CN107153059A - A kind of preparation method of nanogold colorimetric sensor and its application in dimercurion detection - Google Patents
A kind of preparation method of nanogold colorimetric sensor and its application in dimercurion detection Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of nanogold colorimetric sensor and its colorimetric detection dimercurion（Hg2+）Application, it is therefore intended that solving existing ICP, AAS, AFS etc. is used for the problem of method of mercury ion detecting has the defects such as strict sample storage condition, analysis method cost height, analysis time length, operation be strongly professional mostly.The present invention originates by golden nanometer particle of gold salt, using lysine sodium salt simultaneously as reducing agent and part, is reacted under conditions of the boiling of gold salt solution, obtains stabilization, the nanogold colorimetric sensor of water miscible lysine sodium salt modification.Sensor of the invention has the series of advantages such as be easy to carry, sensitivity is high, selectivity is strong, stability is good, can realize to Hg2+Quick detection, have the advantages that detection speed is fast, sensitivity is high, have broad application prospects and higher market application value.
Description
Technical field
The present invention relates to environmental science, examine chemistry and analytical chemistry field, specially a kind of nanogold colorimetric sensor
Preparation method and its dimercurion detection in application, be further a kind of preparation method of nanogold colorimetric sensor
And its application of colorimetric detection dimercurion.The present invention provides a kind of rapid sensitive for dimercurion, visualization and examined
Sensor and its application of analysis are surveyed, it has preferable effect.
Background technology
Mercury is the environmental poisonous substance for seriously endangering health, and its ion includes monovalence mercury ion, two kinds of shapes of dimercurion
Formula, it exists in nature in the form of mercury metal, inorganic mercury and organic mercury.Mercury metal often pollutes big as a vapor
Gas, can enter human body by respiratory tract.Meanwhile, mercury metal is soluble in lipid, is operated and is distributed easily by biomembrane,
Also brain tissue is entered easily by blood-brain barrier.Mercury metal is after brain tissue is oxidized to dimercurion, fat-soluble reduction, water
Dissolubility strengthens, it is difficult to reverse by blood-brain barrier, returns to blood flow, so as to be put aside in brain tissue, forms detrimental effect.In addition,
Mercury ion enters after blood, and whole body can be distributed rapidly, and transhipment therewith is gathered in liver and kidney, and through kidney by urine ejection body
Outside.If taking in a large amount of inorganic mercury salts in a short time, or eat mercurous material by mistake, acute mercury poisoning can be caused.
At present, conventional mercury ion detecting analytical instrument mainly includes：Be electrically coupled plasma emission spectrometer (ICP),
Atomic absorption (AAS) and atomic fluorescence absorb (AFS) etc..But foregoing detection method exist mostly sample storage condition it is strict, point
The shortcomings of analysis method cost height, analysis time length, strongly professional operation.
Therefore, Fast Detection Technique simple to operate, easy to carry, with low cost is developed very necessary.
The content of the invention
The goal of the invention of the present invention is：Deposited mostly for the method for being used for mercury ion detecting such as existing ICP, AAS, AFS
Sample storage condition is strict, the defect such as analysis method cost height, analysis time length, operation be strongly professional the problem of there is provided one
Plant the preparation method of nanogold colorimetric sensor and its application in dimercurion detection.The present invention is using gold salt as gold nano
Particle source, using lysine sodium salt simultaneously as reducing agent and part, is reacted under conditions of the boiling of gold salt solution, is obtained
The nanogold colorimetric sensor of stable, water miscible lysine sodium salt modification.The preparation method of the present invention is simple to operate, the time
It is short, it is easy to prepare.Meanwhile, sensor of the invention have be easy to carry, sensitivity is high, selectivity is strong, stability is good etc. one is
Row advantage, can be realized to Hg2+Quick detection, have broad application prospects and higher market application value, be worth big
Scale promotion and application.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of nanogold colorimetric sensor, comprises the following steps：Gold salt solution is heated to after boiling, then
Add Sodium lysinate salting liquid thereto under agitation, be heated to reflux after 4~8h, stop heating, continue to stir to solution cooling
To room temperature, claret solution is obtained, the nanogold colorimetric sensor of lysine sodium salt modification is produced.By the lysine sodium salt of preparation
The nanogold colorimetric sensor lucifuge of modification, normal temperature are preserved, standby.
The mol ratio of the gold salt GOLD FROM PLATING SOLUTION salt and lysine sodium salt is 1:2~8.
The gold salt is chlorauride, aurous chloride, gold chloride, three hydration gold chlorides, four hydration gold chlorides, two hydration chlorine gold
One or more in sour potassium, two hydration sodium chloraurates.
