CN103278497B - Copper ion colorimetry detecting kit and detecting method thereof - Google Patents

Copper ion colorimetry detecting kit and detecting method thereof Download PDF

Info

Publication number
CN103278497B
CN103278497B CN201310178095.1A CN201310178095A CN103278497B CN 103278497 B CN103278497 B CN 103278497B CN 201310178095 A CN201310178095 A CN 201310178095A CN 103278497 B CN103278497 B CN 103278497B
Authority
CN
China
Prior art keywords
ctab
solution
copper ion
gold nanorods
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310178095.1A
Other languages
Chinese (zh)
Other versions
CN103278497A (en
Inventor
陈兆鹏
张志阳
陈令新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Institute of Coastal Zone Research of CAS
Original Assignee
Yantai Institute of Coastal Zone Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Institute of Coastal Zone Research of CAS filed Critical Yantai Institute of Coastal Zone Research of CAS
Priority to CN201310178095.1A priority Critical patent/CN103278497B/en
Publication of CN103278497A publication Critical patent/CN103278497A/en
Application granted granted Critical
Publication of CN103278497B publication Critical patent/CN103278497B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention relates to the technical field of environmental and biological analysis, and in particular relates to a copper ion colorimetry detecting kit and a detecting method thereof. The kit comprises a hydrobromic acid solution, a gold nanorod solution containing cetyl trimethyl ammonium bromide (CTAB), a standard colorimetric card C and a colorimetric tube, wherein the gold nanorod solution containing the CTAB is formed by dissolving gold nanorods in a CTAB solution under the condition that the concentration of the gold nanorods is within 0.5 to 10nM and the concentration of the CTAB is with 0.01 to 100mM; and the concentration of hydrobromic acid in the hydrobromic acid solution is within 0.05 to 5.0M. The kit for detecting copper ions has the advantages of being high in sensitivity, good in selectivity, easy to operate, easy in naked-eye observation and the like. Under the debugging of a systematic experiment condition, the detection on the copper ions in environmental and biological samples can be realized.

