CN118090716A - Analysis method for colorimetric detection of Cr (VI) based on copper-guanylic acid complex - Google Patents
Analysis method for colorimetric detection of Cr (VI) based on copper-guanylic acid complex Download PDFInfo
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- 239000004226 guanylic acid Substances 0.000 title claims abstract description 37
- 238000001514 detection method Methods 0.000 title claims abstract description 29
- 238000004458 analytical method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- RQFCJASXJCIDSX-UUOKFMHZSA-N guanosine 5'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O RQFCJASXJCIDSX-UUOKFMHZSA-N 0.000 claims abstract description 21
- 235000013928 guanylic acid Nutrition 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007853 buffer solution Substances 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 8
- 230000031700 light absorption Effects 0.000 claims abstract description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 15
- 238000002835 absorbance Methods 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 2
- 239000003593 chromogenic compound Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 102000004316 Oxidoreductases Human genes 0.000 abstract 1
- 108090000854 Oxidoreductases Proteins 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 60
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000002452 interceptive effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008351 acetate buffer Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 231100000315 carcinogenic Toxicity 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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Abstract
The invention discloses an analysis method for colorimetric detection of Cr (VI) based on a copper-guanylic acid complex, which is characterized by comprising the following steps: 1) Uniformly mixing a copper chloride solution and a guanylic acid solution to obtain a copper-guanylic acid compound; 2) Adding the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution in the step 1) into a centrifuge tube, uniformly mixing the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution, then adding Cr 6+ solutions with different concentrations into the centrifuge tube, uniformly mixing the mixture, reacting the mixture at 20-45 ℃ for 3-10min, then adding the H 2SO4 solution to terminate the reaction, obtaining a reaction solution, judging the existence of Cr 6+ by observing the color change of the reaction solution, or detecting the content of Cr 6+ by ultraviolet-visible light absorption spectrum of the reaction solution. The copper-guanylic acid compound has good oxidase activity, can catalyze chromogenic substrates and Cr (VI) to generate oxidation-reduction reaction, so that the color of the substrate TMB changes, the color shade of the system is in positive correlation with the concentration of the Cr (VI), and further analysis of Cr 6+ is realized.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and detection, and particularly relates to an analysis method for colorimetric detection of Cr (VI) based on a copper-guanylic acid compound.
Background
Cr (VI) is one of typical heavy metal pollutants, and has various adverse effects on the environment and human body. Cr (VI) has strong toxicity, the skin is allergic when in contact with the Cr (VI), and the Cr (VI) can cause great damage to internal organs such as skin mucous membrane, respiratory tract, alimentary canal and the like of a human body when being swallowed, inhaled or contacted for a long time, and is listed as a first-class cancerogenic substance by the International cancer research center. According to the world health organization 'drinking water quality standard', the Cr (VI) content in drinking water cannot exceed 50 mug/L.
The present analysis methods for detecting Cr (VI) include atomic spectroscopy, ion chromatography, mass spectrometry, electrochemical method, fluorescence spectroscopy, and the like. The traditional large instrument has the defects of expensive equipment, longer detection period, complicated pretreatment, required professional operation skills and the like although the detection of Cr (VI) is accurate and reliable, and is not suitable for on-site rapid detection. Colorimetric detection biosensors have been attracting attention for their advantages of simplicity, practicality, economy, and the like. In recent years, with development of nanotechnology, an analysis method for colorimetric detection of Cr (VI) has been mainly realized by catalytic oxidation of chromogenic substrate 3,3', 5' -Tetramethylbenzidine (TMB) by catalytic activity of a metal nanomaterial. However, complicated steps of nanomaterial synthesis and nanoparticle separation are required in the experimental procedure. In addition, the use of expensive noble metal nanoparticles limits the popularization of the detection method.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the main object of the present invention is to provide an analytical method for colorimetric detection of Cr (VI) based on copper-guanylate complexes.