The nanogold colorimetric sensor of lysine sodium salt modification prepared by aforementioned preparation process.
The UV, visible light maximum absorption band of the sensor is 510~550nm, and particle diameter is 10~100nm.
Application of the sensor as aforementioned in dimercurion detection.
Comprise the following steps：The nanogold ratio modified with test solution volume identical lysine sodium salt is added into test solution
Colour sensor solution, then buffer solution is added thereto, regulation solution ph is stood to 7~9 after shaking up, and observation solution colour becomes
Change；
If solution colour is changed into containing Hg in bluish violet, test solution from red2+, and Hg solution2+Concentration is more than or waited
In 0.4 μM；If solution colour changes, but is not changed into bluish violet from red, then Hg in test solution2+Concentration is less than 0.4 μM；
If solution colour does not change, there is no Hg in test solution2+, or Hg solution2+Concentration is not up to Visual retrieval limit.
Preferably, time of repose is 1~30min.
Comprise the following steps：
(1) configure a without Hg2+The aqueous solution, be used as blank control liquid；A testing sample solution is taken, as tested
Liquid；
(2) the nanogold colorimetric that the modification of identical lysine sodium salt is accumulated with blank control liquid is added into blank control liquid
Sensor solution, then buffer solution is added thereto, regulation solution ph to 7~9 forms the first mixed liquor；Add into test solution
Enter the nanogold colorimetric sensor solution modified with test solution volume identical lysine sodium salt, then add buffer solution thereto,
Solution ph is adjusted to 7~9, the second mixed liquor is formed；
(3) using the first mixed liquor as reference, the color of the second mixed liquor is observed, if the color of the second mixed liquor is with respect to first
The color of mixed liquor changes, then there is Hg in test solution2+If, the colors of two mixed liquors with respect to the first mixed liquor color not
Change, then Hg is not present in test solution2+；
Or in the step (3), using the first mixed liquor as reference, the second mixed liquor of contrast and the ultraviolet of the first mixed liquor can
See absorption intensity, peak value, if the second blended liquid phase changes to the ultravioletvisible absorption intensity of the first mixed liquor, peak value,
There is Hg in test solution2+If the second blended liquid phase does not change to the ultravioletvisible absorption intensity of the first mixed liquor, peak value,
Hg is then not present in test solution2+。
The buffer solution includes borate buffer solution, citrate buffer, phosphate buffer, potassium dihydrogen phosphate-hydrogen
Sodium oxide molybdena buffer solution, barbital sodium-hydrochloride buffer, tris-HCI buffer, Glycine-NaOH,
One or more in sodium carbonate-bicarbonate buffer solution.
Dimercurion is quantitatively detected using following steps：
(a) one group of mercuric salt aqueous solution with same concentrations difference is configured；
(b) the nanogold colorimetric sensor solution for taking lysine sodium salt to modify, be separately added into it is isometric, the two of various concentrations
In the valency mercury salt aqueous solution, and buffer solution regulation pH value is added thereto to 7~9, stand 1min-30min after being well mixed, respectively
Ultraviolet-visible absorption spectroscopy is determined, with lg (A1/A0) it is ordinate, Hg2+Concentration is abscissa, draws standard curve；
(c) ultraviolet-visible absorption spectroscopy of testing sample solution is determined, is determined by standard curve in testing sample solution
Hg2+Content.
The mercuric salt includes the one or more in mercuric nitrate, mercury bichloride, mercuric sulfate, mercuric bromide, mercury cyanide.
In order to realize above-mentioned technical purpose, inventor have developed one kind in long-term theory and process of experimental
Nanogold colorimetric sensor, specially a kind of nanogold colorimetric sensor of lysine sodium salt modification.
Sensor of the invention is prepared using hydro-thermal method, gold salt solution first is heated into boiling, then add under magnetic stirring
Enter Sodium lysinate salting liquid, be heated to reflux after 4~8h, stop heating, continue to be stirred to solution being cooled to room temperature, obtain claret
The nanogold colorimetric sensor of solution, i.e. lysine sodium salt modification is (referred to as：Lys-AuNPs), lucifuge normal temperature is saved backup.Its
In, the mol ratio of gold salt GOLD FROM PLATING SOLUTION salt and lysine sodium salt is 1:2~8.After measured, the lysine sodium salt prepared by the present invention
The nanogold colorimetric sensor UV, visible light maximum absorption band of modification is 510~550nm, 10~100nm of particle diameter.Wherein, gold salt
Gold salt in solution is selected from chlorauride, aurous chloride, gold chloride, three hydration gold chlorides, four hydration gold chlorides, two hydration gold chlorides
Potassium, two hydration sodium chloraurates.
