CN103808717B - A kind of method using colorimetric determination mercury ion - Google Patents
A kind of method using colorimetric determination mercury ion Download PDFInfo
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- CN103808717B CN103808717B CN201410051728.7A CN201410051728A CN103808717B CN 103808717 B CN103808717 B CN 103808717B CN 201410051728 A CN201410051728 A CN 201410051728A CN 103808717 B CN103808717 B CN 103808717B
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- mercury ion
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Abstract
It is an object of the invention to provide a kind of method using colorimetric determination mercury ion, the method uses colorimetric determination mercury ion, and folic acid silver solution is after mixing 13 hours with mercury ion, produce fluorescent emission, having good sensitivity and selectivity, probe is highly sensitive, selectivity good, and detection limit is low.Need not large-scale instrument, by naked eye or test its spectrum, can recognition detection result.
Description
Technical field
The invention belongs to nanometer detection technical field, be specifically related to a kind of silver nano-grain and examine with fluorescent probe as colorimetric
The method surveying mercury ion.
Background technology
Along with economic fast development, a large amount of undressed waste water, waste residue are discharged in rivers and lake, cause water body
It is contaminated.Through checking its pollutant to be mainly heavy metal ion, for heavy metal ion (hydrargyrum Hg2+；Lead Pb2+；Cadmium Cd2+；Copper
Cu2+), particularly hydrargyrum, cadmium, lead, copper etc. have significant bio-toxicity.They can not be degraded by microorganisms in water body, can only
Various chemical form is occurred mutually to convert and migrate.Will retain, accumulate and migrate after entering environment or ecosystem, cause
Harm.Wherein, the high toxicity generally existed during hydrargyrum is environment, the harmful substance that human health is had extreme influence.From physiology
On say, the steam of mercury metal and organomercurial derivant (such as methyl mercury) are to the brain of the mankind and other relevant physical function very
Many-side all can produce injurious effects.Inorganic mercury can be become methyl mercury by the Bacterial Transformation in environment, and the hydrargyrum of this form is dirty
Dye can pass to or be gathered in more higher leveled organic-biological body by food chain.And the heart of inorganic mercury energy loss victimization class,
The organs such as kidney, stomach, intestinal.Water miscible dimercurion (Hg2+) be in various forms of mercury pollution material the most generally and the most stable
One, it is the major way of water environment and soil pollution.Therefore, the water miscible Hg in environment2+Detection and monitoring be
Necessary.Traditional method such as Inductively coupled plasma method is used for detecting mercury ion, it is common that high consume, can not portable,
Need complicated Instrumental Analysis.Therefore, it is achieved the detection in real time of the mercury ion in environmental area or organism and original position are quickly
Detection, and reach higher sensitivity and be of great significance and considerable application prospect.
In recent years, research worker is to develop simple and effective Hg2+Detection device is target, and a collection of have highly sensitive high selection
The device of property, is based on gold, silver nano-particle, fluorophor, DNA or DNA enzymatic, polymeric material and protein etc. respectively.?
In these devices, the detection elements of many devices is built upon based on breast present in the nucleotide chain comprising thymus pyrimidine (T)
Gland pyrimidine mismatch structure, the thymus pyrimidine utilizing mispairing can be with Hg2+Form stable structure and detect Hg2+[LiuCW,
HsiehYT,HuangCC,LinZH,ChangHT,Chem.Comm.2008,2242–4;WangH,WangYX,JinJY,
YangRH,Anal.Chem.2008,80,9021–9028;YeBC,YinBC,Angew.Chem.Int.Ed.2008,47,8386–
9;YuCJ,ChengTL,TsengWL,BiosensorsandBioelectronics,2009,25,204-210.].But, profit
It is much more expensive with nucleic acid or enzyme as detection elements, and is also complicated and time-consuming in the preparation process of device, profit
It is difficulty with commonly used by this technology.Further, the drinking water that Environmental Protection Agency USA (EPA) issues allows containing nothing
The high-load of machine mercury ion is 2ppb (10nM).This standard, less than the lowest detectable limit of many detection devices, is many inspections
Survey what device did not reached.Therefore, environment is monitored the device needing design operation the sensitiveest, convenient economic again.
