CN103217416B - 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
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- CN103217416B CN103217416B CN201310091158.XA CN201310091158A CN103217416B CN 103217416 B CN103217416 B CN 103217416B CN 201310091158 A CN201310091158 A CN 201310091158A CN 103217416 B CN103217416 B CN 103217416B
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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 metal ion detection field, be specifically related to a kind of detection composition detecting low concentration dimercurion in aqueous solution, and the method for quick, sensitive, easy detection dimercurion and kit.
Background technology
In recent years, along with rapid development of economy, the energy, resource consume in a large number, also result in plurality of heavy metal pollution problem simultaneously, the health of the serious threat mankind.Along with improving constantly of people's quality of life, higher requirement be it is also proposed to living environment.Heavy metal pollution event occurs in frequent succession, and such as " blood lead event ", " mercury poisoning ", " chromium capsule " etc., cause showing great attention to of the common people, thus proposes higher requirement to environment measuring means.
The industry relating 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, lakes and reserviors etc. greatly, not only make Environment-Ecosystem be destroyed, and the water source of potable water is also often polluted, and harm humans is healthy.In all heavy metal elements, mercury is to one of the most serious metallic element of harm.The minamata disease that nineteen fifty-three betides Japanese Minamata bay is exactly that local resident eats caused by the fish of enrichment methyl mercury for a long time, does not still have effective methods for the treatment of until now.This also makes people have deep understanding to mercury pollution.
Mercury element is to one of larger element of harm, when human body excess intake, serious to central lesion, show as headache, dizziness, sleep-disorder, emotional, point tremble, constitutional symptom and the stomatitis such as unable, low-heat.Wherein typical illness is minamata disease.Mercury in Drinking Water upper content limit standard setting has been at present 0.001mg/L by China's related standards.
The method of detection mercury ion conventional both at home and abroad at present has atomic absorption spectrography (AAS), inductively coupled plasma ~ mass spectroscopy etc., but these methods often exist the defects such as sample preparation steps complexity, ion interference is serious, instrument price is expensive, detection time is long.Biology sensor detection method based on DNA functionalization noble metal nano particles has higher sensitivity for mercury detection in water quality, on-the-spot detection in real time can be realized, the important research direction that after being, in environmental water sample, mercury detects, but also there is a lot of defect in the method, mainly anti-interference is low, is difficult to be applied to reagent environmental system.
The method utilizing general chemistry reagent functionalization noble metal nano particles to detect other heavy metal ion is seen in report, such as Chinese patent is announced or notification number 201010251278.8, 201110299385.2, 201110363954.5, 201110378260.9, 201210310138.2, 201010194041.0 etc., utilize at the different specific detection agents of gold/silver nano particle finishing, by the specific binding with fixing metal ions, redox reaction etc., cause the pattern of gold/silver nano particle to change (to reunite, particle diameter diminishes), and then cause the change of color and uv absorption peak position and intensity.These methods are quick, easy, sample preparation is simple, economical, can Hg be realized
2+, Cr
3+, Cr
6+, Co
2+, Pb
2+and Mn
2+color comparison of naked eye detect, wherein the patent No. is in the patent of 201010194041.0, applicant achieves a kind of method that rapid sensitive detects mercury, the method utilizes the hydrolysate of sulfide to modify golden nanometer particle, generate mercuric sulphide quantum dot by the sulphion specific binding on mercury ion and golden nanometer particle surface to be coated on golden nanometer particle surface and to form nucleocapsid structure, gold nano surface plasmon resonance absorption is caused to change, along with the existence of mercury ion and increasing of amount, there is obvious blue shift in gold particle surface plasma resonance absorbtion peak, thus the object reached mercury ion detecting.But this detection sensitivity is lower slightly, us are impelled to accelerate to study novel detection method, causing golden nanometer particle to be reunited by adding of mercury ion, there is obvious red shift in gold particle surface plasma resonance absorbtion peak, thus reaches sensitiveer to mercury ion, detects fast.
A kind of detection Hg is disclosed in document " Facile and One Pot Synthesis of Gold Nanoparticles UsingTetraphenylborate and Polyvinylpyrrolidone for Selective Colorimetric Detection ofMercury Ions in Aqueous Medium (Volume2012; Article ID348965, p6) "
2+method, it utilizes polyvinylpyrrolidone (PVP) protection, tetraphenylboron sodium reduction prepares golden nanometer particle, under strongly alkaline conditions 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 μMs), inapplicable for low concentration dimercurion water solution system testing sample, cannot meet completely on market or academicly to detection Hg
2+demand.
Therefore, explore a kind of economy, quick, easy and detect composition and the method for dimercurion in water solution system in real time, and be applied to the fields such as actual environment detection, wastewater treatment, food analysis, medical analysis, air and soil quality analysis, there is important using value.
Summary of the invention
The object of this invention is to provide a kind of minimum Hg
2+detectable concentration is lower and energy is economical, quick, easy and in real-time detection water solution system, compound and method are examined in the detection of dimercurion.