Sensor of the invention is originated by golden nanometer particle of gold salt, using lysine sodium salt simultaneously as reducing agent with matching somebody with somebody
Body, is reacted, the water miscible nanogold colorimetric sensor stablized under conditions of the boiling of gold salt solution.Nanogold ratio
Color detection theoretical foundation be utilize its SPR performance, the characteristic plasma absworption peak of nanogold particle at 510-550nm,
With the increase or the reduction of interparticle distance of particle size, red shift occurs for the position of absworption peak.Nanogold is macroscopically being presented as
Solution has vivid red, and when gold nano grain gathers certain degree, obvious change will occur for the color of solution,
Bluish violet is changed into from original red.And the present invention exactly utilizes the specific binding of metal ion and decorated by nano-gold group,
Cause the aggregation or depolymerization of nanogold and occur the change of color to reach the purpose of detection.
The nanogold colorimetric sensor for taking the above method to prepare, the testing sample of same volume is added thereto, after shaking up
Add buffer solution and adjust its pH (pH scope：7~9), stand (preferred time range：1min~30min), observe the face of mixed liquor
The change of the ultraviolet-visible absorption spectroscopy of color change or detection mixed liquor, can be to Hg2+Qualitative and quantitative analysis is carried out, test limit can
Up to 0.05 μM (0.01PPM).
Compared with conventional method, preparation method of the invention has the advantages that simple and easy to apply, reproducible；In course of reaction
In, lysine sodium salt is simultaneously as reducing agent and part, stable golden nanometer particle while gold salt is reduced, the product of gained without
It need to be further purified, can be directly used for next step operation.
Sensor prepared by the present invention is to Hg2+Detection speed it is fast, sensitivity is high, works as Hg2+In the presence of, gold nano grain
It can reunite rapidly, solution colour is also changed into bluish violet from claret, and the characteristic absorption peak generation of its uv-vis spectra is bright
Aobvious red shift.Meanwhile, test result indicates that：Sensor of the invention is to Hg2+Selectivity it is strong；There are a variety of different metal ions
Solution in, lysine sodium salt modification nanogold can select recognize Hg2+, cause nanogold to be reunited so that solution colour is rapid
Change.Therefore, nanogold colorimetric sensor of the invention can be realized to Hg2+Rapid, accurate detection.
Further, the present invention proposes the nanogold colorimetric sensor based on the modification of lysine sodium salt to Hg2+Detection side
Method.The present invention recognizes Hg in aqueous using the nanogold colorimetric sensor2+Speed is fast, to Hg2+Selectivity is strong, nanometer
Particle diameter becomes big after gold is reunited, and its surface plasmon absorption changes, so that nano-Au solution color is ultraviolet with it
The characteristic that visible absorbance intensity, peak value change, color change is directly observed by naked eyes or UV, visible light light splitting is utilized
Photometer tests the change of its absorption intensity and peak value, you can realize to Hg in the aqueous solution2+Quick detection.
Testing sample is detected using sensor of the invention, if testing sample solution color is changed into royal purple from red
Color, then contain Hg in testing sample solution2+, and Hg solution2+Concentration is more than or equal to 0.4 μM；If solution colour becomes
Change, but bluish violet is not changed into from red, illustrate Hg in testing sample solution2+Concentration is less than 0.4 μM；If solution colour does not become
Change, illustrate there is no Hg in testing sample solution2+, or Hg in testing sample solution2++Concentration is not up to Visual retrieval limit.
Further, adopt and carry out qualitative detection with the following method.
(1) preparation method of the nanogold colorimetric sensor of the lysine sodium salt modification provided according to the present invention, is prepared into
The nano-Au solution modified to lysine sodium salt.
(2) configure a without Hg2+The aqueous solution, be used as blank control liquid；Take the testing sample of a same volume molten
Liquid, is used as test solution.
(3) two parts and liquor capacity identical detection sample in (2) are measured in nano-Au solution made from step (1)；
First part of detection sample is mixed with the blank control liquid phase of configuration in (2) of same volume, buffer solution is added, by mixed solution
PH is adjusted to neutral or alkalescent (pH scopes：7~9), stood after shaking up (preferably, time range：1min-30min), formed
First mixed liquor；The test solution of configuration in (2) of second part of detection sample and same volume is mixed, buffer solution, shape is added
Into the second mixed liquor.