The invention aims at realizing the following technical scheme:
an analytical method for colorimetric detection of Cr (VI) based on a copper-guanylate complex, comprising the steps of:
1) Uniformly mixing a copper chloride solution and a guanylic acid solution to obtain a copper-guanylic acid compound;
2) Adding the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution in the step 1) into a centrifuge tube, uniformly mixing the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution, then adding Cr 6+ solutions with different concentrations into the centrifuge tube, uniformly mixing the mixture, reacting the mixture at 20-45 ℃ for 3-10min, then adding the H 2SO4 solution to terminate the reaction, obtaining a reaction solution, judging the existence of Cr 6+ by observing the color change of the reaction solution, or detecting the content of Cr 6+ by ultraviolet-visible light absorption spectrum of the reaction solution.
In certain specific embodiments, the molar concentration of the copper chloride solution in step 1) is 100mmol/L, the molar concentration of the guanylate solution is 100. Mu. Mol/L, and the volume ratio of the copper chloride solution to guanylate solution is 1 (1-3).
In certain specific embodiments, the molar concentration of the TMB solution is in the range of 20-40mmol/L.
In certain specific embodiments, the volume ratio of copper-guanylate complex, acetate buffer, and TMB solution in step 2) is 10:2.5:1, and the pH of the acetate buffer is 3.0-4.5.
In certain specific embodiments, the molar concentration of the H 2SO4 solution is 2mol/L.
In certain specific embodiments, the volume ratio of the mixture of copper-guanylate complex, acetate buffer, and TMB solution to the reaction solution is 1 (4-6).
In certain specific embodiments, the method of detecting the content of Cr 6+ in the reaction solution in step 2) by ultraviolet-visible absorption spectrum comprises: firstly, ultraviolet-visible absorption spectrums corresponding to Cr 6+ with different concentrations are measured, then, the absorbance ratio is used as an ordinate, the concentration of Cr 6+ is used as an abscissa, a standard curve of Cr 6+ is drawn, and the concentration of Cr 6+ in the reaction solution is obtained through the absorbance ratio corresponding to the reaction solution.
In certain specific embodiments, the method for determining the presence or absence of Cr 6+ by observing the color change of the reaction solution in step 2) is as follows: judging that the reaction liquid contains Cr 6+ if the color of the reaction liquid is changed from yellow, wherein the concentration of Cr 6+ in the reaction liquid is more than or equal to 0.75 mu M; if the color of the reaction solution is unchanged, the reaction solution does not contain Cr 6+ or Cr 6+ with the concentration less than 0.75 mu M.
Compared with the prior art, the invention has at least the following advantages:
The invention provides an analysis method for rapidly, simply and highly sensitively detecting Cr (VI), which is characterized in that copper chloride dihydrate (CuCl 2·2H2 O) and guanylic acid (GMP) are mixed according to a certain proportion at normal temperature to obtain a copper-guanylic acid (Cu-GMP) compound. In combination with the good electron transfer ability of the Cu-GMP complex and the electrostatic attraction ability with 3,3', 5' -tetramethyl benzidine (TMB), cu-GMP can catalyze Cr (VI) to oxidize colorless TMB to generate blue oxidation products (ox-TMB) under acidic conditions, cr (VI) is reduced to Cr (III) by itself, H 2SO4 is introduced to terminate the reaction, and the solution is converted from blue to yellow, so that the absorbance can be measured by a spectrophotometer. Compared with the traditional colorimetric detection method based on nano materials, the detection means is easy to implement and low in cost, and because the experimental process is homogeneous solution detection, complex synthesis of materials, strict storage conditions and advanced equipment are not needed, and the detection means has a good practical application prospect for the minimum detection concentration of Cr (VI) of 0.25 mu M.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows the color change of the reaction solution at different Cr (VI) concentrations in example 2 of the present invention;
FIG. 2 is a graph showing the relationship between the concentration of Cr (VI) and the absorbance (A 450) in example 2 according to the present invention;
FIG. 3 is a graph showing the relationship between the concentration of Cr (VI) and the absorbance (A 620) in example 2 according to the present invention;
FIG. 4 is a graph showing the comparison of ultraviolet absorption change curves of Cr (VI) and interfering ions added into the reaction solution;
FIG. 5 is a graph showing the catalytic effect of copper chloride, guanylic acid and copper-guanylic acid in the present invention.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings and examples which are given by way of illustration only and not by way of limitation, and are not intended to limit the scope of the invention.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as an upper range limit, or as a lower range limit, it is to be understood that any range is specifically disclosed by combining any pair of the upper range limit or preferred value with any lower range limit or preferred value, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values set forth herein are intended to include the endpoints of the range, and all integers and fractions within the range.
