CN108827897A - The method for detecting mercury ion - Google Patents
The method for detecting mercury ion Download PDFInfo
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- CN108827897A CN108827897A CN201810869508.3A CN201810869508A CN108827897A CN 108827897 A CN108827897 A CN 108827897A CN 201810869508 A CN201810869508 A CN 201810869508A CN 108827897 A CN108827897 A CN 108827897A
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000010931 gold Substances 0.000 claims abstract description 103
- 239000002105 nanoparticle Substances 0.000 claims abstract description 81
- 238000001514 detection method Methods 0.000 claims abstract description 71
- 229910052737 gold Inorganic materials 0.000 claims abstract description 71
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 34
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 11
- 235000013339 cereals Nutrition 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 238000002835 absorbance Methods 0.000 claims description 7
- -1 mercury ions Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 231100001261 hazardous Toxicity 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 133
- 239000000523 sample Substances 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CMZYGFLOKOQMKF-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)-3,5-dimethylbenzene Chemical group CC1=CC(C)=CC(C=2C=C(C)C=C(C)C=2)=C1 CMZYGFLOKOQMKF-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of methods for detecting mercury ion, are related to test chemical analysis field.The method of the detection mercury ion includes the following steps：The changing features that solution colour and ultra-violet absorption spectrum are shown after mercury ion and polyethyleneimine-gold nanoparticle effect, detect mercury ion according to the proportional relation between the difference of solution colour or the variation and ion concentration of mercury of ultra-violet absorption spectrum.The detection method process is easy, quick, and selectivity is good, is convenient for Hg2+Quick detection.And polyethyleneimine used-gold nanoparticle detection solution is safe and non-toxic, and it is non-hazardous to detection operator, to detection environmental nonpollution.
Description
Technical field
The present invention relates to test chemical analysis fields, in particular to a kind of method for detecting mercury ion.
Background technique
Mercury is a kind of heavy metal with very big toxicity, it can enter human body by food chain or environment, right
The body of people causes extremely serious harm.And dimercurion (Hg2+) it is the most common existing way of mercury again.Thus, to Hg2 +Monitoring and quickly detection it is all significant to environment, food safety and human health.Currently used mercury detection method
Including x ray fluorescence spectrometry, inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrography (AAS)
Deng.
However, there is the defects of such as time-consuming, laborious, equipment valuableness and complicated sample pretreatment in the existing above method.
The active colorimetric determination of nano material peroxidase sample provides a new way for mercury ion detecting, such as disclosed patent
CN108037090A, does not need expensive equipment, and detection time is also very fast.But the detection of this method is in addition to probe nano grain
Except son, also needs to adjust pH, 3,3', 5,5'- tetramethyl biphenyl amine aqueous solutions and hydrogen peroxide solution is added.These are all mercury ion
Rapid field detection brings obstacle.In addition, the hydrogen peroxide used in the detection process is a kind of strong oxidizer.According to 2017
The carcinogenic substance inventory edit reference that international cancer research institution of the World Health Organization on October 27 announces, hydrogen peroxide (peroxide
Change hydrogen) in 3 class carcinogenic substance inventories.Institute while detecting mercury ion, also brings to environment and operator in this way
It is potentially hazardous.Therefore, a kind of method for developing simple, quick detection mercury ion suitable for on-site test is extremely urgent.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of method for detecting mercury ion, gold nanoparticle is due to gathering on surface in this method
The protection of aziridine has dispersibility well in the solution, and mercury ion detecting can be carried out by not needing other reagents are added；
Again because the atomic nucleus of mercury ion is larger, and the combination of gold nanoparticle is better than other metal ions, thus other common metals from
Son will not interfere the measurement of mercury ion.Therefore the detection method process is easy, quick, and selectivity is good, is convenient for Hg2+Quick inspection
It surveys.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
The present invention provides a kind of methods for detecting mercury ion, include the following steps：
The feature of solution colour and ultra-violet absorption spectrum is shown after mercury ion and polyethyleneimine-gold nanoparticle effect
Variation, according to the proportional relation between the difference of solution colour or the variation and ion concentration of mercury of ultra-violet absorption spectrum to mercury ion
It is detected.