(4) using the first mixed liquor as reference, color of the second blended liquid phase of observation for the first mixed liquor；If the second mixing
There is color change in liquid, then be detected in the aqueous solution and there is Hg2+；If in the absence of color change, being detected in the aqueous solution and not depositing
In Hg2+。
Or, ultravioletvisible absorption intensity, the peak value of the second mixed liquor of contrast and the first mixed liquor；If the second blended liquid phase
Ultravioletvisible absorption intensity, peak value for the first mixed liquor change, then are detected in the aqueous solution and there is Hg2+；If no
Change, be then detected in the aqueous solution and Hg is not present2+, so as to realize to Hg2+Qualitative analysis.
Further, the present invention provides the method that quantitative measurment is carried out to dimercurion, i.e., in quantitative analysis, sets up mark
Directrix curve is quantitatively detected that its operating procedure is as follows.
1) aqueous solution for configuring the mercuric salt of one group of suitable concentration difference (configures the mercuric salt of one group of various concentrations
The aqueous solution)；2) nano-Au solution for taking the lysine sodium salt of certain volume to modify, is separately added into isometric, various concentrations
The aqueous solution of mercuric salt, and pH of mixed is adjusted to neutral or alkalescent (pH scopes by addition buffer solution into mixed liquor：7~
9) (preferred time range is stood after, being well mixed：1min-30min), the ultravioletvisible absorption light of mixed solution is determined respectively
Spectrum, with lg (A1/A0) it is ordinate, Hg2+Concentration is abscissa, standard curve is drawn, for Hg2+Quantitative detection.
Nanogold colorimetric sensor provided in an embodiment of the present invention is the water-soluble nano gold solution of lysine sodium salt modification,
Shown in the synthetic line of its preparation technology flow such as following formula (1)：
Test bivalent mercury detection
The nanogold colorimetric sensor and certain density mercuric salt that the lysine sodium salt of above-mentioned preparation is modified are water-soluble
Liquid phase is mixed, and change of the corresponding uv-vis spectra in 1min~30min is detected using ultraviolet-visual spectrometer (Uv-Vis)
Change.Test result indicates that, the ultraviolet and visible absorption peak of nano-Au solution of the invention is substantially reduced in a short time, observes feature
The ratio between the corresponding absorption value of absorbing wavelength (A1/A0) change with time, it can be seen that the Nano-Au probe of lysine sodium salt modification
Hg can be detected rapidly2+。
Test two selectivity tests
The nanogold colorimetric sensor that the lysine sodium salt of above-mentioned preparation is modified is used for finite concentration Hg2+Detection.Take
The certain density mercuric salt aqueous solution, then measure same volume, finite concentration successively (concentration can be with Hg2+It is identical, can also
More than Hg2+Concentration) (the Fe containing other metal ions3+,Fe2+,K+,Cu2+,Mn2+,Cd2+,Co2+,Ni2+,Pb2+,Zn2+,Mg2+,Ca2 +, Al3+,Cr3+,Cr2O7 2-) concentration the aqueous solution.Respectively will be with being modified containing above-mentioned metal ion volume identical lysine sodium salt
Nanogold colorimetric sensor with being mixed containing the solution of above-mentioned metal ion, and add during mixed solution pH is adjusted to by buffer solution
Property or alkalescent (pH scopes：7~9), observe its color change.Test result indicates that, only containing Hg2+Nano-Au solution by red
Discoloration is blueness.
Meanwhile, characterized using ultraviolet-visual spectrometer (Uv-Vis) in the nano-Au solution detection that the lysine sodium salt is modified
The uv-vis spectra of metal ion is stated, discovery only contains Hg2+The ultraviolet-visible absorption spectroscopy of nano-Au solution there occurs
Obvious red shift.Make the ratio between each corresponding ultraviolet and visible absorption peak value of metal ion of detection (A1/A0), as a result show：Detection one
Determine the Hg of concentration2+Nano-Au solution ultraviolet-visible absorption spectroscopy and the ratio between absorption value (A1/A0) differ markedly from and make blank
The ratio between the ultraviolet-visible absorption spectroscopy and absorption value of the pure nano-Au solution of reference (A1/A0)；Detection is containing other certain density gold
Belong to the ratio between the ultraviolet-visible absorption spectroscopy and absorption value of the nano-Au solution of ion (A1/A0), the relative pure nanometer for making blank reference
The ratio between the ultraviolet-visible absorption spectroscopy and absorption value of gold solution (A1/A0), change is little.
It is above-mentioned test result indicates that, the present invention prepare lysine sodium salt modification nanogold colorimetric sensor detection Hg2+
With good selectivity.
