CN110118769A - A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion - Google Patents

A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion Download PDF

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CN110118769A
CN110118769A CN201910410944.9A CN201910410944A CN110118769A CN 110118769 A CN110118769 A CN 110118769A CN 201910410944 A CN201910410944 A CN 201910410944A CN 110118769 A CN110118769 A CN 110118769A
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ion
gold nanoparticle
heavy metal
aqueous solution
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李星
邱教艳
吴爱国
张玉杰
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Wuxi Zodolabs Biotech Co ltd
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Ningbo University
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Abstract

The invention discloses a kind of gold nanoparticles and preparation method thereof for detecting heavy metal ion, the technical method is based on Agglomeration Mechanism, using on organic compound amino and/or carboxyl be capable of forming strong hydrogen bond action or strong pi-pi accumulation formed by the phenyl ring on organic compound and act on, so as to cause gold nanoparticle reunion, so that solution colour changes, the peak position and absorption intensity for causing gold nanoparticle surface plasma resonance absorbtion peak change, the variation directly occurred using the peak position and intensity of naked eyes and ultraviolet and visible absorption peak, rapidly whether can contain Cd in test sample2+、Ba2+、Pb2+Ion and its concentration are realized to Cd in sample2+、Ba2+、Pb2+The quick detection of ion.The technology has many advantages, such as easy to operate, at low cost, applied widely.

Description

A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion
Technical field
The invention belongs to nano materials and ion detection field, and in particular to one kind is for detecting Cd2+、Ba2+、Pb2+With much money Belong to the gold nanoparticle and preparation method thereof of ion.
Background technique
With the rapidly development of industry and society, the ecological environments such as soil, atmosphere and water body are by heavy metal ion dirt Seriously threatening for dye, causes the concern of numerous environmentalists.Heavy metal pollution is different from organic matter or biological pollution, pollution Be difficult to eliminate, and can be accumulated in vivo by the enrichment of nature biotechnology, into human body after can with protein and Enzyme generates certain effect, inactivates organ, leads to slow poisoning or causes the intracorporal disease of people and nervous system and interior The disorder of excretory system, therefore, heavy metal pollution constitute serious potential hazard to the health of organism.
Barium is heavy metal, is commonly used to various industrial process, such as be electroplated, glass industry, petroleum industry, emerging pigment industry and Corrosion inhibitor etc., compound are also used for painting, ceramics and rubber etc..So far, the Ba in water pollution2+Ion is still It is most common.Ba2+Ionic soil soil and water resource, especially barium salt water soluble compound and acid-soluble compound have higher Toxicity (for example, barium sulphide).The Ba of water middle and high concentration2+Ion can be accumulated and be turned by plant with soluble status It moves on to other animals.
In heavy metal, lead ion Pb2+With cadmium ion Cd2+Use it is also very universal, such as baked foods, paint, vapour Oil, cosmetics etc..Cd2+And Pb2+Highest attention because of its environmental pollution, to the harm that the mankind generate by society.Nowadays, Lake, river and tap water are considered as providing the natural storage of fresh water for the mankind and the ecosystem.Therefore, it monitors in drinking water The pollution of heavy metal ion, and quickly detection identification heavy metal ion pollution, and reduction pollution risk becomes to the maximum extent Inevitable choice.Traditional sensing technology has sensitive, flexible feature such as AAS, ICP-AES and ICP-MS, but complicated, holds high It is expensive, and need to be not suitable for real-time detection using large-scale instrument and equipment.In order to solve these problems, people successfully develop electricity Chemical detection method, part heavy metal ion for identification, for example, anodic stripping voltammetry (ASV), have it is highly sensitive, The features such as easy to operate and inexpensive is a kind of for detecting the strong tools of heavy metal ion.But ASV on-site test needs Sensor-based system needs a small amount of miniature instrument equipment that could complete effectively to detect.
