CN105115963B - The detection method of heavy metal Hg - Google Patents
The detection method of heavy metal Hg Download PDFInfo
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- CN105115963B CN105115963B CN201510423401.2A CN201510423401A CN105115963B CN 105115963 B CN105115963 B CN 105115963B CN 201510423401 A CN201510423401 A CN 201510423401A CN 105115963 B CN105115963 B CN 105115963B
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of detection methods of heavy metal Hg, solution to be measured is added to containing nanogold particle, papain and 2, it is reacted in the reaction system of 6 pyridinedicarboxylic acids, the heavy metal Hg in solution to be measured is qualitatively and quantitatively detected according to the variation of color in the absorbance change and reaction system of ultraviolet-visible absorption spectroscopy detection.The present invention constitutes reaction system, reaction system and Hg using nanogold particle, papain and 2,6 pyridinedicarboxylic acids2+Altogether by covalently bonded, whether red shift is occurred by the nano Au particle surface plasmon absorption peak at 520nm, heavy metal Hg is detected, there are high sensitivity, selectively good, quick and easy etc. advantages.
Description
Technical field
The present invention relates to technological field of biochemistry more particularly to a kind of detection methods of heavy metal Hg.
Background technology
Recently as industrialized development, heavy metal pollution is also increasingly severe, increasingly attracts attention.Mercury
As can uniquely be improved in the ecosystem cycle heavy metal, into water body after can be enriched with by food chain, especially
Fish are finally absorbed by the body, and are damaged to human body.Mercury metal can lead to brain, kidney, central nervous system, immune system
It is severely damaged with internal system, therefore, in water the detection of mercury be just particularly important.The biography of detection heavy metal Hg at present
System detection method has：Flame atomic absorption method, atomic fluorescence spectrometry, inductively coupled plasma mass spectrometry, fluorescence method, test paper
Method etc..Although the accuracy of these methods and sensitivity are all relatively good, they generally require large-scale instrument, complicated inspection
Step is surveyed, testing staff is needed to have certain professional knowledge, it is expensive, it is time-consuming and laborious.
Occurred some in recent years and uses nanogold, organic light emission group, fluorescent dye, oligonucleotides, DNA enzymatic and electrochemistry
The methods of detect heavy metal.Wherein nanogold particle has unique physico-chemical and optical characteristics, and size is small, and surface is easy
Modification, extinction coefficient is several times of common organic dyestuff, therefore nanogold can detect metal ion, anion, small as probe
Molecular substance, protein, nucleic acid etc..The research that nanogold detects heavy metal ion is very universal, all kinds of various.But big portion
The shortcomings of presence detection limit divided is narrow, and detection limit is higher than the maximum concentration standard of country's formulation, and specificity is to be improved.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of high sensitivity, selectivity it is good,
Quick and easy mercury ion detecting method.
In order to solve the above technical problems, provide a kind of detection method of heavy metal Hg, by solution to be measured be added to containing
Nanogold particle, papain and 2 are reacted in the reaction system of dipicolimic acid 2, according to ultravioletvisible absorption light
The variation for composing color in the absorbance change and reaction system of detection carries out qualitatively and quantitatively the heavy metal Hg in solution to be measured
Detection.
Above-mentioned detection method, it is preferred that the preparation method of the reaction system is：By the solution of nano-golden particle-containing with
Papain is mixed to get mixed solution under the conditions of being protected from light, by mixed solution centrifugation weight 2,6- of molten rear addition pyridines two
Carboxylic acid is stood after oscillation under the conditions of being protected from light, and forms reaction system.
Above-mentioned detection method, it is preferred that a concentration of the 1.0 × 10 of the papain solution-5M~1.0 × 10- 8M.It is further preferred that a concentration of the 1.0 × 10 of papain solution-7M。
Above-mentioned detection method, it is preferred that in the solution of the nano-golden particle-containing, nanogold particle a concentration of 2~
10nM。
Above-mentioned detection method, it is preferred that described 2, a concentration of the 5 × 10 of dipicolimic acid 2-3M~5.0 × 10-5M。
A concentration of the 5 × 10 of further preferred 2,6- pyridinedicarboxylic acids-4M。
Above-mentioned detection method, it is preferred that the molar ratio of nanogold particle, papain and PDCA is 2: 100: 5.0
×105。
Above-mentioned detection method, it is preferred that the nanogold particle is prepared using following methods：By chlorauric acid solution
It is stirred under fluidized state with citric acid three sodium solution, until acquired solution color faint yellow switchs to limpid claret by initial
When stop heating, continue to stir 15min~20min, nanogold particle solution be made.