Description

A kind of copper ion colorimetric determination kit and detection method thereof
Technical field
The present invention relates to environment and bioassay technique field, specifically a kind of copper ion colorimetric determination kit and detection method thereof.
Background technology
Copper ion is one of indispensable element of wanting of body weight for humans, and he plays an important role in the function of many cellular enzymes and protein.But will cause copper metabolic disorder when the accumulation of copper ion in human body exceedes certain limit, thus bring very large harm to human body, such as, copper metabolic disorder can increase the probability of suffering from senile dementia and Parkinson's disease.In water body environment, because copper ion can not decompose, thus have biological concentration and biological amplification in vivo, thus make for the higher biology of food chain, in its body, content of copper ion also increase at double, also larger to its harm caused.As the mankind on food chain top, when edible these contain the heavy metal ion aqueous bio of high concentration, the harm be subject to also is maximum.Thus, the detection of the copper ion in environment and biological sample is necessary.
At present, Atomic absorption is mainly contained to the detection means of copper ion, atomic emissions, inductivity coupled plasma mass spectrometry coupling technique etc.But these technology all need large-scale instrument, expensive, on-the-spot in situ detection and Technique Popularizing can not be realized! Relatively above detection technique, colorimetric analysis advantage is that its naked eyes are easy to observation, is very suitable for on-the-spot detecting in real time, simple to operate and low price.Golden nanometer particle has very large molar extinction coefficient because of its surface plasmon absorption, and thus it applies to have obvious advantage in colorimetric analysis.The present invention utilizes copper ions catalyze to etch gold nanorods colorimetric determination copper ion, and have highly sensitive, selectivity is good, simple to operate, and speed is fast, and naked eyes are easily observed, and is applicable to the advantages such as on-the-spot detection in real time.And the domestic kit based on copper ions catalyze etching gold nanorods colorimetric determination copper ion have not been reported at present.
Summary of the invention
The object of the invention is to provide a kind of copper ion colorimetric determination kit and detection method thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of copper ion colorimetric determination kit, is characterized in that: kit comprises hydrobromic acid solution, gold nanorods solution, standard color comparison card C and color comparison tube containing cetyl ammonium bromide (CTAB);
Described is that gold nanorods is dissolved in CTAB solution containing cetyl ammonium bromide (CTAB) gold nanorods solution, and wherein the concentration of nanometer rods is 0.5-10nM, CTAB concentration is 0.01-100mM;
In described hydrobromic acid solution, hydrobromic acid concentration is 0.05-5.0M.
Further, preparation containing CTAB gold nanorods solution is that gold nanorods is turned the/centrifugal 5-30 minute of min at 7000-10000, collecting precipitation dilute with water, / centrifugal the 5-30 minute of min is turned with 6000-9000 again after dilution, precipitation uses cetyl ammonium bromide (CTAB) solution dilution of 0.01-100mM mM again, stand-by.
800 μ L hydrobromic acid solutions are added in color comparison tube by the method for the detection copper ion of copper ion colorimetric determination kit, add 5-50 μ L testing sample and rock mixing, add the gold nanorods 200 μ L containing CTAB again, shake up after mixing; Then at 40-90 DEG C of temperature, hatch 5-30 minute, observe color by naked eyes or ultraviolet-visual spectrometer, contrast with standard color comparison card C and determine content of copper ion.
The preparation of described standard color comparison card C is, gets 0-1mM variable concentrations copper standard color range solution and is positioned over respectively in color comparison tube, add hydrobromic acid solution and rock mixing, add the gold nanorods containing CTAB again, shake up after mixing; Then at 50-90 DEG C of temperature, hatch 5-40 minute, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, form copper standard color comparison card C with the picture by color gradient.
Described 0-1mM variable concentrations copper standard color range solution concentration is respectively 0,10,50,100,500,1000,10 4, 10 5, 10 6nM.
In described hydrobromic acid solution, hydrobromic acid concentration is 0.5M.
Described is that gold nanorods is dissolved in cetyl ammonium bromide (CTAB) solution containing cetyl ammonium bromide (CTAB) gold nanorods solution, and wherein the concentration of nanometer rods is 2.3nM, CTAB concentration is 1.0mM.
