CN103471889B - Utilize the stable gold nano grain of gamma-polyglutamic acid-to detect the method for trivalent chromic ion - Google Patents

Utilize the stable gold nano grain of gamma-polyglutamic acid-to detect the method for trivalent chromic ion Download PDF

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CN103471889B
CN103471889B CN201310410725.3A CN201310410725A CN103471889B CN 103471889 B CN103471889 B CN 103471889B CN 201310410725 A CN201310410725 A CN 201310410725A CN 103471889 B CN103471889 B CN 103471889B
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polyglutamic acid
gold nano
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CN103471889A (en
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史向阳
袁欣
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Donghua University
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Abstract

The present invention relates to a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion, comprise: (1) adds chlorauric acid solution in gamma-polyglutamic acid-solution, after stirring, add sodium borohydride solution, stirring reaction 1-3h, obtains the stable gold nano grain solution of gamma-polyglutamic acid-through dialysis; (2) get the stable gold nano grain solution of gamma-polyglutamic acid-of above-mentioned preparation, add trivalent chromic ion solution, room temperature is placed 10min, and the UV absorption of test gold nano grain changes, and obtains the quantitative relationship of trivalent chromic ion content and UV absorption. The present invention utilizes the macromolecular structural property of gamma-polyglutamic acid-to prepare at normal temperatures gold nano grain, and preparation method is simple, reaction condition gentleness, and easy operating, is a kind of preparation method of green; And the stable gold nano grain of gamma-polyglutamic acid-prepared by the present invention has good selective and sensitivity to the detection of trivalent chromic ion.

Description

Utilize the stable gold nano grain of gamma-polyglutamic acid-to detect the method for trivalent chromic ion
Technical field
The invention belongs to trivalent chromic ion detection method field, particularly a kind of stable gold nano of gamma-polyglutamic acid-of utilizingGrain detects the method for trivalent chromic ion.
Background technology
Chromium is one of element distributed more widely in the earth's crust, is also comparatively common heavy metal element in life. The common chemical combination of chromiumIf owner+3 ,+6 valencys. Toxicity is very strong because oxidisability is very strong for Cr VI, and has very strong mutagenesis, is generally acknowledgedStrong carcinogen. And chromic toxicity is only second to Cr VI, but it is of many uses. On physiology, trivalent chromium is human bodyMust obligato trace element. First, trivalent chromium can regulate glycometabolism, is the important component part of GTF,Can prevent to a certain extent diabetes; Moreover trivalent chromium can inhibitory mutagenesis, has certain protective effect on cancer risk; And, threeValency chromium has the effect of regulating lipid metabolism, can reduce the content of triglycerides and cholesterol, but human body is to chromicDemand is trace, and China's chromic content of regulation surface water is only 0.5mg/L. Industrial, trivalent chromium content pairThe quality of chromium coating is most important. In using, product do not have chromic material to call environmental protection material containing chromicMaterial. And Cr VI or trivalent chromium are all that in industrial processes, institute must be obligato, as coating, pigment, leather systemMake, timber preservative etc., along with the raising of people's living standard, for the demand of decorating day by day increase cause increasingChromium is exposed in environment, and this is the one burden to environment beyond doubt, to the mankind's one harm greatly. Therefore one easily and fastThe method that detects chromium is all particularly important with monitoring to the protection of environment. And we know, Cr VI is at certain reducing agentUnder effect, can be converted to trivalent chromium, and chromic harm is less, therefore find one have good specificity, sensitivity,Fast, the chromic method of convenient detection is particularly important for the detection of chromium.
The detection of traditional trivalent chromic ion is mainly by means of large-scale instrument, most use atomic absorption spectrography (AAS)s, voltammetry,Resonant light scattering and the colorimetric detection method receiving much concern recently etc. that surface plasma field strengthens, although these methods canTrivalent chromic ion detected, detect but be difficult to realize in real time because volume is heavy. Such as common diphenylcarbazide light splittingIt is simple that photometry has equipment, and detectability is low, accurate and be widely used, but in the use of this method, need heating to boilClear up, easily cause bumping, boil the difficult assurance of water sample residual volume, thus accuracy and accuracy that impact detects. Sulfuric acid AsiaAlthough iron ammonium titration can be used for measuring trivalent chromic ion, the vanadium containing in sample can produce considerable influence to system,Limit the use of this kind of method. Inductively coupled plasma emission spectrography is to utilize induction coupled plasma torch for exciting lightThe one class spectroscopic analysis methods in source is widely used in conventional analysis, has that precision is high, analysis speed is fast etc. excellentPoint, but test sample and need to clear up, and need to be by means of large-scale instrument, and be unfavorable for real-time detection. And colorimetric method masterIf based on the degree of scatter of nano particle and heavy metal ion effect change nano particle, cause the optical signal of nano particle to changeBecome, and can be by visually observing the variation of color, have simply, fast, the advantages such as sensitivity height.