Above-mentioned detection method, it is preferred that the temperature of the reaction is 30 DEG C~60 DEG C.Further preferred reaction temperature
It is 30 DEG C.
Above-mentioned detection method, it is preferred that the pH value of the reaction is 6.0~9.0.Further preferred pH value in reaction is
6.0。
Above-mentioned detection method, it is preferred that the reaction time of the reaction is 15~25min.
Above-mentioned detection method, it is preferred that the qualitative checking method is：Judged according to color change in reaction system
Hg2+It whether there is, when containing Hg in solution to be measured2+When, with Hg2+Concentration gradually rise, the color of reaction system is by red
Gradually become lilac, darkviolet, blue；When in solution to be measured do not contain Hg2+When, the color of reaction system is red.
Above-mentioned detection method, it is preferred that the qualitative checking method is：It is according to the ultraviolet absorption peak of nanogold particle
No generation red shift, judges Hg solution to be measured2+It whether there is, when containing Hg in solution to be measured2+When, nanogold particle it is ultraviolet
Red shift occurs for absorption peak；When in solution to be measured do not contain Hg2+When, red shift does not occur for the ultraviolet absorption peak of nanogold particle.
Above-mentioned detection method, it is preferred that the quantitative detecting method is：By the Hg of known concentration2+It is dense to be configured to gradient
Degree, is added in the reaction system, and the absorbance change at 520nm and 650nm is detected by ultraviolet-visible absorption spectroscopy,
According to A650/A520Ratio and Hg2+Concentration establish equation of linear regression：
Y=0.0252x+0.1139；
Wherein, y is the ratio A of the absorbance at 650nm and 520nm in ultraviolet-visible absorption spectroscopy650/A520, x is described
Hg solution to be measured2+Content, unit be μM.
Above-mentioned detection method, it is preferred that in the equation of linear regression, Hg2+Linear detection range be 0.01 μM~
14μM。
The innovation of the invention consists in that：
The present invention provides a kind of detection methods of heavy metal Hg, using nanogold particle, papain and 2,6- pyrroles
Diphosphoglyceric acid constitutes reaction system, and wherein papain is a kind of endopeptidase containing sulfydryl, has protease and esterase
Activity.It has 212 amino acid residues, wherein there is 7 cysteine residues, can directly connect with nanogold particle surface
Connect, the amino having again can and Hg2+In conjunction with nanogold particle and Hg can be connected simultaneously2+.So that there is Hg2+In the presence of, nanometer
Gold particle is heavy poly-, and color change occurs, and red shift occurs for surface plasmon absorption peak.Individually with papain to receiving
After rice gold particle is surface modified, to Hg2+Detection application in, specificity and sensitivity need to be improved.And PDCA mono-
End is connect by carboxyl with nanogold particle surface, the other end and Hg2+Combine, the electronics on nanogold particle surface collects
Oscillation body, so as to cause at 520nm surface plasmon absorption peak occur red shift, nanogold particle aggregation, solution by
Limpid claret becomes lavender, darkviolet, even blue, can determine whether in solution to be measured according to the variation of color in solution
Whether heavy metal Hg is contained.Simultaneously at 520nm the intensity at plasmon absorption peak also with Hg2+The variation of concentration and become
Change, and then according to A650/A520Ratio achieve the purpose that carry out quantitative detection to heavy metal Hg in solution to be measured.PDCA is added
Afterwards, method of the present invention is to Hg2+Detection, sensitivity and specificity are significantly improved, and detection limit reaches 10nM, meets
Hg in the drinking water of EPA (Environmental Protection Agency) defined2+Maximum concentration standard.
Compared with the prior art, the advantages of the present invention are as follows：
(1) the present invention provides a kind of detection methods of heavy metal Hg, with nanogold particle, papain and PDCA shapes
It at reaction system, is connected with each other by covalent bond, the sensitivity of detection can be improved, detection limit can reach EPA (U.S. environments
Protection administration) for the maximum concentration standard of Mercury in Drinking Water content, while the specificity of the detection method is also improved.