First aspect present invention provides a kind of detection composition detecting dimercurion, and it comprises:
The golden nanometer particle that surface modification agent is modified, described coating material comprises:
Water soluble oxalate;
Non-ionics; And
Oxinoid compounds;
Water; With
Solubilized oxinoid compounds and the solvent dissolved each other with water.
In another preference, this detection composition is colloidal.
In another preference, this water soluble oxalate comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
In another preference, this non-ionics is polyvinylpyrrolidone.
In another preference, the mean molecular weight of polyvinylpyrrolidone is 10,000 to 130,000, is more preferably 30,000 to 58,000.
In another preference, this oxinoid compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
In another preference, this solubilized oxinoid compounds and be methyl alcohol, ethanol, acetone with the solvent that water dissolves each other, or their combination.
In another preference, this detection composition has the pH value between 4 to 6.
In another preference, this detection composition is obtained by step below:
I () prepares reduction protection liquid and golden nanometer particle precursor water solution respectively, this reduction protection liquid comprises water soluble oxalate, non-ionics and water, and this golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mixing golden nanometer particle precursor water solution and reduction protection liquid are to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid to form the detection composition containing the golden nanometer particle that surface modification agent is modified, this functionalized modification liquid comprises oxinoid compounds and solubilized oxinoid compounds and the solvent dissolved each other with water.
In another preference, this golden nanometer particle presoma comprises the golden salt of solubility, solubility and containing the acid of gold, or their combination.
In another preference, this solubility and containing gold acid be tetra chlorauric acid.
In another preference, [molal quantity of gold ion contained by golden nanometer particle presoma] that use in step (i) to (iii): [molal quantity of oxalate denominationby contained by water soluble oxalate]: [molal quantity of oxinoid compounds] is 1:1:10 to 1:10:30.Be more preferably 1:3:25 to 1:6:30.Be 1:4:26 to 1:5:29 best.
In another preference, [in golden nanometer particle presoma the contained gold atom weight] that uses in step (i) to (iii): [weight of non-ionics] is 1:0.5 to 1:4.Be more preferably 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 that the oxalates aqueous solution by being 0.01 to 0.10mol/L mixes with the non-ionics of 3 to 9mg by the concentration of 20mL, and adjust ph to 3.5 obtains to 6.0 afterwards.Preferably, the adjustment of the pH value of reduction protection liquid is reached by adding acid (such as hydrochloric acid) adjustment.
In another preference, the golden nanometer particle precursor water solution of this step (i) is by being mixed with water by golden nanometer particle presoma, and oil bath is afterwards heated to 70 to 95 DEG C and stirring obtains.
In another preference, the concentration of this solubility gold precursor water solution is 0.1 to 1.0mmol/L.
In another preference, the golden nanometer particle stoste of this step (ii) is by first reduction protection liquid being heated to boiling, mixes afterwards, stirs 0.5 to 2h and place at least to obtain after 24h with golden nanometer particle precursor water solution.
In another preference, the pH value of this golden nanometer particle stoste is between 3.0 to 5.0.Be more preferably 4.0.
In another preference, this step (iii) comprises and first golden nanometer particle stoste is diluted to golden nanometer particle dilution with the ethanol of 1 to 3 times of volume, then the functionalized modification liquid being 0.05 ~ 0.20mol/L by golden nanometer particle dilution and concentration mixes and stirs, and the volume ratio for the golden nanometer particle stoste that mixes and functionalized modification liquid is 7:1 to 10:1.
Second aspect present invention provides the method detecting dimercurion, comprises the following steps:
A () provides as aforementioned detection composition of the present invention;
B () adds sample to be tested in this detection composition, formed and detect potpourri;
C color and/or the ultraviolet-visible spectrum of this detection potpourri are observed or measured to (), and compare compared with the control or with standard diagram, thus show whether sample to be tested exists the measurement result of the concentration of dimercurion and/or dimercurion.
In another preference, this contrast is the following control mixture formed: add not containing the aqueous solution of dimercurion in this detection composition, form control mixture, and meet following formula V1/V2=V3/V4,
In formula,
V1 is containing the volume of aqueous solution of dimercurion for the formation of this of control mixture;
V2 is the volume of this detection composition for the formation of control mixture;
V3 is the volume for the formation of this sample to be tested detecting potpourri;
V4 is the volume for the formation of this detection composition detecting potpourri.
In another preference, this standard diagram obtains by the following method:
(I) in this detection composition, the dimercurion aqueous solution of variable concentrations is added, obtained multiple detection potpourri;
(II) the ultraviolet-visible spectral absorption of each detection potpourri is measured;
(III) draw " the ultraviolet-visible spectral absorbance values-dimercurion concentration detecting potpourri " curve, or draw " relative ultraviolet-visible absorption value-dimercurion concentration " collection of illustrative plates, as standard diagram;
In another preference, this ultraviolet-visible spectral absorption measures under 450 ~ 800nm wavelength.Preferably 500 ~ 700nm, more preferably 522 and about 625nm.
