclosed by the invention have the advantages of high sensitivity, good selectivity, quickness, easiness for observation by unaided eyes and the like when used for detecting the cobalt ions and can realize the detection of namely the cobalt ions in environmental and biological samples, under an optimized experiment condition.

Description

A kind of cobalt ions colorimetric determination kit and detection method thereof
Technical field
The present invention relates to environment and bioassay technique field, specifically a kind of cobalt ions colorimetric determination kit and detection method thereof.
Background technology
Cobalt ions is as one of biosome indispensable element, serving as in vivo very important status, it is one of constituent of cobalamin. this reason is not very concerned to the research of the detection of cobalt ions just, yet, the report explanation has been arranged when the cobalt ions finite concentration in blood plasma, it will cause some serious diseases.Cobalt and his compound have been noted may be become the aetology toxin and carcinogenic tendency is arranged.In addition, cobalt ions, as a metal ion species, can not be decomposed, thereby has the effect of biological concentration and biomagnification, has so more increased the food chain top mankind's risk, thereby the detection of cobalt ions is necessary.
What traditional method detected cobalt ions has atomic absorption spectrum (AAS), inductively coupled plasma mass spectrometry coupling technique (ICP-MS), a voltammetry etc.AAS, ICP-MS need large-scale instrument, not only expensive and be not suitable for Site Detection, and voltammetry is relatively simple and fast, but often need poisonous mercury film electrode or the complicated chemically modified electrode of needs.With respect to above method, the colorimetric analysis advantage is that its naked eyes are easy to observation, is very suitable for on-the-spot detection in real time, simple to operate and low price.Golden nanometer particle is extensively used in colorimetric analysis in recent years, this is to be absorbed and made its good molar extinction coefficient by the golden nanometer particle surface plasma body resonant vibration, the present invention utilizes cobalt ions catalysis generation superoxide radical etching gold nanorods to realize highly sensitive, the purpose of fast detecting cobalt ions, in this way detect the method for cobalt ions, at present the domestic report that yet there are no.
Summary of the invention
The object of the invention is to provide a kind of cobalt ions colorimetric determination kit and detection method thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of cobalt ions colorimetric determination kit, kit comprise that cetyl ammonium bromide (CTAB) borate buffer solution, sodium bicarbonate are molten, hydrogen peroxide, potassium rhodanide, gold nanorods solution, standard color comparison card F and color comparison tube;
Described cetyl ammonium bromide (CTAB) borate buffer solution that contains, pH is 7.4-9.6, concentration is 10-200mM;
Described sodium bicarbonate solution concentration is 0.01-1M;
Described H 2O 2Solution concentration is 0.01-1M;
Described potassium rhodanide solution concentration is 0.01-1M.
It is described that to contain CTAB concentration in cetyl ammonium bromide (CTAB) borate buffer solution be 0.1-20mM.
Further, in described kit, containing cetyl ammonium bromide (CTAB) borate buffer solution pH is 9.0, and concentration is 50mM, contains the concentration of CTAB for being 2mM; Gold nanorods solution is that concentration is that the length-diameter ratio of 2.3nM is the gold nanorods solution of 2:1; Sodium bicarbonate solution concentration is 0.1M; H 2O 2Solution concentration is 0.1M; The potassium rhodanide solution concentration is 0.1M.
Gold nanorods solution is turned at 6000-10000/the centrifugal 5-30min of min, collecting precipitation also dilutes with intermediate water, with 5000-9000, turns/the centrifugal 5-30min of min after dilution again, and precipitation is again with the intermediate water dilution, stand-by.
The method of the detection copper ion of cobalt ions colorimetric determination kit, by the testing sample color comparison tube, add the borate buffer solution that contains CTAB, add sodium bicarbonate, H 2O 2With potassium rhodanide, rock and mix, after mixing, add again gold nanorods solution, shake up; Then at 60-100 ℃ of temperature, hatch 2-20 minute, observe color by naked eyes or ultraviolet-visual spectrometer, determine cobalt ions content with standard color comparison card F contrast.