(2) the present invention provides a kind of qualitative checking method of heavy metal Hg, sentenced according to color change in reaction system
Disconnected Hg2+It whether there is, when containing Hg in solution to be measured2+When, with Hg2+Concentration gradually rise, the color of nanogold particle
Lilac, darkviolet, blue are gradually become by red, can directly observe to obtain detectable substance by naked eyes and whether there is, is detected
Method is simple and convenient to operate.
(3) the present invention provides a kind of qualitative checking methods of heavy metal Hg, according to the ultraviolet absorption peak of nanogold particle
Whether red shift occurs, judges Hg solution to be measured2+It whether there is, have detection sensitivity high, do not need the instrument of special expensive,
The advantages such as easy to operate.
(4) the present invention provides a kind of quantitative detecting methods of heavy metal Hg, and solution to be measured is carried out ultravioletvisible absorption
Spectral detection, according to the ratio A of 650nm in ultraviolet-visible absorption spectroscopy and the absorbance at 520nm650/A520To solution to be measured
Middle mercury concentration is detected, and detection sensitivity is high；Specific concentration can be detected using ultraviolet-uisible spectrophotometer, be not required to
The instrument for wanting special expensive has the characteristics that high sensitivity, high specificity, of low cost, easy to operate and environmental sound.
Description of the drawings
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical solution in the embodiment of the present invention carries out clear, complete description.
Fig. 1 is that different molar concentration papain solutions and same molar ratio is added in the embodiment of the present invention 1
The ultraviolet spectra that PDCA is obtained.
Fig. 2 is according to A in Fig. 1650/A520Ratio draw block diagram.
Fig. 3 is the block diagram of absorbance ratio at the 650nm and 520nm obtained under different temperatures in the embodiment of the present invention 2.
Fig. 4 is various concentration Hg in the embodiment of the present invention 42+(0.01 μM, 0.1 μM, 2 μM, 4 μM, 6 μM, 8 μM, 14 μM)
UV-visible spectrum.
Fig. 5 is according to A in Fig. 4650/A520Ratio draw standard curve.
Fig. 6 is variety classes particle (Al in the embodiment of the present invention 53+、Ca2+、Cd2+、Cu2+、Fe2+、Hg2+、Fe3+、K+、Mg2 +、Mn2+、NH4 +、Pb2+、Zn2+、Na+) UV-visible spectrum.
Fig. 7 is according to A in Fig. 6650/A520Ratio draw block diagram.
Specific implementation mode
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Embodiment
Material and instrument employed in following embodiment are commercially available, and the result that all embodiments obtain has been done 3 times
It is above to repeat to test.
Embodiment 1：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) preparation of nanogold particle：Take the chlorauric acid solution (solvent is water) of a concentration of 0.1g/L of 100mL on electric furnace
It is heated to boiling and keeps fluidized state 2min, then rapidly join 6mL mass while stirring the chlorauric acid solution of boiling
The citric acid three sodium solution of a concentration of 10g/L, mixing speed 1000r/min continuous heating and are kept stirring in whipping process
Speed is constant, until acquired solution color is continued to stir by initial faint yellow stopping heating after switching to limpid claret
The solution of nano-golden particle-containing is made after cooling under room temperature (referring generally to 25 DEG C~35 DEG C) in 15min.
(2) P-PDCA-AuNPs solution is prepared：With the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1)
Solution adjusts a concentration of 2.12nM of nanogold particle in solution；Nanogold particle solution (pH value 6.0) after taking 2mL to dilute,
0.2mL a concentration of 1.0 × 10 is added-7The papain solution of M centrifuges after vibrating 30min under the rotating speed of 12000r/min
Weight is molten, and 12 hours are stood under the conditions of being protected from light.Then 0.2mL a concentration of 5.0 × 10 is added-4The PDCA solution of M vibrates 30min
6 hours are stood under the conditions of being protected from light afterwards, the P-PDCA-AuNPs solution prepared.
P-PDCA-AuNPs solution is prepared according to the same method of step (2), and wherein papain solution is mole dense
Degree is respectively 1.0 × 10-5M (number a), 1.0 × 10-6M (number b), 1.0 × 10-7M (number c), 1.0 × 10-8M (number d).
