CN105784612B - The method for detecting mercury ion by assembling gold nanorods - Google Patents
The method for detecting mercury ion by assembling gold nanorods Download PDFInfo
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- CN105784612B CN105784612B CN201610127658.8A CN201610127658A CN105784612B CN 105784612 B CN105784612 B CN 105784612B CN 201610127658 A CN201610127658 A CN 201610127658A CN 105784612 B CN105784612 B CN 105784612B
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 67
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 79
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 238000006722 reduction reaction Methods 0.000 claims abstract description 21
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 15
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 15
- 239000007853 buffer solution Substances 0.000 claims abstract description 14
- 238000002835 absorbance Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 4
- 229940024606 amino acid Drugs 0.000 claims description 17
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004472 Lysine Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- 229960000310 isoleucine Drugs 0.000 claims description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 2
- 229930182817 methionine Natural products 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000011896 sensitive detection Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 description 22
- 235000001014 amino acid Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- -1 caddy Chemical compound 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
-
- 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
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
Abstract
The invention discloses a kind of methods for detecting mercury ion by assembling gold nanorods, this method comprises: more parts of isometric mercury ion solution 1) are separately added into formation multiple groups mixed solution in more parts of identical gold nanorods aqueous solutions；2) ascorbic acid solution and PBS buffer solution are added separately in the multiple groups mixed solution to carry out reduction reaction；3) amino acid solution is added to the assembling for carrying out gold nanorods into the solution after the reduction reaction, and UV absorbance detection is carried out to the solution after the assembling, wherein A1, A2 are respectively two absorption peaks of ultra-violet absorption spectrum；4) using the solubility of mercury ion solution as abscissa, working curve is drawn by ordinate of the value of A2/A1.The method achieve to the highly sensitive detection of mercury ion and excellent selectivity.
Description
Technical field
The present invention relates to the detection methods of mercury ion, and in particular, to the side of mercury ion is detected by assembling gold nanorods
Method.
Background technique
Mercury ion is a kind of heavy metal ion being distributed widely in biosystem and environment, due to it to nervous system and
The toxicity of kidney realizes that its fast high-sensitive Clinical significance of detecting is great.
Currently, the detection method of mercury ion has atomic emission spectrometry, atomic absorption spectrography (AAS), mass spectrography, these methods
Although high sensitivity, selectivity is good, and instrument price is expensive, takes time and effort.It is at present it has been reported that many for detecting mercury
The colorimetric sensing method of ion concentration, and such detection method has the concentration progress using the aggregation of gold nanoparticle to mercury ion
Detection realized by the principle of aggregation, also have the assembling that gold nanorods are modulated by the ionic strength for controlling solution realize mercury from
Son detection, and both methods is vulnerable to the interference of other metal ions, anti-interference ability is weak.It would therefore be desirable to a kind of
It is at low cost, easy to operate, rapid and handy, the method for the detection mercury ion of strong antijamming capability.
Summary of the invention
The object of the present invention is to provide a kind of methods for detecting mercury ion by assembling gold nanorods, and the method achieve right
The highly sensitive detection of mercury ion and excellent selectivity.
To achieve the goals above, the present invention provides the present invention provides one kind by assembling gold nanorods detect mercury from
The method of son, comprising:
1) more parts of isometric mercury ion solution are separately added into more parts of identical gold nanorods aqueous solutions and form multiple groups
Mixed solution；
2) ascorbic acid solution and PBS buffer solution are added separately in multiple groups mixed solution to carry out reduction reaction；
3) amino acid solution is added in the solution to reduction reaction to the assembling for carrying out gold nanorods, and to described group
Solution after dress carries out UV absorbance detection, and wherein A1, A2 are respectively two absorption peaks of ultra-violet absorption spectrum；
4) using the solubility of mercury ion solution as abscissa, working curve is drawn by ordinate of the value of A2/A1.