Further, testing sample is regulated to pH with the borate buffer solution that contains CTAB, and to keep final volume be 800-900 μ L, add sodium bicarbonate, H 2O 2With potassium rhodanide, rock and mix, after mixing, add again the gold nanorods solution of 200-300 μ L, shake up; Then at 60-100 ℃ of temperature, hatch 2-20 minute, observe color by naked eyes or ultraviolet-visual spectrometer, determine cobalt ions content with standard color comparison card F contrast.
The preparation of described standard color comparison card F is, gets 0-300nM variable concentrations cobalt standard color range solution and is positioned over respectively in color comparison tube, adds the borate buffer solution, sodium bicarbonate, the H that contain CTAB 2O 2With potassium rhodanide, rock and mix, after mixing, add again gold nanorods, shake up; Then at 50-100 ℃ of temperature, hatch 2-30 minute, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, use the picture by color gradient to form cobalt standard color comparison card F.
Described cetyl ammonium bromide (CTAB) borate buffer solution that contains, pH is 7.4-9.6, concentration is 10-200mM; Described sodium bicarbonate solution concentration is 0.01-1M; Described H 2O 2Solution concentration is 0.01-1M; Described potassium rhodanide solution concentration is 0.01-1M.
Further, described to contain cetyl ammonium bromide (CTAB) borate buffer solution pH be 9.0, and concentration is 50mM, contains the concentration of CTAB for being 2mM; Gold nanorods solution is that concentration is that the length-diameter ratio of 2.3nM is the gold nanorods solution of 2:1; Sodium bicarbonate solution concentration is 0.1M; H 2O 2Solution concentration is 0.1M; The potassium rhodanide solution concentration is 0.1M.
Gold nanorods solution is turned at 6000-10000/the centrifugal 5-30min of min, collecting precipitation also dilutes with intermediate water, with 5000-9000, turns/the centrifugal 5-30min of min after dilution again, and precipitation is again with the intermediate water dilution, stand-by.
Principle (see figure 1) of the present invention is in containing the borate buffer solution of sodium bicarbonate, the cobalt ions catalyzing hydrogen peroxide produces the superoxide radical with strong oxidizing property, thereby the oxidation dissolution that accelerates gold nanorods make its radially absorption spectrum generation blue shift (see figure 3) be accompanied by obvious change color, this variation and the concentration of cobalt ions (see figure 5) that is proportionate.
The present invention has advantages of: the present invention utilizes cobalt ions catalysis etching gold nanorods colorimetric determination cobalt ions, have highly sensitive (detect and be limited to 1.0nM), selectivity good (seeing Fig. 4), speed is fast, do not need instrument, be applicable to the advantages such as on-the-spot detection in real time.
The accompanying drawing explanation
Fig. 1 is the principle that cobalt ions catalysis provided by the invention produces superoxide radical etching gold nanorods.
Fig. 2 is that cobalt ions catalysis provided by the invention produces superoxide radical etching gold nanorods front and back images of transmissive electron microscope, wherein (left side) rear (right side) before cobalt ions catalysis generation superoxide radical etching gold nanorods.
Fig. 3 is the abosrption spectrogram after cobalt ions provided by the invention (concentration from low to high) catalysis etching gold nanorods.
Fig. 4 is selectivity experimental result and the corresponding photo of detection cobalt ions provided by the invention.
Fig. 5 is standard color comparison card C provided by the invention.
Fig. 6 is detection cobalt ions process flow diagram provided by the invention.
Fig. 7 is the cobalt ions range of linearity in detection potable water provided by the invention.
Fig. 8 is cobalt ions (mark-on) design sketch in detection potable water provided by the invention.
