CN106680232A - Reagent composition and reagent solution for detecting Hg<2+> in aqueous solution, preparation method of reagent solution and detection method - Google Patents
Reagent composition and reagent solution for detecting Hg<2+> in aqueous solution, preparation method of reagent solution and detection method Download PDFInfo
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- CN106680232A CN106680232A CN201710168634.1A CN201710168634A CN106680232A CN 106680232 A CN106680232 A CN 106680232A CN 201710168634 A CN201710168634 A CN 201710168634A CN 106680232 A CN106680232 A CN 106680232A
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- 239000000243 solution Substances 0.000 title claims abstract description 166
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 148
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 71
- 238000001514 detection method Methods 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000004885 piperazines Chemical class 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 94
- 239000006228 supernatant Substances 0.000 claims description 50
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 claims description 48
- 230000004048 modification Effects 0.000 claims description 44
- 238000012986 modification Methods 0.000 claims description 44
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 40
- 239000010931 gold Substances 0.000 claims description 40
- 229910052737 gold Inorganic materials 0.000 claims description 40
- 238000000862 absorption spectrum Methods 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract 1
- GIZQLVPDAOBAFN-UHFFFAOYSA-N HEPPSO Chemical compound OCCN1CCN(CC(O)CS(O)(=O)=O)CC1 GIZQLVPDAOBAFN-UHFFFAOYSA-N 0.000 description 30
- 238000006555 catalytic reaction Methods 0.000 description 27
- 238000010521 absorption reaction Methods 0.000 description 22
- 230000009102 absorption Effects 0.000 description 21
- 230000009467 reduction Effects 0.000 description 20
- 229910021645 metal ion Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 229910000497 Amalgam Inorganic materials 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 208000011580 syndromic disease Diseases 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 piperazine Piperazine ethyl sulfonic acid Chemical compound 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses reagent composition for detecting Hg<2+> in an aqueous solution. The reagent composition comprises AuNPs (nanoparticles) and a piperazine derivative. The invention further discloses a preparation method of a mixed reagent solution for detecting Hg<2+> in the aqueous solution. The preparation method comprises the following steps: the preferred piperazine derivative is dissolved in water, the piperazine derivative aqueous solution is obtained, and pH of the solution is regulated to 7.0-8.5; a pre-prepared AuNP aqueous solution is added to the piperazine derivative aqueous solution, the mixed solution is stirred, and the mixed reagent solution for detecting Hg<2+> in the aqueous solution is obtained. Compared with the prior art, a detection method is simple to operate and high in recognition sensitivity and selectivity and can be used for detecting Hg<2+> in the aqueous solution.
Description
Technical field
The present invention relates to field of chemical detection, specifically provide a kind of for detecting Hg in the aqueous solution2+Reagent composition,
Reagent solution and preparation method thereof and detection method.
Background technology
Mercury, as one of most typical toxic heavy metal, due to its accumulation and toxicity in the environment, is recognized extensively
To be most dangerous environmental contaminants and toxicity element very high.In the water environment of inorganic nature, the most common presence of mercury
Form is Hg2+.Long-term intake Hg containing high concentration2+Drinking water, the central nervous system of the mankind and other organic organizations can be produced
The serious permanent lesion of life.In view of the bioaccumulation of Hg, non-biodegradable and its global circulation are to human health
Threaten, design new, sensitive Hg2+Detection instrument may finally help prevent and reduce Hg2+Harm.
In the detection technique based on golden nanometer particle, prior art has been disclosed for various detecting Hg in aqueous2+
Method, such as based on golden nanometer particle (AuNPs) colorimetric method (chemical communication, Chem.Commun., 2007,12,1215~
1217) and with 6808) other technologies combination (analytical chemistry, Anal.Chem., 2008,80, the 6805~method such as.Existing skill
Art is to modify in AuNPs surfaces metal ion recognition ligand from Cleaning Principle, all, by the use of recognizing molecule as metal ion
Receive molecule to realize its testing goal.Therefore, the sensitivity of above-mentioned detection method and selectivity depend on these gold
Belong to the property of ion identification molecule, and AuNPs only serves booster action in detection process.Therefore, this allows for above-mentioned side
Method haves the shortcomings that some general character, and such as sensitivity is low and poor selectivity, also makes it upper for example glimmering with other optical means in application
Light method is compared with chemoluminescence method, is lacked competitiveness.