In another preference, this sample to be tested comprises environmental water sample, solid-state environment sample, blood sample, organizes the aqueous solution of leachate sample, food leachate sample, treated solid and the aqueous solution of gaseous sample.
Third aspect present invention provides a kind of kit detecting dimercurion, comprising:
Golden nanometer particle presoma;
Water soluble oxalate;
Non-ionics; With
Oxinoid compounds;
Wherein, this golden nanometer particle presoma, non-ionics, water soluble oxalate and oxinoid compounds are for the preparation of the detection composition of a golden nanometer particle modified containing surface modification agent.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 be illustrate variable concentrations in the embodiment of the present invention 2 containing Hg
2+the testing result of aqueous standard product.
Fig. 2 is ultraviolet-visible spectral absorbance values (absorbance log)-dimercurion concentration that the detection potpourri that the embodiment of the present invention 3 obtains is described " curve.
Fig. 3 is the relative ultraviolet-visible absorption value-dimercurion concentration illustrating that the embodiment of the present invention 3 obtains " collection of illustrative plates.
Fig. 4 illustrates that the embodiment of the present invention 4 detects the specific result of the present composition and method.
Fig. 5 illustrates that the embodiment of the present invention 4 detects the specific result of the present composition and method.
Embodiment
The present inventor finds through extensive and deep research; utilize non-ionics (as polyvinylpyrrolidone (PVP)) protect, water soluble oxalate reduction prepare golden nanometer particle; then utilize oxinoid compounds to carry out functionalization and can obtain the golden nanometer particle that surface modification agent modifies, the golden nanometer particle that this surface modification agent is modified comes and Hg by the oxalate denominationby on it or oxalic acid hydrogen radical ion and oxinoid compounds
2+carry out selective coordination complexing, cause solution of gold nanoparticles color to change, cause the peak position at golden nanometer particle surface plasmon absorption peak and intensity to change, realize Hg in aqueous solution
2+quick, sensitive, easy detection.Complete the present invention on this basis.
Detect the detection composition of dimercurion
The detection composition that the present invention detects dimercurion comprises golden nanometer particle, the water that surface modification agent is modified, the solvent dissolved each other with solubilized oxinoid compounds and with water, described coating material comprises water soluble oxalate, non-ionics, and oxinoid compounds.
In another preference, this detection composition is colloidal.
In another preference, this water soluble oxalate comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
In another preference, this non-ionics is polyvinylpyrrolidone.
In another preference, the mean molecular weight of polyvinylpyrrolidone is 10,000 to 130,000, is more preferably 30,000 to 58,000.
In another preference, this oxinoid compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
In another preference, this solubilized oxinoid compounds and be methyl alcohol, ethanol, acetone with the solvent that water dissolves each other, or their combination.
In another preference, this detection composition has the pH value between 4 to 6.
In another preference, this detection composition is obtained by step below:
I () prepares reduction protection liquid and golden nanometer particle precursor water solution respectively, this reduction protection liquid comprises water soluble oxalate, non-ionics and water, and this golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mixing golden nanometer particle precursor water solution and reduction protection liquid are to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid to form the detection composition containing the golden nanometer particle that surface modification agent is modified, this functionalized modification liquid comprises oxinoid compounds and solubilized oxinoid compounds and the solvent dissolved each other with water.
In another preference, this golden nanometer particle presoma comprises the golden salt of solubility, solubility and containing the acid of gold, or their combination.
In another preference, this solubility and containing gold acid be tetra chlorauric acid.
In another preference, [molal quantity of gold ion contained by golden nanometer particle presoma] that use in step (i) to (iii): [molal quantity of oxalate denominationby contained by water soluble oxalate]: [molal quantity of oxinoid compounds] is 1:1:10 to 1:10:30.Be more preferably 1:3:25 to 1:6:30.Be 1:4:26 to 1:5:29 best.
In another preference, [in golden nanometer particle presoma the contained gold atom weight] that uses in step (i) to (iii): [weight of non-ionics] is 1:0.5 to 1:4.Be more preferably 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 that the oxalates aqueous solution by being 0.01 to 0.10mol/L mixes with the non-ionics of 3 to 9mg by the concentration of 20mL, and adjust ph to 3.5 obtains to 6.0 afterwards.Preferably, the adjustment of the pH value of reduction protection liquid is reached by adding acid (such as hydrochloric acid) adjustment.
In another preference, the golden nanometer particle precursor water solution of this step (i) is by being mixed with water by golden nanometer particle presoma, and oil bath is afterwards heated to 70 to 95 DEG C and stirring obtains.
In another preference, the concentration of this solubility gold precursor water solution is 0.1 to 1.0mmol/L.
In another preference, the golden nanometer particle stoste of this step (ii) is by first reduction protection liquid being heated to boiling, mixes afterwards, stirs 0.5 to 2h and place at least to obtain after 24h with golden nanometer particle precursor water solution.
In another preference, the pH value of this golden nanometer particle stoste is between 3.0 to 5.0.Be more preferably 4.0.