So far, detection of heavy metal ion method has been rapidly developed, but is different its detection of detection architecture Method is different, and the technology applied is in difference, includes flame atomic absorption spectrometry, fibre optical sensor and electrochemistry side Method.The Kanokwan Chaichana of Kasetsart university, Thailand develops part heavy metal analysis method, detection method tool There are the features such as high sensitivity, but its sample preparation complexity and time and effort consuming etc..In recent years, the hair that nanotechnology is advanced by leaps and bounds Exhibition makes it also have system in terms of detection of heavy metal ion and in-depth study, and obtains certain achievement.The present invention passes through synthesis A kind of 6 derivative of -18 crown- of amino benzo, then modifies gold nanoparticle with the derivative and 3- mercaptopropionic acid jointly, using repairing Gold nanoparticle and Cd after decorations2+、Ba2+、Pb2+The specific function of heavy metal ion causes the color of gold nanoparticle and ultraviolet The variation of absorption spectrum is realized to Cd2+、Ba2+、Pb2+The quick detection of heavy metal ion.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficienciess of the prior art, provide a kind of stability it is good, operation Step is simple, can quickly, accurately detect Cd in aqueous solution2+、Ba2+、Pb2+The method of heavy metal ion.
The present invention solves the technical solution that above-mentioned technical problem is taken are as follows: a kind of for detecting the Jenner of heavy metal ion The preparation method of rice corpuscles, using sodium citrate, 4'- amino-Benzo-18-crown-6 and 3- mercaptopropionic acid respectively as reduction The gold of trivalent, is reduced into the gold of zeroth order by agent, dressing agent and stabilizer, and stable, evengranular gold nanoparticle is made (Fig. 1);The aqueous solution of prepared gold nanoparticle is added separately to containing certain density Cd2+、Ba2+、Pb2+Heavy metal ion Solution in, solution colour becomes grey or grey black from red.4'- amino-Benzo-18-crown-6 and 3- mercaptopropionic acid are made It is acted on for dressing agent and gold nanoparticle, gold nanoparticle has rich and varied hydrogen bond action, passes through its amino-NH2Or carboxylic Base-COOH forms strong hydrogen bond action or forms strong pi-pi accumulation effect by phenyl ring, reunites so as to cause gold nanoparticle, So that solution colour changes, realize to Cd in solution2+、Ba2+、Pb2+The naked eye of heavy metal ion quickly detects;Pass through gold The reunion of nanoparticle causes the peak position of gold nanoparticle surface plasma resonance absorbtion peak and intensity to change, realization pair Cd in solution2+、Ba2+、Pb2+The quantitative detection of heavy metal ion.
The structure of 4'- amino-Benzo-18-crown-6 and 3- mercaptopropionic acid is as shown below:
4'- amino-Benzo-18-crown-6 structure diagram and 3- mercaptopropionic acid structure diagram
A kind of preparation method of gold nanoparticle provided by the invention, specifically comprises the following steps:
Certain density aqueous solution of chloraurate is added in round-bottomed flask, is heated with stirring to boiling, rapidly joins citric acid The aqueous solution of sodium reacts 5~15 minutes, and the second of 4'- amino-Benzo-18-crown-6 DMF solution and 3- mercaptopropionic acid is added Alcoholic solution obtains reaction mixture solution, and the pH value of reaction mixture solution is adjusted to 10~13 with HCl, and solution colour is by light yellow Become red, standing is cooled to room temperature, and gold nanoparticle is made, is put into 0~4 DEG C of refrigerator and saves backup;
The concentration of the aqueous solution of chloraurate is 3~6mM;The mass fraction of the sodium citrate aqueous solution is 1%;
The concentration of the DMF solution of the 4'- amino-Benzo-18-crown-6 is 0.1mM;
The concentration of the ethanol solution of the 3- mercaptopropionic acid is 0.15mM;
The DMF is N,N-dimethylformamide;The substance for participating in reaction is that analysis is pure.