Therefore, how to improve golden nanometer particle and detect Hg in aqueous2+Detection sensitivity and selectivity, as people
Problem demanding prompt solution.
The content of the invention
In consideration of it, it is an object of the invention to provide one kind for detecting Hg in the aqueous solution2+Reagent composition, reagent it is molten
Liquid and preparation method thereof and detection method, at least to solve to detect Hg based on golden nanometer particle system in the past2+Exist sensitivity it is low,
The problems such as poor selectivity.
First, the invention provides one kind for detecting Hg in the aqueous solution2+Reagent composition, the reagent composition bag
Include：Golden nanometer particle and bridged piperazine derivatives.
It is preferred that, the golden nanometer particle is 1 with the mol ratio of the bridged piperazine derivatives：(5×104~1 × 109)。
Further preferably, the particle diameter of the golden nanometer particle is 1~100nm.
Further preferably, the golden nanometer particle is golden nanometer particle or the Jenner of carbonate modification of citrate modification
Rice corpuscles.
Further preferably, the bridged piperazine derivatives are the bridged piperazine derivatives containing end position hydroxyl.
Further preferably, the bridged piperazine derivatives are 4- HEPESs or 3- (hydroxyethyl piperazine) -2- hydroxyls
Propane sulfonic acid.
Further preferably, the golden nanometer particle of the citrate modification is prepared from accordance with the following methods：
The presoma of gold, sodium citrate and water Hybrid Heating are carried out into hydro-thermal reaction, the Jenner of citrate modification is obtained
Rice corpuscles.
Further preferably, the golden nanometer particle of the carbonate modification is prepared from accordance with the following methods：
The presoma of gold, potassium carbonate, sodium borohydride are mixed with water, is reacted, obtain the golden nanometer particle of carbonate modification.
Secondly, present invention also offers one kind for detecting Hg in the aqueous solution2+Reagent solution, the reagent solution is by upper
State any one reagent composition and water composition.
Again, it is above-mentioned for detecting Hg in the aqueous solution present invention also offers one kind2+Reagent solution preparation method, should
Preparation method comprises the following steps：
1) golden nanometer particle is added to the water, obtains the aqueous solution of golden nanometer particle；
2) bridged piperazine derivatives are added to the water, obtain the aqueous solution of bridged piperazine derivatives；
3) by step 1) described in golden nanometer particle the aqueous solution and step 2) described in the aqueous solution of bridged piperazine derivatives mix
Close, obtain Hg in the detection aqueous solution2+Reagent solution.
It is preferred that, step 1) described in golden nanometer particle the aqueous solution in golden nanometer particle concentration be 0.1~20nmol/l.
Further preferably, step 2) described in bridged piperazine derivatives the aqueous solution in bridged piperazine derivatives concentration for 5~
100mmol/l, and the pH value of water solution of the bridged piperazine derivatives is 7.0~8.5.
Further preferably, step 3) described in the aqueous solution of golden nanometer particle mix with the aqueous solution of the bridged piperazine derivatives
Time is 0.5~5min, 5~40 DEG C of mixing temperature.
Finally, present invention also offers Hg in one kind detection aqueous solution2+Method, the detection method is specially：
1) aqueous solution to be detected is mixed with above-mentioned any one reagent composition or above-mentioned any one reagent solution
Uniformly, mixed solution is obtained；
2) by step 1) in mixed solution centrifugation, discard precipitation, obtain centrifuged supernatant；
3) absorption spectrum of the centrifuged supernatant is determined, testing result is obtained according to the absorption spectrum.
Provided by the present invention for Hg in the detection aqueous solution2+Reagent composition, reagent solution and preparation method thereof and inspection
Survey method, is using golden nanometer particle (AuNPs) intrinsic superficial catalytic activation, bridged piperazine derivatives from the angle of nanometer
The property that reproducibility and gold amalgam are specifically merged, to realize testing and analyzing the purpose of thing, different from the past utilization recognizes molecule
Property, and then greatly improve sensitivity and the selectivity of detection.
The reagent composition and reagent solution provided using the present invention carry out Hg in the aqueous solution2+Detection when, without right
Sample is pre-processed, and simple to operate, identification sensitivity is high, while reagent composition and reagent solution composition that the present invention is provided
Prepare simply, it is relatively stable, can preserve for a long time at ambient temperature, using convenient.
