CN103217416A - Detection composition, method and kit for detection of bivalent mercury ions - Google Patents
Detection composition, method and kit for detection of bivalent mercury ions Download PDFInfo
- Publication number
- CN103217416A CN103217416A CN201310091158XA CN201310091158A CN103217416A CN 103217416 A CN103217416 A CN 103217416A CN 201310091158X A CN201310091158X A CN 201310091158XA CN 201310091158 A CN201310091158 A CN 201310091158A CN 103217416 A CN103217416 A CN 103217416A
- Authority
- CN
- China
- Prior art keywords
- water
- detection
- sample
- detection composition
- dimercurion
- 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.)
- Granted
Links
Images
Abstract
The invention relates to a detection composition for detection of bivalent mercury ions, a method for detection of bivalent mercury ions by the detection composition, and a kit for detection of bivalent mercury ions. The detection composition includes: surface modifier modified gold nanoparticles, water, and a solvent that is able to dissolve a hydroxyquinoline compound and is mutually soluble with water. The surface modifier comprises a water soluble oxalate, a nonionic surface active agent, and a hydroxyquinoline compound. The detection composition, the method and the kit provided in the invention can rapidly, sensitively, and conveniently detect low concentration bivalent mercury ions in an aqueous solution.
Description
Technical field
The invention belongs to the metal ion detection field, be specifically related to a kind of detection composition that detects low concentration dimercurion in the aqueous solution and fast, the method and the kit of sensitive, easy detection dimercurion.
Background technology
In recent years, along with rapid development of economy, the energy, resource consume in a large number, have also caused plurality of heavy metal pollution problem, serious threat human beings'health simultaneously.Along with improving constantly of people's quality of life, living environment is also had higher requirement.The heavy metal pollution incident takes place in frequent succession, and for example " blood lead incident ", " mercury poisoning ", " chromium capsule " etc. cause showing great attention to of the common people, thereby the environment measuring means are proposed higher requirement.
The industry that relates to heavy metals emission is a lot, mainly comprises ore extraction, metal smelt, chemical industry, plating, leather, agricultural chemicals and IT etc.Heavy metal contaminants enters pond, rivers, lake and reservoir etc. greatly, make that not only the environmental ecology system is destroyed, and the water source of potable water is also often polluted harm humans health.In all heavy metal elements, mercury is to one of the most serious metallic element of human body harm.The minamata disease that nineteen fifty-three betides Japanese Minamata bay is exactly local resident for a long time due to the fish of edible enrichment methyl mercury, does not still have effective methods of treatment until now.This also makes people that mercury pollution has been had deep understanding.
Mercury element is to one of bigger element of human body hazard ratio, and is serious to central lesion when the human body excess intake, shows as headache, dizziness, sleep-disorder, emotional, constitutional symptom and stomatitis such as finger trembles, unable, low-heat.Wherein typical illness is minamata disease.China's related standards has been 0.001mg/L with mercury content upper limit standard setting in the potable water at present.
The method of detection mercury ion commonly used has atomic absorption spectrography (AAS), inductively coupled plasma～mass spectroscopy etc. both at home and abroad at present, yet often there are defectives such as sample preparation steps complexity, ion interference is serious, instrument costs an arm and a leg, grow detection time in these methods.Biology sensor detection method based on DNA functionalization noble metal nano particles has higher sensitivity for mercury detection in the water quality, can realize on-the-spot detection in real time, the important research direction that mercury detects in the environmental water sample after being, but also there are a lot of defectives in this method, mainly be that anti-interference is low, be difficult to be applied to the reagent environmental system.
The method of utilizing general chemistry reagent functionalization noble metal nano particles to detect other heavy metal ion has been seen in report, for example Chinese patent is announced or notification number 201010251278.8,201110299385.2,201110363954.5,201110378260.9,201210310138.2,201010194041.0 etc., utilization is at the different specific detection reagent of gold/silver nano particle finishing, by combining with the specificity of fixing metal ions, redox reaction etc., cause the pattern of gold/silver nano particle to change and (reunite, particle diameter diminishes etc.), and then cause the variation of color and uv absorption peak position and intensity.These methods are quick, easy, sample preparation is simple, economical, can realize Hg
2+, Cr
3+, Cr
6+, Co
2+, Pb
2+And Mn
2+Color comparison of naked eye detect, wherein the patent No. is in 201010194041.0 the patent, the applicant has realized that a kind of rapid sensitive detects the method for mercury, this method utilizes the hydrolysate of sulfide to modify golden nanometer particle, combine generation mercuric sulphide quantum dot with the sulphion specificity on golden nanometer particle surface by mercury ion and be coated on golden nanometer particle surface formation nucleocapsid structure, causing the gold nano surface plasma resonance to absorb changes, along with the existence of mercury ion and increasing of amount, tangible blue shift takes place in gold particle surface plasma resonance absorption peak, thereby reaches the purpose to mercury ion detecting.But this detection sensitivity is lower slightly, impel us to accelerate to study novel detection method, adding by mercury ion causes golden nanometer particle to be reunited, and tangible red shift takes place gold particle surface plasma resonance absorption peak, thereby reaches, fast detection sensitive more to mercury ion.
Document " Facile and One Pot Synthesis of Gold Nanoparticles Using Tetraphenylborate and Polyvinylpyrrolidone for Selective Colorimetric Detection of Mercury Ions in Aqueous Medium (Volume2012; Article ID348965, p6) " a kind of detection Hg of middle disclosure
2+Method, it utilizes polyvinylpyrrolidone (PVP) protection, tetraphenylboron sodium reduction preparation golden nanometer particle, under strong alkaline condition by protective agent PVP and Hg
2+Selectively acting, realize Hg
2+Color comparison of naked eye detects, but the minimum Hg that this detection method is suitable for
2+Detectable concentration higher (about 10 μ M) at low concentration dimercurion water solution system testing sample and inapplicable, can't satisfy on the market or academicly to detecting Hg fully
2+Demand.
Therefore, explore a kind of economy, quick, easy and detect the composition and the method for dimercurion in the water solution system in real time, and be applied to fields such as actual environment detection, wastewater treatment, food analysis, medical analysis, air and soil quality analysis, have important use and be worth.