Embodiment
Embodiment 1: cobalt ions in potable water (mark-on) detects
Kit comprises that borate buffer, sodium bicarbonate are molten, hydrogen peroxide, potassium rhodanide, the gold nanorods solution that contains cetyl ammonium bromide (CTAB), standard color comparison card F and color comparison tube;
Described borate buffer solution is formulated with intermediate water with analytically pure borax and boric acid, and the pH of buffer after preparation is 9.0, and concentration is 50mM; The CTAB that adds again high concentration, making CTAB concentration in damping fluid is 2mM;
Described sodium bicarbonate solution concentration is 0.1M, is dissolved in the intermediate water acquisition by analyzing pure sodium bicarbonate;
Described H 2O 2Solution concentration is 0.1M, obtains with the intermediate water dilution by analyzing pure 30% hydrogen peroxide;
Described potassium rhodanide solution concentration is 0.1M, is dissolved in the intermediate water acquisition by analyzing the bright sulfur potassium cyanate.Contain the preparation of cetyl ammonium bromide (CTAB) gold nanorods solution:
1) gold nanorods obtains as follows:
Synthetic gold seeds liquid: chlorauric acid solution is added in cetyl ammonium bromide (CTAB) solution and stirs, in the mixed liquor stirred, add again iced sodium borohydride, make mixed liquor by glassy yellow to purplish grey, then under 26 ℃, standing 2 hours, stand-by;
Nanometer rods is synthetic: add 1200 μ L gold chloride (50mM) solution to 100mL, to contain in cetyl ammonium bromide (CTAB) solution of 0.1M and stir and evenly mix, add silver nitrate (0.01M) solution of 300 μ L to mix, add subsequently 960 μ L ascorbic acid (0.1M) solution, now solution is become colorless by yellowish-brown, finally add 200 μ L gold seeds liquid (first step is synthetic), about 10-20 minute, solution colour has the five colors to gradually become blue-green, stop stirring, use after standing 20 hours.Uv-visible absorption spectra figure radially absorption peak is shown in figure tri-abosrption spectrograms 0 at 670nM(), according to langbobier law, the concentration that estimates nanometer rods is 2.3nM.
2) the required gold nanorods solution of this method obtains: synthetic gold nanorods is turned at 6000-10000/the centrifugal 5-30min of min, collecting precipitation also dilutes with intermediate water, after dilution, with 5000-9000, turn/the centrifugal 5-30min of min, precipitation with the intermediate water dilution, obtains again again.
The preparation of described standard color comparison card F is,, get 10 μ L concentration and be respectively 0,5,40,50,60,100,300nM cobalt standard color range solution, join and be equipped with in the color comparison tube of borate buffer solution that 800 μ L contain CTAB, shakes up, then add respectively 25 μ L sodium bicarbonates, 20 μ L H 2O 2With 7.5 μ L potassium rhodanides, rock and mix, after mixing, add again the gold nanorods that contains CTAB, shake up; Then at 95 ℃ of temperature, hatched 6 minutes, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, use the picture by color gradient to form cobalt standard color comparison card F(Fig. 5).
Be kit:
Borate buffer solution, pH are that 9.0 concentration are 0.2M;
Sodium bicarbonate solution, concentration are 0.1M;
H 2O 2Solution, concentration are 0.1M;
Potassium rhodanide solution, concentration are 0.1M;
Color comparison tube, 1.5mL;
The glass calibrated pipet;
Cobalt standard color range solution;
The cobalt standard color comparison card.
Cobalt ions in potable water (mark-on) detects
(1) get 3 1.5mL color comparison tubes, add from reagent bottle A, pipetting 200 μ L borate buffer solutions (0.2M) in every color comparison tube, then add successively sodium bicarbonate in 25 μ L reagent bottle B, H in 20 μ L reagent bottle C 2O 2With potassium rhodanide in 7.5 μ L reagent bottle D, mix, then add respectively and contain three kinds of variable concentrations cobalt ions (5nM, 50nM, 100nM) mark-on sample 600 μ L, after fully mixing, mark 1,2, No. 3, then add respectively the gold nanorods 200 μ L that contain CTAB in the E reagent bottle, shake up.
(2) at 95 ℃ of temperature, hatched 6 minutes.