All percentages, parts, ratios, etc. herein are by weight unless otherwise specified.
The materials, methods, and examples herein are illustrative and, unless otherwise indicated, should not be construed as limiting.
The raw materials, production equipment, and detection equipment in the following examples, unless otherwise specified, are commercially available, and the detection method is a conventional detection means in the art.
Example 1: preparation of copper-guanylic acid complexes
The preparation method of the copper-guanylic acid compound comprises the following steps:
1) Preparing a guanylic acid (GMP) solution: guanylic acid (GMP) with the mass of 8.1436g is dissolved in 200ml deionized water to obtain guanylic acid solution with the concentration of 100 mM;
2) Preparing a copper chloride solution: copper chloride dihydrate (0.1705 g) was dissolved in 10mL of water to give a copper chloride (CuCl 2·2H2 O) solution with a concentration of 100 mM; mu.L of 100mM copper chloride solution was taken and diluted to 10mL with deionized water to give 100. Mu.M copper chloride solution.
3) The volume ratio is 1: copper chloride solution 1 (100. Mu.M) and guanylate solution (100 mM) were mixed well to obtain copper-guanylate complex.
Example 2:
1) Preparing TMB solution: 3,3', 5' -tetramethyl benzidine (TMB) with the mass of 0.1201g is weighed and dissolved in 25mL of dimethyl sulfoxide to obtain a TMB solution with the mass of 20 mmol/L;
2) Detection of chromium (vi) ions: adding the copper-guanylic acid compound prepared in the example 1, an acetic acid buffer solution with the pH value of 4.0 and a TMB solution into a centrifuge tube, wherein the volume ratio of the copper-guanylic acid compound to the acetic acid buffer solution with the pH value of 4.0 to the TMB solution is 10:2.5:1, supplementing to 200 mu L with deionized water, uniformly mixing, then adding Cr 6+ solutions with different concentrations, controlling the concentration of Cr 6+ to be 0,0.25,0.5,0.75,1,2.5,5,7.5, 10, 25, 50, 100, 200, 300, 400 mu mol/L in sequence, uniformly mixing and reacting for 5min at 30 ℃, and then adding H 2SO4 solution to terminate the reaction to obtain a reaction solution;
In this embodiment, the presence or absence of Cr 6+ is determined by observing the color change of the prepared reaction solution, or the content of Cr 6+ is detected by the ultraviolet-visible absorption spectrum of the reaction solution, specifically: according to the application, the color change of the reaction solution or the absorption intensity of the solution at 450nm is respectively tested by naked eyes, and as shown in a result shown in figure 1, when the concentration of Cr (VI) is 0.75 mu mol/L, the color change (colorless-yellow) can be obviously observed by naked eyes, and the color change is more and more obvious along with the increase of the concentration of Cr (VI).
Meanwhile, the absorbance A 450 of the reaction solution in the microplate at 450nm (TMB oxidation product) is tested by an enzyme-labeled instrument to quantify the reaction solution, meanwhile, the absorbance A 620 of the reaction solution at 620nm is detected to eliminate the nonspecific absorption value in the microplate, A 450-A620 is selected as an ordinate, the concentration of Cr (VI) is selected as an abscissa to draw a curve, as shown in figures 2 and 3, and as can be seen from the figures, the absorbance value is gradually increased along with the continuous increase of the concentration of Cr (VI) in the range of 0-200 mu mol/L. In addition, the absorption intensity has a good linear relationship with the Cr (VI) concentration in the range of 0 to 25. Mu. Mol/L (y=0.06603x+0.00806, R 2 =0.999). By the method, the concentration of Cr (VI) can be accurately detected, and the detection Limit (LOD) of the Cr (VI) is 0.025 mu M.
