CN109724970A - A method of based on gold nanoparticle colorimetric detection mercury ion - Google Patents

A method of based on gold nanoparticle colorimetric detection mercury ion Download PDF

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CN109724970A
CN109724970A CN201910095086.3A CN201910095086A CN109724970A CN 109724970 A CN109724970 A CN 109724970A CN 201910095086 A CN201910095086 A CN 201910095086A CN 109724970 A CN109724970 A CN 109724970A
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于亚明
洪颖
闫卿
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Huaqiao University
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Abstract

The invention belongs to ion detection technical fields, disclose a kind of method based on gold nanoparticle colorimetric detection mercury ion, and ultrapure water is added in three neck round bottom first, and simultaneously HAuCl is added in high degree of agitation4·4H2O solution rapidly joins sodium citrate solution, and ebuillition of heated is cooled to room temperature after ten minutes, obtains AuNPs solution;Then metal ion storing liquid is configured, AuNPs, metal ion, 6-TG solution and ultrapure water are added in colorimetric test tube, buffer is added, ultra-violet absorption spectrum characterization, measurement selectivity are carried out to reaction solution;Hg is finally added in colorimetric cylinder2+Buffer is added in ion, 6-TG solution, AuNPs, observes color change, carries out ultra-violet absorption spectrum characterization, measurement sensitivity to reaction solution.The colorimetric determination Hg that the present invention is to provide a kind of " aggregation-dispersion " based on AuNPs2+The method of ion can directly be observed with the naked eye, easy to operate, the detection used time it is short and of the invention selectivity is good, high sensitivity.

Description

A method of based on gold nanoparticle colorimetric detection mercury ion
Technical field
The invention belongs to ion detection technical fields more particularly to a kind of based on gold nanoparticle colorimetric detection mercury ion Method.
Background technique
Currently, the prior art commonly used in the trade is such that mercury as the number one killer in heavy metal pollution, is good for human body There is very big harm for health.Mercury pollution comes from various natural resources and trade waste, as volcanic eruption, gold are opened It adopts, chlorine industry etc..Hg2+Ion tires out in animal and plant body step by step as form most common in mercury pollution, by food chain Product, enters eventually into mankind's body.As the Hg of human body excess intake2+When ion, nervous system will receive serious damage, show as It trembles, nephrotoxicity, stomatitis and minamata disease.Therefore, it realizes to Hg in water body2+The efficient detection of ion is of great significance.
Currently, both at home and abroad about Hg2+The more traditional detection method of ion is mainly by instrument, such as atomic absorption spectrography (AAS) (AAS), inductively coupled plasma emission spectrography (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), electrification Learn sensing, high performance liquid chromatography, fluorescence method etc..However, the above method comes with some shortcomings mostly.For example, require greatly using Large-scale instrument, large-scale instrument are not only expensive (price is differed from hundreds of thousands RMB to millions of to ten million RMB);It surveys The process of examination, experiment condition is harsh, as sample needs lasting carrier gas (high-purity argon gas) to introduce detection system to ICP-MS in testing System maintains the costly of instrumentation operating;In addition, large-scale instrument cannot achieve real-time live detection.
In recent years, the AuNPs colorimetric detection Hg of functionalization is utilized2+The method of ion obtains relatively broad research1416。 Such methods largely utilize the AuNPs of functionalization to have unique SPR absorption peak and its dimensional effect, pass through Hg2+Ion with The interaction of AuNPs, induction AuNPs size change, and the AuNPs in aqueous solution is made to be converted into coherent condition by dispersing (dispersion-aggregation), while the color of AuNPs becomes blue from claret, to realize to Hg in water body2+The detection of ion.Mesh Before, for Hg2+The colorimetric detection (dispersion-aggregation) of ion is mainly based upon T-Hg-T structure, utilizes the base thymus gland for containing-SH The mispairing principle of pyrimidine analogue " T " is realized to Hg2+The detection 17,18 of ion, although, it can be enzyme rapidly and sensitively using the principle Detect Hg2+Ion.But these modifications need complicated program synthesis in the DNA on the surface AuNPs, and mostly expensive. In addition, when the colorimetric method based on " dispersion-aggregation " detects the heavy metal ion in practical water body, be easy by other external worlds because The interference of element, and then influence the selectivity of system19
In conclusion problem of the existing technology is: currently with the base thymine analog " T " for containing-SH Mispairing principle realize to Hg2+The detection of ion, analog is expensive, and complicated process is needed to synthesize, so that testing cost is high, separately Outside, detection process is easy to be influenced by extraneous factor, so that the poor selectivity of system.