Heavy metal nano particle (NPs), if AuNPs and AgNPs are due to its surface plasma body resonant vibration (SPR) absworption peakAnd there is unique optical property. Research shows the variation along with particle diameter and the aggregation extent of nano particle, its SPR summitChange, this variation can be carried out quantitative assessment by the change of UV absorption, and for colorimetric chemical sensor.This kind of sensor, have highly sensitive, selectively good, the response time is short, detect the advantages such as effect naked eyes are visible. Therefore IConsider the stable gold nano grain of gamma-polyglutamic acid-that utilizes gamma-polyglutamic acid-and the distinctive chelation of trivalent chromic ion to causeGathering realize the quantitative measurment to trivalent chromic ion. Its concrete principle is: gamma-polyglutamic acid-contains abundant-COOH,-NH2, in the time adding trivalent chromic ion, on gamma-polyglutamic acid--COOH ,-NH2, the phase due to the existence of trivalent chromic ionClose mutually, thus the stable gold nano grain of gamma-polyglutamic acid-is assembled, cause solution colour to occur obviously to change, andProduce the variation of UV absorption. Set up a kind of three according to the relation of the variation of its SPR ultraviolet absorption value and trivalent chromic ion concentrationThe assay method of valency content of chromium ion.
Consult pertinent literature, the method for utilizing at present the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion yet there are noRelevant report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of stable gold nano grain of gamma-polyglutamic acid-that utilizes and detects trivalent chromiumThe method of ion, the method is simple, reaction condition gentleness, easy operating, low energy consumption is pollution-free, meets wanting of Green ChemistryAsk, the stable size of nanometer gold grain of synthetic gamma-polyglutamic acid-is even, and particle diameter is distributed in narrower scope, and stabilityGood, can preserve by normal temperature, can be used for different field.
A kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion of the present invention, comprising:
(1) in gamma-polyglutamic acid-solution, add chlorauric acid solution, after stirring, add sodium borohydride solution, stirring reaction 1-3h,Obtain the stable gold nano grain solution of gamma-polyglutamic acid-through dialysis, wherein the mass ratio of gamma-polyglutamic acid-and gold chloride is 1:5,The mol ratio of gold chloride and sodium borohydride is 1:3;
(2) get the stable gold nano grain solution of gamma-polyglutamic acid-of above-mentioned preparation, add trivalent chromic ion solution, room temperature is placed10min, the UV absorption of test gold nano grain changes, and obtains the quantitative relationship of trivalent chromic ion content and UV absorption,Wherein the stable gold nano grain solution of gamma-polyglutamic acid-and the volume ratio of trivalent chromic ion solution are 1:4.
In described step (1), gamma-polyglutamic acid-is pharmaceutical grade, and molecular weight is 1,000,000.
In described step (1), the concentration of gamma-polyglutamic acid-solution is 0.2mg/mL, and the concentration of chlorauric acid solution is 30mg/mL,The concentration of sodium borohydride solution is 3mg/mL.
In described step (1), dialysis adopts distilled water, dialyses three days, changes water every day three times.
In described step (1), the stable gold nano grain solution colour of gamma-polyglutamic acid-is claret.
The concentration of the stable gold nano grain solution of gamma-polyglutamic acid-is 0.04 μ g/mL in described step (2).
In described step (2) final concentration of trivalent chromic ion be respectively 0,0.5,2,4,6,8,10,20,30,40,50、60、70、80、90、100、120、140ng/mL。
After in described step (2), the stable gold nano grain solution of gamma-polyglutamic acid-adds trivalent chromic ion, solution colour is for purpleGrey.
In described step (2), the SPR absorbing wavelength of gold nano grain is 519nm, trivalent chromic ion content and UV absorptionQuantitative relationship in be quantitatively to increase and raise as foundation with trivalent chromic ion concentration taking the light absorption value of sample.