Silver nanoparticle solution has vivid color, due to the character of the surface plasma body resonant vibration of silver nano-grain,
The size of silver nano-grain, intergranular distance and the change of scattered state can be detected by ultraviolet-visible spectrum, grand
See the color change showing solution, can arrive with naked eye, therefore, be preferably to detect device.In the present invention, Wo Menyan
Studied carefully a kind of silver nano-grain utilizing folic acid functionalization as colorimetric with fluorescent probe to the method detecting heavy metal ion.And
And the method is by simple disposable green syt route, possesses low cost and synthesize easy feature, it is possible to be quickly fixed
Amount detection mercury ion, has high sensitivity and selectivity.
Summary of the invention
It is an object of the invention to provide a kind of method using colorimetric determination mercury ion, it is characterised in that include following step
Rapid:
Step one, the synthesis of the nano-Ag particles (FA-AgNPs) of folic acid functionalization:
AgNO by the 2M of 30 μ L3Solution and 50mL tap water are mixed and heated to boiling, under conditions of magnetic agitation, add
The aqueous ascorbic acid of the 0.6% folic acid aqueous solution and 1mL0.1M that enter 2mL prepares mixed solution, the color of described mixed solution
From the colourless peony that becomes, after boiling 10min, it is cooled to room temperature, centrifugal 30min, supernatant discarded under conditions of 10000 turns
Liquid, again disperses in 2mL water by the centrifugal material obtained, i.e. obtains the nano-Ag particles (FA-AgNPs) of folic acid functionalization, institute
The FA-AgNPs concentration prepared is 40～60nM；
Step 2, detection adds the 0.1-0.5MNaCl solution of 50-100 μ L in the FA-AgNPs prepared by step one and mixes
Cooperation is detection probe, is mixed with obtained detection probe respectively by the mercury ion solution of variable concentrations, passes through ultraviolet-visible
Spectrum, the absworption peak of FA-AgNPs may occur in which blue-shifted phenomenon.
FA-AgNPs obtained in step one has an absworption peak at 414nm and 531nm respectively.
In step 2, the concentration of mercury ion solution is 1nM-50 μM.
Described detection probe in detecting Hg2+Can reach 1nM.
Present invention have the advantage that
1, the present invention provide colorimetric, fluorescent detection probe is highly sensitive, selectivity good, detection limit low.
2, need not large-scale instrument, by naked eye or test its spectrum, can recognition detection result.
3, the present invention easily prepares and preserves；8 can be preserved under the conditions of 4 DEG C～do not change for 15 months.
4, agents useful for same of the present invention and operating process all have no side effect.
5, the inventive method is simply, quickly, easily operate, and can carry out on-the-spot the most quickly detection.
Accompanying drawing explanation
Accompanying drawing 1 is 50 μMs of Hg of FA-AgNPs and addition2+The uv-visible absorption spectra of the FA-AgNPs of solution；
Fig. 2 is the transmission electron microscope photo of FA-AgNPs；
Fig. 3 is for adding 50 μMs of Hg2+The transmission electron microscope photo of the FA-AgNPs of solution；
Fig. 4 be FA AgNPs be the contribution ratios A of colorimetric detection probes531/414With Hg2+Concentration (0.001-1 μM) linear
Relation；
Detailed description of the invention
The silver nano-grain of folic acid functionalization, by the method for colorimetric with fluoroscopic examination, can detect that in aqueous sample and contains
Heavy metal ion Hg of some trace2+。
One, the synthesis of the nano-Ag particles (FA-AgNPs) of folic acid functionalization:
AgNO by the 2M of 30 μ L3Solution and 50mL water are mixed and heated to boiling, under conditions of magnetic agitation, add
The 0.6% folic acid aqueous solution (pH is between 11 12) of 2mL and the 0.1M aqueous ascorbic acid of 1mL, the color of mixed solution by
The colourless peony that becomes, after boiling 10min, is cooled to room temperature, centrifugal 30min, supernatant discarded under conditions of 10000 turns
Liquid, again disperses in 2mL water by the centrifugal material obtained, i.e. obtains the nano-Ag particles (FA-AgNPs) of folic acid functionalization.