Summary of the invention
The purpose of this invention is to provide a kind of minimum Hg
2+Detectable concentration lower and can be economical, quick, easy and the detection that detects dimercurion in the water solution system in real time examine compound and method.
First aspect present invention provides a kind of detection composition that detects dimercurion, and it comprises:
Surface modification agent gold nano-particles modified, described coating material comprises:
Water-soluble oxalates;
Non-ionics; And
The hydroxyquinoline compounds;
Water; With
Solubilized hydroxyquinoline compounds and the solvent that dissolves each other with water.
In another preference, this detection composition is colloidal.
In another preference, this water-soluble oxalates comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
In another preference, this non-ionics is a polyvinylpyrrolidone.
In another preference, the mean molecular weight of polyvinylpyrrolidone is 10,000 to 130,000, more preferably is 30,000 to 58,000.
In another preference, this hydroxyquinoline compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
In another preference, this solubilized hydroxyquinoline compounds and with solvent that water dissolves each other be methyl alcohol, ethanol, acetone, or their combination.
In another preference, this detection composition has the pH value between 4 to 6.
In another preference, this detection composition is to obtain by following step:
(i) prepare reduction protection liquid and golden nanometer particle precursor water solution respectively, this reduction protection liquid comprises water-soluble oxalates, non-ionics and water, and this golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mix golden nanometer particle precursor water solution and reduction protection liquid to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid and contain the detection composition of surface modification agent gold nano-particles modified, the solvent that this functionalized modification liquid comprises hydroxyquinoline compounds and solubilized hydroxyquinoline compounds and dissolves each other with water with formation.
In another preference, this golden nanometer particle presoma comprises golden salt, the solubility of solubility and contains the acid of gold, or their combination.
In another preference, this solubility and contain the gold acid be tetra chlorauric acid.
In another preference, at step (i) employed [molal quantity of contained gold ion in the golden nanometer particle presoma] in (iii): [molal quantity of contained oxalate denominationby in the water-soluble oxalates]: [molal quantity of hydroxyquinoline compounds] is 1:1:10 to 1:10:30.More preferably be 1:3:25 to 1:6:30.Be 1:4:26 to 1:5:29 best.
In another preference, in step (i) employed [contained gold atom weight in the golden nanometer particle presoma] in (iii): [weight of non-ionics] is 1:0.5 to 1:4.More preferably be 1:1 to 1:2.Be 1:1 to 1:1.5 best.
In another preference, the reduction protection liquid of this step (i) is, and to be 0.01 to 0.10mol/L oxalates aqueous solution by the concentration with 20mL mix with 3 to 9mg non-ionics, regulates pH value to 3.5 afterwards and obtain to 6.0.Preferably, the adjusting of the pH value of reduction protection liquid is to reach by adding acid (for example hydrochloric acid) adjusting.
In another preference, the golden nanometer particle precursor water solution of this step (i) is by the golden nanometer particle presoma is mixed with water, and oil bath afterwards is heated to 70 to 95 ℃ and stirring and obtains.
In another preference, the concentration of this solubility gold precursor water solution is 0.1 to 1.0mmol/L.
In another preference, this step golden nanometer particle stoste (ii) is by earlier reduction protection liquid being heated to boiling, mixes, stirs 0.5 to 2h and place at least and obtain behind the 24h with the golden nanometer particle precursor water solution afterwards.
In another preference, the pH value of this golden nanometer particle stoste is between 3.0 to 5.0.More preferably be 4.0.
In another preference, this step comprises that (iii) elder generation is diluted to the golden nanometer particle dilution with golden nanometer particle stoste with 1 to 3 times of volume of ethanol, be that the functionalized modification liquid of 0.05～0.20mol/L mixes and stirs then with golden nanometer particle dilution and concentration, the golden nanometer particle stoste that is used to mix and the volume ratio of functionalized modification liquid are 7:1 to 10:1.
Second aspect present invention provides the method that detects dimercurion, may further comprise the steps:
(a) provide detection composition of the present invention as described above;
(b) in this detection composition, add sample to be tested, form and detect potpourri;
(c) observe or measure the color and/or the ultraviolet-visible spectrum of this detection potpourri, and compare compared with the control or with standard diagram, thereby draw the measurement result whether sample to be tested exists the concentration of dimercurion and/or dimercurion.
In another preference, this contrast is the control mixture of following formation: in this detection composition, add the aqueous solution that does not contain dimercurion, form control mixture, and satisfy following formula V1/V2=V3/V4,
In the formula,
V1 is that this that be used to form control mixture do not contain the volume of the aqueous solution of dimercurion;
V2 is the volume that is used to form this detection composition of control mixture;
V3 is the volume that is used to form this sample to be tested that detects potpourri;
V4 is the volume that is used to form this detection composition that detects potpourri.
In another preference, this standard diagram is to make by the following method:
(I) the dimercurion aqueous solution of adding variable concentrations in this detection composition makes a plurality of detection potpourris;
(II) measure the ultraviolet-visible spectral absorption that respectively detects potpourri;
(III) draw " the ultraviolet-visible spectral absorption value-dimercurion concentration that detects potpourri " curve, or draw " UV, visible light absorbance value-dimercurion concentration relatively " collection of illustrative plates, as standard diagram;
In another preference, this ultraviolet-visible spectral absorption is measured under 450～800nm wavelength.500～700nm preferably, more preferably 522 and 625nm about.
In another preference, this sample to be tested comprises environmental water sample, solid-state environment sample, blood sample, organizes the leachate sample, the aqueous solution of food leachate sample, treated solid, and the aqueous solution of gaseous sample.
Third aspect present invention provides a kind of kit that detects dimercurion, comprising:
The golden nanometer particle presoma;
Water-soluble oxalates;
Non-ionics; With
The hydroxyquinoline compounds;
Wherein, this golden nanometer particle presoma, non-ionics, water-soluble oxalates and hydroxyquinoline compounds are used to prepare a detection composition that contains surface modification agent gold nano-particles modified.