In another preference, this step (iii) comprises and first golden nanometer particle stoste is diluted to golden nanometer particle dilution with the ethanol of 1 to 3 times of volume, then the functionalized modification liquid being 0.05 ~ 0.20mol/L by golden nanometer particle dilution and concentration mixes and stirs, and the volume ratio for the golden nanometer particle stoste that mixes and functionalized modification liquid is 7:1 to 10:1.
Detect the method for dimercurion
The method that the present invention detects dimercurion comprises the following steps:
A () provides as aforementioned detection composition of the present invention;
B () adds sample to be tested in this detection composition, formed and detect potpourri;
C color and/or the ultraviolet-visible spectrum of this detection potpourri are observed or measured to (), and compare compared with the control or with standard diagram, thus show whether sample to be tested exists the measurement result of the concentration of dimercurion and/or dimercurion.
In another preference, this contrast is the following control mixture formed: add not containing the aqueous solution of dimercurion in this detection composition, form control mixture, and meet following formula V1/V2=V3/V4,
In formula,
V1 is containing the volume of aqueous solution of dimercurion for the formation of this of control mixture;
V2 is the volume of this detection composition for the formation of control mixture;
V3 is the volume for the formation of this sample to be tested detecting potpourri;
V4 is the volume for the formation of this detection composition detecting potpourri.
In another preference, this standard diagram obtains by the following method:
(I) in this detection composition, the dimercurion aqueous solution of variable concentrations is added, obtained multiple detection potpourri;
(II) the ultraviolet-visible spectral absorption of each detection potpourri is measured;
(III) draw " the ultraviolet-visible spectral absorbance values-dimercurion concentration detecting potpourri " curve, or draw " relative ultraviolet-visible absorption value-dimercurion concentration " collection of illustrative plates, as standard diagram;
In another preference, this ultraviolet-visible spectral absorption measures under 450 ~ 800nm wavelength.Preferably 500 ~ 700nm, more preferably 522 and about 625nm.
This sample to be tested comprises environmental water sample, solid-state environment sample, blood sample, organizes the aqueous solution (as the aqueous solution that floating dust in an atmosphere obtains after treatment) of leachate sample, food leachate sample, treated solid and the aqueous solution of gaseous sample.This sample to be tested is the water sample of such as river, lake water; From the water sample of the industries such as chlor-alkali, plastics, battery electron; Environmental water sample in soil; Food; The whole blood sample of human body or blood serum sample; Urine sample; Cosmetics; And the water sample etc. of pellet in air.
Another preference that the present invention detects the method for dimercurion comprises the steps:
(1) prepare the golden nanometer particle precursor water solution of 72mL0.1 ~ 1.0mmol/L, oil bath is heated to 70 ~ 95 DEG C, constantly stirs and keeps this temperature-resistant; Preparation 20mL0.01 ~ 0.10mol/L oxalates aqueous solution, and add 3 ~ 9mg non-ionics and dissolve and obtain reduction protection liquid, regulate pH to 3.5 ~ 6.0; Be heated to boiling, reduction protection liquid poured into rapidly in golden nanometer particle precursor water solution, keep being stirred to 0.5 ~ 2h, stop heating and stir, place room temperature cooling and obtain golden nanometer particle stoste, placing and at least use after 24h.
(2) the golden nanometer particle stoste that portion prepares is got, regulate pH to 3.0 ~ 5.0, dilute than for 1:1 ~ 1:3 with stoste and ethanol contend, 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 stir 15 minutes, modify complete, obtain the detection composition of the golden nanometer particle modified containing surface modification agent.
(3) detection composition that the identical step (2) of two parts of volumes is obtained is measured out, with not containing Hg
2+aqueous solution solution as a comparison, the sample to be tested of comparative solution and same volume is added in two parts of described detection composition respectively, formed first detect potpourri and second detect potpourri;
(4) contrast second and detect the color that potpourri and first detects potpourri, if there is color change, then there is Hg in sample to be tested
2+if there is not color change, then there is not Hg in sample to be tested
2+or the concentration of the mercury existed is lower than 4 × 10
-7μM; Or contrast second detects ultravioletvisible absorption intensity and the peak value that potpourri and first detects potpourri, if its ultravioletvisible absorption intensity and peak value change, then there is Hg in sample to be tested
2+if do not change, then there is not Hg in sample to be tested
2+.
In above-mentioned testing process, first detects potpourri (without Hg
2+) time color be claret, when the second color detecting potpourri to detect relative to first the color of potpourri become purplish grey or color burn time, then judge in sample to be tested containing Hg
2+, and Hg
2+concentration be more than or equal to 4 × 10
-7mol/L.