The present invention also provides the purposes of the gold nanoparticle, which is characterized in that the gold nanoparticle is used for Detect Cd2+、Ba2+、Pb2+Heavy metal ion specifically comprises the following steps:
By the aqueous solution of prepared gold nanoparticle respectively with various concentration Cd2+、Ba2+、Pb2+The mark of heavy metal ion Quasi- solution reaction is made standard card (Fig. 2), the card including blank assay result according to different color changes, for not With the on-site test of sample to be tested under environment;Or
By the aqueous solution of prepared gold nanoparticle and various concentration Cd2+、Ba2+、Pb2+The standard of heavy metal ion is molten Then liquid reaction passes through ultraviolet-visible absorption spectroscopy, the gold nanoparticle surface plasma resonance absorbtion peak after test reaction The variation that peak position and intensity occur, draws ultraviolet-visible absorption spectroscopy and standard curve (Fig. 3), for be checked under varying environment Test result is substituted into standard curve by the detection of sample, is compared, is calculated, and is judged in sample to be tested with the presence or absence of Cd2+、 Ba2+、Pb2+Ion calculates Cd in sample to be tested2+、Ba2+、Pb2+The concentration of ion, to realize to Cd in sample2+、Ba2+、 Pb2+The quantitative detection of heavy metal ion;
Open hole detection is limited to Cd2+For 10nM, Ba2+For 20nM, Pb2+For 50nM;
Uv-vis spectra detection is limited to Cd2+For 5nM, Ba2+For 10nM, Pb2+For 20nM;
The sample to be tested can be mineral water, tap water or lake water.
In conclusion the present invention provides a kind of gold nanoparticles and preparation method thereof, and with prepared gold nano Particle is for detecting Cd2+、Ba2+、Pb2+The technology of heavy metal ion;The technical method is based on Agglomeration Mechanism, has using dressing agent Amino or carboxyl on machine compound are capable of forming strong specific hydrogen bond action or are formed by the phenyl ring on organic compound Strong pi-pi accumulation effect, so that solution colour changes, causes gold nanoparticle table so as to cause gold nanoparticle reunion The peak position and absorption intensity at face plasma resonance absorption peak change, and therefore, are directly divided using naked eyes and UV, visible light Luminosity determined, rapidly whether can contain Cd in test sample2+、Ba2+、Pb2+The content of heavy metal ion or ion, It realizes to Cd in sample2+、Ba2+、Pb2+The quick detection of heavy metal ion.
Compared with the prior art, the advantages of the present invention are as follows: the present invention mention a kind of gold nanoparticle and preparation method thereof with The application technology of different kinds of ions detection, the technical method is simple to operate, raw material is cheap and easy to get, at low cost, detection is quick, spirit Sensitivity is high, selectivity is strong and implementable live naked eye colorimetric detection, is suitable for mineral water, tap water, lake water and other are multiple Cd in miscellaneous system2+、Ba2+、Pb2+Quick detection, have extensive potential using value.
Detailed description of the invention
The TEM figure of Fig. 1, gold nanoparticle of the present invention, particle diameter range 10-20nm;
The standard card of Fig. 2, different detected components of the present invention, the card including blank assay result;Wherein, scheme 2a is Cd2+The standard card of concentration (μM), Fig. 2 b are Ba2+The standard card of (μM) concentration, Fig. 2 c are Pb2+The mark of (μM) concentration Quasi- card;
The ultraviolet-visible absorption spectroscopy and standard curve of Fig. 3, different detected components of the present invention, standard curve is institute The linear relationship between the ultravioletvisible absorption volume efficiency and concentration of metal ions of detection metal ion is stated, ordinate is test The ratio of the corresponding absorption intensity of two maximum absorption wavelengths of component, abscissa are the concentration of corresponding metal ion;
The particle surface plasma resonance ultraviolet-visible absorption spectroscopy of Fig. 4, different component, abc is 4'- amino-benzene in figure And -18- crown ether -6,3-MPA is 3- mercaptopropionic acid, AuNPs is gold nanoparticle.
Specific embodiment
The present invention is further described below by specific embodiment, but does not limit the contents of the present invention.