In should be understood that within the scope of the present invention, can make up mutually between above-mentioned each technical characterictic of the present invention and specifically described in below (eg embodiment) each technical characterictic, thereby constitute new or optimized technical scheme.As space is limited, this tired no longer one by one stating.
Description of drawings
Fig. 1 be in the explanation embodiment of the invention 2 variable concentrations contain Hg
2+The testing result of aqueous standard product.
Fig. 2 is ultraviolet-visible spectral absorption value (the absorbance log)-dimercurion concentration of the detection potpourri that obtains of the explanation embodiment of the invention 3 " curve.
Fig. 3 is relative UV, visible light absorbance value-dimercurion concentration that the explanation embodiment of the invention 3 obtains " collection of illustrative plates.
Fig. 4 is the specific result that the explanation embodiment of the invention 4 detects the present composition and method.
Fig. 5 is the specific result that the explanation embodiment of the invention 4 detects the present composition and method.
Embodiment
The inventor is through extensive and deep discovering; utilize non-ionics (as polyvinylpyrrolidone (PVP)) protection, water-soluble oxalates reduction preparation golden nanometer particle; utilize the hydroxyquinoline compounds to carry out functionalization then and can obtain surface modification agent gold nano-particles modified, this surface modification agent gold nano-particles modified can by oxalate denominationby on it or oxalic acid hydrogen radical ion and the hydroxyquinoline compounds be next and Hg
2+Carry out the selective coordination complexing, cause the solution of gold nanoparticles color to change, cause that the peak position and the intensity of golden nanometer particle surface plasma body resonant vibration absorption peak changes, realize Hg in the aqueous solution
2+Fast, sensitive, easy detection.Finished the present invention on this basis.
Detect the detection composition of dimercurion
The detection composition that the present invention detects dimercurion comprises surface modification agent gold nano-particles modified, water, with solubilized hydroxyquinoline compounds and the solvent that dissolves each other with water, described coating material comprises water-soluble oxalates, non-ionics, and the hydroxyquinoline compounds.
In another preference, this detection composition is colloidal.
In another preference, this water-soluble oxalates comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
In another preference, this non-ionics is a polyvinylpyrrolidone.
In another preference, the mean molecular weight of polyvinylpyrrolidone is 10,000 to 130,000, more preferably is 30,000 to 58,000.
In another preference, this hydroxyquinoline compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
In another preference, this solubilized hydroxyquinoline compounds and with solvent that water dissolves each other be methyl alcohol, ethanol, acetone, or their combination.
In another preference, this detection composition has the pH value between 4 to 6.
In another preference, this detection composition is to obtain by following step:
(i) prepare reduction protection liquid and golden nanometer particle precursor water solution respectively, this reduction protection liquid comprises water-soluble oxalates, non-ionics and water, and this golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mix golden nanometer particle precursor water solution and reduction protection liquid to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid and contain the detection composition of surface modification agent gold nano-particles modified, the solvent that this functionalized modification liquid comprises hydroxyquinoline compounds and solubilized hydroxyquinoline compounds and dissolves each other with water with formation.
In another preference, this golden nanometer particle presoma comprises golden salt, the solubility of solubility and contains the acid of gold, or their combination.
In another preference, this solubility and contain the gold acid be tetra chlorauric acid.
In another preference, at step (i) employed [molal quantity of contained gold ion in the golden nanometer particle presoma] in (iii): [molal quantity of contained oxalate denominationby in the water-soluble oxalates]: [molal quantity of hydroxyquinoline compounds] is 1:1:10 to 1:10:30.More preferably be 1:3:25 to 1:6:30.Be 1:4:26 to 1:5:29 best.
In another preference, in step (i) employed [contained gold atom weight in the golden nanometer particle presoma] in (iii): [weight of non-ionics] is 1:0.5 to 1:4.More preferably be 1:1 to 1:2.Be 1:1 to 1:1.5 best.
In another preference, the reduction protection liquid of this step (i) is, and to be 0.01 to 0.10mol/L oxalates aqueous solution by the concentration with 20mL mix with 3 to 9mg non-ionics, regulates pH value to 3.5 afterwards and obtain to 6.0.Preferably, the adjusting of the pH value of reduction protection liquid is to reach by adding acid (for example hydrochloric acid) adjusting.
In another preference, the golden nanometer particle precursor water solution of this step (i) is by the golden nanometer particle presoma is mixed with water, and oil bath afterwards is heated to 70 to 95 ℃ and stirring and obtains.
In another preference, the concentration of this solubility gold precursor water solution is 0.1 to 1.0mmol/L.
In another preference, this step golden nanometer particle stoste (ii) is by earlier reduction protection liquid being heated to boiling, mixes, stirs 0.5 to 2h and place at least and obtain behind the 24h with the golden nanometer particle precursor water solution afterwards.
In another preference, the pH value of this golden nanometer particle stoste is between 3.0 to 5.0.More preferably be 4.0.
In another preference, this step comprises that (iii) elder generation is diluted to the golden nanometer particle dilution with golden nanometer particle stoste with 1 to 3 times of volume of ethanol, be that the functionalized modification liquid of 0.05～0.20mol/L mixes and stirs then with golden nanometer particle dilution and concentration, the golden nanometer particle stoste that is used to mix and the volume ratio of functionalized modification liquid are 7:1 to 10:1.
Detect the method for dimercurion
The method that the present invention detects dimercurion may further comprise the steps:
(a) provide detection composition of the present invention as described above;
(b) in this detection composition, add sample to be tested, form and detect potpourri;
(c) observe or measure the color and/or the ultraviolet-visible spectrum of this detection potpourri, and compare compared with the control or with standard diagram, thereby draw the measurement result whether sample to be tested exists the concentration of dimercurion and/or dimercurion.
In another preference, this contrast is the control mixture of following formation: in this detection composition, add the aqueous solution that does not contain dimercurion, form control mixture, and satisfy following formula V1/V2=V3/V4,
In the formula,
V1 is that this that be used to form control mixture do not contain the volume of the aqueous solution of dimercurion;
V2 is the volume that is used to form this detection composition of control mixture;
V3 is the volume that is used to form this sample to be tested that detects potpourri;
V4 is the volume that is used to form this detection composition that detects potpourri.