Principle (see figure 1) of the present invention is in an acidic solution, copper ion gold oxide nanometer rods and generate cuprous ion, cuprous ion can be copper ion by the dissolved oxygen DO rapid oxidation in solution again, thus form circulation catalysis etching gold nanorods (see figure 2), make its absorption spectrum change (see figure 3) changing along with obvious color, this change and the linear (see figure 5) of copper ion concentration simultaneously.
The advantage that the present invention has: the present invention utilizes copper ions catalyze to etch gold nanorods colorimetric determination copper ion, have highly sensitive (detect and be limited to 0.5nM), selectivity good (see Fig. 4), simple to operate, speed is fast, naked eyes are easily observed, and are applicable to the advantages such as on-the-spot detection in real time.
Accompanying drawing explanation
Fig. 1 is the principle of copper ions catalyze provided by the invention etching gold nanorods.
Images of transmissive electron microscope before and after the copper ions catalyze etching gold nanorods that Fig. 2 provides for the embodiment of the present invention; Wherein, gold nanorods (left side), afterwards (centre is low concentration, and the right side is high concentration) before copper ions catalyze etching.
Abosrption spectrogram after copper ion (concentration from low to high) the catalysis etching gold nanorods that Fig. 3 provides for the embodiment of the present invention.
The selectivity experimental result of the detection copper ion that Fig. 4 provides for the embodiment of the present invention and corresponding photo.
Fig. 5 for the embodiment of the present invention provide copper ion standard color comparison card C.
The detection copper ion process flow diagram that Fig. 6 provides for the embodiment of the present invention.
Fig. 7 is that the present invention detects copper ion typical curve
Embodiment
Embodiment 1: copper in drinking water ion detection
Kit comprises hydrobromic acid solution, gold nanorods solution, standard color comparison card C and color comparison tube containing cetyl ammonium bromide (CTAB);
Described hydrobromic acid preparation: the pure hydrobromic acid of the analysis by 38% dilutes and obtains, and concentration is 0.5M hydrobromic acid solution.
Preparation containing cetyl ammonium bromide (CTAB) gold nanorods solution:
1) gold nanorods obtains as follows:
Synthesis gold seeds liquid: get 50 μ L gold chloride (50mM) solution and shake up a few second to 7.7mL containing in cetyl ammonium bromide (CTAB) solution of 0.1M, add 600 μ L ice sodium borohydride (0.01M) accelerate rock a few minutes, color is stopped to during purplish grey by glassy yellow, under 26 degrees Celsius of environment, leave standstill after 2 hours and use.
Nanometer rods is synthesized, gold chloride (50mM) solution is joined in cetyl ammonium bromide (CTAB) solution of 0.1M and stir and evenly mix, then add silver nitrate (0.01M) solution and the mixing of ascorbic acid (0.1M) solution again, the gold seeds solution liquid adding above-mentioned synthesis when solution is become colorless by yellowish-brown under stirring has the five colors to gradually become blue-green to solution colour, stop stirring, leave standstill 20 hours, namely obtain gold nanorods.From transmission electron microscope wherein gold nanorods length-diameter ratio be about 2:1(and see Fig. 2 (left side)), the radial absorption peak of uv-visible absorption spectra figure is shown in figure tri-abosrption spectrogram 0 at 670nm(), according to langbobier law, the concentration estimating nanometer rods is 2.3nM.
2) containing cetyl ammonium bromide (CTAB) gold nanorods solution: by gold nanorods (its maximum absorption wavelength is at 670nM) at 8000 turns/min centrifugal 15 minutes, collecting precipitation dilute with water, after dilution with 7000 turns/min centrifugal 15 minutes again, precipitation uses cetyl ammonium bromide (CTAB) solution dilution of 1mM again, to obtain final product.
The preparation of standard color comparison card C is, getting concentration is 0,10,50,100,500,1000,10 4, 10 5, 10 6the copper standard color range solution 10 μ L of nM joins 800 μ L hydrobromic acid solutions respectively and rocks mixing, adds the gold nanorods containing CTAB again, shake up after mixing; Then at 75 DEG C of temperature, hatch 20 minutes, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, form copper standard color comparison card C(with the picture by color gradient and see Fig. 5), corresponding uv-visible absorption spectra figure can be gathered simultaneously, and according to peak shift production standard curve (as Fig. 7).
I.e. kit:
Hydrobromic acid solution, concentration is 0.5M;
Color comparison tube, 1.5mL;
Glass scales suction pipe;
Copper standard color range solution;
Copper standard color comparison card.