Further, on the basis of technical solution provided by the invention, according to the variation of solution colour and ion concentration of mercury
Between proportional relation to mercury ion carry out detection include the following steps：
The mercury ion solution of various concentration is added in polyethyleneimine-solution of gold nanoparticles, solution generates after effect
Difference in color；When the concentration of mercury ion in test sample, the difference of contrast solution color determines the concentration model of mercury ion
It encloses.
Further, on the basis of technical solution provided by the invention, according to the variation of ultra-violet absorption spectrum and mercury ion
Proportional relation between concentration carries out detection to mercury ion and includes the following steps：
The mercury ion solution of various concentration, the purple of solution after effect are added in polyethyleneimine-solution of gold nanoparticles
Outer absorption spectrum changes, and obtains absorbance A528nm/A725nmRatio and ion concentration of mercury linear relationship；When detection sample
In product when the concentration of mercury ion, the concentration that the linear relationship determines mercury ion is compareed.
Further, on the basis of technical solution provided by the invention, ion concentration of mercury within the scope of 0~500nmol/L,
Absorbance A528nm/A725nmRatio and ion concentration of mercury it is in a linear relationship, detection be limited to 14~16nmol/L.
Further, on the basis of technical solution provided by the invention, polyethyleneimine-solution of gold nanoparticles and mercury from
The volume ratio of sub- solution is (2.5~7.5):1.
Further, on the basis of technical solution provided by the invention, polyethyleneimine-gold nanometer particle grain size be 4~
15nm。
Further, on the basis of technical solution provided by the invention, mercury ion and polyethyleneimine-gold nanoparticle are made
Condition includes：Temperature is 20~70 DEG C, and the time is 5~15min.
Compared with prior art, beneficial effects of the present invention are：
(1) method of detection mercury ion provided by the invention, this method utilize mercury ion and polyethyleneimine-Jenner's grain of rice
Son effect leads to the aggregation of gold nanoparticle and shows the changing features of solution colour and ultra-violet absorption spectrum, according to solution
Proportional relation between the difference of color and the variation of ultra-violet absorption spectrum and ion concentration of mercury detects mercury ion.The party
Due to the protection of surface polyethyleneimine in method, polyethyleneimine-gold nanoparticle has good dispersibility in the solution, no
Mercury ion can be detected by needing to be added other reagents；Knot again because the atomic nucleus of mercury ion is larger, with gold nanoparticle
Conjunction is better than other metal ions, so other common metal ions will not interfere the measurement of mercury ion.Therefore the detection method mistake
Journey is easy, quick, and selectivity is good, is convenient for Hg2+Quick detection.
(2) polyethyleneimine provided by the invention-gold nanoparticle detection mercury ion method, polyethyleneimine-used
Gold nanoparticle detection solution is safe and non-toxic, non-hazardous to detection operator, to detection environmental nonpollution.
Detailed description of the invention
Fig. 1 is the transmission that the PEI-Au nanoparticle on (left side) and rear (right side) before mercury ion is added in the embodiment of the present invention three
Electron microscopic picture；
Fig. 2 is PEI-Au nanoparticle ultravioletvisible absorption light after various concentration mercury ion is added in the embodiment of the present invention two
The variation diagram and A of spectrum528nm/A725nmLine chart between ratio and ion concentration of mercury, wherein a is that PEI-Au nanoparticle is purple
The variation diagram of outer visible absorption spectra, b A528nm/A725nmLine chart between ratio and ion concentration of mercury；
Fig. 3 is that four PEI-Au nanoparticle of the embodiment of the present invention detects Hg2+Selective experimental result picture, wherein a be it is molten
Liquid color change figure, b are the ultraviolet-visible absorption spectroscopy figure of dissimilar metals ion, c A528nm/A725nmRatio is to difference
The histogram of type of metal ion.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of methods for detecting mercury ion, include the following steps：
The feature of solution colour and ultra-violet absorption spectrum is shown after mercury ion and polyethyleneimine-gold nanoparticle effect
Variation, according to the proportional relation between the difference of solution colour or the variation and ion concentration of mercury of ultra-violet absorption spectrum to mercury ion
It is detected.