Example 3
Selectivity and interference testing of copper-guanylate complexes on the basis of example 2: taking a plurality of centrifuge tubes, adding 40 mu L of copper-guanylic acid (Cu-GMP) compound, 10 mu L of acetic acid buffer solution with pH of 4.0 and 4 mu L of TMB solution into each centrifuge tube, and adding Cr (VI) (the molar concentration of Cr (VI) is 10 mu mol/L) into one centrifuge tube; interfering ions (the molar concentration of the interfering ions is 100 mu M) are respectively added into other centrifuge tubes, the interfering ions are Na+,K+,Mg2+,Zn2+,Pb2+,Ca2 +,Ni2+,Co2+,Al3+,Cd2+,Mn2+,Ba2+,Fe3+,Cu2+ and Cr 3+, only one interfering ion is added into each centrifuge tube, deionized water is used for filling up to 200 mu L to obtain a mixed solution, the mixed solution is incubated for 3min at 25 ℃, 50 mu L of 2mol/L H 2SO4 solution is immediately added to terminate the reaction, the absorbance of the mixed solution is measured after mixing different interfering ions with Cr (VI) ions, and finally, the graph is plotted with A 450-A620 as an ordinate, as shown in FIG. 4, only the Cr (VI) solution system shows a remarkable absorption response, and other ions show weaker absorption signals. In addition, the anti-interference experimental result shows that the mixing of different ions and Cr (VI) has no obvious influence on the absorbance of the system, so that the reaction system has very good selectivity for detecting Cr (VI), and under the same condition, the concentration of the detected Cr (VI) is 10 times lower than Na+,K+,Mg2+,Zn2+,Pb2+,Ca2+,Ni2+,Co2+,Al3+,Cd2+,Mn2+,Ba2 +,Fe3+,Cu2+ and Cr 3, which indicates that the analysis method based on the colorimetric detection of Cr (VI) by the copper-guanylic acid compound provided by the application has good selectivity and anti-interference performance.
Example 4
To verify the practicality of this assay, samples of lake water and laboratory tap water from campuses were randomly taken in centrifuge tubes and treated with 0.22 μm filter heads to remove insoluble and macromolecular materials from the samples for later use. Taking a plurality of centrifuge tubes, adding 40 mu L of copper-guanylic acid (Cu-GMP) compound, 10 mu L of acetic buffer with pH of 4.0 and 4 mu L of TMB solution into each centrifuge tube, then adding Cr 6+ solution with different concentrations, controlling the concentration of Cr 6+ to be 2,5 and 15 mu mol/L in sequence, then adding 100 mu L of lake water or tap water sample, finally adding deionized water to 200 mu L to obtain mixed solution, incubating the mixed solution at 25 ℃ for 3min, immediately adding 50 mu L of 2mol/L H 2SO4 solution to terminate the reaction, and measuring absorbance. Recovery was calculated from the linear relationship of fig. 3, and the results are shown in table 1:
TABLE 1 experiment of the actual sample recovery by labeling
From the data in Table 1, the standard recovery rate of the copper-guanylic acid compound in the application to Cr 6+ in lake water is 91.0-102.4%, and the relative standard deviation is 0.7% -1.23%, which shows that the method has potential for practical application.