Therefore, in order to realize live real-time detection heavy metal ion, testing cost is reduced, we devise detection Hg2+From The sensing system of son.The system does not need complicated synthesis process preparation modification in the ligand on gold nanoparticle surface, and ligand can To buy.Detection process is easy to operate, can be detected by naked eye or ultraviolet specrophotometer.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of based on gold nanoparticle colorimetric detection mercury ion Method.
The invention is realized in this way a method of based on gold nanoparticle colorimetric detection mercury ion are as follows:
(1) it takes 90mL ultrapure water in 250mL three neck round bottom, 5mL5 × 10 is added with vigorous stirring-3Mol/L's HAuCl4·4H2O solution.Then, the sodium citrate solution for rapidly joining 1.7 × 10-2mol/L of 5mL is heated to boiling, and keeps Stop heating after boiling 10min, AuNPs solution is made in cooled to room temperature.
(2) certain density each metal ion species storing liquid is accurately prepared, is added respectively into the colorimetric cylinder containing 1mLAuNPs Enter different metal ion and 6-TG solution, and be settled to 3mL with ultrapure water, buffer is added, ultraviolet suction is carried out to reaction solution Spectral characterization is received, selectivity of the invention is measured.
(3) by the Hg of various concentration2+Ion and the 6-TG solution of same concentrations are added separately to the colorimetric cylinder of 1mL AuNPs In, buffer is added, observes with Hg2+The changing rule of AuNPs color after ion concentration increases carries out UV absorption to reaction solution Spectral characterization measures sensitivity of the invention.
Further, the optium concentration of the 6-TG solution is 1.2 μM, so that the sensitivity of detection is best.
Further, the optimal pH of reaction system is 6.6, so that resistant to aggregation phenomenon is best.
Further, the optimal volume of buffer is 100 μ L.
Further, the optimum detection time is 15 minutes.
Further, open hole detection is limited to 700nM, and the detection of ultra-violet absorption spectrum is limited to 8nM.
In conclusion advantages of the present invention and good effect are as follows: " the aggregation-based on AuNPs that the present invention is to provide a kind of The colorimetric determination Hg of dispersion "2+The method of ion can directly be observed with the naked eye, easy to operate, and the detection used time is short, and the present invention Selectivity is good, high sensitivity.Following table lists the comparison that the experiment is carried out with the parameter in the paper delivered.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention based on gold nanoparticle colorimetric detection mercury ion method flow diagram.
Fig. 2 is provided in an embodiment of the present invention in gold nanoparticle colorimetric detection mercury ion methods experiment schematic illustration.
Fig. 3 is provided in an embodiment of the present invention based on AuNPs resistant to aggregation method detection Hg2+Its UV-vis spectroscopy of ion Spectrum.
Fig. 4 is AuNPs (a), 6-TG-AuNPs (b) and 6-TG-AuNPs-Hg provided in an embodiment of the present invention2+(c) TEM Figure, AuNPs (d), 6-TG-AuNPs (e) and 6-TG-AuNPs-Hg2+(f) particle diameter distribution histogram and Zeta potential figure (g).
Fig. 5 is ultraviolet-visible spectrum (a) of the AuNPs provided in an embodiment of the present invention at various concentration 6-TG, photo (b) and absorbance ratio (c).
Fig. 6 is 6-TG-AuNPs (a) provided in an embodiment of the present invention and 6-TG-AuNPs-Hg2+(b) at various ph values Photo and A520/A720With the relation curve (c) of pH.
Fig. 7 is 6-TG-Hg provided in an embodiment of the present invention2+Photo (a) of-AuNPs under different volumes buffer solution and Absorbance ratio (b).
Fig. 8 is the reaction time provided in an embodiment of the present invention to detection Hg2+The influence of ion.