(3) Hg of a concentration of 1mM of 0.2mL is added into above-mentioned solution respectively2+Solution forms reaction system and starts anti-
It answers, pH is 6.0 in reaction process.After reaction 15 minutes, the ultraviolet-visible absorption spectroscopy of each group system is detected, Fig. 1 is this implementation
The ultraviolet spectrogram of example, Fig. 2 are according to A in Fig. 1650/A520Ratio draw block diagram.
It was found from Fig. 1 and Fig. 2：With the reduction of Papain enzyme concentration, absorption peak red shift must be bigger.And
Absorption peak at 520nm is substantially reduced, but when concentration drops to 1.0 × 10-8When M, red shift degree is not so good as 1.0 × 10 instead- 7M.This may be to be connected with each other due to papain between nanogold because when Papain enzyme concentration is too big, occur
Plasma resonance and generate aggregation, the group in papain can not be with Hg2+In conjunction with to red shift degree it is smaller, and
When concentration is small, group is very few in papain, and the distance between nanogold particle can not become smaller, to red shift occur
The phenomenon that dying down.So preferably 1.0 × 10 in reaction system Initial Composition-5M~1.0 × 10-8The papain solution of M into
Row subsequent experimental, wherein 1.0 × 10-7M is a concentration of most preferably.
Embodiment 2：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) P-PDCA-AuNPs solution is prepared：With the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1)
Solution adjusts a concentration of 2.12nM of nanogold particle in solution.It is the nano-Au solution after the dilution of 2mL to take 9 parts of volumes,
Be respectively placed in temperature be 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, in 90 DEG C of refrigerator and water-bath.Point
0.2mL a concentration of 1.0 × 10 is not added in every a nano-Au solution-7The papain solution of M, after vibrating 30min,
It is molten that weight is centrifuged under the rotating speed of 12000r/min, and 12 hours are stood under the conditions of being protected from light.Then 0.2mL a concentration of 5.0 × 10 is added- 4The PDCA solution of M stands 6 hours, the P-PDCA-AuNPs solution prepared after vibrating 30min under the conditions of being protected from light.
(3) Hg of a concentration of 1mM of 0.2mL is added into above-mentioned solution respectively2+Solution forms reaction system and starts anti-
It answers, reaction pH is 6.0.After reaction 15 minutes, the ultraviolet-visible absorption spectroscopy of each group system is detected, testing result is referring to Fig. 3.
As shown in figure 3, with the raising of temperature, A650/A520Value also with raising, illustrate that red shift degree increases, work as temperature
When degree is raised to 30 DEG C, red shift degree reaches maximum.It is gradually reduced after 60 DEG C, 90 DEG C of whens are preferably minimized.It can thus be seen that wooden
The Acclimation temperature range of melon protease is wider, and optimum range is 30 DEG C~60 DEG C, and when to 90 DEG C, papain starts
Inactivation, so A650/A520Value also decline.Ranging from 30 DEG C~60 DEG C of initial temperature condition in reaction system as a result, preferably
Optimum temperature is 30 DEG C.
Embodiment 3：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) P-PDCA-AuNPs solution is prepared：What is prepared in the step of diluting above-mentioned preparation with ultra-pure water (1) contains nanogold
The solution of particle adjusts a concentration of 2.12nM of nanogold particle in solution；Nano-Au solution after taking 2mL to dilute is added
0.2mL a concentration of 1.0 × 10-7The papain solution of M after vibrating 30min, centrifuges weight under the rotating speed of 12000r/min
Molten, under the conditions of being protected from light standing 12 hours obtains mixed solution.3 parts of the mixed solution of above-mentioned preparation is taken, 0.2mL concentration point is added
It Wei 5 × 10-3M、5×10-4M、5.0×10-5The PDCA solution of M stands 6 hours under the conditions of being protected from light after vibrating 30min, obtains
To the P-PDCA-AuNPs solution 1, P-PDCA-AuNPs solution 2, P-PDCA-AuNPs solution 3 prepared.