Through the above technical solutions, testing principle of the invention leads to as shown in Figure 1, firstly, in the presence of buffer solution
It crosses weak reductant (ascorbic acid) and mercury ion is reduced into mercury atom in the head both ends of gold nanorods formation gold amalgam, then lead to
It crosses amino acid and two adjacent gold nanorods assembles to (wherein, the attachment point at amino acid both ends is the mercury on gold nanorods
Atom), the gold nanorods after assembling for the gold nanorods individually restored with ascorbic acid, amplify (such as by output signal
Shown in Fig. 7, Hg2+Concentration is consistent, and signal changes obvious after assembling), the induction sensitivity to mercury ion is improved, and then realize
Highly sensitive detection to mercury ion.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the principle of detection method provided by the invention；
Fig. 2 is the UV absorption figure for detecting gold nanorods aqueous solution in example 2；
Fig. 3 is the scanning electron microscope (SEM) photograph for detecting gold nanorods aqueous solution in example 1；
Fig. 4 is the partial size statistical chart for detecting gold nanorods aqueous solution in example 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of gold nanorods in the system detected in example 1 after reduction reaction；
Fig. 6 is the partial size statistical chart of gold nanorods in the system detected in example 1 after reduction reaction；
Fig. 7 is the UV absorption figure for detecting the system in example 2 after reduction reaction；
Fig. 8 is the UV absorption figure of gold nanorods in the system detected after assembling in example 2；
Fig. 9 is the scanning electron microscope (SEM) photograph of gold nanorods in the system detected after assembling in example 1；
Figure 10 is the UV absorption statistical chart for detecting the mercury ion solution of various concentration in example 2；
Figure 11 is to detect the working curve diagram that mercury ion is detected in example 2；
Figure 12 is the result statistical chart for detecting Interference Detection in example 3.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods for detecting mercury ion by assembling gold nanorods, comprising:
1) more parts of isometric mercury ion solution are separately added into more parts of identical gold nanorods aqueous solutions and form multiple groups
Mixed solution；
2) ascorbic acid solution and PBS buffer solution are added separately in multiple groups mixed solution to carry out reduction reaction；
3) amino acid solution is added in the solution to reduction reaction to the assembling for carrying out gold nanorods, and to described group
Solution after dress carries out UV absorbance detection, and wherein A1, A2 are respectively two absorption peaks of ultra-violet absorption spectrum；
4) using the solubility of mercury ion solution as abscissa, working curve is drawn by ordinate of the value of A2/A1.
In step 1) of the invention, gold nanorods concentration of aqueous solution can select in a wide range, but in order into
One step improves the sensitivity to mercury ion detecting, it is preferable that gold nanorods concentration of aqueous solution is 6-8pmol/L.
In step 1) of the invention, the partial size of gold nanorods can select in a wide range in gold nanorods aqueous solution
It selects, but in order to further increase the sensitivity to mercury ion detecting, it is preferable that the grain of gold nanorods in gold nanorods aqueous solution
Diameter is 30-80nm, preferably 40-60nm.
In step 1) of the invention, mercury ion solution usage can select in a wide range, but in order to further
Improve the sensitivity to mercury ion detecting, it is preferable that in step 1), relative to the gold nanorods aqueous solution of 2ml, mercury ion is molten
Liquid dosage is 150-250 μ L.
In step 2) of the invention, the concentration and dosage of ascorbic acid solution and PBS buffer solution can be in wide models
Interior selection is enclosed, but in order to further increase the sensitivity to mercury ion detecting, it is preferable that in step 2), ascorbic acid is molten
The concentration of liquid is 0.05-0.15mmol/L, and the concentration of PBS buffer solution is 1.5-2.5mmol/L；Also, the gold relative to 2ml
Nanometer rods aqueous solution, the dosage of ascorbic acid solution are that the dosage of 25-35 μ L, PBS buffer solution is 150-250 μ L.
In addition, in the present invention, the order of addition of ascorbic acid solution and PBS buffer solution can become under conditions of width
Change, but in order to further increase the sensitivity to mercury ion detecting, it is preferable that in step 2), it is molten first to add ascorbic acid
Then liquid adds PBS buffer solution again.
In step 2) of the invention, the condition of reduction reaction can select in a wide range, but in order to further
Improve the sensitivity to mercury ion detecting, it is preferable that reduction reaction at least meets the following conditions: reaction time 5-15min, instead
Answering temperature is 15-35 DEG C.
In step 3) of the invention, the concentration and dosage of amino acid solution can select in a wide range, but be
Further increase the sensitivity to mercury ion detecting, it is preferable that in step 3), the concentration of amino acid solution is 8-
10mmol/L；Also, relative to the gold nanorods aqueous solution of 2ml, the dosage of amino acid solution is 150-250 μ L.