As preferably, first can draw and can reflect Hg in aqueous solution
2+the canonical plotting of concentration and ultravioletvisible absorption strength relationship, then contrasts ultravioletvisible absorption intensity and this canonical plotting of the second described detection potpourri, thus obtains Hg in the second detection potpourri
2+concentration.The concrete method for drafting of this canonical plotting is as follows:
First the compound method detecting potpourri according to above-mentioned second is prepared a series of containing different Hg
2+second of concentration detects potpourri, is its ultravioletvisible absorption intensity of scope interscan of 450nm ~ 800nm respectively at wavelength.Found that, the described second determined wavelength peak value detecting the ultravioletvisible absorption intensity of potpourri is 522nm, works as Hg
2+when concentration is larger, understand at the new peak of 625nm place appearance one.Detect the ratio of 625nm and 522nm place ultravioletvisible absorption intensity in potpourri for ordinate with second, each second detects the Hg in potpourri
2+concentration is horizontal ordinate curve plotting, can obtain canonical plotting.
Detect the kit of dimercurion
The present invention detects the kit of dimercurion, comprising:
Golden nanometer particle presoma;
Water soluble oxalate;
Non-ionics; With
Oxinoid compounds;
Wherein, this golden nanometer particle presoma, non-ionics, water soluble oxalate and oxinoid compounds are for the preparation of the detection composition of a golden nanometer particle modified containing surface modification agent.
Main beneficial effect of the present invention comprises:
(1) naked eyes or ultraviolet-visible pectrophotometer directly can be utilized to judge, whether namely can judge to detect in sample containing Hg
2+, thus realize Hg in aqueous solution
2+easy, detect fast.
(2) by conjunction with Hg
2+the canonical plotting of concentration and ultravioletvisible absorption strength relationship, the present invention can also detect Hg in detected sample
2+levels.
(3) Hg in water solution system is not only applicable to
2+detection, be also suitable for the aqueous solution of the water-soluble formation of other sample, but also by indirect method, the mercury element of other valence states can be converted into dimercurion, recycling the present composition and method detected.
(4) generally speaking, the inventive method is easy and simple to handle, quick, sensitive, testing cost is low and sampling amount is few.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.
< material source >
1. sodium oxalate: purchased from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
2. polyvinylpyrrolidone: purchased from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
3.8-hydroxyquinoline: purchased from Aladdin reagent company limited; Model: analyze pure (AR).
4. tetra chlorauric acid: purchased from traditional Chinese medicines chemical reagent company limited; Model: analyze pure (AR).
Embodiment 1: detection composition
The preparation process of the detection composition of the present embodiment comprises:
(1) prepare the golden nanometer particle precursor water solution of 5mmol/L, oil bath is heated to 90 DEG C, constantly stirs and keeps this temperature-resistant; Preparation 20mL0.02mol/L oxalates aqueous solution, and add 7mg non-ionics and dissolve and obtain reduction protection liquid, regulate pH to 5.
(2) reduction protection liquid is heated to boiling, pours into rapidly afterwards in golden nanometer particle precursor water solution, keep being stirred to 0.5h, stop heating and stir, place room temperature cooling and obtain golden nanometer particle stoste, placing and at least use after 24h.
(3) the golden nanometer particle stoste that portion prepares is got, regulate pH to 3.8, dilute than for 2:3 with stoste and ethanol contend, then with volume ratio be 9:1 scope in add the hydroxyquinoline class alcoholic solution (functionalized modification liquid) of the 0.1mol/L of a volume, and constantly stir 15 minutes, modify complete, obtain the detection combination liquid of the golden nanometer particle modified containing surface modification agent.
Embodiment 2: that detects variable concentrations contains Hg
2+aqueous standard product
2.1 configurations are containing Hg
2+aqueous standard product:
Getting 20.056mg mercuric sulfate is dissolved in the deionized water of 10ml, and obtaining concentration is 0.01mol/L mercuric sulfate solution.Then obtain containing Hg with the form of stepwise dilution
2+concentration be respectively blank product (concentration is 0 μM) and the standard items of 0,0.4,0.6,1,4,10,40 and 100 μM.
2.2 detections, colorimetric and result:
Respectively to the detection composition that the embodiment 1 adding 0.95mL in 8 test tubes of same specification obtains, add the 2.1 blank product obtained and the standard items (detected sample) of 50 μ L afterwards respectively to these 8 test tubes, and obtain the detection potpourri of 8 test tubes.Observe the color situation of change of these 8 test tubes.
Testing result as shown in Figure 1, as seen from Figure 1, in the test tube of blank product (0 μM), aqueous solution is in claret, and in the test tube of 0.4,0.6,1 μM, aqueous solution is the claret in deepening, and in the test tube of 4,10,40 and 100 μMs, aqueous solution is in purplish grey.The detection composition representing embodiment 1 detects containing Hg by color comparison of naked eye
2+the aqueous solution of concentration more than 0.4 μM.
Embodiment 3: draw " the ultraviolet-visible spectral absorbance values-dimercurion concentration detecting potpourri " curve and relative ultraviolet-visible absorption value-dimercurion concentration " collection of illustrative plates
3.1 configuration concentrations are respectively the blank product of 0,0.008,0.01,0.1,1,10,100 μM and contain Hg
2+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 its ultravioletvisible absorption intensity of scope interscan of 450nm ~ 800nm respectively at wavelength.As shown in Figure 2, found that, the determined wavelength peak value of the ultravioletvisible absorption intensity of described detection potpourri is 522nm, works as Hg
2+when concentration is larger, understand at the new peak of 625nm place appearance one.