Prepared FA-AgNPs is carried out ultraviolet-visible spectrum test, from accompanying drawing 1, FA-AgNPs be can be observed exist
Having an absworption peak at 414nm and 531nm respectively, the absworption peak at 414nm is the characteristic absorption of Ag nano-particle, and
It is owing to FA-AgNPs assembles the surface plasmon absorption peak forming chain and cause at 531nm.By its transmission electricity
Mirror TEM photo (accompanying drawing 2) is it can be seen that FA-AgNPs in chain.
Two, colorimetric determination mercury ion (Hg2+)
As the 50 μMs of Hg adding equivalent in FA-AgNPs2+After solution, test its ultraviolet-visible spectrum, can from figure
Going out, the absworption peak of FA-AgNPs occurs in that blue-shifted phenomenon, and the intensity of absworption peak substantially weakens, the change of its absworption peak be by
In adding Hg2+And cause, this is because the amino on silver nano-grain surface, carboxylic group and the Hg of folic acid functionalization2+It
Between define stable coordination structure, the existence of this structure causes the distance between silver nano-grain to there occurs change, Yin Na
Rice grain occurs in that obvious coherent condition.TEM photo Fig. 3 of sample further demonstrates the gathering of FA-AgNPs, defines
The stacking states of FA-AgNPs.Thus show that FA-AgNPs is to Hg2+There is certain response, these response can pass through ultraviolet-
Visible spectrum, naked eye, it was demonstrated that the method is to Hg2+Detection.
1, detection sensitivity
In order to improve the sensitivity of FA-AgNPs detection probe, add NaCl solution and change the ionic strength of solution.I
In FA-AgNPs add 50-100 μ L 0.1-0.5M NaCl solution as detection probe.Preparation variable concentrations (1nM-
50 μMs) mercury ion solution respectively with FA-AgNPs detection probe mix.Observe its color change and carry out ultraviolet-visible spectrum
Test.Along with Hg2+The increase of concentration, the color of mixed solution is gradually become light yellow by peony, as the Hg of 50 μMs2+Solution
After addition, the color of mixed solution is almost colourless transparent, and this is owing to introducing Hg2+Afterwards, FA-AgNPs particle aggregation is made to lead
The color caused changes.It is carried out ultraviolet-visible spectrum test, it is observed that along with Hg from spectrogram2+Concentration
Increasing, the absworption peak of FA-AgNPs engenders blue-shifted phenomenon, and the intensity of absworption peak the most gradually weakens.By naked eye and purple
Outer detection can show that FA-AgNPs is to Hg2+There is higher sensitivity.The Yin Na of folic acid functionalization can be drawn from accompanying drawing 4
Rice grain is as the contribution ratios A of colorimetric detection probes531/414With Hg2+Concentration has good linear relationship between 1nM 1 μM,
Therefore, the silver nano-grain of folic acid functionalization as colorimetric detection probes to Hg2+Detection limit can reach 1nM.
2, selectivity
Under the same terms, the Pb of preparation 50 μMs respectively2+,Cu2+,Mg2+,Zn2+,Ni2+,Co2+,Ca2+,Mn2+,Fe2+,Mg2+,
Cr3+,Cr6+,Cd2+And Ba2+As other solion, mix with FA-AgNPs detection probe respectively.Observe its color to change also
Carry out ultraviolet-visible spectrum test.Other ion still keeps red with the color of the mixed solution of FA-AgNPs, and adds Hg2+
The color of mixed solution become colorless by redness.Can be seen that FA-AgNPs is to Hg by the change of mixed solution color2+'s
Selectivity.Test the ultraviolet-visible spectrum of each reaction solution, it may be seen that Hg from spectrogram2+The absorption of mixed solution
Spectrum compares the absorption spectrum of other Ar ion mixing solution and occurs in that obvious blue-shifted phenomenon, and the intensity of absworption peak substantially drops
Low.This can prove out that FA-AgNPs is to Hg further2+There is preferable selectivity.