In step 3) of the invention, the time of assembling can select in a wide range, but in order to further increase
Sensitivity to mercury ion detecting, it is preferable that the time of assembling is 25-35min.
In step 3) of the invention, the specific type of amino acid solution can select in a wide range, but in order to
Further increase the sensitivity to mercury ion detecting, it is preferable that amino acid solution is selected from lysine solution, tryptophan solution, benzene
One of alanine solution, methionine solution, Threonine solution, isoleucine solution, leucine solution and valine solution
Or a variety of, more preferable lysine solution.
On the basis of the above, the A2 and A1 of the mercury ion solution of unknown concentration can be detected according to the above method,
Then the specific concentration of the mercury ion solution of unknown concentration is found out according to working curve, but in order to improve the accurate of result
Property, it is preferable that the corresponding equation of working curve are as follows: y=0.115+1.38 × 10-4X, wherein x is the solubility of mercury ion solution, y
For A2/A1；Also, the corresponding absorbing wavelength of A1 is 738mm, and the corresponding absorbing wavelength of A2 is 1030mm.
The present invention will be described in detail by way of examples below.
Preparation example 1
According to " [1] Nikoobakht, B.；El-Sayed,M.A.Preparation and Growth Mechanism
of Gold Nanorods(NRs)Using Seed-Mediated Growth Method[J],Chem.Mater.,2003,
15,1957–1962.[2]Xia,Y.；Song,L.；Zhu,C.Turn-On and Near-Infrared Fluorescent
Sensing for 2,4,6-Trinitrotoluene Based on Hybrid(Gold Nanorod)-(Quantum
Dots)Assembly[J],Anal.Chem.,2011,83,1401–1407.[3]Song,L.；Wang,S.；Kotov,N.A.；
Xia,Y.Nonexclusive Fluorescent Sensing forL/DEnantiomers Enabled by Dynamic
Nanoparticle-Nanorod Assemblies [J], Anal.Chem., 2012,84,7330-7335. " the method system recorded
Standby gold nanorods, specific as follows:
Seed solution is prepared first: weighing 0.3645g cetyl trimethylammonium bromide in 50mL conical flask, is added
The dissolution of 10mL secondary water, the 0.01mol/L gold chloride for adding 250 μ L shake uniformly, are eventually adding the 600 prior ice water of μ L and now prepare
Sodium borohydride, Quick shaking is uniform, after 2min, places it in 30 DEG C of thermostat water baths and is incubated for 2 hours.
It followed by prepares growth-promoting media: weighing 5.4675g cetyl trimethylammonium bromide in 250mL volumetric flask, be added
After the dissolution of 150mL secondary water, the 0.01mol/L gold chloride of 7.5mL is added, the 0.01mol/L nitric acid of 1.2mL is added after shaking uniformly
The 1mol/L hydrochloric acid of 3mL is added in silver after shaking uniformly, the 0.1mol/L ascorbic acid of 1.2mL is added after shaking uniformly.Mixing is shaken
After homoepitaxial liquid, takes 210 μ L seed liquors to be rapidly injected wherein and shake up to be placed on 12 hours in 30 DEG C of thermostat water baths and obtain
Gold nanorods solution.
Purifying gold nanorods: take the above-mentioned synthetic gold nanorods solution of 10mL in centrifuge with the speed of 8000 turns/min
Rate is centrifuged 10min, is carefully taken out supernatant liquor with liquid-transfering gun, lower sediment is diluted to 10mL with secondary water, in repetition
The centrifugally operated stated will be put into refrigerator stand-by after the secondary water dispersion of lower sediment.Its concentration is according to langbobier law meter
It calculates.
Embodiment 1
1) by the mercury ion solution of 200 μ L various concentrations (respectively 7.6pmol/L, 76pmol/L, 3.8nmol/L,
38nmol/L, 76nmol/L, 0.76 μm of ol/L, 1.9 μm of ol/L, 3.8 μm of ol/L, 7.6 μm of ol/L) 2mL gold nanorods are added
In (6.9pmol/L) aqueous solution；
2) 30 μ L ascorbic acid (0.114mmol/L) are then sequentially added, the PBS (2mmol/L) of 200 μ L restore instead
It answers, after reacting 10min；UV absorbance detection is carried out to system after reaction；
3) 200 μ L lysine solutions (8.9mmol/L) are added, 30min is placed and is assembled, to system after assembling
Carry out UV absorbance detection, wherein the corresponding absorbing wavelength of two absorption peaks is respectively 738nm and 1030nm, the suction at 738nm
Receipts value is A738, the absorption value at 1030nm is A1030；
4) using the solubility of mercury ion solution as abscissa, with A1030/A738Value be ordinate draw working curve (result
See Figure 10 and Figure 11).