(3) observe change color (as Fig. 8), color comparison tube and standard color comparison card F(be shown in to Fig. 5) compare, determine the concentration range of potable water mark-on sample cobalt ions, can find out very consistent with colorimetric card concentration correspondence; Outside can passing through simultaneously, the visible light spectrogram obtains peak shift, and according to typical curve, determines definite content of cobalt ions, the recovery of standard addition of this method testing result at 95-102%(in Table 1), the reliability of the practical application of this method has been described.
Table 1 cobalt ions mark-on test result
Figure BDA00003195765800041

Claims (10)

1. cobalt ions colorimetric determination kit is characterized in that: kit comprises that cetyl ammonium bromide (CTAB) borate buffer solution, sodium bicarbonate are molten, hydrogen peroxide, potassium rhodanide, gold nanorods solution, standard color comparison card F and color comparison tube;
Described cetyl ammonium bromide (CTAB) borate buffer solution that contains, pH is 7.4-9.6, concentration is 10-200mM;
Described sodium bicarbonate solution concentration is 0.01-1M;
Described H 2O 2Solution concentration is 0.01-1M;
Described potassium rhodanide solution concentration is 0.01-1M.
2. by cobalt ions colorimetric determination kit claimed in claim 1, it is characterized in that: described to contain CTAB concentration in cetyl ammonium bromide (CTAB) borate buffer solution be 0.1-20mM.
3. by the described cobalt ions colorimetric determination of claim 1 or 2 kit, it is characterized in that: in described kit, containing cetyl ammonium bromide (CTAB) borate buffer solution pH is 9.0, and concentration is 50mM, contains the concentration of CTAB for being 2mM; Gold nanorods solution is that concentration is that the length-diameter ratio of 2.3nM is the gold nanorods solution of 2:1; Sodium bicarbonate solution concentration is 0.1M; H 2O 2Solution concentration is 0.1M; The potassium rhodanide solution concentration is 0.1M.
4. by cobalt ions colorimetric determination kit claimed in claim 1, it is characterized in that: gold nanorods solution is turned at 6000-10000/the centrifugal 5-30min of min, collecting precipitation also dilutes with intermediate water, after dilution, with 5000-9000, turn/the centrifugal 5-30min of min again, precipitation is again with the intermediate water dilution, stand-by.
5. the method for the detection copper ion of a cobalt ions colorimetric determination kit claimed in claim 1 is characterized in that: by the testing sample color comparison tube, add the borate buffer solution that contains CTAB, add sodium bicarbonate, H 2O 2With potassium rhodanide, rock and mix, after mixing, add again gold nanorods solution, shake up; Then at 60-100 ℃ of temperature, hatch 2-20 minute, observe color by naked eyes or ultraviolet-visual spectrometer, determine cobalt ions content with standard color comparison card F contrast.
6. by the method for the detection copper ion of cobalt ions colorimetric determination kit claimed in claim 5, it is characterized in that: testing sample is regulated to pH with the borate buffer solution that contains CTAB, and to keep final volume be 800-900 μ L, add sodium bicarbonate, H 2O 2With potassium rhodanide, rock and mix, after mixing, add again the gold nanorods solution of 200-300 μ L, shake up; Then at 60-100 ℃ of temperature, hatch 2-20 minute, observe color by naked eyes or ultraviolet-visual spectrometer, determine cobalt ions content with standard color comparison card F contrast.
7. press the method for the detection cobalt ions of the described cobalt ions colorimetric determination of claim 5 or 6 kit, it is characterized in that: the preparation of described standard color comparison card F is, get 0-300nM variable concentrations cobalt standard color range solution and be positioned over respectively in color comparison tube, add the borate buffer solution, sodium bicarbonate, the H that contain CTAB 2O 2With potassium rhodanide, rock and mix, after mixing, add again gold nanorods, shake up; Then at 50-100 ℃ of temperature, hatch 2-30 minute, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, use the picture by color gradient to form cobalt standard color comparison card F.
8. press the method for the detection cobalt ions of the described cobalt ions colorimetric determination of claim 5 or 6 kit, it is characterized in that: described cetyl ammonium bromide (CTAB) borate buffer solution that contains, pH is 7.4-9.6, concentration is 10-200mM; Described sodium bicarbonate solution concentration is 0.01-1M; Described H 2O 2Solution concentration is 0.01-1M; Described potassium rhodanide solution concentration is 0.01-1M.