(3) and respectively to above-mentioned P-PDCA-AuNPs solution 1, P-PDCA-AuNPs solution 2, P-PDCA-AuNPs solution 3
The Hg of a concentration of 1mM of 0.2mL is added2+Solution forms reaction system and starts reaction, and reaction pH is 6.0.After reaction 15 minutes,
Detect the ultraviolet-visible absorption spectroscopy of each group system.
Testing result is shown：After the PDCA of various concentration is added, P-PDCA-AuNPs solution 1, P-PDCA-AuNPs are molten
Liquid 2, P-PDCA-AuNPs solution 3 have a little color change.The color change of P-PDCA-AuNPs solution 2 is more obvious, becomes
Blue.P-PDCA-AuNPs solution 1 and P-PDCA-AuNPs solution 3 become hyacinthine.Ultraviolet-visible absorption spectroscopy also turns out,
The red shift of P-PDCA-AuNPs solution 2 is more obvious.A concentration of 5 × 10 are selected as a result,-4The PDCA of M.
Embodiment 4：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) P-PDCA-AuNPs solution is prepared：With the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1)
Solution adjusts a concentration of 2.12nM of nanogold particle in solution；0.2mL concentration is added in nano-Au solution after taking 2mL to dilute
It is 1.0 × 10-7The papain solution of M, after vibrating 30min, centrifugation weight is molten under the rotating speed of 12000r/min, is being protected from light item
12 hours are stood under part.Then 0.2mL a concentration of 5.0 × 10 is added-4The PDCA solution of M, vibrate 30min after under the conditions of being protected from light
6 hours are stood, the P-PDCA-AuNPs solution prepared.
(3) 7 parts of the P-PDCA-AuNPs solution of above-mentioned preparation is taken.It is dense that 0.2mL is added into 7 parts of P-PDCA-AuNPs solution
Degree is respectively 0.01 μM, 0.1 μM, 2 μM, 4 μM, 6 μM, 8 μM, 14 μM of Hg2+Solution forms reaction system and starts reaction, instead
PH is 6.0 during answering.After reaction 15 minutes, the ultraviolet-visible absorption spectroscopy of each group system is detected.Fig. 4 is different in the present invention
Concentration Hg2+UV-visible spectrum；Fig. 5 is according to A in Fig. 4650/A520Ratio draw standard curve.
As can be seen from Figure 4：The Hg of various concentration is added2+Absorbance of the obtained product system at 520nm is with Hg2+Concentration
Increase and be gradually decrease to stablize, also it is therefore evident that the ultraviolet-visible absorption spectroscopy of product system can be used in 520nm
Locate absorbance as Hg2+Quantitative Testing index.
As shown in figure 5, by measuring a series of Hg containing different molar concentrations2+The ultravioletvisible absorption light of product system
Spectrum, obtains Hg2+Hg solution2+Molar concentration and product system between absorbance at 520nm it is in a linear relationship ranging from
0.01 μM~14 μM, equation of linear regression y=0.0252x+0.1139；Wherein y is the ultravioletvisible absorption light of product system
Absorbance in spectrum at 520nm, x Hg2+Hg solution2+Content (i.e. molar concentration, unit μM), related coefficient is
0.9959, and obtain the detection of this detection method by measuring blank test standard deviation calculation three times and be limited to 10nM.By detection limit
10nM is substituted into above-mentioned equation of linear regression, obtains Hg solution2+Content in detection limit product system in 650nm and
The ratio A of absorbance at 520nm650/A520It is 0.114, can qualitatively judges in solution whether contain Hg according to the absorbance2+。
In the reaction system that the present invention is added in solution to be measured, products therefrom system absorbance at 650nm and 520nm
Ratio A650/A520It can be qualitatively judged in solution to be measured when more than 0.114 and contain Hg2+, by product system in 650nm and
The ratio A of absorbance at 520nm650/A520Substitute into above-mentioned equation of linear regression, you can Hg solution to be measured is calculated2+Contain
Amount.
Embodiment 5：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) P-PDCA-AuNPs solution is prepared：With the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1)
Solution adjusts a concentration of 2.12nM of nanogold particle in solution；0.2mL concentration is added in nano-Au solution after taking 2mL to dilute
It is 1.0 × 10-7The papain solution of M, after vibrating 30min, centrifugation weight is molten under the rotating speed of 12000r/min, is being protected from light item
12 hours are stood under part.Then 0.2mL a concentration of 5.0 × 10 is added-4The PDCA solution of M, vibrate 30min after under the conditions of being protected from light
6 hours are stood, the P-PDCA-AuNPs solution prepared.