The detection example that the embodiments of each step are seen below in the above method.
Detect example 1
By scanning electron microscope (SEM, Hitachi S-4800) to the body after gold nanorods aqueous solution, reduction reaction
System after system and assembling is scanned Electronic Speculum detection, wherein Fig. 3 is the scanning electron microscope (SEM) photograph of gold nanorods aqueous solution, and Fig. 4 is
The partial size statistical chart of gold nanorods aqueous solution, Fig. 5 are the scanning electron microscope (SEM) photographs of gold nanorods in system after reduction reaction, and Fig. 6 is
The partial size statistical chart of gold nanorods in system after reduction reaction, Fig. 9 be assembling after system in gold nanorods scanning electron microscope
Figure.As seen from the figure, the gold nanoparticle before assembling individually exists, and partial size is between 30-80nm, predominantly 50-60nm；And
After amino acid is added, the gold nanorods after system are successfully assembled into chain between any two.
Detect example 2
Through ultraviolet-visible spectrophotometer (U-3010, Hitachi), after gold nanorods aqueous solution, reduction reaction
System after system and assembling carries out UV absorbance detection, and Fig. 2 is the UV absorption figure of gold nanorods aqueous solution, and Fig. 7 is also
Original reaction after system UV absorption figure, Fig. 8 be assembling after system in gold nanorods UV absorption figure；Figure 10 is different
Mercury ion solution (respectively 7.6pmol/L, 76pmol/L, 3.8nmol/L, 38nmol/L, 76nmol/L, 0.76 μ of concentration
Mol/L, 1.9 μm of ol/L, 3.8 μm of ol/L, 7.6 μm of ol/L) UV absorption statistical chart, Figure 11 be detect mercury ion work it is bent
(working curve equation is y=0.115+1.38 × 10 to line chart-4x).By upper figure it is found that the work that method provided by the invention obtains
Curve has excellent linear, has excellent sensitivity, the mercury ion solution of either 7.6pmol/L simultaneously for mercury ion
Or 7.6 μm of ol/L mercury ion solution can be detected accurately.
Detect example 3
By 7.6 μm of ol/L chaff interferents of 200 μ L (respectively plumbi nitras, titanium sulfate, iron chloride, barium chloride, frerrous chloride,
Nickel chloride, aluminium chloride, copper sulphate, caddy, silver nitrate and gold chloride and above-mentioned mixture) 2mL gold nanorods are added
In (6.9pmol/L) aqueous solution；Then the PBS (2mmol/L) of 30 μ L ascorbic acid (0.114mmol/L), 200 μ L are sequentially added
Reduction reaction is carried out, after reacting 10min；200 μ L lysine solutions (8.9mmol/L) are added, 30min is placed and is assembled,
UV absorbance detection is carried out to system after assembling, wherein the absorption value at 738nm is A738, the absorption value at 1030nm is
A1030, with above-mentioned system with A1030/A738Value counted, concrete outcome is shown in Figure 12, and the figure is it is found that inspection provided by the invention
Survey method can resist plumbi nitras, titanium sulfate, iron chloride, barium chloride, frerrous chloride, nickel chloride, aluminium chloride, copper sulphate, caddy,
The interference of silver nitrate and gold chloride further relates to this method for the selective enumeration method of mercury ion.
Embodiment 2
The procedure of Example 1 was followed except that the gold nanorods concentration of aqueous solution in step 1) is 6pmol/
L.It is learnt by detecting accordingly, which also to mercury ion can detect selectively, with sensitivity.
Embodiment 3
The procedure of Example 1 was followed except that the gold nanorods concentration of aqueous solution in step 1) is 8pmol/
L.It is learnt by detecting accordingly, which also to mercury ion can detect selectively, with sensitivity.
Embodiment 4
The procedure of Example 1 was followed except that the dosage of ascorbic acid solution is 25 μ L in step 2),
The dosage of the PBS buffer solution is 150 μ L.It is learnt by detecting accordingly, which can also select mercury ion
Selecting property, detect with sensitivity.