The production of standard card
The chlorauric acid solution of 5mL5mM is added in the deionized water of 91mL by step (1), and while stirring, while be heated to Under conditions of boiling, it is 1% sodium citrate solution as reducing agent that 4mL mass fraction, which is added, and after reacting 15min, lemon is made The aqueous solution of the gold nanoparticle of the reduction of lemon acid group and modification;
Step (2) configures 10 μM of 3-MPA-abc solution: the 3- mercaptopropionic acid (being abbreviated as 3-MPA) of 0.1mmol is dissolved in In the ethyl alcohol of 90mL, heating stirring, dissolution;Then 4'- amino-phendioxin 8- crown ether-of 0.1mmol is added in the above solution 6 (being abbreviated as abc) and DMF solvent 10mL, heating stirring, reaction 30min, add ethyl alcohol, make the volume 100mL of solution, obtain Obtain mixture solution;Said mixture solution 1.0mL is taken, the ethyl alcohol of 99mL is added to be diluted, it is molten to obtain final 3-MPA-abc The concentration of liquid is 10 μM;
A series of aqueous solution of concentration of cadmium ions is prepared with deionized water and cadmium nitrate, final concentration is followed successively by 0 μM, 0.01 μ M, 0.02 μM, 0.05 μM, 0.1 μM, 0.3 μM, 1 μM, 5 μM, 7 μM and 8 μM of standard solution, takes the standard of various concentration molten respectively Each 0.1mL of liquid, and the aqueous solution of gold nanoparticle prepared by 0.9mL step (1) is respectively added, and system in step (2) is added Standby 10 μ L of 3-MPA-abc solution obtains mixed solution, stands 20 minutes, different variations is presented in the color of mixed solution, obtains Cd2+The standard card (Fig. 2 a) of ion concentration, the card including blank assay result.
A series of aqueous solution of barium ions concentration is prepared with deionized water and barium nitrate, final concentration is followed successively by 0 μM, 0.02 μ M, 0.05 μM, 0.08 μM, 0.5 μM, 1 μM, 5 μM, 8 μM, 10 μM and 15 μM of standard solution, takes the standard of various concentration molten respectively Each 0.1mL of liquid, and the aqueous solution of gold nanoparticle prepared by 0.9mL step (1) is respectively added, and system in step (2) is added Standby 10 μ L of 3-MPA-abc solution obtains mixed solution, stands 20 minutes, different variations is presented in the color of mixed solution, obtains Ba2+The standard card (Fig. 2 b) of ion concentration, the card including blank assay result.
A series of aqueous solution of plumbum ion concentrations is prepared with deionized water and plumbi nitras, final concentration is followed successively by 0 μM, 0.05 μ M, 0.1 μM, 0.3 μM, 0.5 μM, 0.8 μM, 1 μM, 3 μM, 5 μM and 6 μM of standard solution, takes the standard of various concentration molten respectively Each 0.1mL of liquid, and the aqueous solution of gold nanoparticle prepared by 0.9mL step (1) is respectively added, and system in step (2) is added Standby 10 μ L of 3-MPA-abc solution obtains mixed solution, stands 20 minutes, different variations is presented in the color of mixed solution, obtains Pb2+The standard card (Fig. 2 c) of ion concentration, the card including blank assay result.
Draw standard curve:
Uv-visible absorption spectra measurement is carried out to the above-mentioned standard sample being prepared, in the section 400~800nm The variation of the ultraviolet-ray visible absorbing intensity measured, and record the absorbance ratio at 525nm and 685nm, 695nm, 690nm.With The concentration of standard sample is made standard curve (Fig. 3) as abscissa, absorbance ratio as ordinate;By linear fit, Obtain Cd2+The linear equation of solion standard curve is y=0.9937 X+0.1588, R2=0.9917;Ba2+Solion The linear equation of standard curve is y=0.0524 X+0.0289, R2=0.9984;Pb2+The linear side of solion standard curve Journey is y=0.0823 X+0.0213, R2=0.9934.
Using standard card and standard curve to various concentration Cd2+、Ba2+、Pb2+Heavy metal ion is detected, naked eye inspection Survey limit: Cd2+For 10nM, Ba2+For 20nM, Pb2+For 50nM;Uv-vis spectra detection limit: Cd2+For 5nM, Ba2+For 10nM, Pb2 +For 20nM;The calculation formula of uv-vis spectra detection limit is K × SD/S, and K=3, SD are standard deviation, and S is slope.
Embodiment 1
The aqueous solution of chloraurate of 10mL6mM concentration is added in round-bottomed flask, is heated with stirring to boiling, rapidly joins 20mL 4'- amino-phendioxin 8- crown ether-of 30mL0.1mM is added after reaction 15 minutes in the aqueous solution of 1% sodium citrate of mass fraction The ethanol solution of the 3- mercaptopropionic acid of 6 DMF solution and 30mL0.15mM, obtains reaction mixture solution, reaction mixture solution PH value be regulated to 10 with HCl, solution colour becomes red from light yellow, and standing is cooled to room temperature, and gold nanoparticle is made.It will Gold nanoparticle is made and carries out TEM test, pattern is as shown in Figure 1.