In described step (2), the stable gold nano grain solution of gamma-polyglutamic acid-to the detection range of trivalent chromic ion solution is0.5-140ng/mL。
Selectivity test: get the stable gold nano grain solution of gamma-polyglutamic acid-, concentration is 0.04 μ g/mL, adds ultra-pure waterSolution dilution, room temperature is placed 10min, tests its ultraviolet absorption curve, with same method, gets a series of gamma-polyglutamic acid-sStable gold nano grain solution, adds the aqueous solution of chromic nitrate and mercuric sulfate, copper sulphate, cobalt chloride, sodium chloride, chlorineChange potassium, potassium bichromate, iron chloride, aluminum sulfate, lithium sulfate, plumbi nitras, magnesium chloride, zinc chloride, nickel nitrate, calcium nitrate,The ultra-pure water solution of manganese sulfate, cadmium sulfate and barium chloride, room temperature is placed 10min, and test nanogold particle UV absorption changes,Wherein the stable gold nano grain solution of gamma-polyglutamic acid-and the volume ratio of ultra-pure water solution are 1:4, to verify gold nano grainTo the detection specificity of trivalent chromic ion. Wherein chromic nitrate, mercuric sulfate, lithium sulfate, aluminum sulfate, potassium chloride, sodium chloride,Potassium bichromate, copper sulphate, cobalt chloride, iron chloride, plumbi nitras, magnesium chloride, zinc chloride, nickel nitrate, calcium nitrate, sulfuric acidThe concentration of manganese, cadmium sulfate and barium chloride is 130ng/mL.
Application of sample recovery test: get the aqueous solution 200 μ L of the stable gold nano grain of gamma-polyglutamic acid-, concentration is 0.04 μ g/mL,Add respectively lake water sample, running water, river sample, mineral spring water sample 800 μ L, room temperature is placed 10min, its ultraviolet of rear testAbsorption curve. The aqueous solution 200 μ L that in kind get the stable gold nano grain of gamma-polyglutamic acid-, add and contain trivalent chromiumIon concentration is each water sample solution of 800 μ L of 50ng/mL.
The present invention uses transmission electron microscope (TEM), ultraviolet-visible spectrophotometer (UV-Vis), dynamic laser lightThe method such as scattering (DLS), application of sample recovery test characterizes the stable gold nano grain of gamma-polyglutamic acid-prepared by the present invention and rightThe detection application of trivalent chromic ion, concrete test result is as follows:
(1) test result of ultraviolet-visible spectrophotometer
The stable gold nano grain of gamma-polyglutamic acid-prepared by the present invention has a characteristic absorption peak at 519nm place, this is goldThe SPR peak of nano particle, referring to accompanying drawing 1; And this gold nano grain material is in different pH values (pH=5-8) and differenceIn temperature (4 DEG C-50 DEG C) scope, all there is extraordinary stability. The stable gold nano of gamma-polyglutamic acid-prepared by the present inventionParticle adds the ultraviolet test result of the trivalent chromic ion of variable concentrations to show, SPR peak with the increase of trivalent chromic ion concentration byGradually rise, referring to accompanying drawing 4. From ultraviolet figure, can find out, trivalent chromic ion add the UV absorption to gold nano grainCurve has larger impact, and along with the increase of trivalent chromic ion concentration, its SPR ultraviolet absorption value increases gradually simultaneously, andRed shift gradually, can quantitatively calculate trivalent chromic ion content with the rising of SPR ultraviolet absorption value within the specific limits. Test knotFruit shows, when trivalent chromic ion concentration is during at 0.5-140ng/mL, its concentration and gold nano grain SPR ultraviolet absorption valueRise and be certain relation. Lowest detection is limited to 0.2ng/mL, shows good actual application value.
Selectivity test experimental result: from uv-spectrogram, can find out, mercuric sulfate, sodium chloride, potassium chloride, potassium bichromate,Lithium sulfate, aluminum sulfate, copper sulphate, cobalt chloride, iron chloride, plumbi nitras, magnesium chloride, zinc chloride, nickel nitrate, calcium nitrate,Adding of manganese sulfate, cadmium sulfate and barium chloride affects far away from chromic nitrate the ultraviolet absorption curve of gold nano grain, prove γ-The stable gold nano grain of polyglutamic acid has specific selectivity (Fig. 6) to trivalent chromic ion.