Test three standard curve determinations
One group of same volume, the mercuric salt aqueous solution with concentration gradient are configured, respectively with the above-mentioned system of same volume
The nano-Au solution mixing of standby lysine sodium salt modification, and add buffer solution pH of mixed is adjusted to neutral or alkalescent (pH
Scope：7~9), while characterizing the different Hg of above-mentioned detection using ultraviolet-visual spectrometer (Uv-Vis)2+The nanogold of concentration is molten
The uv-vis spectra of liquid.Test result indicates that：With Hg2+The increase of concentration, lysine sodium salt modification nanogold it is ultraviolet
The red shift degree of visible spectrum gradually increases.Make Hg2+The ultravioletvisible absorption for the nanogold that concentration is modified with lysine sodium salt
Logarithm value lg (the A of the ratio between peak value1/A0) between relation.Quantitative determination Hg is drawn according to the relation of measure2+The standard of content is bent
Line, and obtain corresponding calculation formula.
Compared to traditional detection means, the present invention does not need large-scale instrument and complicated operating process, with quick, spirit
The series of advantages such as quick, easy to operate.Meanwhile, nanogold colorimetric sensor sensitivity prepared by the present invention is high, selective strong, steady
It is qualitative good, and there is the series of advantages such as detection speed is fast, cheap, be easy to carry, and the limitation (GB that can be up to state standards
7916-1987).The present invention is in fields such as environmental science, inspection chemistry and analytical chemistry, with higher application value and extensively
Wealthy application prospect.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1) present invention has synthesized the water-soluble nano gold solution modified with lysine sodium salt with simple experiment flow, can
Strong operability, common laboratory is had ready conditions completion, with higher application value；
2) present invention being capable of very sensitive, quick, optionally micro Hg in the detection aqueous solution2+, with very strong reality
The property used；
3) present invention detection Hg2+Sensitivity it is high, 0.05 μM (0.01PPM) can be reached, with the excellent of high sensitivity
Point；
4) present invention can be realized to Hg2+Qualitative and quantitative detection, with preferable application prospect；
5) the features such as present invention has that detection speed is fast, selectivity is good, with low cost, is easy to carry, practicality is very strong, energy
It is enough in environmental science, the fields such as chemistry and analytical chemistry is examined, with important application value.
Brief description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein：
Fig. 1 is the ultraviolet-visible spectrogram of the nanogold of lysine sodium salt modification of the present invention.
Fig. 2 is that the nanogold of lysine sodium salt modification of the present invention is adding Hg2+When its ultravioletvisible absorption intensity, peak value with
The variation diagram of time.
Fig. 3 be lysine sodium salt of the present invention modification nanogold 650nm locate and 521nm at ultravioletvisible absorption intensity
Ratio (A650/A521) change with time figure.
Fig. 4 be pictorial diagram of the nanogold of lysine sodium salt of the present invention modification when adding different metal ions with its
With the ratio (A of ultravioletvisible absorption intensity at 521nm at 650nm650/A521)。
Fig. 5 is uv-vis spectra of the nanogold of lysine sodium salt modification of the present invention when adding different metal ions
Figure.
Fig. 6 is that the nanogold of lysine sodium salt modification of the present invention is adding the Hg of various concentrations2+When uv-vis spectra
Figure.
Fig. 7 is that the nanogold of lysine sodium salt modification of the present invention is adding Hg2+When, Hg2+Concentration and lg (A650/A521) it
Between relation and quantitative measurement standard curve map.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent by other or with similar purpose
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
Embodiment 1
The water of 0.24mM tetra- is added into 250mL conical flasks (brand-new chloroazotic acid soaked overnight, ultra-pure water is cleaned, dried, standby)
Gold chloride 100mL is closed, is heated under boiling, magnetic agitation adding 0.034M Sodium lysinate salting liquid 4mL, is heated to reflux 5h, it is molten
Liquid is changed into claret from faint yellow, stops heating, continues stirring until room temperature, and lucifuge normal temperature is preserved.
Determine the ultraviolet-visible absorption spectroscopy of the nano-Au solution of lysine sodium salt modification manufactured in the present embodiment, such as Fig. 1
It is shown.From figure 1 it appears that occurring characteristic absorption peak at 521nm.
Embodiment 2
The nanogold colorimetric sensor that the lysine sodium salt of above-mentioned preparation is modified is 1 × 10 with isometric concentration-6M's
The mercury bichloride aqueous solution is mixed, using ultraviolet-visual spectrometer (Uv-Vis) detect corresponding uv-vis spectra 1~
Change in 10min, experimental result is as shown in Figure 2.From figure 2 it can be seen that the ultraviolet and visible absorption peak of this nano-Au solution
Start substantially reduction in 1min.