Embodiment 2
The aqueous solution of chloraurate of 20mL3mM is added in round-bottomed flask, is heated with stirring to boiling, rapidly joins 20mL mass After five minutes, 4'- amino-Benzo-18-crown-6 of 20mL0.1mM is added in the aqueous solution of 1% sodium citrate of score, reaction The ethanol solution of DMF solution and 30mL0.15mM3- mercaptopropionic acid, obtains reaction mixture solution, and regulating and controlling its pH value with HCl is 13, Solution colour becomes red from light yellow, and standing is cooled to room temperature, and gold nanoparticle is made.
Embodiment 3
The aqueous solution of chloraurate of 20mL5mM concentration is added in round-bottomed flask, is heated with stirring to boiling, rapidly joins 30mL After ten minutes, 4'- amino-phendioxin 8- hat of 40mL 0.1mM is added in the aqueous solution of 1% sodium citrate of mass fraction, reaction The DMF solution of ether -6 and the ethanol solution of 40mL0.15mM3- mercaptopropionic acid, the pH value of reaction mixture solution are regulated to HCl 12, solution colour becomes red from light yellow, and standing is cooled to room temperature, and gold nanoparticle is made.
Embodiment 4
Cd in " mineral water "2+、Ba2+、Pb2+The detection of ion
(a) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Cd2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " mineral water " is separately added into Into two parts of gold nanoparticle aqueous solutions, mixed liquor A and mixed liquid B are formed;After reaction 15 minutes, mixed liquid B is compared With the color of mixed liquor A, if color change, there are Cd in " mineral water " solution to be detected2+Ion, color becomes if it does not exist Change, then Cd is not present in " mineral water " solution to be detected2+Ion or comparing calculation mixed liquid B and the ultraviolet of mixed liquor A can See absorption intensity and peak value, if its absorption intensity and peak value change, there are Cd in " mineral water " solution to be detected2+From Son, if Cd is not present in " mineral water " solution to be detected there is no variation2+Ion.
(b) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Ba2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " mineral water " is separately added into Into two parts of gold nanoparticle aqueous solutions, mixed liquor C and mixed liquor D is formed;After reaction 15 minutes, mixed liquor D is compared With the color of mixed liquor C, if color change, there are Ba in " mineral water " solution to be detected2+Ion, color becomes if it does not exist Change, then Ba is not present in " mineral water " solution to be detected2+Ion or comparing calculation mixed liquor D and the ultraviolet of mixed liquor C can See absorption intensity and peak value, if its absorption intensity and peak value change, there are Ba in " mineral water " solution to be detected2+From Son, if Ba is not present in " mineral water " solution to be detected there is no variation2+Ion.
(c)) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Pb2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " mineral water " is separately added into Into the aqueous solution of two parts of gold nanoparticles, mixed liquor E and mixed liquor F is formed;After reaction 15 minutes, mixed liquor is compared The color of F and mixed liquor E, if color change, there are Pb in " mineral water " solution to be detected2+Ion, if it does not exist color Change, then Pb is not present in " mineral water " solution to be detected2+Ion or comparing calculation mixed liquor F and mixed liquor E's is ultraviolet Visible absorbance intensity and peak value, if its absorption intensity and peak value change, there are Pb in " mineral water " solution to be detected2+ Ion, if Pb is not present in " mineral water " solution to be detected there is no variation2+Ion.
Embodiment 5
Cd in " tap water "2+、Ba2+、Pb2+The detection of ion
(a) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Cd2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " tap water " is separately added into Into the aqueous solution of two parts of gold nanoparticles, mixed liquor A and mixed liquid B are formed;After reaction 15 minutes, mixed liquor is compared The color of B and mixed liquor A, if color change, there are Cd in " tap water " solution to be detected2+Ion, if it does not exist color Change, then Cd is not present in " tap water " solution to be detected2+Ion or comparing calculation mixed liquid B and mixed liquor A it is ultraviolet Visible absorbance intensity and peak value, if its absorption intensity and peak value change, there are Cd in " tap water " solution to be detected2+ Ion, if Cd is not present in " tap water " solution to be detected there is no variation2+Ion.