Polyethyleneimine-gold nanoparticle (PEI-Au) refers to the composite Nano that polyethyleneimine package gold nanoparticle is formed
Particle.Polyethyleneimine has good hydrophily, exists in the form of macromolecular in water phase, can be with adsorbing metal ions.PEI-
Au has dispersibility well due to the protection of surface polyethyleneimine in the solution, can be abundant with mercury ion to be detected
Detection time is shortened in contact.
Mercury ion can be acted on PEI-Au nanoparticle, so that gold nanoparticle be made to assemble, show solution colour change
Change, ultraviolet-visible absorption spectroscopy also changes therewith.The gold nanoparticle (such as being dispersed in water) of dispersity, particle it
Between spacing when being greater than average grain diameter the color of solution be in claret, and when gold nanoparticle is assembled, interparticle distance is small
When average grain diameter, for color from claret to black transitions, spacing is smaller more to tend to black.This is because gold nanoparticle surface
Caused by plasma resonance, i.e. gold nanoparticle spacing becomes smaller, and plasmon absorption red shift, color is by claret
To black transitions.
In the method for the detection mercury ion, due to the protection of surface polyethyleneimine, polyethyleneimine-gold nanoparticle exists
There is dispersibility well, mercury ion can be detected by not needing other reagents are added in solution；Again because of the original of mercury ion
Daughter nucleus is larger, and the combination of gold nanoparticle is better than other metal ions, thus other common metal ions will not interfere mercury from
The measurement of son.Therefore the detection method process is easy, quick, and selectivity is good, is convenient for Hg2+Quick detection.
It is preferably carried out in mode in one kind, according to the proportional relation pair between the variation and ion concentration of mercury of solution colour
Mercury ion carries out detection and includes the following steps：
The mercury ion solution of various concentration is added in polyethyleneimine-solution of gold nanoparticles, solution generates after effect
Difference in color；When the concentration of mercury ion in test sample, the difference of control color determines the concentration range of mercury ion.
When the mercury ion solution that concentration is gradually increased being added in polyethyleneimine-solution of gold nanoparticles, the color of solution
Peony is gradually become from claret, until black.Pass through the directly visually variation of observation solution colour, the difference of contrast solution color
Not Pan Ding mercury ion concentration range method it is easy, fast.
It is preferably carried out in mode in one kind, is closed according to the direct ratio between the variation and ion concentration of mercury of ultra-violet absorption spectrum
System carries out detection to mercury ion and includes the following steps：
The mercury ion solution of various concentration, the purple of solution after effect are added in polyethyleneimine-solution of gold nanoparticles
Outer absorption spectrum changes, and obtains absorbance A528nm/A725nmRatio and ion concentration of mercury linear relationship；When detection sample
In product when the concentration of mercury ion, the concentration that the linear relationship determines mercury ion is compareed.
Preferably, a kind of typical method for drawing standard curve, includes the following steps：
Take the concentration of 20 μ L for the Hg of 0nM, 24nM, 48nM, 97nM, 146nM, 195nM, 293nM, 488nM respectively2+It is molten
Liquid is added in the PEI-Au solution of 100 μ L, reacts 10min under the conditions of 25 DEG C, observes the variation of solution colour, then with purple
Outer sub-ray spectrometer is detected.