In another preference, this standard diagram is to make by the following method:
(I) the dimercurion aqueous solution of adding variable concentrations in this detection composition makes a plurality of detection potpourris;
(II) measure the ultraviolet-visible spectral absorption that respectively detects potpourri;
(III) draw " the ultraviolet-visible spectral absorption value-dimercurion concentration that detects potpourri " curve, or draw " UV, visible light absorbance value-dimercurion concentration relatively " collection of illustrative plates, as standard diagram;
In another preference, this ultraviolet-visible spectral absorption is measured under 450～800nm wavelength.500～700nm preferably, more preferably 522 and 625nm about.
This sample to be tested comprises environmental water sample, solid-state environment sample, blood sample, organizes the leachate sample, the aqueous solution (as swimming in the aqueous solution that the dust in the atmosphere obtains after treatment) of food leachate sample, treated solid, and the aqueous solution of gaseous sample.This sample to be tested is the water sample of river, lake water for example; Water sample from industries such as chlor-alkali, plastics, battery electrons; Environmental water sample in the soil; Food; The whole blood sample of human body or blood serum sample; Urine sample; Cosmetics; And the water sample etc. of pellet in the atmosphere.
Another preference that the present invention detects the method for dimercurion comprises the steps:
(1) the golden nanometer particle precursor water solution of preparation 72mL0.1～1.0mmol/L, oil bath is heated to 70～95 ℃, constantly stirs and keeps this temperature-resistant; Prepare 20mL0.01～0.10mol/L oxalates aqueous solution, and add 3～9mg non-ionics and dissolving and obtain reduction protection liquid, regulate pH to 3.5～6.0; Be heated to boiling, reduction protection liquid is poured into rapidly in the golden nanometer particle precursor water solution, keep being stirred to 0.5～2h, stop heating and stirring, place the room temperature cooling and obtain golden nanometer particle stoste, place at least and use behind the 24h.
(2) get the golden nanometer particle stoste that portion prepares, regulate pH to 3.0～5.0, with stoste and ethanol volume ratio is that 1:1～1:3 dilutes, then to add the hydroxyquinoline class alcoholic solution (functionalized modification liquid) of 0.05～0.20mol/L of a volume in the scope of volume ratio 7:1～10:1, and constantly stirred 15 minutes, modification finishes, and obtains containing the detection composition of surface modification agent gold nano-particles modified.
(3) measure out the detection composition that two parts of identical steps (2) of volume make, not contain Hg
2+Aqueous solution solution as a comparison, add respectively in described two parts of detection composition with comparative solution with the sample to be tested of volume, form first and detect potpourri and second and detect potpourri;
(4) contrast second detects potpourri and first and detects the color of potpourri, if there is change color, then has Hg in the sample to be tested
2+,, then do not have Hg in the sample to be tested if there is not change color
2+Perhaps the concentration of the mercury of Cun Zaiing is lower than 4 * 10
-7μ M; Perhaps, contrast second detects UV, visible light absorption intensity and the peak value that potpourri and first detects potpourri, if its UV, visible light absorption intensity and peak value change, then has Hg in the sample to be tested
2+,, then do not have Hg in the sample to be tested if do not change
2+
In the above-mentioned testing process, first detects potpourri (no Hg
2+) time color be claret, when second color that detects potpourri becomes purplish grey or color burn with respect to first color that detects potpourri, then judge and contain Hg in the sample to be tested
2+, and Hg
2+Concentration more than or equal to 4 * 10
-7Mol/L.
As preferably, can draw earlier and can reflect Hg in the aqueous solution
2+The canonical plotting of concentration and UV, visible light absorption intensity relation contrasts described second then and detects UV, visible light absorption intensity and this canonical plotting of potpourri, detects Hg in the potpourri thereby obtain second
2+Concentration.The concrete method for drafting of this canonical plotting is as follows:
At first prepare a series of different Hg that contain according to above-mentioned second compound method that detects potpourri
2+Second of concentration detects potpourri, is respectively its UV, visible light absorption intensity of scope interscan of 450nm～800nm at wavelength.Found that the described second detection wavelength peak that detects the UV, visible light absorption intensity of potpourri is 522nm, works as Hg
2+When concentration was big, a new peak can appear at the 625nm place.Ratio with 625nm and 522nm place UV, visible light absorption intensity in the second detection potpourri is ordinate, each second Hg that detects in potpourri
2+Concentration is the horizontal ordinate curve plotting, can obtain canonical plotting.
Detect the kit of dimercurion
The present invention detects the kit of dimercurion, comprising:
The golden nanometer particle presoma;
Water-soluble oxalates;
Non-ionics; With
The hydroxyquinoline compounds;
Wherein, this golden nanometer particle presoma, non-ionics, water-soluble oxalates and hydroxyquinoline compounds are used to prepare a detection composition that contains surface modification agent gold nano-particles modified.
Main beneficial effect of the present invention comprises:
(1) can directly utilize naked eyes or ultraviolet-visible pectrophotometer to judge, promptly can judge whether contain Hg in the test sample
2+Thereby, realize Hg in the aqueous solution
2+Easy, fast detecting.
(2) pass through in conjunction with Hg
2+The canonical plotting of concentration and UV, visible light absorption intensity relation, the present invention can also detect Hg in the detected sample
2+Concentration content.
(3) be not only applicable to Hg in the water solution system
2+Detection, also be suitable for the aqueous solution of the water-soluble formation of other sample, but also can the mercury element of other valence states be converted into dimercurion by indirect method, utilize the present composition and method to be detected again.
(4) generally speaking, the inventive method is easy and simple to handle, quick, sensitive, the detection cost is low and sampling amount is few.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
＜material source 〉
1. sodium oxalate: available from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
2. polyvinylpyrrolidone: available from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
3.8-hydroxyquinoline: available from Aladdin reagent company limited; Model: analyze pure (AR).