3.2 configuration concentrations are respectively 0.008,0.01,0.04,0.08,0.3,0.4 μM and contain Hg
2+aqueous standard product, distinctly join in the detection composition of embodiment 1, and form 6 detection potpourris, measure these respectively and detect the ultravioletvisible absorption intensity of potpourris at wavelength 522 and 625nm, the dimercurion according to six kinds of concentration is got regression straight line in the relative absorption value of this two wavelength and draws " relative absorbance spectrum-concentration " figure.As shown in Figure 3, found that, wherein substantially linear within the scope of 0.008 μM to 0.4 μM, therefore " relative absorbance spectrum-concentration " figure of Fig. 3 can be used as the standard diagram of the sample detected containing the unknown of dimercurion concentration, the minimal detectable concentration of 0.4 μM when utilizing colorimetric detection compared to embodiment 2, the standard diagram that the present embodiment obtains can detect containing lower concentration Hg
2+aqueous solution.
Embodiment 4: the specificity detecting the inventive method
4.1 with detection composition obtained in 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(containing Hg
2+the mixed sample of above cited all ions), M
n+(except Hg
2+the mixed sample of above cited all ions in addition)) detect, the ion concentration in each solion is respectively 10 μm of ol/L.
It the results are shown in Figure 4, the detection potpourri formed after only having the solution containing mercury ion to mix with detection composition in Fig. 4 as seen shows purplish grey, and the detection potpourri that other solions are formed after mixing with detection composition shows claret, illustrate that the specificity that the golden nanometer particle that surface modification agent of the present invention is modified measures ion concentration of mercury is higher thus, other ions are noiseless.
4.2 carry out ultravioletvisible absorption measurement (A for the detection potpourri containing each solion and blank product of configuration in 4.1
0represent that the detection potpourri containing blank product is the absorption intensity at 625nm place at wavelength; The detection potpourri that A represents containing different ions solution is the absorption intensity at 625nm place at wavelength), the visible Fig. 5 of its result, illustrates that the relative ultravioletvisible absorption value of the mercury ion detected with the present invention and other zwitterions have notable difference.Unexpectedly, mixed solution M
n+1with mercury ion relative ultravioletvisible absorption value no significant difference, this result is pointed out, because the combination between mercury ion and oxalate (or oxalic acid hydrogen root) and oxine is far longer than the combination of other ion and oxalate (or oxalic acid hydrogen root) and oxine, even if so under other ion existence conditions, the inventive method also can not produce the interference measured ion concentration of mercury.
Embodiment 5: Hg in the water samples such as river, lake water, seawater
2+detect
5.1 detected sample collections: in river, the same depth water sampling in the different location bottle in lake gathers water sample S5.1 ~ S5.4, places to be checked.
5.2 detection composition preparations: with embodiment 1.
5.3 detection modes: with 2.2 of embodiment 2.
5.4 testing results: about 10 minutes, having a color detecting potpourri not change, is claret, illustrates in water sample to be detected not necessarily containing Hg
2+if, containing Hg
2+, then its concentration is less than 4 × 10
-7mol/L; There are two parts to detect potpourri color and become purplish grey, have a detection potpourri color burn, the Hg in water sample to be measured in these three parts of water samples is described
2+higher than 4 × 10
-7mol/L.
Measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection potpourri, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting potpourri calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, in 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 collections: be in 8 points, 12 points, 18 water samples gathering same volumes in the discharge of wastewater mouth of Battery Plant, after mixed, obtain water sample S6.1 and S6.2 to be detected.
6.2 detection composition preparations: with embodiment 1.
6.3 detection modes: with 2.2 of embodiment 2.
6.4 testing results: about ten minutes, 2 parts are detected potpourri color and all become purplish grey, the Hg in water sample to be measured in these two parts of water samples is described
2+content is all higher than 4 × 10
-7mol/L.
Embodiment 7: air can the detection of Hg element in inhalation
7.1 detected sample collections: by specific air sampler, the air of certain volume is extracted with constant speed needing surveyed area, the suspended particulate substance making particle diameter in air be less than 100 μm is trapped within specific filter membrane, by the hcl acidifying of suspended particulate substance 0.1mol/L collected, it is made to dissolve.Because air-borne mercury element normally exists with the form of gaseous elementary mercury, reactive gaseous mercury and gaseous oxidation mercury, be therefore oxidized to bivalent mercury detected sample with nitric acid etc. before testing, finally obtained water sample S7.1 and S7.2.。
7.2 detection composition preparations: with embodiment 1.
7.3 detection modes: with 2.2 of embodiment 2.