Copper in drinking water ion detection:
(1) pipette 800 μ L hydrobromic acid solutions in 1.5mL color comparison tube, add water body example 10 μ L to be measured, after rocking mixing, add containing CTAB gold nanorods 200 μ L, shake up;
(2) at 75 DEG C of temperature, 20 minutes are hatched.
(3) color change is observed, color comparison tube and standard color comparison card C are compared, determine the concentration range of copper ion, respective absorption spectrogram can be measured simultaneously, determined the concrete content of copper ion by typical curve (Fig. 7), experimental result shows this method testing result and ICP-MS measurement result basically identical (table 1).
Table 1 this method and ICP-MS are to actual water sample copper ion testing result
Embodiment 2: in biological sample, copper ion detects
Kit comprises hydrobromic acid solution, gold nanorods solution, standard color comparison card C and color comparison tube containing cetyl ammonium bromide (CTAB);
Described hydrobromic acid preparation: the pure hydrobromic acid of the analysis by 38% dilutes and obtains, and concentration is 0.5M hydrobromic acid solution.
Preparation containing cetyl ammonium bromide (CTAB) gold nanorods solution:
1) gold nanorods obtains as follows:
Synthesis gold seeds liquid: get 50 μ L gold chloride (50mM) solution and shake up a few second to 7.7mL containing in cetyl ammonium bromide (CTAB) solution of 0.1M, add 600 μ L ice sodium borohydride (0.01M) accelerate rock a few minutes, color is stopped to during purplish grey by glassy yellow, under 26 degrees Celsius of environment, leave standstill after 2 hours and use
Nanometer rods is synthesized, gold chloride (50mM) solution is joined in cetyl ammonium bromide (CTAB) solution of 0.1M and stir and evenly mix, then add silver nitrate (0.01M) solution and the mixing of ascorbic acid (0.1M) solution again, the gold seeds solution liquid adding above-mentioned synthesis when solution is become colorless by yellowish-brown under stirring has the five colors to gradually become blue-green to solution colour, stop stirring, leave standstill 20 hours, namely obtain gold nanorods.From transmission electron microscope wherein gold nanorods length-diameter ratio be about 2:1(and see Fig. 2 (left side)), the radial absorption peak of uv-visible absorption spectra figure is shown in figure tri-abosrption spectrogram 0 at 670nM(), according to langbobier law, the concentration estimating nanometer rods is 2.3nM.
2) containing cetyl ammonium bromide (CTAB) gold nanorods solution: by gold nanorods (its maximum absorption wavelength is at 670nM) at 8000 turns/min centrifugal 15 minutes, collecting precipitation dilute with water, after dilution with 7000 turns/min centrifugal 15 minutes again, precipitation uses cetyl ammonium bromide (CTAB) solution dilution of 1mM again, to obtain final product.
The preparation of standard color comparison card C is, getting concentration is 0,10,50,100,500,1000,10 4, 10 5, 10 6the copper standard color range solution 10 μ L of nM joins 800 μ L hydrobromic acid solutions respectively and rocks mixing, adds the gold nanorods containing CTAB again, shake up after mixing; Then at 75 DEG C of temperature, hatch 20 minutes, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, form copper standard color comparison card C(with the picture by color gradient and see Fig. 5).
I.e. kit:
Hydrobromic acid solution, concentration is 0.5M;
Color comparison tube, 1.5mL;
Glass scales suction pipe;
Copper standard color range solution;
Copper standard color comparison card.
In biological sample, copper ion detects (for sea cowry):
(1) sample pretreatment: shell is removed in the biological sample fetched cleaning, obtains the active component that need detect stand-by, then clean three times with intermediate water, then refrigerator freezing Cheng Bing is put into, and then put into freeze-dryer removal moisture, after drying, then in mortar, pulverize is stand-by.
(2) Specimen eliminating: get 0.3 gram of above-mentioned sample, join in the red fuming nitric acid (RFNA) of 10mL, clear up 6 hours at 150 DEG C, finally by solution dilution to 50mL.
(3) get 800 microlitre hydrobromic acid solutions in 1.5mL centrifuge tube, add and above-mentionedly clear up sample 10 μ L, after rocking mixing, to add in reagent bottle B containing CTAB gold nanorods 200 μ L, shake up.
(4) at 75 DEG C of temperature, 20 minutes are hatched.
(5) by naked eyes, color comparison tube and standard color comparison card C are compared, determine the concentration range of copper ion, respective absorption spectrogram can be measured simultaneously, determined the concrete content of copper ion by typical curve (Fig. 7), experimental result shows this method testing result and ICP-MS measurement result basically identical (table 2).
Table 2 this method testing result and ICP-MS measurement result