Observe the ratio between the corresponding absorption value of characteristic absorption wavelength (A650/A521) change with time, as shown in Figure 3.From Fig. 3
In as can be seen that 3min after numerical value it is basicly stable, therefore lysine sodium salt modification Nano-Au probe can detect Hg rapidly2+。
Embodiment 3
The nanogold colorimetric sensor of lysine sodium salt modification prepared by embodiment 1 is used for 1 × 10-6M Hg2+Inspection
Survey, it is 1 × 10 to take 1.5mL concentration-6The M mercury bichloride aqueous solution, then measure successively 1.5mL contain other metal ions
(FeCl3, FeCl2,KCl,CuCl2,MnCl2,CdCl2,CoCl2,NiCl2,Pb(NO3)2,ZnCl2,MgCl2,CaCl2,AlCl3,
CrCl3,Cr2O7 2-) concentration be 2 × 10-5The M aqueous solution, the nanogold for respectively modifying above-mentioned lysine sodium salt is with containing above-mentioned gold
The solution of category ion is mixed, and adds 0.2M disodium hydrogen phosphates-μ L of phosphate sodium dihydrogen buffer solution (pH=7) 100, observes its face
Color change, experimental result is as shown in Figure 4.As a result find：It was found that only containing Hg2+Nano-Au solution from red be changed into blueness.
Meanwhile, determine the nanogold of lysine sodium salt modification and inhaled with the UV, visible light of the mixed solution containing above-mentioned metal ion
Spectrum is received, as shown in Figure 5.Test result indicates that, only containing Hg2+Mixed solution ultraviolet-visible absorption spectroscopy occur substantially it is red
Move.Make the ratio between each corresponding ultraviolet and visible absorption peak value of metal ion of detection (A650/A521), as a result show：Detection is certain dense
The Hg of degree2+Nano-Au solution ultraviolet-visible absorption spectroscopy and the ratio between absorption value (A650/A521) differ markedly from and make blank ginseng
The ratio between the ultraviolet-visible absorption spectroscopy and absorption value of the pure nano-Au solution of ratio (A650/A521)；Detection containing it is certain density other
The ratio between the ultraviolet-visible absorption spectroscopy and absorption value of the nano-Au solution of metal ion (A650/A521), it is relative to make blank reference
The ratio between the ultraviolet-visible absorption spectroscopy and absorption value of pure nano-Au solution (A650/A521), change is little.
Embodiment 4
The nanogold colorimetric sensor that the lysine sodium salt prepared according to embodiment 1 is modified, draws standard curve, tool
Body step is as follows.
Configure the mercury bichloride of various concentrations ultra-pure water solution (concentration is respectively 0.1 μM, 0.2 μM, 0.3 μM, 0.4 μM,
0.5 μM, 0.6 μM, 0.7 μM, 0.8 μM, 0.9 μM, 1 μM), the nano-Au solution for taking 1.5mL lysines sodium salt to modify is separately added into
The aqueous solution of the mercury bichloride of 1.5mL various concentrations, and addition 0.2M sodium dihydrogen phosphate-disodium hydrogen phosphate delays into mixed liquor
The μ L of fliud flushing (pH=7) 100,1min is stood after being well mixed, and the ultraviolet-visible absorption spectroscopy of mixed solution, such as Fig. 6 are determined respectively
It is shown.
With lg (A650/A521) it is ordinate, Hg2+Concentration is abscissa, draws standard curve, as shown in Figure 7.From Fig. 7
As can be seen that it is at 0.05 μM -0.3 μM, (nano-Au solution is mixed with mercury ion solution one to one, is surveyed ion concentration of mercury and is become
For initial concentration two/mono-) in the range of meet linear relationship, fit linear relationship is Y=-0.75813+2.98149X, line
Property coefficient R2For 0.99089, available for Hg2+Quantitative detection.
Embodiment 5
Weigh constant volume after 2g brand toners, plus ultra-pure water dissolving and in 25mL volumetric flasks, be used as prepare liquid 1.Weigh
The above-mentioned brand toners of 2g, add mercury bichloride, and constant volume is configured to contain Hg containing the above-mentioned toners of 2g in 25mL volumetric flasks2+It is dense
The mixed solution for 0.3 μM is spent, (Hg in former toner can be extrapolated as prepare liquid 22+Concentration is 0.75ppm).Weigh on 2g
Brand toner is stated, mercury bichloride is added, constant volume is configured to contain Hg containing the above-mentioned toners of 2g in 25mL volumetric flasks2+Concentration is 1
μM mixed solution, (Hg in former toner can be extrapolated as prepare liquid 32+Concentration is 2.5ppm).