Through sensitivity and selective experimentation, it was demonstrated that the nano-Ag particles of folic acid functionalization can be examined with for colorimetric
Survey probe in detecting Hg2+, detection limit can reach 1nM.
Embodiment 1:
In order to improve the sensitivity of FA-AgNPs detection probe, add NaCl solution and change the ionic strength of solution.I
In the FA-AgNPs of 5mL, add the 0.1MNaCl solution of 75 μ L as detection probe.Preparation mercury ion concentration be 1nM,
10nM, 50nM, 100nM, 500nM, 1 μM, 2 μMs, 3 μMs, 4 μMs, 5 μMs, 10 μMs, 15 μMs, 20 μMs, 50 μMs of solution, respectively with equivalent
FA-AgNPs detection probe mixing.Observe its color change and carry out ultraviolet test.It will be seen that along with Hg from photo2+
The increase of concentration, the color of mixed solution is gradually become light yellow by peony, as the Hg of 50 μMs2+After solution adds, mix molten
The color of liquid is almost colourless transparent, and this is owing to introducing Hg2+Afterwards, the color making FA-AgNPs assemble and to cause changes.
It is carried out ultraviolet-visible spectrum test, it is observed that along with Hg from spectrogram2+The increase of concentration, the suction of FA-AgNPs
Receiving peak and engender blue-shifted phenomenon, the intensity of absworption peak the most gradually weakens.FA-can be drawn by naked eye and ultraviolet detection
AgNPs is to Hg2+There is higher sensitivity.
Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that
After having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, these
The equivalent form of value falls within the application appended claims limited range equally.
Claims (4)
1. the method using colorimetric determination mercury ion, it is characterised in that comprise the following steps:
Step one, the synthesis of the nano-Ag particles (FA-AgNPs) of folic acid functionalization:
AgNO by the 2M of 30 μ L3Solution and 50mL tap water are mixed and heated to boiling, under conditions of magnetic agitation, add 2mL
The 0.1M aqueous ascorbic acid that mass percent concentration is 0.6% folic acid aqueous solution and 1mL prepare mixed solution, described mixed
The color of conjunction solution, from the colourless peony that becomes, after boiling 10min, is cooled to room temperature, centrifugal under conditions of 10000 turns
30min, abandoning supernatant, again disperse, in 2mL water, i.e. to obtain the nano-Ag particles of folic acid functionalization by the centrifugal material obtained
(FA-AgNPs), obtained FA-AgNPs concentration is 40～60nM；
Step 2, detection:
The 0.1-0.5M NaCl solution mixing adding 50-100 μ L in the FA-AgNPs prepared by step one is visited as detection
Pin, mixes the mercury ion solution of variable concentrations with obtained detection probe, respectively by ultraviolet-visible spectrum, FA-
The absworption peak of AgNPs may occur in which blue-shifted phenomenon.
A kind of method using colorimetric determination mercury ion the most as claimed in claim 1, it is characterised in that described folic acid is water-soluble
The pH of liquid is between 11 12.
A kind of method using colorimetric determination mercury ion the most as claimed in claim 1, it is characterised in that made in step one
The FA-AgNPs obtained has an absworption peak at 414nm and 531nm respectively.
A kind of method using colorimetric determination mercury ion the most as claimed in claim 1, it is characterised in that described detection probe
Detection Hg2+Can reach 1nM.
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| CN109030473A (en) * | 2018-06-13 | 2018-12-18 | 盐城工学院 | Utilize the method for Nano silver grain detection mercury ion |
| CN113960021A (en) * | 2020-07-03 | 2022-01-21 | 吉林化工学院 | Test paper for rapidly detecting mercury ions by nano silver particles based on green synthesis |
| CN115414274A (en) * | 2022-09-29 | 2022-12-02 | 宁波博雅格致健康科技有限公司 | Application of She Suanyin ionic material in preparation of scalp care composition, scalp care composition and preparation method |
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