(b) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Ba2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " tap water " is separately added into Into the aqueous solution of two parts of gold nanoparticles, mixed liquor C and mixed liquor D is formed;After reaction 15 minutes, mixed liquor is compared The color of D and mixed liquor C, if color change, there are Ba in " tap water " solution to be detected2+Ion, if it does not exist color Change, then Ba is not present in " tap water " solution to be detected2+Ion or comparing calculation mixed liquor D and mixed liquor C's is ultraviolet Visible absorbance intensity and peak value, if its absorption intensity and peak value change, there are Ba in " tap water " solution to be detected2+ Ion, if Ba is not present in " tap water " solution to be detected there is no variation2+Ion.
(c)) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Pb2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " tap water " is separately added into Into the aqueous solution of two parts of gold nanoparticles, mixed liquor E and mixed liquor F is formed;After reaction 15 minutes, mixed liquor is compared The color of F and mixed liquor E, if color change, there are Pb in " tap water " solution to be detected2+Ion, if it does not exist color Change, then Pb is not present in " tap water " solution to be detected2+Ion or comparing calculation mixed liquor F and mixed liquor E's is ultraviolet Visible absorbance intensity and peak value, if its absorption intensity and peak value change, there are Pb in " tap water " solution to be detected2+ Ion, if Pb is not present in " tap water " solution to be detected there is no variation2+Ion.
Embodiment 6
Cd in " lake water "2+、Ba2+、Pb2+The detection of ion
(a) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Cd2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " lake water " is added separately to In the aqueous solution of two parts of gold nanoparticles, mixed liquor A and mixed liquid B are formed;After reaction 15 minutes, mixed liquid B is compared With the color of mixed liquor A, if color change, there are Cd in " lake water " solution to be detected2+Ion, color becomes if it does not exist Change, then Cd is not present in " lake water " solution to be detected2+The UV, visible light of ion or comparing calculation mixed liquid B and mixed liquor A Absorption intensity and peak value, if its absorption intensity and peak value change, there are Cd in " lake water " solution to be detected2+Ion, If Cd is not present in " lake water " solution to be detected there is no variation2+Ion.
(b) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Ba2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " lake water " is added separately to In the aqueous solution of two parts of gold nanoparticles, mixed liquor C and mixed liquor D is formed;After reaction 15 minutes, mixed liquor D is compared With the color of mixed liquor C, if color change, there are Ba in " lake water " solution to be detected2+Ion, color becomes if it does not exist Change, then Ba is not present in " lake water " solution to be detected2+The UV, visible light of ion or comparing calculation mixed liquor D and mixed liquor C Absorption intensity and peak value, if its absorption intensity and peak value change, there are Ba in " lake water " solution to be detected2+Ion, If Ba is not present in " lake water " solution to be detected there is no variation2+Ion.
(c)) aqueous solution of two parts of isometric identical prepared gold nanoparticles is taken;It prepares and is free of Pb2+Ion (is being examined Survey in range) aqueous solution solution as a comparison, the isometric solution to be detected of comparative solution and " lake water " is added separately to In the aqueous solution of two parts of gold nanoparticles, mixed liquor E and mixed liquor F is formed;After reaction 15 minutes, mixed liquor F is compared With the color of mixed liquor E, if color change, there are Pb in " lake water " solution to be detected2+Ion, color becomes if it does not exist Change, then Pb is not present in " lake water " solution to be detected2+The UV, visible light of ion or comparing calculation mixed liquor F and mixed liquor E Absorption intensity and peak value, if its absorption intensity and peak value change, there are Pb in " lake water " solution to be detected2+Ion, If Pb is not present in " lake water " solution to be detected there is no variation2+Ion.
Embodiment 7
Identify and distinguishes Cd2+、Ba2+、Pb2+Ion
The aqueous solution of the gold nanoparticle of 0.9mL, be separately added into different sample cells the 0.1mM cadmium of 0.1mL, barium, The aqueous solution of plumbum ion concentration after mixing, adds 10uL10 μM of 3-MPA-abc solution, reacts 15min, carry out it is ultraviolet-can See that absorption spectrum is tested, as a result as shown in figure 4, different fractions tested ultravioletvisible absorption intensity, peak value it is different and they Color change different distinguish Cd, it can be achieved that identifying2+、Ba2+、Pb2+Heavy metal ion.