4. tetra chlorauric acid: available from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
Embodiment 1: detection composition
The preparation process of the detection composition of present embodiment comprises:
(1) the golden nanometer particle precursor water solution of preparation 5mmol/L, oil bath is heated to 90 ℃, constantly stirs and keeps this temperature-resistant; Prepare 20mL0.02mol/L oxalates aqueous solution, and add 7mg non-ionics and dissolving and obtain reduction protection liquid, regulate pH to 5.
(2) reduction protection liquid is heated to boiling, pours into rapidly afterwards in the golden nanometer particle precursor water solution, keep being stirred to 0.5h, stop heating and stirring, place the room temperature cooling and obtain golden nanometer particle stoste, place at least and use behind the 24h.
(3) get the golden nanometer particle stoste that portion prepares, regulate pH to 3.8, with stoste and ethanol volume ratio is that 2:3 dilutes, be the hydroxyquinoline class alcoholic solution (functionalized modification liquid) that adds the 0.1mol/L of a volume in the scope of 9:1 then with the volume ratio, and constantly stirred 15 minutes, modification finishes, and obtains containing the detection combination liquid of surface modification agent gold nano-particles modified.
Embodiment 2: the Hg that contains that detects variable concentrations
2+The aqueous standard product
2.1 configuration contains Hg
2+The aqueous standard product:
Get in the deionized water that the 20.056mg mercuric sulfate is dissolved in 10ml, obtaining concentration is 0.01mol/L mercuric sulfate solution.Form with stepwise dilution obtains containing Hg then
2+Concentration be respectively blank product (concentration is 0 μ M) and the standard items of 0,0.4,0.6,1,4,10,40 and 100 μ M.
2.2 detection, colorimetric and result:
The detection composition that the embodiment 1 of adding 0.95mL obtains in 8 test tubes of same specification adds 2.1 blank product and the standard items (detected sample) that obtain of 50 μ L afterwards respectively to these 8 test tubes respectively, and obtains the detection potpourri of 8 test tubes.Observe the change color situation of these 8 test tubes.
Testing result as shown in Figure 1, as seen from Figure 1, aqueous solution is to be claret in the test tube of blank product (0 μ M), aqueous solution is the claret that is intensification in the test tube of 0.4,0.6,1 μ M, and aqueous solution is to be purplish grey in the test tube of 4,10,40 and 100 μ M.Represent the detection composition of embodiment 1 to detect and contain Hg by color comparison of naked eye
2+The above aqueous solution of concentration 0.4 μ M.
Embodiment 3: draw " the ultraviolet-visible spectral absorption value-dimercurion concentration that detects potpourri " curve and relative UV, visible light absorbance value-dimercurion concentration " collection of illustrative plates
3.1 configuration concentration respectively is the blank product of 0,0.008,0.01,0.1,1,10,100 μ M and contains Hg
2+The aqueous standard product, distinctly join in the detection composition of embodiment 1, and form C
0, C
1, C
2, C
3, C
4, C
5, C
6Totally 7 are detected potpourri, are respectively its UV, visible light absorption intensity of scope interscan of 450nm～800nm at wavelength.As shown in Figure 2, found that the detection wavelength peak of the UV, visible light absorption intensity of described detection potpourri is 522nm, works as Hg
2+When concentration was big, a new peak can appear at the 625nm place.
3.2 respectively being 0.008,0.01,0.04,0.08,0.3,0.4 μ M, configuration concentration contains Hg
2+The aqueous standard product, distinctly join in the detection composition of embodiment 1, detect potpourri and form 6, measure these respectively and detect the UV, visible light absorption intensity of potpourri, fetch in the relative absorption value of this two wavelength according to the dimercurion of six kinds of concentration and return straight line and draw " absorption spectrum-concentration relatively " figure at wavelength 522 and 625nm.As shown in Figure 3, found that, wherein linear substantially in 0.008 μ M to 0.4 μ M scope, therefore " absorption spectrum-concentration relatively " figure of Fig. 3 can be used as the standard diagram that detects the sample that contains the unknown of dimercurion concentration, the minimal detectable concentration of 0.4 μ M when embodiment 2 utilizes colorimetric detection, the standard diagram that present embodiment obtains can detect and contain lower concentration Hg
2+Aqueous solution.
Embodiment 4: the specificity that detects the inventive method
4.1 with prepared detection composition among the embodiment 1 respectively to various ion (Pb
2+, Al
3+, Ba
2+, Mn
2+, K
+, Ca
2+, Zn
2+, Cr
6+, Na
+, Cr
3+, Co
2+, Cu
2+, Cd
2+, Fe
3+, Ni
2+, Mg
2+, Cl
-, NO
3 -, SO
4 2-, PO
4 3-, CO
3 2-, blank product, Hg
2+, M
N+1(contain Hg
2+The mixed sample of all above cited ions), M
N+(remove Hg
2+The mixed sample of all above cited ions in addition)) detect, the ion concentration in each solion is respectively 10 μ mol/L.
It the results are shown in Figure 4, as seen have only mercurous ion solution to mix the detection potpourri demonstration purplish grey that the back forms with detection composition among Fig. 4, and other solions mix the detection potpourri demonstration claret that the back forms with detection composition, illustrate that thus surface modification agent gold nano-particles modified of the present invention is higher to the specificity of ion concentration of mercury mensuration, other ions are noiseless.
4.2 the detection potpourri that contains each solion and blank product at configuration in 4.1 carries out UV, visible light absorptiometry (A
0The detection potpourri that expression contains blank product is the absorption intensity at 625nm place at wavelength; The detection potpourri that A represents to contain different ions solution is the absorption intensity at 625nm place at wavelength), the visible Fig. 5 of its result illustrates that relative UV, visible light absorption value and other zwitterions of the mercury ion that detects with the present invention has notable difference.Unexpectedly, mixed solution M
N+1With mercury ion relative UV, visible light absorption value no significant difference, this results suggest, because the combination between mercury ion and oxalate (or oxalic acid hydrogen root) and the oxine is far longer than the combination of other ion and oxalate (or oxalic acid hydrogen root) and oxine, even so under other ion existence conditions, the inventive method can not produce the interference that ion concentration of mercury is measured yet.
Embodiment 5: Hg in the water samples such as river, lake water, seawater
2+Detect
5.1 detected sample collection: in the river, the same degree of depth place, different location in lake gathers water sample S5.1～S5.4 with the water sample collecting bottle, places to be checked.