Fig. 9 is the photo (a) and absorbance ratio of system in the presence of different metal ions provided in an embodiment of the present invention (b)。
Figure 10 is provided in an embodiment of the present invention with A520/A720For ordinate Hg2+Ion concentration is the mark that abscissa is drawn Quasi- working curve.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
It is of the existing technology in order to solve the problems, such as, the present invention provides one kind based on gold nanoparticle colorimetric detection mercury from The method of son.
As shown in Figure 1, the method provided in an embodiment of the present invention based on gold nanoparticle colorimetric detection mercury ion are as follows:
S101: being added ultrapure water in three neck round bottom, and simultaneously HAuCl is added in high degree of agitation4·4H2O solution quickly adds Enter sodium citrate solution, ebuillition of heated is cooled to room temperature after ten minutes, obtains AuNPs solution.
S102: AuNPs, metal ion, 6-TG solution and ultrapure is added in configuration metal ion storing liquid in colorimetric test tube Buffer is added in water, carries out ultra-violet absorption spectrum characterization, measurement selectivity to reaction solution.
S103: Hg is added in colorimetric cylinder2+Buffer is added in ion, 6-TG solution, AuNPs, observes color change, right Reaction solution carries out ultra-violet absorption spectrum characterization, measurement sensitivity.
Detection method is illustrated in conjunction with attached drawing.
(1) it takes 90mL ultrapure water in 250mL three neck round bottom, 5mL5 × 10-3mol/L is added with vigorous stirring HAuCl44H2O solution.Then, the sodium citrate solution for rapidly joining 1.7 × 10-2mol/L of 5mL is heated to boiling, Stop heating after keeping boiling 10min, AuNPs solution is made in cooled to room temperature, and during this, solution is by original light Xanthochromia is at claret.
(2) certain density each metal ion species storing liquid is accurately prepared, is added respectively into the colorimetric cylinder of the AuNPs containing 1mL Enter different metal ion and 6-TG solution, and be settled to 3mL with ultrapure water, buffer is added, ultraviolet suction is carried out to reaction solution Spectral characterization is received, selectivity of the invention is measured.
(3) the 6-TG solution of the Hg2+ ion of various concentration and same concentrations is added separately to the colorimetric of 1mL AuNPs Buffer is added in Guan Zhong, and the changing rule of AuNPs color after observation is increased with Hg2+ ion concentration carries out reaction solution ultraviolet Absorption spectrum characterization, measures sensitivity of the invention.
Further, the optium concentration of the 6-TG solution is 1.2 μM, so that the sensitivity of detection is best.
Further, the optimal pH of reaction system is 6.6, so that resistant to aggregation phenomenon is best.
Further, the optimal volume of buffer is 100 μ L.
Further, the optimum detection time is 15 minutes.
The working principle of present invention detection mercury ion are as follows:
As shown in Fig. 2, making firstly, since produce electrostatic repulsion between the citrate ion on the surface AuNPs AuNPs is evenly dispersed in solution.When in system be free of Hg2+When ion, add 6-TG into AuNPs solution, system color by Red becomes blue.This is because 6-TG contains-SH, AuNPs is assembled by forming Au-S covalent bond between-SH and 6-TG. However, when containing Hg in solution2+When ion, certain density 6-TG is added into gold nano solution, system color keep is red It is constant.On the one hand due to Hg2+Ion and-SH and Hg2+Ion compares with the surface AuNPs, there is stronger binding force21;It is another Aspect, Hg2+Ion is also easy to form coordinate bond with the N atom in 6-TG aromatic ring structure.When existing simultaneously Hg in system2+ Ion and when 6-TG, Hg2+Ion can preferentially generate Hg in conjunction with the nitrogen-atoms in 6-TG on-SH and aromatic rings2+Ion-S key And Hg2+Ion-N key loses the ability of induction AuNPs aggregation, to generate resistant to aggregation phenomenon.
The present invention will be further described with experiment with reference to the accompanying drawing.