(2) transmission electron microscope test result
The gold nano grain TEM picture that gamma-polyglutamic acid-prepared by this method is stable and size distribution histogram are (referring to accompanying drawing2-a), show that the gold nano grain forming is quite even, particle size is 4.6nm, is distributed in narrower scope. AddTEM picture and the particle diameter distribution histogram (ginseng of the stable gold nano grain of gamma-polyglutamic acid-after 100ppb trivalent chromic ionSee accompanying drawing 2-b), show that certain reunion occurs the gold nano grain forming, and the change of individual particle particle diameter is large, particle size is5.0nm. Show that chelation occurs the gold nano that adding of trivalent chromic ion can be stable with gamma-polyglutamic acid-, thereby makeThe particle diameter that obtains gold nano grain increases.
(3) dynamic laser light scattering experimental particle diameter test
Get the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation), add surpassing of 800 μ LPure water solution, room temperature is placed after 10min and is tested its particle diameter, result shows that its particle diameter is 36.93nm, illustrate the γ of formation-The particle diameter of the stable gold nano grain of polyglutamic acid is less, but is significantly greater than the result of transmission electron microscope test, mainBe because its nano particle and the macromolecular hydration of gamma-polyglutamic acid-around, making its particle diameter is the group of multiple nano particlesBunch particle diameter.
In the present invention, get the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation), add and containHave trivalent chromic ion 800 μ L ultra-pure water solution (final concentration of trivalent chromic ion is respectively 5,10,20,30,40,50,60,70,80,90,100ng/mL), room temperature is tested its particle diameter after placing 10min, and result shows to containTrivalent chromic ion concentration be the particle diameter of the sample of 5-100ng/mL be respectively 51.74,72.03,74.65,78.73,78.97,89.75,112.90,128.67,148.37,180.60,221.60nm. With the gold nano that does not add trivalent chromic ionGrain is compared its particle diameter and is enlarged markedly, and the chelation of the two enlarges markedly particle diameter. But be significantly greater than transmission electron microscopyThe result of mirror, is mainly because its nano particle and the macromolecular hydration of gamma-polyglutamic acid-around, makes its particle diameter for moreThe particle diameter of the cluster of many nano particles.
(4) application of sample recovery test
In this test, get the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation), add lakeWater sample, running water, river sample, mineral spring water sample 800 μ L, room temperature is tested its ultraviolet absorption curve after placing 10min. WithSame method is got the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation), add and contain trivalentChromium ion concentration is each water sample solution of 800 μ L of 50ng/mL. Lake water sample, running water, river sample, mineral spring water sampleThe rate of recovery test result of application of sample is respectively 100.51%, 82.0%, 89.5%, 95.2%.
A kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion of the present invention, by by γ-poly-Glutamic acid solution and chlorauric acid solution mix, and can at room temperature utilize sodium borohydride as the synthetic gold nano grain of reducing agent, withTime gamma-polyglutamic acid-can be used as again stabilizing agent and stablize gold nano grain, stop it to assemble, ensure the gold nano grain generatingDistribution of sizes narrower, form homogeneous. Utilization adds before and after trivalent chromic ion solution colour whether to change to determine by naked eyesIn solution, whether contain trivalent chromic ion, the spy who simultaneously utilizes the SPR peak of gold nano grain to change with the difference of grain diameterProperty is applied to colorimetric chemical sensor, and is successfully applied in the quantitative detection of trivalent chromic ion.
Beneficial effect:
(1) the present invention utilizes the special construction character of gamma-polyglutamic acid-to prepare at normal temperatures gold nano grain, preparation method's letterSingle, reaction condition gentleness, easy operating, low energy consumption is pollution-free, meets the requirement of Green Chemistry;
(2) it is even that the present invention designs the stable size of nanometer gold grain of synthetic gamma-polyglutamic acid-, and particle diameter is distributed in narrowerIn scope, and particle diameter is less, and stability is better, can be used for different field;
(3) characteristic that the present invention utilizes the SPR peak of gold nano grain to change with the difference of grain diameter is applied to ratioColour chemistry sensor, and be successfully applied to the mensuration of trivalent chromic ion content, thus make them there is the environment of being widely used inThe potentiality in monitoring field;
(4) the stable gold nano grain of gamma-polyglutamic acid-that prepared by the present invention detects and has good selection trivalent chromic ionProperty and sensitivity.