Embodiment 5
The procedure of Example 1 was followed except that the dosage of ascorbic acid solution is 35 μ L in step 2),
The dosage of the PBS buffer solution is 250 μ L.It is learnt by detecting accordingly, which can also select mercury ion
Selecting property, detect with sensitivity.
Embodiment 6
The procedure of Example 1 was followed except that the time of reduction reaction is 5min in step 2).Pass through
Corresponding detection learns that the embodiment also to mercury ion can detect selectively, with sensitivity.
Embodiment 7
The procedure of Example 1 was followed except that the time of reduction reaction is 15min in step 2).It is logical
It crosses corresponding detection to learn, which also to mercury ion can detect selectively, with sensitivity.
Embodiment 8
The procedure of Example 1 was followed except that the time of assembling is 25min in step 3).Pass through phase
The detection answered learns that the embodiment also to mercury ion can detect selectively, with sensitivity.
Embodiment 9
The procedure of Example 1 was followed except that the time of assembling is 35min in step 3).Pass through phase
The detection answered learns that the embodiment also to mercury ion can detect selectively, with sensitivity.
Embodiment 10
The procedure of Example 1 was followed except that the dosage of amino acid solution is 150 μ L in step 3).
It is learnt by detecting accordingly, which also to mercury ion can detect selectively, with sensitivity.
Embodiment 11
The procedure of Example 1 was followed except that the dosage of amino acid solution is 250 μ L in step 3).
It is learnt by detecting accordingly, which also to mercury ion can detect selectively, with sensitivity.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (7)
1. a kind of method for detecting mercury ion by assembling gold nanorods characterized by comprising
1) more parts of isometric mercury ion solution are separately added into more parts of identical gold nanorods aqueous solutions and form multiple groups mixing
Solution；
2) ascorbic acid solution and PBS buffer solution are successively added into the multiple groups mixed solution to carry out reduction reaction；
3) amino acid solution is added to the assembling that gold nanorods are carried out into the solution after the reduction reaction, and to described group
Solution after dress carries out UV absorbance detection, and wherein A1, A2 are respectively two absorption peaks of ultra-violet absorption spectrum；
4) using the solubility of mercury ion solution as abscissa, working curve is drawn by ordinate of the value of A2/A1；
Wherein, in step 1), the gold nanorods concentration of aqueous solution is 6-8pmol/L；In step 1), the gold nanorods
The partial size of gold nanorods is 30-80nm in aqueous solution；In step 1), relative to the gold nanorods aqueous solution of 2ml, the mercury from
Sub- solution usage is 150-250 μ L；In step 2), the concentration of the ascorbic acid solution is 0.05-0.15mmol/L, described
The concentration of PBS buffer solution is 1.5-2.5mmol/L；Also, relative to the gold nanorods aqueous solution of 2ml, the ascorbic acid
The dosage of solution is 25-35 μ L, and the dosage of the PBS buffer solution is 150-250 μ L；In step 3), the amino acid is molten
The concentration of liquid is 8-10mmol/L；Also, relative to the gold nanorods aqueous solution of 2ml, the dosage of the amino acid solution is
150-250μL。
2. the method for detection mercury ion according to claim 1, which is characterized in that Jenner in the gold nanorods aqueous solution
The partial size of rice stick is 40-60nm.
3. the method for detection mercury ion according to claim 1, which is characterized in that the reduction reaction at least meets following
Condition: reaction time 5-15min, reaction temperature are 15-35 DEG C.
4. the method for detection mercury ion according to claim 1, which is characterized in that the time of the assembling is 25-
35min。
5. the method for detection mercury ion according to claim 1, which is characterized in that the amino acid solution is selected from lysine
Solution, tryptophan solution, Phe solution, methionine solution, Threonine solution, isoleucine solution, leucine solution and
One of valine solution is a variety of.
6. the method for detection mercury ion according to claim 5, which is characterized in that the amino acid solution is that lysine is molten
Liquid.
7. the method for mercury ion is detected described in any one of -6 according to claim 1, which is characterized in that the working curve
Corresponding equation are as follows: y=0.115+1.38 × 10-4X, wherein x is the solubility of mercury ion solution, y A2/A1；Also, A1 pairs
The absorbing wavelength answered is 738mm, and the corresponding absorbing wavelength of A2 is 1030mm.
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