7.4 testing results: about 10 minutes, a copy of it detects potpourri color and becomes aubergine, and the Hg in these increment product is described
2+content is higher than 4 × 10
-7mol/L; There is not color change in another part, illustrates in this part of testing sample not containing Hg
2+or Hg wherein
2+content is lower than 4 × 10
-7mol/L, measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection potpourri, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting potpourri calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, in table 2.
Table 2
Embodiment 8: Hg in soil
2+detection
8.1 detected sample collections: first at Soil K+adsorption region multi-point sampling, then that sample mix is even, obtain pedotheque to be detected.In pedotheque to be detected, add deionized water, stir and repeatedly leave standstill afterwards, until upper solution presents transparence.Then with the transparent supernatant acidifying that the hydrochloric acid of 0.1mol/L will obtain, detected sample S8.1 and S8.2 is obtained.
8.2 detection composition preparations: with embodiment 1.
8.3 detection modes: with 2.2 of embodiment 2.
8.4 testing results: about 10 minutes, two parts of colors detecting potpourri all do not change, and are claret, illustrate in detected sample not necessarily containing Hg
2+; If containing Hg
2+, then its concentration is less than 4 × 10
-7mol/L.
Measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection potpourri, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting potpourri calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, in table 3.
Table 3
Embodiment 9: Hg in cosmetics
2+detection
9.1 detected sample collections: take certain skin-lightening cosmetic sample a certain amount of, digest with digestion method to sample, rear adjustment pH to 7.0, obtains detected sample S9.
9.2 detection composition preparations: with embodiment 1.
9.3 detection modes: with 2.2 of embodiment 2.
9.4 testing results: about ten minutes, there is not color change in this detection potpourri, illustrates in this sample not containing Hg
2+or Hg wherein
2+content is lower than 4 × 10
-7mol/L, measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection mixed liquor, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting mixed liquor calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, detects and finds, within the scope of detectability, do not find Hg
2+.
Embodiment 10: Hg in blood of human body
2+detection
10.1 detected sample collections: the aqueous solution of nitric acid of obtain two parts of Human Blood 3mol/L is processed, organic component in blood sample is fully oxidized, here the ratio of blood sample and aqueous solution of nitric acid is 5:1, then neutralize with the NaOH of 0.1mol/L, filter, finally obtain detected sample.
10.2 detection composition preparations: with embodiment 1.
10.3 detection modes: with 2.2 of embodiment 2.
10.4 testing results: about ten minutes, these two parts are detected potpourri and color change are not all occurred, are claret, illustrate in detected sample not necessarily containing Hg
2+; If containing Hg
2+, then its concentration is less than 4 × 10
-7mol/L.Prove that in these two parts of Human Bloods, mercury content does not exceed standard.(in normal human blood, mercury upper limit of concentration is 1.5 × 10
-6mol/L)
Embodiment 11: Hg in food
2+detection
11.1 detected sample collections: by water-soluble for food samples to be measured (about 2 grams), the red fuming nitric acid (RFNA) that concentration is 98% is added in food samples, the volume ratio of red fuming nitric acid (RFNA) and food samples is 1:1, organic component in food samples is fully oxidized, neutrality is dropped to again with 0.1mol/L NaOH, filter, detected sample S11.1 ~ S11.3 can be obtained.
11.2 detection composition preparations: with embodiment 1.
11.3 detection modes: with 2.2 of embodiment 2.
11.4 testing results: about 10 minutes, three parts are detected potpourri and color change are not all occurred, and illustrate in testing sample not containing Hg
2+or Hg wherein
2+content is lower than 4 × 10
-7mol/L, measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection mixed liquor, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting mixed liquor calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, in table 4.
Table 4
Embodiment 12: the detection of mercury in urine
12.1 detected sample collections: by obtain two parts of sour heating and decomposes of human urine sample, the organic component in blood sample is fully oxidized, finally regulate pH to neutral with NaOH, filter, namely obtain detected sample S12.1 and S12.2.
12.2 detection composition preparations: with embodiment 1.
12.3 detection modes: with 2.2 of embodiment 2.
12.4 testing results: about 10 minutes, two parts are detected potpourri and color change are not all occurred, and illustrate in testing sample not containing Hg
2+or Hg wherein
2+content is lower than 4 × 10
-7mol/L, measurement of ultraviolet-visible spectrophotometer is carried out to taint-free detection mixed liquor, in the change of 450 ~ 800nm place ultravioletvisible absorption intensity, to compare detecting mixed liquor calculating at Fig. 3 of obtaining of 625nm and 522nm place absorbance ratio substitution embodiment 3, obtaining Hg in liquid to be detected
2+the result of concentration, in table 5.