Brief description of the drawings
Fig. 1 is the uv absorption spectra of the stable gold nano grain of the gamma-polyglutamic acid-prepared of the present invention;
Fig. 2 be the TEM picture of the stable gold nano grain of the gamma-polyglutamic acid-prepared of the present invention and particle diameter distribution histogram (a) withAnd add after 100ng/mL trivalent chromic ion the TEM picture of the stable gold nano grain of the gamma-polyglutamic acid-of preparation and grainFootpath distribution histogram (b);
Fig. 3 is the solution that adds the stable gold nano grain of gamma-polyglutamic acid-after the variable concentrations trivalent chromic ion purple at 519nm placeOuter absorption value reaches the stable time;
Fig. 4 is the solution uv absorption spectra that adds the stable gold nano grain of gamma-polyglutamic acid-after variable concentrations trivalent chromic ionAnd change color figure (b) (a), digitized representation trivalent chromic ion concentration in figure, unit is ng/mL;
Fig. 5 is that the SPR peak absorption value of the stable gold nano grain of gamma-polyglutamic acid-is with the quantitative relationship of trivalent chromic ion concentration.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be understood that these embodiment are only for illustrating the present inventionLimit the scope of the invention and be not used in. In addition should be understood that after having read the content of the present invention's instruction art technologyPersonnel can make various changes or modifications the present invention, and these equivalent form of values fall within equally the application's appended claims and limitFixed scope.
Embodiment 1
Take gamma-polyglutamic acid-10mg, be dissolved in 50mL water, then add while stirring 1667 μ L chlorauric acid solutions(30mg/mL), stir 20min, then add 4.6mL sodium borohydride solution (3mg/mL), room temperature reaction 2h,Obtain the aqueous solution of the stable gold nano grain of gamma-polyglutamic acid-, by this aqueous solution dialysis, be placed in normal temperature and save backup subsequently.
The test result of ultraviolet-visible spectrophotometer shows that its SPR absorbing wavelength is 519nm(accompanying drawing 1), transmission electricitySub-microscope measurement result shows that the gold nano grain forming is even, and Average Particle Diameters is 4.60nm, is distributed in narrowerIn scope (accompanying drawing 2). Hydrodynamic force particle diameter test result shows that its particle diameter is about 36.93nm.
Embodiment 2
Get the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation in embodiment 1), add800 μ L ultra-pure water solution, test its after mixing different time at the ultraviolet absorption value at 519nm place. In kind getStep (1) gained solution 200 μ L(0.04 μ g/mL), add the solution 800 μ L(tri-of the trivalent chromic ion of variable concentrationsThe final concentration of valency chromium ion is respectively 10,20,50,100,150,200ng/mL), test its different time after mixingAt the ultraviolet absorption value at 519nm place. Result shows that the stable gold nano grain of gamma-polyglutamic acid-adds the trivalent of variable concentrationsAfter chromium ion, in its concentration, during lower than 100ng/mL, its ultraviolet absorption value reached stable after 6 minutes, and worked as chromium ionConcentration is during higher than 100ng/mL, at once reaches stable after adding chromium ion solution, as accompanying drawing 3.
Embodiment 3
Get the stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation in embodiment 1), add800 μ L ultra-pure water solution, room temperature is tested its ultraviolet absorption curve after placing 10min. In kind get step (1) instituteSolution 200 μ L(0.04 μ g/mL), add the solution 800 μ L(trivalent chromic ions of the trivalent chromic ion of variable concentrationsFinal concentration is respectively 0.5,2,4,6,8,10,20,30,40,50,60,70,80,90,100,120,140Ng/mL), room temperature is tested its ultraviolet absorption curve after placing 10min, and result shows the gold nano that gamma-polyglutamic acid-is stableGrain adds after the trivalent chromic ion of variable concentrations, and its SPR peak rises gradually with the increase of trivalent chromic ion concentration, as accompanying drawing 4.By to gold nano grain SPR peak intensity with trivalent chromic ion change in concentration curve plotting relation, its linearly dependent coefficient R2Be 0.9974, can be used for quantitative (accompanying drawing 5) of trivalent chromic ion.
Simultaneously aobvious to adding the stable gold nano grain of gamma-polyglutamic acid-after 100ng/mL trivalent chromic ion to carry out transmitted electronMicro mirror test, the mutual chelating of gamma-polyglutamic acid-and trivalent chromic ion, and particle diameter change is large, and particle size is 5.0nm(accompanying drawing 2).Dynamic light scattering particle diameter test result also shows, be respectively 5,10,20,30,40,50,60 in trivalent chromic ion concentration,The particle diameter of the gold nano grain of 70,80,90, measuring under 100ng/mL is respectively 51.74,72.03,74.65,78.73,78.97,89.75,112.90,128.67,148.37,180.60,221.60nm. With the gold that does not add trivalent chromic ionNano particle (36.93nm) is compared particle diameter and is become large.