(3) specific assay：Match the Al of 1mM respectively3+、Ca2+、Cd2+、Cu2+、Fe2+、Hg2+、Fe3+、K+、Mg2+、Mn2+、NH4 +、Pb2+、Zn2+、Na+Solution.
(4) 14 parts of the P-PDCA-AuNPs solution of above-mentioned preparation is taken.According to the method for embodiment 1 in above-mentioned 14 parts of P-
The Al of 0.2mL is separately added into PDCA-AuNPs solution3+、Ca2+、Cd2+、Cu2+、Fe2+、Hg2+、Fe3+、K+、Mg2+、Mn2+、NH4 +、
Pb2+、Zn2+、Na+Solution forms reaction system and starts reaction, and pH is 6.0 in reaction process.After reaction 15 minutes, detection is each
The ultraviolet-visible absorption spectroscopy of group system.(Hg is replaced with ultra-pure water as a contrast with blank2+Solution).
The results are shown in Figure 6, and Fig. 7 is according to A in Fig. 6650/A520Ratio draw block diagram.
It was found from Fig. 6 and Fig. 7：The Hg of 1mM2+Solution in this reaction system, the ultravioletvisible absorption of the product system
Spectrum absorbance at 520nm is decreased obviously, and apparent red shift occurs at 650nm, and other ions are under the concentration of 1mM
Effect is not significantly interfered with.Due to PDCA and Hg2+The relatively other ions of binding force for be strongest, can be tight between them
Tight knot is combined, to eliminate the interference of other ions.Therefore this method is able to specific detection Hg2+。
Comparative example 1
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) with the solution of the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1), nanogold in solution is adjusted
A concentration of 2.12nM of particle；Nanogold particle solution (pH value 6.0) after taking 2mL to dilute, addition 0.2mL a concentration of 1.0 ×
10-7The papain solution of M, after vibrating 30min, centrifugation weight is molten under the rotating speed of 12000r/min, quiet under the conditions of being protected from light
It sets 12 hours, the P-AuNPs solution prepared.
(3) two parts of P-AuNPs solution are taken, are separately added into above-mentioned 2 parts of P-AuNPs solution according to the method for embodiment 1
The Cu of 0.2mL2+And Pb2+Solution (1mM) forms reaction system and starts reaction, and pH is 6.0 in reaction process.Reaction 15 minutes
Afterwards, the uv-vis spectra of each system is detected.
Testing result shows that solution colour becomes navy blue by red, and apparent red shift, card occur for uv-vis spectra
It is bright without in the presence of PDCA, Cu2+And Pb2+There is interference to detection.
Embodiment 6：
It is a kind of the present invention based on Hg in papain colorimetric detection water2+Detection method, include the following steps：
(1) solution of nano-golden particle-containing is prepared Following the procedure of Example 1.
(2) P-PDCA-AuNPs solution is prepared：With the nano-golden particle-containing prepared in ultra-pure water dilution above-mentioned steps (1)
Solution adjusts a concentration of 2.12nM of nanogold particle in solution；0.2mL concentration is added in nano-Au solution after taking 2mL to dilute
It is 1.0 × 10-7The papain solution of M, after vibrating 30min, centrifugation weight is molten under the rotating speed of 12000r/min, is being protected from light item
12 hours are stood under part.Then 0.2mL a concentration of 5.0 × 10 is added-4The PDCA solution of M, vibrate 30min after under the conditions of being protected from light
6 hours are stood, the P-PDCA-AuNPs solution prepared.
(3) accuracy measures：The Hg of known concentration is prepared according to table 12+Standard solution, respectively by Hg above-mentioned 0.2mL2+
Standard solution is added in P-PDCA-AuNPs solution, forms reaction system and starts reaction, and pH is 6.0 in reaction process.Reaction
After 15 minutes, the ultraviolet-visible absorption spectroscopy of each group system is detected, and thus calculates the Hg in standard solution2+Concentration, and it is known
Concentration compared, the accuracy of this method is detected with this.Simultaneously using traditional FAAS (Flame Atomic Absorption Spectrometry) method (inspection
Survey method is referring to GB/T 12687.4-1990)) it compares, detection and result of calculation are listed in Table 1 below.