The ultraviolet-visible absorption spectroscopy variation diagram of the typical method for drawing examination criteria curve is shown in a in Fig. 2,
The PEI-Au nanoparticle initially prepared has an absorption peak at 528nm, is the characteristic peak of monodispersed gold nanoparticle.And with
The addition of mercury ion, ultraviolet absorption curve significant change has occurred, occur a new peak, new peak wavelength at longer wavelength
Increase in 725nm and no longer with the increase of ion concentration of mercury.The appearance of new peak is because gold nanoparticle is assembled.Therefore,
The ratio of the absorption of absorption and 725nm at 528nm can correspond to the number of dispersion and aggregation gold nanoparticle.With
A528nm/A725nmRatio curve is done to ion concentration of mercury, obtain the b in Fig. 2, it is found that with the increasing of ion concentration of mercury
Greatly, A528nm/A725nmRatio gradually decrease, and it has good linear relationship to ion concentration of mercury.
With absorbance A528nm/A725nmRatio be ordinate, ion concentration of mercury be abscissa draw curve as detection
The standard curve of mercury ion solution can enable the method for the detection mercury ion more accurately measure the concentration of mercury ion.
It being preferably carried out in mode in one kind, the concentration of mercury ion solution is 0~500nmol/L, detection is limited to 14~
16nmol/L。
The concentration of mercury ion solution it is typical but non-limiting be, for example, 0nmol/L, 24nmol/L, 48nmol/L,
97nmol/L, 146nmol/L, 195nmol/L, 293nmol/L, 488nmol/L or 500nmol/L；
Detection limit it is typical but non-limiting be, for example, 14nmol/L, 14.5nmol/L, 15nmol/L, 15.5nmol/L or
16nmol/L。
It is preferred that with absorbance A528nm/A725nmRatio be ordinate, mercury ion solution concentration be abscissa draw standard
Mercury ion solution concentration and detection limit, can enable the measurement mercury ion that the method for the detection mercury ion is more accurate in curve
Concentration.
It can make the method for detection mercury ion more with the concentration of preferred polyethyleneimine-solution of gold nanoparticles by limiting
It is accurate to add, reasonable control cost, is conducive to detection method provided by the invention and promotes and applies.
It is preferably carried out in mode in one kind, the volume ratio of polyethyleneimine-solution of gold nanoparticles and mercury ion solution
For (2.5~7.5):1, preferably (3~7):1, further preferably (4~6):1.
Polyethyleneimine-solution of gold nanoparticles and the volume ratio of mercury ion solution are typical but non-limiting for example,
2.5:1,3:1,3.5:1,4:1,4.5:1,5:1,5.5:1,6:1,6.5:1,7:1 or 7.5:1.
The testing result of the volume ratio and ion concentration of mercury of polyethyleneimine-solution of gold nanoparticles and mercury ion solution
Accuracy is closely related.If polyethyleneimine-solution of gold nanoparticles and the volume ratio of mercury ion solution are excessively high, poly- second will cause
The waste of alkene imines-solution of gold nanoparticles increases testing cost, and will cause the detection to the mercury ion solution of low concentration
As a result inaccurate；If polyethyleneimine-solution of gold nanoparticles and the volume ratio of mercury ion solution are too low, and will cause can not be quasi-
The really mercury ion solution of detection higher concentration.
It can make to detect by the volume ratio of restriction and preferred polyethyleneimine-solution of gold nanoparticles and mercury ion solution
The method of mercury ion is more accurate, expands the Concentration Testing range of mercury ion solution, and reasonable control cost is conducive to the present invention and mentions
The detection method of confession promotes and applies.
Be preferably carried out in mode in one kind, polyethyleneimine-gold nanometer particle grain size be 4~15nm, preferably 5~
13nm, further preferably 8~12nm.
Polyethyleneimine-gold nanometer particle grain size it is typical but non-limiting be, for example, 4nm, 5nm, 6nm, 7nm, 8nm,
9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm.
By limit and preferred polyethyleneimine-gold nanometer particle grain size can to avoid partial size it is too small caused by detection time
The problems such as testing result caused by too long and partial size is excessive is inaccurate keeps the method for detecting mercury ion more quick and accurate.
It is preferably carried out in mode in one kind, mercury ion includes with polyethyleneimine-gold nanoparticle effect condition：Temperature
Degree is 20~70 DEG C, preferably 20~50 DEG C, further preferably 20~30 DEG C；Time be 5~15min, preferably 7~
13min, further preferably 8~11min.