Table 5
In sum, detection composition provided by the invention, method and kit, not only can pass through color comparison of naked eye whether to confirm in aqueous solution containing dimercurion, also can pass through drafting " the ultraviolet-visible spectral absorbance values-dimercurion concentration of detection potpourri " curve further, or draw " relative ultraviolet-visible absorption value-dimercurion concentration " collection of illustrative plates as standard diagram, detect the concentration of contained dimercurion in unknown sample, the method is easy and simple to handle, fast, sensitive, testing cost is low and sampling amount is few, applied range, also the aqueous solution of the water-soluble formation of other sample can be detected, be with a wide range of applications.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (13)
1. detect a detection composition for dimercurion, comprising:
The golden nanometer particle that surface modification agent is modified, described coating material comprises:
Water soluble oxalate;
Non-ionics; And
Oxinoid compounds;
Water; With
Solubilized oxinoid compounds and the solvent dissolved each other with water;
Further, described detection composition is obtained by step below:
I () prepares reduction protection liquid and golden nanometer particle precursor water solution respectively, described reduction protection liquid comprises water soluble oxalate, non-ionics and water, and described golden nanometer particle precursor water solution comprises golden nanometer particle presoma and water;
(ii) mixing golden nanometer particle precursor water solution and reduction protection liquid are to form golden nanometer particle stoste; With
(iii) mix golden nanometer particle stoste and functionalized modification liquid to form the detection composition containing the golden nanometer particle that surface modification agent is modified, described functionalized modification liquid comprises oxinoid compounds and solubilized oxinoid compounds and the solvent dissolved each other with water.
2. detection composition as claimed in claim 1, it is characterized in that, [molal quantity of gold ion contained by golden nanometer particle presoma] that use in described step (i) to (iii): [molal quantity of oxalate denominationby contained by water soluble oxalate]: [molal quantity of oxinoid compounds] is 1:1:10 to 1:10:30; [in golden nanometer particle presoma the contained gold atom weight] that uses in described step (i) to (iii): [weight of non-ionics] is 1:0.5 to 1:4.
3. detection composition as claimed in claim 1, it is characterized in that, described water soluble oxalate comprises sodium oxalate, potassium oxalate, ammonium oxalate, or their combination.
4. detection composition as claimed in claim 1, it is characterized in that, described non-ionics is
Polyvinylpyrrolidone.
5. detection composition as claimed in claim 1, it is characterized in that, described oxinoid compounds comprises oxine, 6-hydroxyquinoline, 4-hydroxyquinoline, 2-hydroxyquinoline, or their combination.
6. detection composition as claimed in claim 1, it is characterized in that, described detection composition has the pH value between 4 to 6.
7. detection composition as claimed in claim 1, is characterized in that, described golden nanometer particle presoma comprises the golden salt of solubility, solubility and containing the acid of gold, or their combination.
8. detect a method for dimercurion, comprise the following steps:
A () provides as the detection composition as described in arbitrary in claim 1 to 7;
B () adds sample to be tested in described detection composition, formed and detect potpourri;
C color and/or the ultraviolet-visible spectrum of described detection potpourri are observed or measured to (), and compare compared with the control or with standard diagram, thus show whether sample to be tested exists the measurement result of the concentration of dimercurion and/or dimercurion.
9. method as claimed in claim 8, is characterized in that, described contrast is the following control mixture formed: add not containing the aqueous solution of dimercurion in described detection composition, form control mixture, and meet following formula V1/V2=V3/V4,
In formula,
V1 is for the formation of the volume of aqueous solution not containing dimercurion described in control mixture;
V2 is the volume of the described detection composition for the formation of control mixture;
V3 is the volume for the formation of the described sample to be tested detecting potpourri;
V4 is the volume for the formation of the described detection composition detecting potpourri.
10. method as claimed in claim 8, it is characterized in that, described standard diagram obtains by the following method:
(I) in described detection composition, the dimercurion aqueous solution of variable concentrations is added, obtained multiple detection potpourri;
(II) the ultraviolet-visible spectral absorption of each detection potpourri is measured;
(III) draw " the ultraviolet-visible spectral absorbance values-dimercurion concentration detecting potpourri " curve, or draw " relative ultraviolet-visible absorption value-dimercurion concentration " collection of illustrative plates, as standard diagram.
11. methods as claimed in claim 8, it is characterized in that, described ultraviolet-visible spectral absorption measures under 450-800nm wavelength.
12. methods 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 aqueous solution of leachate sample, food leachate sample, treated solid and the aqueous solution of gaseous sample.
13. 1 kinds of kits detecting dimercurion, comprising:
Golden nanometer particle presoma;
Water soluble oxalate;
Non-ionics; With
Oxinoid compounds;
Wherein, described golden nanometer particle presoma, non-ionics, water soluble oxalate and oxinoid compounds are for the preparation of the detection composition of a golden nanometer particle modified containing surface modification agent.
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| CN109900692B (en) * | 2019-04-04 | 2021-11-26 | 青岛大学 | Preparation method of gel for green and efficient detection of mercury ions and application of gel |
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| 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 |
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| 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 |
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| 8-Hydroxyquinoline Benzoates as Highly Sensitive Fluorescent Chemosensors for Transition Metal Ions;Han Zhang, et al.;《Organic Letters》;20050813;第7卷(第19期);第4217页第1段，第4220页左栏第2段 * |
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