Example 5
This example tests the catalytic performance of copper chloride, guanylic acid and copper-guanylic acid respectively: taking 4 centrifuge tubes, and marking the centrifuge tubes as No. 1-4 in sequence. To each centrifuge tube, 10. Mu.L of acetic acid buffer solution at pH 4.0, 4. Mu.L of TMB solution and Cr 6+ solution were added, respectively, and the concentration of Cr 6+ was controlled to 10. Mu. Mol/L. The centrifuge tube No. 1 is directly filled with deionized water to 200 mu L to obtain a mixed solution as a blank control; adding 20 mu L of copper chloride solution into a No. 2 centrifuge tube; centrifuge tube No. 3 adding 20 μl GMP solution; and adding 40 mu L of copper-guanylic acid (Cu-GMP) compound into a No. 4 centrifuge tube, and filling the last 3 centrifuge tubes with deionized water until 200 mu L of the mixture solution is obtained, so that the concentration of Cu 2+ in the final reaction solution is 10 mu mol/L and the concentration of GMP is 10mmol/L. The above mixed solution was incubated at 25℃for 3min, then 50. Mu.L of 2mol/L H 2SO4 solution was immediately added to terminate the reaction, and the absorbance was measured, and finally, A 450-A620 was plotted on the ordinate, as shown in FIG. 5, cr 6+ itself was not able to oxidize TMB to develop color. In addition, comparing the respective catalytic results of Cu 2+, GMP and Cu-GMP, it was found that the simultaneous presence of Cu 2+ and GMP in the reaction system can greatly improve the reaction efficiency. Thus, in summary, the selective Cu-GMP metalloenzyme colorimetric method can be used for detecting Cr (VI) in solution.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (8)
1. An analytical method for colorimetric detection of Cr (vi) based on a copper-guanylate complex, characterized by comprising the steps of:
1) Uniformly mixing a copper chloride solution and a guanylic acid solution to obtain a copper-guanylic acid compound;
2) Adding the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution in the step 1) into a centrifuge tube, uniformly mixing the copper-guanylic acid compound, the acetic acid buffer solution and the TMB solution, then adding Cr 6+ solutions with different concentrations into the centrifuge tube, uniformly mixing the mixture, reacting the mixture at 20-45 ℃ for 3-10min, then adding the H 2SO4 solution to terminate the reaction, obtaining a reaction solution, judging the existence of Cr 6+ by observing the color change of the reaction solution, or detecting the content of Cr 6+ by ultraviolet-visible light absorption spectrum of the reaction solution.
2. The method according to claim 1, wherein the molar concentration of the copper chloride solution in step 1) is 100. Mu. Mol/L, the molar concentration of the guanylate solution is 100mmol/L, and the volume ratio of the copper chloride solution to guanylate solution is 1 (1-3).
3. The method for the analysis of Cr (vi) based on the colorimetric detection of copper-guanylic acid complexes according to claim 1, characterized in that the molar concentration of the TMB solution is 20-40mmol/L.
4. The method according to claim 1, wherein the volume ratio of copper-guanylic acid complex, acetic acid buffer solution and TMB solution in step 2) is 10:2.5:1, and the pH value of acetic acid buffer solution is 3.0-4.5.
5. The method for the colorimetric detection of Cr (VI) based on a copper-guanylate complex according to claim 4 wherein the molar concentration of said H 2SO4 solution is 2mol/L.
6. The method according to claim 5, wherein the volume ratio of the mixture of the copper-guanylate complex, the acetic acid buffer with ph=4.0 and the TMB solution to the reaction solution is 1 (4-6).
7. The method for colorimetric detection of Cr (vi) based on a copper-guanylate complex according to claim 1 wherein step 2) the method for detecting the content of Cr 6+ by ultraviolet-visible absorption spectrum of the reaction solution is: firstly, ultraviolet-visible absorption spectrums corresponding to Cr 6+ with different concentrations are measured, then, the absorbance ratio is used as an ordinate, the concentration of Cr 6+ is used as an abscissa, a standard curve of Cr 6+ is drawn, and the concentration of Cr 6+ in the reaction solution is obtained through the absorbance ratio corresponding to the reaction solution.
8. The method for colorimetric detection of Cr (vi) based on a copper-guanylic acid complex according to claim 7, wherein the method for judging the presence or absence of Cr 6+ by observing the color change of the reaction solution in step 2) is as follows: judging that the reaction liquid contains Cr 6+ if the color of the reaction liquid is changed from yellow, wherein the concentration of Cr 6+ in the reaction liquid is more than or equal to 0.75 mu M; if the color of the reaction solution is unchanged, the reaction solution does not contain Cr 6+ or Cr 6+ with the concentration less than 0.75 mu M.
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