Typical but non-limiting temperature is, for example, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60
DEG C, 65 DEG C or 70 DEG C；
The typical but non-limiting time is, for example, 5min, 7min, 9min, 11min, 13min or 15min.
Temperature is excessively high and too low can all influence mercury ion and polyethyleneimine-gold nanoparticle exercising result, Jin Erying
Ring testing result；Overlong time will cause detection method and take long time, cannot be quickly to sample detection；Time is too short and is easy to make
At testing result inaccuracy.The temperature and time acted on by restriction and preferred mercury ion and polyethyleneimine-gold nanoparticle,
The process for detecting mercury ion can be made quicker, testing result is more accurate.
It is preferably carried out in mode in one kind, polyethyleneimine-gold nanoparticle preparation method includes the following steps：
By aq. polyethyleneimine and HAuCl4Reaction obtains polyethyleneimine-gold nanoparticle after solution mixing；
Preferably, the concentration of aq. polyethyleneimine is 0.3~1.2mol/L, HAuCl4The concentration of solution be 0.05~
0.15mol/L mol/L。
Preferably, aq. polyethyleneimine and HAuCl4The volume ratio of solution is (45~55):1.
The typical but non-limiting concentration of aq. polyethyleneimine is, for example, 0.3mol/L, 0.4mol/L, 0.6mol/
L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L or 1.2mol/L；
HAuCl4The concentration of solution it is typical but non-limiting be, for example, 0.05mol/L, 0.7mol/L, 0.09mol/L,
0.11mol/L, 0.13mol/L or 0.15mol/L；
Aq. polyethyleneimine and HAuCl4The typical but non-limiting volume ratio of solution is, for example, 45:1,46:1,
47:1,48:1,49:1,50:1,51:1,52:1,53:1,54:1 or 55:1.
The too low range shorter that can make to detect ion concentration of mercury of polyethyleneimine-solution of gold nanoparticles concentration, and be easy
Cause testing result inaccurate；Polyethyleneimine-solution of gold nanoparticles excessive concentration can be such that testing cost increases, and be unfavorable for examining
The popularization and application of survey method.Therefore rationally polyethyleneimine-solution of gold nanoparticles concentration of the control for detection is needed.
By limiting and preferred aq. polyethyleneimine and HAuCl4The concentration of solution and two kinds of solution participate in reaction
Volume ratio, the polyethyleneimine-solution of gold nanoparticles being prepared can be made uniformly dispersed more preferable, polyethyleneimine
Amine-solution of gold nanoparticles concentration is suitable for, in order to preferably detect to mercury ion.
It is preferably carried out in mode in one kind, reaction condition includes in polyethyleneimine-gold nanoparticle preparation method：
Reaction temperature is 50~70 DEG C, preferably 55~65 DEG C；Reaction time is 40~80min, preferably 50~70min.
Typical but non-limiting reaction temperature is, for example, 50 DEG C, 53 DEG C, 55 DEG C, 57 DEG C, 60 DEG C, 63 DEG C, 65 DEG C, 67 DEG C
Or 70 DEG C；
Reaction time it is typical but non-limiting be, for example, 40min, 45min, 50min, 55min, 60min, 65min,
70min, 75min or 80min.
By limiting reaction temperature and reaction time in the preparation method with preferred polyethyleneimine-gold nanoparticle,
It can shorten preparation time with save the cost, can also make the polyethyleneimine-solution of gold nanoparticles being prepared evenly dispersed
Property is more preferable.
Preferably, a kind of preparation method of typical polyethyleneimine-gold nanoparticle, includes the following steps：It will
The aq. polyethyleneimine of 0.7mol/L and the HAuCl of 0.1mol/L4Solution by volume 50:After 1 mixing, in 65 DEG C of water-baths
Middle reaction 60min, it is cooling, obtain polyethyleneimine-solution of gold nanoparticles.