5.2 detection composition preparation: with embodiment 1.
5.3 detection mode: with 2.2 of embodiment 2.
5.4 testing result: about 10 minutes, have a color that detects potpourri not change, be claret, illustrate and not necessarily contain Hg in the water sample to be detected
2+, if contain Hg
2+, then its concentration is less than 4 * 10
-7Mol/L; There are two parts of detection potpourri colors to become purplish grey, a potpourri color burn that detects is arranged, the Hg in the water sample to be measured in these three parts of water samples is described
2+Be higher than 4 * 10
-7Mol/L.
Taint-free detection potpourri is carried out measurement of ultraviolet-visible spectrophotometer, variation in 450～800nm place UV, visible light absorption intensity, with detecting Fig. 3 that potpourri obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing, obtain Hg in the liquid to be detected
2+Concentration result sees Table 1.
Table 1
Embodiment 6: Hg in the water samples such as mining area, Battery Plant, chlor-alkali industry
2+Detection
6.1 detected sample collection: be in 8 points, 12 points, 18 water samples of gathering equal volume in the discharge of wastewater mouth of Battery Plant, after it is mixed, obtain water sample S6.1 to be detected and S6.2.
6.2 detection composition preparation: with embodiment 1.
6.3 detection mode: with 2.2 of embodiment 2.
6.4 testing result: about ten minutes, 2 parts of detection potpourri colors all become purplish grey, and the Hg in the water sample to be measured in these two parts of water samples is described
2+Content all is higher than 4 * 10
-7Mol/L.
Embodiment 7: but the detection of Hg element in the atmosphere inhalation
7.1 detected sample collection: by specific air sampler, extract the air of certain volume with constant speed at the need surveyed area, particle diameter in the air is trapped within the specific filter membrane less than the suspended particulate substance of 100 μ m, with the suspended particulate substance collected hcl acidifying, make its dissolving with 0.1mol/L.Because the air-borne mercury element normally exists with the form of elementary gas mercury, active gaseous mercury and gaseous oxidation mercury, therefore before detecting, it is oxidized to divalence mercury detected sample with nitric acid etc., finally obtain water sample S7.1 and S7.2.。
7.2 detection composition preparation: with embodiment 1.
7.3 detection mode: with 2.2 of embodiment 2.
7.4 testing result: about 10 minutes, a copy of it detects the potpourri color and becomes aubergine, and the Hg in this duplicate samples is described
2+Content is higher than 4 * 10
-7Mol/L; Change color does not take place in another part, illustrates not contain Hg in this part testing sample
2+Perhaps Hg wherein
2+Content is lower than 4 * 10
-7Mol/L, taint-free detection potpourri is carried out measurement of ultraviolet-visible spectrophotometer, in the variation of 450～800nm place UV, visible light absorption intensity,, obtain Hg in the liquid to be detected with detecting Fig. 3 that potpourri obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing
2+Concentration result sees Table 2.
Table 2
Embodiment 8: Hg in the soil
2+Detection
8.1 detected sample collection: at first, then that sample mix is even at soil surveyed area multi-point sampling, obtain pedotheque to be detected.In pedotheque to be detected, add deionized water, leave standstill after the stirring repeatedly, present transparence until upper solution.The transparent supernatant acidifying that will obtain with the hydrochloric acid of 0.1mol/L obtains detected sample S8.1 and S8.2 then.
8.2 detection composition preparation: with embodiment 1.
8.3 detection mode: with 2.2 of embodiment 2.
8.4 testing result: about 10 minutes, two parts of colors that detect potpourri all do not change, and are claret, illustrate and not necessarily contain Hg in the detected sample
2+If contain Hg
2+, then its concentration is less than 4 * 10
-7Mol/L.
Taint-free detection potpourri is carried out measurement of ultraviolet-visible spectrophotometer, variation in 450～800nm place UV, visible light absorption intensity, with detecting Fig. 3 that potpourri obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing, obtain Hg in the liquid to be detected
2+Concentration result sees Table 3.
Table 3
Embodiment 9: Hg in the cosmetics
2+Detection
9.1 detected sample collection: take by weighing a certain amount of certain skin-lightening cosmetic sample, with digestion method sample is digested, pH to 7.0 is regulated in the back, obtains detected sample S9.
9.2 detection composition preparation: with embodiment 1.
9.3 detection mode: with 2.2 of embodiment 2.
9.4 testing result: about ten minutes, change color does not take place in this detection potpourri, illustrates not contain Hg in this sample
2+Perhaps Hg wherein
2+Content is lower than 4 * 10
-7Mol/L, taint-free detection mixed liquor is carried out measurement of ultraviolet-visible spectrophotometer, in the variation of 450～800nm place UV, visible light absorption intensity,, obtain Hg in the liquid to be detected with detecting Fig. 3 that mixed liquor obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing
2+Concentration result detects and finds, does not find Hg in the detectability scope
2+
Embodiment 10: Hg in the blood of human body
2+Detection
10.1 detected sample collection: two parts of human body blood samples that will obtain are handled with the aqueous solution of nitric acid of 3mol/L, make organic component in the blood sample by complete oxidation, here the ratio of blood sample and aqueous solution of nitric acid is 5:1, NaOH with 0.1mol/L neutralizes then, filter, obtain detected sample at last.
10.2 detection composition preparation: with embodiment 1.
10.3 detection mode: with 2.2 of embodiment 2.
10.4 testing result: about ten minutes, change color does not all take place in these two parts detection potpourris, is claret, illustrates and not necessarily contains Hg in the detected sample
2+If contain Hg
2+, then its concentration is less than 4 * 10
-7Mol/L.Prove that mercury content does not exceed standard in these two parts of human body blood samples.(the mercury upper limit of concentration is 1.5 * 10 in normal human's blood
-6Mol/L)
Embodiment 11: Hg in the food
2+Detection
11.1 detected sample collection: food samples to be measured (about 2 grams) is water-soluble, adding concentration is 98% red fuming nitric acid (RFNA) in food samples, the volume ratio of red fuming nitric acid (RFNA) and food samples is 1:1, make organic component in the food samples by complete oxidation, drip to neutrality with 0.1mol/L NaOH again, filter, can obtain detected sample S11.1～S11.3.