Table 1：Hg2+Testing result compares
From the testing result of table 1 it is found that the method for the present invention is compared with traditional FAAS assay methods, testing result accuracy
It is relatively high, and this method is easy to operate, high sensitivity, specificity it is good, of low cost, and with environmental sound spy
Point has widened the range of choice of its detection method.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Though
So the present invention has been disclosed with preferred embodiment as above, and however, it is not intended to limit the invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from the Spirit Essence and technical solution of the present invention, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations.Therefore,
Every content without departing from technical solution of the present invention is made to the above embodiment any simple according to the technical essence of the invention
Modification, equivalent replacement, equivalence changes and modification, still fall within technical solution of the present invention protection in the range of.
Claims (8)
1. the detection method of heavy metal Hg, which is characterized in that being added to solution to be measured containing nanogold particle, papain
It with 2, is reacted in the reaction system of dipicolimic acid 2, according to the absorbance change of ultraviolet-visible absorption spectroscopy detection and anti-
The variation of color in system is answered qualitatively and quantitatively to detect the heavy metal Hg in solution to be measured；The preparation of the reaction system
Method is：The solution of nano-golden particle-containing and papain are mixed to get mixed solution under the conditions of being protected from light, it will be described mixed
The molten rear addition 2 of solution centrifugation weight is closed, dipicolimic acid 2 is stood after oscillation under the conditions of being protected from light, and forms reaction system；The wood
A concentration of the 1.0 × 10 of melon protein enzyme solution-5M~1.0 × 10-8M；Nanogold particle in the solution of the nano-golden particle-containing
A concentration of 2nM~10nM；A concentration of the 5 × 10 of the 2,6- pyridinedicarboxylic acids-3M~5 × 10-5M。
2. detection method according to claim 1, which is characterized in that in the reaction system, the nanogold particle, wood
Melon protease, 2,6- pyridinedicarboxylic acids molar ratio be 2: 100: 5.0 × 105。
3. detection method according to claim 1, which is characterized in that the nanogold particle is prepared into using following methods
It arrives：Chlorauric acid solution is stirred with citric acid three sodium solution under fluidized state, until acquired solution color is by initial yellowish
Color switchs to stop heating when limpid claret, continues to stir 15min~20min, nanogold particle solution is made.
4. detection method according to claim 1, which is characterized in that the condition of the reaction is：30 DEG C~60 DEG C of temperature,
PH value 6.0~9.0,15~25min of reaction time.
5. detection method according to any one of claim 1 to 4, which is characterized in that the qualitative checking method is：Root
Judge Hg according to color change in reaction system2+It whether there is, when containing Hg in solution to be measured2+When, with Hg2+Concentration by
Edge up height, and the color of reaction system gradually becomes lilac, darkviolet, blue by red；When in solution to be measured do not contain Hg2+
When, the color of reaction system is red.
6. detection method according to any one of claim 1 to 4, which is characterized in that the qualitative checking method is：Root
Whether red shift occurs according to the ultraviolet absorption peak of nanogold particle, judges Hg solution to be measured2+It whether there is, contain when in solution to be measured
There is Hg2+When, red shift occurs for the ultraviolet absorption peak of nanogold particle；When in solution to be measured do not contain Hg2+When, nanogold particle
Red shift does not occur for ultraviolet absorption peak.
7. detection method according to any one of claim 1 to 4, which is characterized in that the quantitative detecting method is：It will
The Hg of known concentration2+It is configured to gradient concentration, is added in the reaction system, is detected by ultraviolet-visible absorption spectroscopy
Absorbance change at 520nm and 650nm, according to A650/A520Ratio and Hg2+Concentration establish equation of linear regression：
Y=0.0252x+0.1139；
Wherein, y is the ratio A of the absorbance at 650nm and 520nm in ultraviolet-visible absorption spectroscopy650/A520, x is described to be measured
Hg solution2+Content, unit be μM.
8. detection method according to claim 7, which is characterized in that in the equation of linear regression, Hg2+Linearity test
Ranging from 0.01 μM~14 μM.
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