The preparation method of the typical polyethyleneimine-gold nanoparticle defines aq. polyethyleneimine and HAuCl4
The concentration of solution and two kinds of solution participate in the volume ratio of reaction, also define reaction temperature and reaction time.This is typically made
Preparation Method can make the polyethyleneimine-solution of gold nanoparticles being prepared uniformly dispersed more preferable, use the polyethylene
Imines-solution of gold nanoparticles detects mercury ion more quick and accurate.
In order to further appreciate that the present invention, the method for the present invention and effect are done further in detail combined with specific embodiments below
Explanation.Each raw material of the present invention can pass through commercially available acquisition.
Embodiment one
A kind of preparation method of polyethyleneimine-solution of gold nanoparticles, includes the following steps：
By the HAuCl of the aq. polyethyleneimine of 0.7mol/L and 0.1mol/L4Solution by volume 50:After 1 mixing,
60min is reacted in 65 DEG C of water-baths, it is cooling, obtain polyethyleneimine-solution of gold nanoparticles.
Embodiment two
It is a kind of to detect Hg with PEI-Au solution2+Method concrete operations：
1, the preparation of standard curve
(1) Hg of 0nM, 24nM, 48nM, 97nM, 146nM, 195nM, 293nM, 488nM concentration is prepared2+Solution, for use；
(2) Hg for each concentration for taking 20 μ L to prepare2+Solution is added to the PEI-Au solution of 100 μ L (embodiment one is made)
In, 25 DEG C of effect 10min；
(3) solution after above-mentioned effect is subjected to ultra-violet absorption spectrum detection, at the same measure solution in wavelength 528nm and
Light absorption value at 725nm, i.e. A528nmAnd A725nm, and calculate A528nm/A725nmRatio；
(4) with A528nm/A725nmRatio be ordinate, ion concentration of mercury is abscissa, draw standard curve (such as Fig. 2 institute
Show).
2, the Hg in sample is measured2+Concentration
(1) 5 parts respectively from number 1-5 contain Hg2+Sample to be tested in take 20 μ L to be added to the PEI-Au solution of 100 μ L
In (embodiment one is made), 25 DEG C, 10min is acted on；
(2) solution after above-mentioned effect is subjected to ultra-violet absorption spectrum detection, at the same measure solution in wavelength 528nm and
Light absorption value at 725nm, and calculate A528nm/A725nmRatio；
(3) by absorbance ratio A528nm/A725nmIt is compared with the standard curve of drafting, calculates Hg in sample to be tested2+
Concentration.
3, interpretation of result
(1) standard curve regression equation
Hg2+Concentration is within the scope of 0~200nmol/L：Y=4.8255-0.02x, R2=0.99；Hg2+Concentration 200~
Within the scope of 500nmol/L：Y=1.1182-0.0015x, R2=0.90.
(2) Hg in sample2+Concentration Testing result
Table 1
Embodiment three
PEI-Au nano-particle solution detects Hg2+Feasibility analysis experiment, include the following steps：
(1) Hg of 20 μ L 197nM is taken2+It is added in solution into the PEI-Au solution of 100 μ L (embodiment one is made), 25
DEG C effect 10min；
(2) by after above-mentioned effect solution and PEI-Au solution (embodiment one be made) carry out ultra-violet absorption spectrum detection,
The two is respectively placed under transmission electron microscope simultaneously and is observed；
(3) the characteristic change curve and transmission electron microscope picture of ultra-violet absorption spectrum are recorded.
Can be seen that prepared PEI-Au nano-particles size size by left hand view in Fig. 1 is about 10nm, dispersion compared with
Uniformly.And Hg is added2+Apparent reunion has occurred in (Fig. 1 right part of flg) later, PEI-Au nanoparticle, and particle aggregation is together.