1, laboratory apparatus and reagent
As shown in table 1, table 2:
Table 1
Table 2
2, spectrum analysis and characterization are tested
To prove that Hg is being added in AuNPs resistant to aggregation system2+Really, changed before and after ion, test respectively to AuNPs, 6-TG-AuNPs and 6-TG-AuNPs-Hg2+Three kinds of solution carry out ultraviolet-visible spectrum measurement, and experimental result is as shown in Figure 3. When containing only AuNPs in system, solution takes on a red color, and absorption peak shows the uniform particle sizes of AuNPs and divide about at 520nm Divergence is good;If 6-TG solution is added thereto, solution colour rapidly goes to blue, and absorption peak occurs obvious red shift, about exists At 720nm;And to contain a certain concentration Hg2+6-TG is added in the AuNPs solution of ion, system still takes on a red color, and absorption peak is still It is maintained at 520nm.Since the absorbance at 520nm and 720nm is related with the dispersion of AuNPs (or aggregation) state respectively. Therefore, with the ratio (A of absorbance at 520nm and 720nm520/A720) indicate the dispersion and coherent condition of system.Work as A520/ A720When numerical value is larger, AuNPs is dispersed in system, and color is red;Work as A520/A720When numerical value is smaller, AuNPs's is poly- Collection degree is bigger, and solution then shows blue.
In order to further study Hg2+The resistant to aggregation process of ion colorimetric sensor carries out TEM table to three kinds of different solution Sign.TEM in Fig. 4 (a) schemes explanation, AuNPs uniform particle sizes of synthesis and well dispersed.In Fig. 4 (b), the addition of 6-TG solution Make AuNPs that obvious reunion have occurred.And in Fig. 4 (c), due to Hg2+The presence of ion does not go out after 6-TG is added in AuNPs The now clustering phenomena similar with Fig. 4 (b).It follows that Hg2+Ion plays really in the system and prevents 6-TG and AuNPs In conjunction with effect.
In addition, measuring the particle diameter distribution of AuNPs and zeta current potential under different condition by ZetaPALS.From Fig. 4 (d)- (f) finding out the state of AuNPs, there are apparent differences, and the particle diameter distribution of AuNPs is respectively in 30nm, 250nm and 80nm or so, table The introducing of bright 6-TG can cause AuNPs to assemble really, and Hg2+Ion also plays anti-really in 6-TG-AuNPs system Aggtegation.Shown in the test result of Zeta potential such as Fig. 4 (g), the zeta current potential (43 ± 5mV) of AuNPs is apparently higher than 6-TG- AuNPs (3 ± 0.5mV), the results showed that as the stability of the addition AuNPs of 6-TG reduces, assemble.And 6-TG- AuNPs-Hg2+Zeta current potential be (- 47 ± 2.5mV), significantly increased compared to 6-TG-AuNPs, illustrate Hg2+The presence of ion Improve the stability of AuNPs, congregational rate weakens, and further demonstrates Hg2+The resistant to aggregation of 6-TG-AuNPs system is made With.
3, condition optimizing is tested
(1) 6-TG concentration optimization
Hg2+Ion and AuNPs are added 6-TG's by vying each other in conjunction with 6-TG, therefore in AuNPs solution system The difference of condition will directly affect detection Hg2+The result of ion.When concentration of the 6-TG in AuNPs solution is lower, aggregation is existing As less obvious, so that later period Hg2+The detection range of ion is relatively narrow.However, then needing to be added more when 6-TG is when concentration is higher Hg2+Ion just will appear obvious resistant to aggregation phenomenon, this leads to Hg again2+The detection of ion limits higher, the i.e. spirit of system Sensitivity is not high.Therefore, the concentration of 6-TG in system need to be optimized.In experiment, investigate in 3mL reaction system, when When AuNPs concentration is 83 μM, the optium concentration of 6-TG.
In Fig. 5 (a), as 6-TG concentration is gradually increased, the color of solution, which gradually becomes purple again from red, becomes blue. By Fig. 5 (b) it is found that with 6-TG concentration increase, absorbance of the wavelength at 520nm reduce, the absorbance liter at 720nm It is high.A can be obtained from Fig. 5 (c)520/A720With the relationship of 6-TG concentration.A520/A720Numerical value is reduced with the increase of 6-TG dosage, is said The aggregation extent of bright AuNPs increases.When the concentration of 6-TG is greater than 1.2 μM, A520/A720Numerical value reaches balance.Due to 6-TG's Concentration is bigger, needs more Hg2+Ion generates resistant to aggregation effect in conjunction with 6-TG, so that detection Hg can be reduced2+Ion Sensitivity.Therefore, comprehensively consider, selecting the optium concentration of 6-TG is 1.2 μM, i.e. for 6-TG when optimizing concentration, AuNPs both can be with Preferable aggregation occurs, and detection Hg will not be reduced2+The sensitivity of ion.