Embodiment 8
Using uv-visible absorption spectra instrument, measurement contains Cd2+The A of the sample to be tested of ion695nm/A525nmRatio is 0.6, Substitute into Cd2+The linear equation y=0.9937 X+0.1588 of solion standard curve, can calculate X=0.4440 to get Cd2+The concentration of ion is 0.4440 μM;
Embodiment 9
Using uv-visible absorption spectra instrument, measurement contains Ba2+The A of the sample to be tested of ion685nm/A525nmRatio is 0.6, Substitute into Ba2+The linear equation y=0.0524 X+0.0289 of solion standard curve, can calculate X=10.90 to get Ba2+The concentration of ion is 10.90 μM;
Embodiment 10
Using uv-visible absorption spectra instrument, measurement contains Pb2+The A of the sample to be tested of ion690nm/A525nmRatio is 0.6, Substitute into Pb2+The linear equation y=0.0823 X+0.0213 of solion standard curve, can calculate X=7.032 to get Pb2+The concentration of ion is 7.032 μM;
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only It for specific embodiments of the present invention, is not intended to restrict the invention, all any modifications made in spirit of the invention With improve etc., should all be included in the protection scope of the present invention.

Claims (2)

1. a kind of for detecting the preparation method of the gold nanoparticle of heavy metal ion, which is characterized in that utilize 4'- amino-benzene And -18- crown ether -6 and 3- mercaptopropionic acid prepare gold nanoparticle as dressing agent, specifically includes the following steps:
Certain density aqueous solution of chloraurate is added in round-bottomed flask, is heated with stirring to boiling, rapidly joins certain density The DMF of certain density dressing agent 4'- amino-Benzo-18-crown-6 is added after reacting 5~15min in sodium citrate aqueous solution The ethanol solution of solution and suitable 3- mercaptopropionic acid obtains reaction mixture solution, the pH value HCl tune of reaction mixture solution Control is 10~13, and solution colour becomes red from light yellow, and standing is cooled to room temperature, and gold nanoparticle is made, is put into 0~4 DEG C Refrigerator in save backup;
The concentration of the aqueous solution of chloraurate is 3~6mM;
The mass fraction of the sodium citrate aqueous solution is 1%;
The concentration of the DMF solution of the 4'- amino-Benzo-18-crown-6 is 0.1mM;
The concentration of the 3- mercaptopropionic acid ethanol solution is 0.15mM;
The DMF is N,N-dimethylformamide;
The substance for participating in reaction is that analysis is pure.
2. a kind of purposes of gold nanoparticle made from method as described in claim 1, which is characterized in that the gold nanoparticle For detecting Cd2+、Ba2+、Pb2+Heavy metal ion specifically comprises the following steps:
By the aqueous solution of prepared gold nanoparticle respectively with various concentration Cd2+、Ba2+、Pb2+The standard of heavy metal ion is molten Liquid reaction, is made standard card according to different color changes, the card including blank assay result, under varying environment to The on-site test of test sample;Or;
By the aqueous solution of prepared gold nanoparticle and various concentration Cd2+、Ba2+、Pb2+The standard solution of heavy metal ion is anti- It answers, then passes through ultraviolet-visible absorption spectroscopy, the peak position of the gold nanoparticle surface plasma resonance absorbtion peak after test reaction And the variation that intensity occurs, ultraviolet-visible absorption spectroscopy and standard curve are drawn, for sample to be tested under varying environment Detection, substitutes into standard curve for test result, is compared, calculates, and judges in sample to be tested with the presence or absence of Cd2+、Ba2+、Pb2+ Ion calculates Cd in sample to be tested2+、Ba2+、Pb2+The concentration of ion, to realize to Cd in sample2+、Ba2+、Pb2+Heavy metal The quantitative detection of ion;
Open hole detection is limited to Cd2+For 10nM, Ba2+For 20nM, Pb2+For 50nM;
Uv-vis spectra detection is limited to Cd2+For 5nM, Ba2+For 10nM, Pb2+For 20nM;
The sample to be tested can be mineral water, tap water or lake water.
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