11.2 detection composition preparation: with embodiment 1.
11.3 detection mode: with 2.2 of embodiment 2.
11.4 testing result: about 10 minutes, change color does not all take place in three parts of detection potpourris, illustrates not contain Hg in the testing sample
2+Perhaps Hg wherein
2+Content is lower than 4 * 10
-7Mol/L, taint-free detection mixed liquor is carried out measurement of ultraviolet-visible spectrophotometer, in the variation of 450～800nm place UV, visible light absorption intensity,, obtain Hg in the liquid to be detected with detecting Fig. 3 that mixed liquor obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing
2+Concentration result sees Table 4.
Table 4
Embodiment 12: the detection of mercury in the urine
12.1 detected sample collection: two parts of human urine samples that will obtain are cleared up with acid heating, make organic component in the blood sample by complete oxidation, regulate pH to neutral with NaOH at last, filter, and promptly obtain detected sample S12.1 and S12.2.
12.2 detection composition preparation: with embodiment 1.
12.3 detection mode: with 2.2 of embodiment 2.
12.4 testing result: about 10 minutes, change color does not all take place in two parts of detection potpourris, illustrates not contain Hg in the testing sample
2+Perhaps Hg wherein
2+Content is lower than 4 * 10
-7Mol/L, taint-free detection mixed liquor is carried out measurement of ultraviolet-visible spectrophotometer, in the variation of 450～800nm place UV, visible light absorption intensity,, obtain Hg in the liquid to be detected with detecting Fig. 3 that mixed liquor obtains at 625nm and 522nm place absorbance ratio substitution embodiment 3 calculating of comparing
2+Concentration result sees Table 5.
Table 5
In sum, detection composition provided by the invention, method and kit, not only can see through color comparison of naked eye and confirm whether contain dimercurion in the aqueous solution, also can see through further and draw " the ultraviolet-visible spectral absorption value-dimercurion concentration that detects potpourri " curve, or draw " UV, visible light absorbance value-dimercurion concentration relatively " collection of illustrative plates as standard diagram, detect the concentration that contains dimercurion in the unknown sample, this method is easy and simple to handle, fast, sensitive, the detection cost is low and sampling amount is few, applied range, also can detect the aqueous solution of the water-soluble formation of other sample, be with a wide range of applications.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (13)
1. detection composition that detects dimercurion comprises:
Surface modification agent gold nano-particles modified, described coating material comprises:
Water-soluble oxalates;
Non-ionics; And
The hydroxyquinoline compounds;
Water; With
Solubilized hydroxyquinoline compounds and the solvent that dissolves each other with water.
2. detection composition as claimed in claim 1 is characterized in that, described water-soluble oxalates comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
3. detection composition as claimed in claim 1 is characterized in that, described non-ionics is a polyvinylpyrrolidone.
4. detection composition as claimed in claim 1 is characterized in that, described hydroxyquinoline compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
5. detection composition as claimed in claim 1 is characterized in that, described detection composition has the pH value between 4 to 6.
6. detection composition as claimed in claim 1 is characterized in that, described detection composition is to obtain by following step:
(i) prepare reduction protection liquid and golden nanometer particle precursor water solution respectively, described reduction protection liquid comprises water-soluble oxalates, non-ionics and water, and described golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mix golden nanometer particle precursor water solution and reduction protection liquid to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid and contain the detection composition of surface modification agent gold nano-particles modified, the solvent that described functionalized modification liquid comprises hydroxyquinoline compounds and solubilized hydroxyquinoline compounds and dissolves each other with water with formation.
7. detection composition as claimed in claim 1 is characterized in that, described golden nanometer particle presoma comprises golden salt, the solubility of solubility and contains the acid of gold, or their combination.
8. method that detects dimercurion may further comprise the steps:
(a) provide as arbitrary described detection composition in the claim 1 to 7;
(b) in described detection composition, add sample to be tested, form and detect potpourri;
(c) observe or measure the color and/or the ultraviolet-visible spectrum of described detection potpourri, and compare compared with the control or with standard diagram, thereby draw the measurement result whether sample to be tested exists the concentration of dimercurion and/or dimercurion.
9. method as claimed in claim 8 is characterized in that, described contrast is the control mixture of following formation: in described detection composition, add the aqueous solution that does not contain dimercurion, form control mixture, and satisfy following formula V1/V2=V3/V4,
In the formula,
V1 is the described volume that does not contain the aqueous solution of dimercurion that is used to form control mixture;
V2 is the volume that is used to form the described detection composition of control mixture;
V3 is the volume that is used to form the described sample to be tested that detects potpourri;
V4 is the volume that is used to form the described detection composition that detects potpourri.
10. method as claimed in claim 8 is characterized in that, described standard diagram is to make by the following method:
(I) the dimercurion aqueous solution of adding variable concentrations in described detection composition makes a plurality of detection potpourris;
(II) measure the ultraviolet-visible spectral absorption that respectively detects potpourri;
(III) draw " the ultraviolet-visible spectral absorption value-dimercurion concentration that detects potpourri " curve, or draw " UV, visible light absorbance value-dimercurion concentration relatively " collection of illustrative plates, as standard diagram.
11. method as claimed in claim 8 is characterized in that, described ultraviolet-visible spectral absorption is measured under the 450-800nm wavelength.
12. method as claimed in claim 8 is characterized in that, described sample to be tested comprises environmental water sample, solid-state environment sample, blood sample, organizes the leachate sample, the aqueous solution of food leachate sample, treated solid, and the aqueous solution of gaseous sample.