(2) pH optimizes
Select citric acid-sodium citrate (C4H2O7·H2O-Na3C6H5O7·2H2O) as buffer, system has been investigated PH value (3.0-6.6) is for Hg2+The influence of ion detection, wherein the concentration of added 6-TG is 1.2 μM.As shown in Fig. 6 (a), 6- (Hg is not present in TG-AuNPs system2+Ion) solution colour at various ph values is blue.The provable 6- of result above TG causes AuNPs to assemble in this acid range in conjunction with AuNPs.When there are Hg2+When ion, 6-TG-Hg2+-AuNPs System is at various ph values shown in phenomenon such as Fig. 6 (b), and the change procedure from blue to claret occurs in solution colour, in conjunction with Fig. 6 (c), with the increase of system pH (increasing to 6.6 from 3.0), A520/A720Numerical value is also gradually increased, and illustrates that raising pH value is advantageous In 6-TG and Hg2+The combination of ion.Therefore, experiment further increases the pH value of system, as a result, it has been found that being respectively 7.0 Hes in pH 8.0 disodium hydrogen phosphate-citric acid (Na2HPO4·12H2O-C4H2O7·H2O) in buffer solution, 6-TG-AuNPs and 6-TG- AuNPs-Hg2+The color of two system solutions is blue, shows Hg2+Resistant to aggregation effect it is unobvious.To sum up, when system PH value is at 6.6, in Hg2+In the competition of ion and AuNPs, Hg2+The active force of ion and 6-TG are stronger, dominant, thus table Reveal good resistant to aggregation phenomenon, therefore selects 6.6 for the optimal pH of system.
(3) optimization of buffer volume
In order to guarantee that buffer solution plays buffer function really, while reducing the introducing ion because of buffer solution as far as possible again The dosage of buffer solution is optimized in the influence that intensity generates system, experiment.In 6-TG-AuNPs-Hg2+Divide in system Not Jia Ru different volumes buffer solution (volume is respectively 0,50,100,150,200,300,400 μ L), as shown in Fig. 7 (a), Experimental result discovery, with the increase of volume of buffer solution, the color of system becomes blue, and A from red520/A720Numerical value exists 2 reach maximum when 100 μ L, are substantially reduced later, indicate the aggregation extent enhancing of system, illustrate the ionic strength pair of buffer solution The influence of resistant to aggregation system can not be ignored.Fig. 7 (b) further illustrates, can be to system when volume of buffer solution is up to 100 μ L Buffer function is played, while the ionic strength in solution is unlikely to too high again, therefore the optimal volume of buffer solution selects 100 μ L.
(4) optimization in system reaction time
In order to find optimal detection time, in above-mentioned optimal pH, optimized buffer liquor capacity and best 6-TG concentration Deng under the conditions of, detection time has been investigated to different Hg2+There are 6-TG-AuNPs-Hg for ion concentration2+The influence of system.Fig. 8 shows A520/A720With the relationship of time.Firstly, A520/A720Numerical value reduces with the extension of reaction time, and Hg2+Ion is dense Spend bigger A520/A720Reduced rate is faster.When detection time is 15 minutes, numerical value tends to be steady, and illustrates that reaction reaches substantially To balance, thus select 15 minutes as the optimum detection time.