Embodiment 6
The nano-Au solution for taking the lysine sodium salt of the above-mentioned preparations of 1.5mL to modify, adds treating for the preparation of 1.5mL embodiments 5
Liquid 3 is surveyed, 100 μ L concentration of addition are 0.2M disodium hydrogen phosphates-phosphate sodium dihydrogen buffer solution (pH=7), are stood after uniform mixing
1min, the color of mixed solution is changed into bluish violet from red, then contains Hg in testing sample solution2+Concentration be more than or equal to
0.2 μM, the ultraviolet-visible absorption spectroscopy of mixed solution is determined, lg (A are obtained650/A528)=0.10729, beyond linear relationship model
Enclose；Therefore, it can sxemiquantitative obtains Hg in testing sample solution2+Concentration be more than 0.4 μM, and extrapolate in former toner
Hg2+Concentration is more than 1ppm (actual is 2.5ppm).
Embodiment 7
The nano-Au solution for taking the lysine sodium salt of the above-mentioned preparations of 1.5mL to modify, adds what is prepared in 1.5mL embodiments 5
(the known Hg of prepare liquid 22+Concentration is 0.3 μM, and concentration is changed into original 1/2nd after being mixed with nano-Au solution one to one, i.e.,
0.15 μM), 100 μ L concentration 0.2M sodium dihydrogen phosphates-disodium hydrogen phosphate buffer solution (pH=7) is added, is stood after uniform mixing
1min, observes the color change of solution.Solution colour changes, but is not changed into bluish violet from red, then contains in prepare liquid
Some Hg2+Concentration is less than 0.4 μM.
Using calibration curve method to Hg in sample2+Concentration carries out quantitative analysis, according to the standard curve of the gained of embodiment 4
(Fig. 7), adds various concentrations Hg2+Lysine sodium salt modification nano-Au solution lg (A650/A521) value and Hg2+Concentration it
Between linear relationship be Y=-0.75813+2.98149X, linearly dependent coefficient R2For 0.99089, according to calibration curve equation and
Lg (the A of mixed solution650/A521) value can calculate Hg in sample2+Concentration.
The ultraviolet-visible absorption spectroscopy of mixed solution is determined, lg (A are obtained650/A521)=- 0.29252.Substituted into implementation
The standard curve of gained in example 4：Y=-0.75813+2.98149X, wherein Y are lg (A650/A521), X is Hg in mixed liquor2+It is dense
Spend (unit μM), solve X=0.156166883, i.e., obtain Hg in mixed liquor by calculating2+Concentration is 0.156 μM, then treats test sample
Hg in product2+2X=0.312 μM of concentration, and extrapolate Hg in former toner2+Concentration is 0.78ppm, close to Hg in toner to be measured2 +Actual concentrations (0.75ppm)).
Embodiment 8
The nano-Au solution for taking the Sodium lysinate of the above-mentioned preparations of 1.5mL to modify, adds the to be measured of the preparation of 1.5mL embodiments 5
Liquid 1, adds 100 μ L concentration 0.2M sodium dihydrogen phosphates-disodium hydrogen phosphate buffer solution (pH=7), stands 1min after uniform mixing, see
Examine the color change of solution.Solution colour is not changed, then Hg is free of in prepare liquid 12+Or Hg in prepare liquid 12+Concentration is less than
Visual retrieval is limited.
It is above-mentioned test result indicates that：The nanogold colorimetric sensor detection Hg of lysine sodium salt modification prepared by the present invention2+
With very strong sensitivity, and it can quickly reach the purpose of quantitative detection.When detecting actual cosmetic water sample, it can examine
Measure Hg2+Concentration is 0.75ppm (or lower) sample, national standard limitation 1pmm of its detection limit less than Mercury In Cosmetics
(GB 7916-1987)。
The invention is not limited in foregoing embodiment.The present invention, which is expanded to, any in this manual to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (10)
1. a kind of preparation method of nanogold colorimetric sensor, it is characterised in that comprise the following steps：Gold salt solution is heated to
After boiling, then add Sodium lysinate salting liquid thereto under agitation, be heated to reflux after 4 ~ 8h, stop heating, continue to stir extremely
Solution is cooled to room temperature, obtains claret solution, produces the nanogold colorimetric sensor of lysine sodium salt modification.
2. the preparation method of nanogold colorimetric sensor according to claim 1, it is characterised in that the gold salt GOLD FROM PLATING SOLUTION
The mol ratio of salt and lysine sodium salt is 1:2~8.
3. the preparation method of nanogold colorimetric sensor according to claim 1 or claim 2, it is characterised in that the gold salt is chlorine
Change gold, aurous chloride, gold chloride, three hydration gold chlorides, four hydration gold chlorides, two hydration potassium chloroaurates, two hydration sodium chloraurates
In one or more.