13. a kit that detects dimercurion comprises:
The golden nanometer particle presoma;
Water-soluble oxalates;
Non-ionics; With
The hydroxyquinoline compounds;
Wherein, described golden nanometer particle presoma, non-ionics, water-soluble oxalates and hydroxyquinoline compounds are used to prepare a detection composition that contains surface modification agent gold nano-particles modified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310091158.XA CN103217416B (en) | 2013-03-20 | 2013-03-20 | Detection composition, method and kit for detection of bivalent mercury ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310091158.XA CN103217416B (en) | 2013-03-20 | 2013-03-20 | Detection composition, method and kit for detection of bivalent mercury ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103217416A true CN103217416A (en) | 2013-07-24 |
| CN103217416B CN103217416B (en) | 2015-03-25 |
Family
ID=48815399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310091158.XA Active CN103217416B (en) | 2013-03-20 | 2013-03-20 | Detection composition, method and kit for detection of bivalent mercury ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103217416B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108519358A (en) * | 2018-03-14 | 2018-09-11 | 华东师范大学 | One kind detecting Hg based on novel gold nano grain2+Method |
| CN109307656A (en) * | 2018-11-16 | 2019-02-05 | 北京雪迪龙科技股份有限公司 | A kind of water quality mercury online auto monitoring system and its method |
| CN109900692A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | Green high-efficient detects the preparation method of the gel of mercury ion and the application of the gel |
| CN109900691A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | The test paper of rapid mercury detection ion, preparation method and applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060021468A1 (en) * | 2004-07-26 | 2006-02-02 | Ah Chil S | Gold nanoparticles and method of synthesizing the same |
| CN101881734A (en) * | 2010-06-07 | 2010-11-10 | 中国科学院宁波材料技术与工程研究所 | Detection method of metal ions |
| CN102371356A (en) * | 2010-08-23 | 2012-03-14 | 清华大学 | Preparation method of gold nanoparticles |
-
2013
- 2013-03-20 CN CN201310091158.XA patent/CN103217416B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060021468A1 (en) * | 2004-07-26 | 2006-02-02 | Ah Chil S | Gold nanoparticles and method of synthesizing the same |
| CN101881734A (en) * | 2010-06-07 | 2010-11-10 | 中国科学院宁波材料技术与工程研究所 | Detection method of metal ions |
| CN102371356A (en) * | 2010-08-23 | 2012-03-14 | 清华大学 | Preparation method of gold nanoparticles |
Non-Patent Citations (2)
| Title |
|---|
| BOOPATHI, S. ET AL.: "Facile and One Pot Synthesis of Gold Nanoparticles Using Tetraphenylborate and Polyvinylpyrrolidone for Selective Colorimetric Detection of Mercury Ions in Aqueous Medium", 《JOURNAL OF ANALYTICAL METHODS IN CHEMISTRY》, vol. 2012, 20 March 2012 (2012-03-20) * |
| HAN ZHANG, ET AL.: "8-Hydroxyquinoline Benzoates as Highly Sensitive Fluorescent Chemosensors for Transition Metal Ions", 《ORGANIC LETTERS》, vol. 7, no. 19, 13 August 2005 (2005-08-13) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108519358A (en) * | 2018-03-14 | 2018-09-11 | 华东师范大学 | One kind detecting Hg based on novel gold nano grain2+Method |
| CN109307656A (en) * | 2018-11-16 | 2019-02-05 | 北京雪迪龙科技股份有限公司 | A kind of water quality mercury online auto monitoring system and its method |
| CN109900692A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | Green high-efficient detects the preparation method of the gel of mercury ion and the application of the gel |
| CN109900691A (en) * | 2019-04-04 | 2019-06-18 | 青岛大学 | The test paper of rapid mercury detection ion, preparation method and applications |
| CN109900691B (en) * | 2019-04-04 | 2021-11-19 | 青岛大学 | Test paper for rapidly detecting mercury ions, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103217416B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Firdaus et al. | Colorimetric detection of mercury (II) ion in aqueous solution using silver nanoparticles | |
| Wang et al. | Electrochemiluminescence of a nanoAg–carbon nanodot composite and its application to detect sulfide ions | |
| CN101949855B (en) | Method for detecting metal cation by utilizing VA group or VIA group element compound | |
| CN103439267B (en) | A kind of test reagent combination and detection method of dimercurion | |
| CN114907837B (en) | Preparation method of ratio-type fluorescent gold-copper nanocluster, product and application thereof | |
| CN110118769A (en) | A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion | |
| CN103217416B (en) | Detection composition, method and kit for detection of bivalent mercury ions | |
| Qi et al. | Nitrogen doped carbon quantum dots (N-CQDs) with high luminescence for sensitive and selective detection of hypochlorite ions by fluorescence quenching | |
| Radwan et al. | Decorated nanosphere mesoporous silica chemosensors for rapid screening and removal of toxic cadmium ions in well water samples | |
| CN103226103A (en) | Colorimetric detection probe of mercury ion and application method thereof | |
| CN106290319B (en) | A kind of method of silver ion in chemiluminescence detection water sample | |
| CN102841061B (en) | Method for detecting nickelous ions | |
| Panhwar et al. | A novel approach for real-time enumeration of Escherichia coli ATCC 47076 in water through high multi-functional engineered nano-dispersible electrode | |
| Chen et al. | N-doped carbon dots as the multifunctional fluorescent probe for mercury ion, glutathione and pH detection | |
| CN103487430A (en) | Trivalent aluminum ion detection reagent and method | |
| CN103808717B (en) | A kind of method using colorimetric determination mercury ion | |
| Thenrajan et al. | Guar gum supported ZIF-8 as an effective catalyst for electrochemical sensing of gallic acid in liquid food samples | |
| CN111715891B (en) | Copper nanoparticle solution and preparation method and application thereof | |
| CN102830078A (en) | Method for detecting bivalent manganese ions | |
| CN110907589B (en) | Visible Cu detection based on GQDs photocatalysis2+Method (2) | |
| Arthy et al. | Detection of Ag+ by synthesizing fluorescent copper nanoparticles through ultrasensitive free label approach | |
| CN103528969A (en) | Method for detecting bivalent copper ions and reagent kit | |
| CN108007923A (en) | A kind of nanogold colorimetric method of quick detection lead ion | |
| CN113588606B (en) | Non-conjugated polymer probe, dual signal ratio sensor, method and application | |
| CN107462579A (en) | A kind of kit and detection method for detecting mercury ion |
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 |