Embodiment 4
Get gained solution 200 μ L(0.04 μ g/mL in embodiment 1), add its ultraviolet of 800 μ L ultra-pure water solution testings to inhaleReceive curve. In kind get series of steps (1) gained solution 200 μ L, adding respectively concentration is 130ng/mL'sChromic nitrate and mercuric sulfate, lithium sulfate, aluminum sulfate, potassium chloride, sodium chloride, potassium bichromate, copper sulphate, cobalt chloride, chlorineChange the ultrapure water-soluble of iron, plumbi nitras, magnesium chloride, zinc chloride, nickel nitrate, calcium nitrate, manganese sulfate, cadmium sulfate and barium chlorideLiquid 800 μ L, room temperature is tested its ultraviolet absorption curve after placing 10min, as accompanying drawing 6. Show, other sun adding fromSon, under identical experiment condition, does not cause the significant change of gold nano grain solution colour and ultra-violet absorption spectrum, provesThe stable gold nano grain of gamma-polyglutamic acid-prepared by the present invention has good selective to the detection of trivalent chromic ion.
Embodiment 5
The application of sample recovery test of trivalent chromic ion, gets gained solution 200 μ L(0.04 μ g/mL in embodiment 1), add respectivelyLake water sample, water sample, river sample, mineral spring water sample 800 μ L from the beginning, room temperature is tested its ultraviolet absorption curve after placing 10min.Get the in kind stable gold nano grain solution 200 μ L(0.04 μ g/mL of gamma-polyglutamic acid-of preparation), add and contain respectivelyHaving trivalent chromic ion concentration is the 800 μ L lake water samples of 50ng/mL, water sample, river sample, mineral spring water sample solution from the beginning. KnotThe average recovery that fruit obtains the absorption value variation at SPR peak is respectively 100.51%, 82.0%, 89.5% and 95.2%. More than cardThe stable gold nano grain of gamma-polyglutamic acid-prepared by bright the present invention has certain practical application to the detection of trivalent chromic ionProperty.

Claims (9)

1. utilize the stable gold nano grain of gamma-polyglutamic acid-to detect a method for trivalent chromic ion, comprising:
(1) in gamma-polyglutamic acid-solution, add chlorauric acid solution, after stirring, add sodium borohydride solution, stirring reaction 1-3h, warpDialysis obtains the stable gold nano grain solution of gamma-polyglutamic acid-, and wherein the mass ratio of gamma-polyglutamic acid-and gold chloride is 1:5, chlorine goldAcid is 1:3 with the mol ratio of sodium borohydride;
(2) get the stable gold nano grain solution of gamma-polyglutamic acid-of above-mentioned preparation, add trivalent chromic ion solution, room temperature places 10Min, the UV absorption of test gold nano grain changes, and obtains the quantitative relationship of trivalent chromic ion content and UV absorption, wherein γ-The gold nano grain solution that polyglutamic acid is stable and the volume ratio of trivalent chromic ion solution are 1:4; The SPR of gold nano grain absorbsWavelength is 519nm, in the quantitative relationship of trivalent chromic ion content and UV absorption, be quantitatively with the light absorption value of sample with trivalent chromium fromSub-concentration increases and raises as foundation.
2. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: in described step (1), gamma-polyglutamic acid-is pharmaceutical grade, and molecular weight is 1,000,000.
3. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: in described step (1), the concentration of gamma-polyglutamic acid-solution is 0.2mg/mL, and the concentration of chlorauric acid solution is 30Mg/mL, the concentration of sodium borohydride solution is 3mg/mL.
4. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: in described step (1), dialysis adopts distilled water, dialyses three days, changes water every day three times.
5. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: the color of the stable gold nano grain solution of gamma-polyglutamic acid-is claret in described step (1).
6. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: the concentration of the stable gold nano grain solution of gamma-polyglutamic acid-is 0.04 μ g/mL in described step (2).
7. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: in described step (2) final concentration of trivalent chromic ion be respectively 0,0.5,2,4,6,8,10,20,30,40、50、60、70、80、90、100、120、140ng/mL。
8. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: the stable gold nano grain solution of gamma-polyglutamic acid-adds solution colour after trivalent chromic ion in described step (2)Become purplish grey.
9. a kind of method of utilizing the stable gold nano grain of gamma-polyglutamic acid-to detect trivalent chromic ion according to claim 1,It is characterized in that: the detection model of the stable gold nano grain solution of gamma-polyglutamic acid-to trivalent chromic ion solution in described step (2)Enclose for 0.5-140ng/mL.
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