9. by the method for the detection cobalt ions of cobalt ions colorimetric determination kit claimed in claim 7, it is characterized in that: described to contain cetyl ammonium bromide (CTAB) borate buffer solution pH be 9.0, and concentration is 50mM, contains the concentration of CTAB for being 2mM; Gold nanorods solution is that concentration is that the length-diameter ratio of 2.3nM is the gold nanorods solution of 2:1; Sodium bicarbonate solution concentration is 0.1M; H 2O 2Solution concentration is 0.1M; The potassium rhodanide solution concentration is 0.1M.
10. press the method for the detection cobalt ions of the described cobalt ions colorimetric determination of claim 5 or 6 kit, it is characterized in that: gold nanorods solution is turned at 6000-10000/the centrifugal 5-30min of min, collecting precipitation also dilutes with intermediate water, after dilution, with 5000-9000, turn/the centrifugal 5-30min of min again, precipitation is again with the intermediate water dilution, stand-by.
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CN106770208A (en) * 2016-12-12 2017-05-31 济南大学 A kind of method that ferrous ion is detected based on gold nanorods
CN108827952A (en) * 2018-07-02 2018-11-16 北京师范大学 NOR logic gate and its construction method
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CN115015230A (en) * 2022-02-22 2022-09-06 中国科学院生态环境研究中心 Rapid detection method and device for hexabromocyclododecane content in EPS/XPS
CN117554362A (en) * 2024-01-10 2024-02-13 中国科学院烟台海岸带研究所 Method for detecting cyanide at normal temperature with high sensitivity and nano colorimetric analysis kit

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CN106290195A (en) * 2016-08-30 2017-01-04 中南林业科技大学 Gold contracted payment nanometer colorimetric sensor preparation method and the method for detection cobalt ion thereof
CN106568773B (en) * 2016-11-22 2020-02-21 中国科学院烟台海岸带研究所 Manganese ion colorimetric detection kit and detection method thereof
CN106568773A (en) * 2016-11-22 2017-04-19 中国科学院烟台海岸带研究所 Manganese ion colorimetry detection kit, and detection method thereof
CN106770208A (en) * 2016-12-12 2017-05-31 济南大学 A kind of method that ferrous ion is detected based on gold nanorods
CN108827952A (en) * 2018-07-02 2018-11-16 北京师范大学 NOR logic gate and its construction method
CN109030476A (en) * 2018-07-20 2018-12-18 安徽原上草节能环保科技有限公司 Preparation method, detection paper tube and the detection method of detection paper tube for cobalt ions
CN109030476B (en) * 2018-07-20 2020-09-01 安徽原上草节能环保科技有限公司 Preparation method of detection paper tube for cobalt ions, detection paper tube and detection method
CN113984751A (en) * 2021-10-29 2022-01-28 中南林业科技大学 Gold nano star colorimetric sensor and preparation method thereof and application of gold nano star colorimetric sensor in Co detection2+Method (2)
CN113984751B (en) * 2021-10-29 2024-05-03 中南林业科技大学 Gold nano star colorimetric sensor, preparation method thereof and Co detection method2+Is a method of (2)
CN115015230A (en) * 2022-02-22 2022-09-06 中国科学院生态环境研究中心 Rapid detection method and device for hexabromocyclododecane content in EPS/XPS
CN115015230B (en) * 2022-02-22 2024-03-01 中国科学院生态环境研究中心 Rapid detection method and device for hexabromocyclododecane content in EPS/XPS
CN117554362A (en) * 2024-01-10 2024-02-13 中国科学院烟台海岸带研究所 Method for detecting cyanide at normal temperature with high sensitivity and nano colorimetric analysis kit
CN117554362B (en) * 2024-01-10 2024-03-12 中国科学院烟台海岸带研究所 Method for detecting cyanide at normal temperature with high sensitivity and nano colorimetric analysis kit

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