Claims (6)

1. a copper ion colorimetric determination kit, is characterized in that: kit comprises hydrobromic acid solution, gold nanorods solution, standard color comparison card C and color comparison tube containing cetyl ammonium bromide (CTAB);
Described is that gold nanorods is dissolved in CTAB solution containing cetyl ammonium bromide (CTAB) gold nanorods solution, and wherein the concentration of nanometer rods is 0.5-10nM, CTAB concentration is 0.01-100mM;
In described hydrobromic acid solution, hydrobromic acid concentration is 0.05-5.0M;
Preparation containing CTAB gold nanorods solution is that gold nanorods is turned the/centrifugal 5-30 minute of min at 7000-10000, collecting precipitation dilute with water, / centrifugal the 5-30 minute of min is turned with 6000-9000 again after dilution, precipitation uses cetyl ammonium bromide (CTAB) solution dilution of 0.01-100mM again, stand-by.
2. the method for the detection copper ion of a copper ion colorimetric determination kit according to claim 1, it is characterized in that: 800 μ L hydrobromic acid solutions are added in color comparison tube, add 5-50 μ L testing sample and rock mixing, add the gold nanorods 200 μ L containing CTAB after mixing again, shake up; Then at 40-90 DEG C of temperature, hatch 5-30 minute, observe color by naked eyes or ultraviolet-visual spectrometer, contrast with standard color comparison card C and determine content of copper ion.
3. by the method for the detection copper ion of copper ion colorimetric determination kit according to claim 2, it is characterized in that: the preparation of described standard color comparison card C is, get 0-1mM variable concentrations copper standard color range solution to be positioned over respectively in color comparison tube, add hydrobromic acid solution and rock mixing, add the gold nanorods containing CTAB after mixing again, shake up; Then at 50-90 DEG C of temperature, hatch 5-40 minute, carry out chromogenic reaction, use professional camera record colour developing result, after gathering picture, form copper standard color comparison card C with the picture by color gradient.
4., by the method for the detection copper ion of copper ion colorimetric determination kit according to claim 3, it is characterized in that: described 0-1mM variable concentrations copper standard color range solution concentration is respectively 0,10,50,100,500,1000,10 4, 10 5, 10 6nM.
5., by the method for the detection copper ion of the copper ion colorimetric determination kit described in Claims 2 or 3, it is characterized in that: in described hydrobromic acid solution, hydrobromic acid concentration is 0.5M.
6. by the method for the detection copper ion of the copper ion colorimetric determination kit described in Claims 2 or 3, it is characterized in that: described is that gold nanorods is dissolved in cetyl ammonium bromide (CTAB) solution containing cetyl ammonium bromide (CTAB) gold nanorods solution, wherein the concentration of nanometer rods is 2.3nM, CTAB concentration is 1.0mM.
CN201310178095.1A 2013-05-15 2013-05-15 Copper ion colorimetry detecting kit and detecting method thereof Expired - Fee Related CN103278497B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310178095.1A CN103278497B (en) 2013-05-15 2013-05-15 Copper ion colorimetry detecting kit and detecting method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310178095.1A CN103278497B (en) 2013-05-15 2013-05-15 Copper ion colorimetry detecting kit and detecting method thereof

Publications (2)

Publication Number Publication Date
CN103278497A CN103278497A (en) 2013-09-04
CN103278497B true CN103278497B (en) 2015-07-01

Family

ID=49061078

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310178095.1A Expired - Fee Related CN103278497B (en) 2013-05-15 2013-05-15 Copper ion colorimetry detecting kit and detecting method thereof

Country Status (1)

Country Link
CN (1) CN103278497B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105277540B (en) * 2015-02-05 2018-03-23 温州医科大学 Copper ion field fast detection method in a kind of water for eliminating reagent blank influence
CN105466920A (en) * 2015-11-20 2016-04-06 鲁翌 A rapid antithrombin III detecting kit based on interaction between thrombin and a chromogenic substrate and a detecting method thereof
CN106198522B (en) * 2016-07-05 2019-02-22 河南城建学院 A kind of fast detection kit for copper ions and its detection method
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
CN107064134A (en) * 2017-06-14 2017-08-18 大连理工大学 A kind of analysis method for organophosphorus pesticide Glassless half-quantitative detection
US11371978B1 (en) 2021-06-23 2022-06-28 Mks Vision, Llc System and method for detecting lead in water