4. according to the preparation method of any one of the claim 1-3 nanogold colorimetric sensors, it is characterised in that the sensor
UV, visible light maximum absorption band be 510~550nm, particle diameter be 10~100nm.
5. application of the sensor prepared according to any one of claim 1-4 methods described in dimercurion detection.
6. application according to claim 5, it is characterised in that comprise the following steps：Added and test solution into test solution
The nanogold colorimetric sensor solution of volume identical lysine sodium salt modification, then buffer solution is added thereto, adjust pH value of solution
Value is stood to 7 ~ 9 after shaking up, observation solution colour change；
If solution colour is changed into containing Hg in bluish violet, test solution from red2+, and Hg solution2+Concentration is more than or equal to 0.4
μM；If solution colour changes, but is not changed into bluish violet from red, then Hg in test solution2+Concentration is less than 0.4 μM；If molten
Liquid color does not change, then does not have Hg in test solution2+, or Hg solution2+Concentration is not up to Visual retrieval limit.
7. application according to claim 5, it is characterised in that comprise the following steps：
（1）Configuration is a to be free of Hg2+The aqueous solution, be used as blank control liquid；A testing sample solution is taken, test solution is used as；
（2）The nanogold colorimetric sensing that the modification of identical lysine sodium salt is accumulated with blank control liquid is added into blank control liquid
Device solution, then buffer solution is added thereto, regulation solution ph to 7 ~ 9 forms the first mixed liquor；Added and quilt into test solution
The nanogold colorimetric sensor solution of liquid product identical lysine sodium salt modification is surveyed, then adds buffer solution thereto, is adjusted molten
Liquid pH value forms the second mixed liquor to 7 ~ 9；
（3）Using the first mixed liquor as reference, the color of the second mixed liquor is observed, if the color of the second mixed liquor is with respect to the first mixing
The color of liquid changes, then there is Hg in test solution2+If the color of two mixed liquors does not occur with respect to the color of the first mixed liquor
Change, then be not present Hg in test solution2+；
Or the step（3）In, using the first mixed liquor as reference, the UV, visible light of the second mixed liquor of contrast and the first mixed liquor is inhaled
Intensity, peak value are received, if the second blended liquid phase changes to the ultravioletvisible absorption intensity of the first mixed liquor, peak value, is tested
There is Hg in liquid2+If the second blended liquid phase does not change to the ultravioletvisible absorption intensity of the first mixed liquor, peak value, by
Survey and Hg is not present in liquid2+。
8. the application according to claim 6 or 7, it is characterised in that the buffer solution includes borate buffer solution, citric acid
Salt buffer, phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution, barbital sodium-hydrochloride buffer, trihydroxy methyl
One or more in aminomethane-hydrochloride buffer, Glycine-NaOH, sodium carbonate-bicarbonate buffer solution.
9. application according to claim 5, it is characterised in that quantitatively examined to dimercurion using following steps
Survey：
（a）Configure one group of mercuric salt aqueous solution with same concentrations difference；
（b）The nanogold colorimetric sensor solution for taking lysine sodium salt to modify, is separately added into the isometric, bivalent mercury of various concentrations
In saline solution, and buffer solution regulation pH value is added thereto to 7~9, stand 1min-30min after being well mixed, determine respectively
Ultraviolet-visible absorption spectroscopy, with lg（A1/A0）For ordinate, Hg2+Concentration is abscissa, draws standard curve；
（c）The ultraviolet-visible absorption spectroscopy of testing sample solution is determined, Hg in testing sample solution is determined by standard curve2+'s
Content.
10. application according to claim 9, it is characterised in that the mercuric salt includes mercuric nitrate, mercury bichloride, sulphur
Change the one or more in mercury, mercuric bromide, mercury cyanide.
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| CN112198152A (en) * | 2020-10-09 | 2021-01-08 | 深圳技术大学 | Rapid detection of Cr3+And Al3+Ligand-nanogold probe and preparation method and application thereof |
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| CN112198152A (en) * | 2020-10-09 | 2021-01-08 | 深圳技术大学 | Rapid detection of Cr3+And Al3+Ligand-nanogold probe and preparation method and application thereof |
| CN114486781A (en) * | 2022-02-10 | 2022-05-13 | 青海大学 | Method for high-sensitivity detection of mercury ions by novel Au/C nano composite sensor |
| CN115178746A (en) * | 2022-07-13 | 2022-10-14 | 宁波大学 | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water |
| CN115178746B (en) * | 2022-07-13 | 2024-03-01 | 宁波大学 | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water |
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