4, selectivity experiment
Under the experiment condition of above-mentioned optimization, influence of the common metal ion to system is investigated, wherein Hg2+、Ag+Ion Concentration is 800nM, and other ion concentrations are 80 μM.As shown in Fig. 9 (a), the experimental results showed that, in addition to Hg2+Ion can make body The solution of system is kept other than claret, other metal ions are without this phenomenon.In conjunction with Fig. 9 (b) it is found that removing Ag+Outside ion, other The concentration of metal ion is Hg2+100 times of ion concentration, Hg2+The A of ionic system520/A720For 6 times of left sides of other metal ions It is right.Show other ion pair systems substantially without response, although Ag+There is certain interference in ion, but with Hg2+Ion comparable sodium Under, it influences to ignore substantially, i.e., to Hg2+The detection of ion does not have an impact substantially.Illustrate the method for the present invention in detection Hg2+ Ion has good selectivity.
5, sensitivity experiment
Under the experiment of optimization, by a series of experiments, find to Hg2+The detection range of linearity of ion is about within 1 μM. In different Hg2+Under the concentration of ion, shown in the response results of system such as Figure 10 (a), as the Hg in solution2+Concentration is 600nM When, system color and no Hg2+System solution color in the presence of ion has notable difference.By Figure 10 (b) it is found that using purple Outside-visible spectrophotometry can be realized to Hg2+The quantitative detection of ion detects, and works as Hg2+Ion concentration is in 400nM-1000nM When, A520/A720With Hg2+Concentration be in good linear relationship y=-1.041159+0.00565x, linearly dependent coefficient (R2) be 0.998, wherein open hole detection is limited to 700nM, and the detection of ultra-violet absorption spectrum is limited to 8nM, and the present invention detects limit and defends lower than the world Raw tissue is to Hg2+Maximum concentration (30nM) in drinking water22
6, actual water sample detects
Huaqiao University's general China Tech skill building, Huaqiao University erythrina indica garden and Xiamen City waterfront cell tap water water sample are taken respectively, are used 0.2 μM of filter membrane filters three times water sample, is then tested respectively with the measuring method of invention, and the mark-on for measuring this method returns Yield.As shown in table 3, the rate of recovery of detection method is within the scope of 89.20-110.94%, relative standard deviation (RSD) between 0.22-0.47%.The result shows that colorimetric method of the invention can be used for Hg in actual water sample2+The inspection of ion It surveys.
Table 3
Wherein: A: Huaqiao University's general China Tech skill building tap water;B: the building tap water of Huaqiao University erythrina indica garden the 4th;C:: Xiamen City Waterfront cell tap water.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (8)

1. a kind of method based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that described to be based on gold nanoparticle ratio Color detect mercury ion method the following steps are included:
(1) ultrapure water is added in three neck round bottom, simultaneously HAuCl is added in high degree of agitation4·4H2O solution, rapidly joins lemon Acid sodium solution, ebuillition of heated are cooled to room temperature after ten minutes, obtain AuNPs solution;
(2) metal ion storing liquid is configured, AuNPs, metal ion, 6-TG solution and ultrapure water are added in colorimetric test tube, adds Enter buffer, ultra-violet absorption spectrum characterization, measurement selectivity are carried out to reaction solution;
(3) Hg is added in colorimetric cylinder2+Buffer is added in ion, 6-TG solution, AuNPs, color change is observed, to reaction solution Carry out ultra-violet absorption spectrum characterization, measurement sensitivity.
2. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that the step (1) in, the three neck round bottom volume is 250mL, and the ultrapure water adds 90mL, the HAuCl4·4H2O solution concentration is 5 ×10-3Mol/L, is added 5mL, and the sodium citrate solution concentration is 1.7 × 10-2Mol/L adds 5mL.
3. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that the step (2) AuNPs is 1mL in, and entire solution of preparing is 3mL.
4. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that the step (3) AuNPs is 1mL in, uses the Hg of various concentration2+The 6-TG solution of ion and same concentrations.
5. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that the 6-TG The concentration of solution is 1.2 μM.
6. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that reaction system Optimal pH be 6.6 good.
7. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that the buffering The volume of liquid is 100 μ L.
8. the method as described in claim 1 based on gold nanoparticle colorimetric detection mercury ion, which is characterized in that detection time It is 15 minutes.
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CN113209938A (en) * 2021-04-12 2021-08-06 上海纳米技术及应用国家工程研究中心有限公司 Preparation of gold nanoparticle @ phosphorus and sulfur co-doped graphene quantum nanocomposite with core-shell structure, product and application

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