Fig. 1 illustrates Hg2+Addition cause PEI-Au nanoparticle aggregation, therefore Hg can detecte using PEI-Au2+。
Example IV
PEI-Au nano-particle solution detects Hg2+Selectivity analyze experiment, include the following steps：
(1) it takes the EP of 13 1.5mL to manage, is labeled as 1~13, the PEI-Au nanoparticle of 100 μ L is added thereto respectively
Solution；
(2) labeled as the Hg for being separately added into 10 μ L water in 1 and 2 EP pipe and 10 μ L concentration are 25nmol/L2+, successively to mark
It is denoted as (the K for being added that 10 μ L concentration are 25nmol/L in 3~13 EP pipe+、Ca2+、Ag2+、Zn2+、Ni2+、Mn2+、Fe3+、Cu2+、
Al3+、Na+、Fe2+) interference metal ion；
(3) after reacting 10min, solution colour variation is observed respectively and detects its ultra-violet absorption spectrum, with the water of addition, mercury
Ion and interference metal ion are abscissa, A528nm/A725nmRatio be ordinate make histogram in rectangular coordinate system (such as
Shown in Fig. 3).
Dissimilar metals ion is added into PEI-Au nano-particle solution, as a result as shown in Figure 3.It can from figure
Out, only the addition of mercury ion can make solution colour blackening, and other metal ions will not be such that solution colour changes.Corresponding
Ultravioletvisible absorption curve it can also be seen that only mercury ion addition, can just make curve that apparent variation occur, in long wavelength
There is new peak in place.A528nm/A725nmRatio further illustrates that other metal ions are not to the histogram of dissimilar metals ion
The detection of mercury ion can be interfered, in this way to the detection of mercury ion have well selectivity.
Embodiment five
PEI-Au nano-particle solution detects Hg2+Analysis of the accuracy experiment, include the following steps：
(1) Hg of 50nM, 150nM, 250nM, 350nM, 450nM, 500nM concentration is prepared2+Solution, for use；
(2) Hg for each concentration for taking 20 μ L to prepare2+Solution is added to the PEI-Au solution of 100 μ L (embodiment one is made)
In, 25 DEG C, act on 10min；
(3) solution after above-mentioned effect is subjected to ultra-violet absorption spectrum detection, at the same measure solution in wavelength 528nm and
Light absorption value at 725nm, i.e. A528nmAnd A725nm, and calculate A528nm/A725nmRatio；
(4) Hg of detection is calculated according to standard curve prepared by embodiment two2+Solution concentration.
Table 2
As seen from Table 2, the standard error of sample detection meets the requirements all within 0.5%, PEI-Au nano-particle solution
Detect Hg2+Accuracy it is higher.
Comparative example one
A kind of preparation method of naked nano Au particle solution, includes the following steps：
By 24.3 μ L 100mM HAuCl4·3H2O is dissolved in 7.95mL water, is vigorously stirred lower dropwise addition 0.2mL 1%
NaBH4.After 10min, the color of solution becomes claret from peony, obtains naked nano Au particle solution.
Comparative example two
It is a kind of to detect Hg with naked nano Au particle solution2+Method concrete operations：
1, the preparation of standard curve
(1) Hg of 0nM, 24nM, 48nM, 97nM, 146nM, 195nM, 293nM, 488nM concentration is prepared2+Solution, for use；
(2) Hg for each concentration for taking 20 μ L to prepare2+Solution is added to the naked nano Au particle solution (comparative example one of 100 μ L
It is made) in, 25 DEG C of effect 10min；
(3) solution after above-mentioned effect is subjected to ultra-violet absorption spectrum detection, at the same measure solution in wavelength 528nm and
Light absorption value at 725nm, i.e. A528nmAnd A725nm, and calculate A528nm/A725nmRatio；
2, standard curve regression equation
Hg2+Concentration is within the scope of 0~500nmol/L：Y=3.6382-0.005x, R2=0.98.
Comparative example three
Naked nano Au particle solution detects Hg2+Analysis of the accuracy experiment, include the following steps：
(1) Hg of 50nM, 150nM, 250nM, 350nM, 450nM, 500nM concentration is prepared2+Solution, for use；
(2) Hg for each concentration for taking 20 μ L to prepare2+Solution is added to the naked nano Au particle solution (comparative example one of 100 μ L
It is made) in, 25 DEG C, act on 10min；
(3) solution after above-mentioned effect is subjected to ultra-violet absorption spectrum detection, at the same measure solution in wavelength 528nm and
Light absorption value at 725nm, i.e. A528nmAnd A725nm, and calculate A528nm/A725nmRatio；
(4) Hg of detection is calculated according to standard curve prepared by comparative example two2+Solution concentration.