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102323312A (en) * 2011-09-21 2012-01-18 福州大学 Detection method and device for portable rapid visual detection of copper ion content
CN102621134A (en) * 2011-01-27 2012-08-01 国家纳米科学中心 Method for detecting copper ions by gold nano-particles
CN102818804A (en) * 2012-08-09 2012-12-12 中国科学院唐山高新技术研究与转化中心 Kit and detection method for determining copper ion concentration in water environment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101047129B1 (en) * 2008-10-22 2011-07-07 고려대학교 산학협력단 Coumarin derivatives having copper ion selectivity, preparation methods thereof, copper ion detection methods and fluorescence chemical sensors using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102621134A (en) * 2011-01-27 2012-08-01 国家纳米科学中心 Method for detecting copper ions by gold nano-particles
CN102323312A (en) * 2011-09-21 2012-01-18 福州大学 Detection method and device for portable rapid visual detection of copper ion content
CN102818804A (en) * 2012-08-09 2012-12-12 中国科学院唐山高新技术研究与转化中心 Kit and detection method for determining copper ion concentration in water environment

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
纳米金比色法快速检测水中重金属的研究进展;戚红卷等;《环境化学》;20130131;第32卷(第1期);第21-28页 *
金纳米棒比色法检测铜离子;刘瑞利等;《广东化工》;20130430;第40卷(第8期);第132-134页 *

Also Published As

Publication number Publication date
CN103278497A (en) 2013-09-04

Similar Documents

Publication Publication Date Title
CN103278497B (en) Copper ion colorimetry detecting kit and detecting method thereof
Peng et al. Determination of total iron in water and foods by dispersive liquid–liquid microextraction coupled with microvolume UV–vis spectrophotometry
Hajizadeh et al. Silver nanoparticles as a cyanide colorimetric sensor in aqueous media
Zhu et al. Detection of Hg2+ based on the selective inhibition of peroxidase mimetic activity of BSA-Au clusters
Wang et al. Cadmium telluride quantum dots as pH-sensitive probes for tiopronin determination
Liu et al. Colorimetric speciation of Cr (III) and Cr (VI) with a gold nanoparticle probe
CN103411962B (en) A kind of cobalt ions colorimetric determination kit and detection method thereof
KR101730801B1 (en) Selective colorimetric detection sensor and method for hexavalent chromium ions using size controlled label-free gold nanoparticles
Huang et al. A novel one-step colorimetric assay for highly sensitive detection of glucose in serum based on MnO 2 nanosheets
Amjadi et al. A highly sensitive plasmonic sensor for detection of selenium based on the shape transformation of silver nanoprisms
Cao et al. Highly sensitive ‘naked-eye’colorimetric detection of thiourea using gold nanoparticles
Li et al. A surface enhanced Raman scattering quantitative analytical platform for detection of trace Cu coupled the catalytic reaction and gold nanoparticle aggregation with label-free Victoria blue B molecular probe
Tao et al. A comparative study of different reagentless plasmon sensors based on Ag–Au alloy nanoparticles for detection of Hg
CN108318471B (en) SERS-based magnetic test paper for detecting nitrite and preparation and use methods thereof
CN113138185B (en) Method for detecting sodium thiocyanate in milk by using SERS (surface enhanced Raman Scattering) technology based on MOF (metal-organic framework)
Liu et al. SERS-based Au@ Ag core-shell nanoprobe aggregates for rapid and facile detection of lead ions
Xiong et al. Simple multimodal detection of selenium in water and vegetable samples by a catalytic chromogenic method
Jannatin et al. A novel spectrophotometric method for determination of histamine based on its complex reaction with Cu (II) and alizarin red S
CN109799215B (en) Pb based on G-quadruplex DNA2+Fluorescence sensing detection method
Alshehri et al. Utilization of a novel PVC-optical sensor for high sensitive and selective determination of zinc ion in real samples
Yazdi et al. Inorganic selenium speciation in water and biological samples by three phase hollow fiber-based liquid phase microextraction coupled with HPLC-UV
KR101939870B1 (en) Detecting method of trivalent chromium using methionine
CN113588606B (en) Non-conjugated polymer probe, dual signal ratio sensor, method and application
CN106568773B (en) Manganese ion colorimetric detection kit and detection method thereof
Abbas et al. Cloud point extraction as a procedure of separation and pre-concentration for cupper (II) determination using spectrofluorometric techniques

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150701

CF01 Termination of patent right due to non-payment of annual fee