Table 3
As seen from Table 3, for the standard error of naked nano Au particle test sample all 2% or more, the error of detection is obviously high
In PEI-Au nano-particle solution.Due to naked gold nanoparticle because surface does not have high molecular protection, though be not added mercury from
Son is also easy spontaneous reunion, so the result surveyed is much higher than actual content, discomfort application measurement Hg2+The concentration of solution.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of method for detecting mercury ion, which is characterized in that include the following steps：
Solution colour is shown after mercury ion and polyethyleneimine-gold nanoparticle effect and the feature of ultra-violet absorption spectrum becomes
Change, according to the proportional relation between the difference of solution colour or the variation and ion concentration of mercury of ultra-violet absorption spectrum to mercury ion into
Row detection.
2. the method for detection mercury ion described in accordance with the claim 1, which is characterized in that according to the variation of solution colour and mercury from
Proportional relation between sub- concentration carries out detection to mercury ion and includes the following steps：
The mercury ion solution of various concentration is added in polyethyleneimine-solution of gold nanoparticles, solution generates color after effect
On difference；When the concentration of mercury ion in test sample, the difference of contrast solution color determines the concentration range of mercury ion.
3. it is described in accordance with the claim 1 detection mercury ion method, which is characterized in that according to the variation of ultra-violet absorption spectrum with
Proportional relation between ion concentration of mercury carries out detection to mercury ion and includes the following steps：
The mercury ion solution of various concentration, the ultraviolet suction of solution after effect are added in polyethyleneimine-solution of gold nanoparticles
It receives spectrum to change, obtains absorbance A528nm/A725nmRatio and ion concentration of mercury linear relationship；When in test sample
When the concentration of mercury ion, the concentration that the linear relationship determines mercury ion is compareed.
4. the method for detection mercury ion described in accordance with the claim 3, which is characterized in that the concentration of the mercury ion solution is 0
~500nmol/L, detection are limited to 14~16nmol/L.
5. according to the method for detection mercury ion described in claim 2 or 3, which is characterized in that the polyethyleneimine-gold nano
The volume ratio of particle solution and the mercury ion solution is (2.5~7.5):1, preferably (3~7):1, further preferably (4
~6):1.
6. according to the method for the described in any item detection mercury ions of claim 1-4, which is characterized in that the polyethyleneimine-
Gold nanometer particle grain size is 4~15nm, preferably 5~13nm, further preferably 8~12nm.
7. according to the method for the described in any item detection mercury ions of claim 1-4, which is characterized in that mercury ion and polyethyleneimine
The condition of amine-gold nanoparticle effect includes：Temperature is 20~70 DEG C, preferably 20~50 DEG C, further preferably 20~30
℃；Time is 5~15min, preferably 7~13min, further preferably 8~11min.
8. according to the method for the described in any item detection mercury ions of claim 1-4, which is characterized in that the polyethyleneimine-
The preparation method of gold nanoparticle, includes the following steps：
By aq. polyethyleneimine and HAuCl4Reaction obtains polyethyleneimine-gold nanoparticle after solution mixing.
9. according to claim 8 detect mercury ion method, which is characterized in that the aq. polyethyleneimine it is dense
Degree is 0.3~1.2mol/L, the HAuCl4The concentration of solution is 0.05~0.15mol/L.
And/or the aq. polyethyleneimine and the HAuCl4The volume ratio of solution is (45~55):1.
10. detecting the method for mercury ion according to claim 8, which is characterized in that the polyethyleneimine-Jenner's grain of rice
Son preparation method in reaction condition include：Reaction temperature is 50~70 DEG C, preferably 55~65 DEG C；Reaction time be 40~
80min, preferably 50~70min.
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