Brief description of the drawings
Fig. 1 is the golden nanometer particle UV-visible absorption spectrum in aqueous of citrate modification；
Fig. 2 is the transmission electron microscope picture of the golden nanometer particle of citrate modification；
Fig. 3 is the golden nanometer particle UV-visible absorption spectrum in aqueous of carbonate modification；
Fig. 4 is that 3- (hydroxyethyl piperazine) -2- hydroxy-propanesulfonic acids (HEPPSO) is mixed with the golden nanometer particle of citrate modification
Close the UV-visible absorption spectrum of solution；
Fig. 5 is the UV-visible absorption spectrum of HEPPSO and the golden nanometer particle mixed solution of carbonate modification；
Fig. 6 is the purple of 4- HEPESs (HEPES) and the golden nanometer particle mixed solution of citrate modification
Outward-visible absorption spectra figure；
Fig. 7 is the UV-visible absorption spectrum of the catalysate that the HEPPSO aqueous solution and gold catalysis HEPPSO are obtained；
Fig. 8 is the catalysate sample photo figure that HEPPSO samples and gold catalysis HEPPSO are obtained；
Fig. 9 is the liquid chromatogram of the catalysate that gold catalysis HEPPSO is obtained；
Figure 10 is the electrospray ionization mass spectrum figure of the catalysate that gold catalysis HEPPSO is obtained；
Figure 11 is the carbon-13 nmr spectra figure of the catalysate that gold catalysis HEPPSO is obtained；
Figure 12 is to add Hg in the reagent solution that HEPPSO mixes with AuNPs2+The ultraviolet-visible of centrifuged supernatant is inhaled afterwards
Receive spectrogram；
Figure 13 is the reagent solution mixed with AuNPs in HEPPSO to Hg2+The concentration range curve map of detection；
Figure 14 is to add Hg in the reagent solution that HEPES mixes with AuNPs2+The ultraviolet-visible of centrifuged supernatant is inhaled afterwards
Receive spectrogram；
Figure 15 is to be catalyzed when the reagent solution mixed with AuNPs in HEPES is detected to the aqueous solution of metal ion
The block diagram of product absorption values at 340nm.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Hg was detected based on golden nanometer particle in aqueous in the past2+When, depend on the property that metal ion recognizes molecule
Matter, and AuNPs only serves booster action in detection process, there are problems that sensitivity it is low,.
At present, " gold is catalyzed " has caused broad interest and has been applied to many organic as one of distinctive properties of AuNPs
In reaction.Wherein, not only AuNPs of the particle diameter less than 5nm is proved to catalysis activity high, in some liquid phase reactors, grain
AuNPs of the footpath more than 5nm is also found to have catalysis activity.Because " gold catalysis " activity places one's entire reliance upon golden watch surface properties, because
This, the small metamorphosis in AuNPs surfaces can influence its catalysis behavior, and then influence the quantity of catalysate.Based on above-mentioned
Reason, the change of gold surface pattern and the corresponding relation of catalysate quantity, can test and analyze as new mentality of designing
Thing.
Above-mentioned mentality of designing is then based on, is considered in the present embodiment using the surface nature of golden nanometer particle, i.e. gold
It is catalyzed the property of organic reaction and is easy to be formed with mercury atom the property of gold amalgam, develop a suitable detection reagent, carries out
Hg in the aqueous solution2+Detection.
Wherein, " gold amalgam " is two kinds of specific fusions of element of golden mercury, based on gold amalgam fusion, using gold nano
Detection of particles Hg2+, it is ensured that the selectivity of detection.
The reagent composition that the present embodiment is provided, specifically, being made up of golden nanometer particle and bridged piperazine derivatives.
Mentioned reagent composition carries out Hg2+The mechanism of detection is as follows.First, bridged piperazine derivatives as golden catalytic reaction bottom
Thing, the nitrogen-atoms in its molecular structure can replace the part on AuNPs surfaces and be adsorbed in golden nanometer particle surface；Then,
AuNPs is catalyzed bridged piperazine derivatives, obtains the catalysate with ultraviolet-ray visible absorbing (340~360nm), and the catalysate is made
It is the signal reports molecule of reaction.Secondly, bridged piperazine derivatives also serve as Hg2+Reducing agent, by Hg2+It is reduced to Hg atoms.Work as quilt
Without Hg in detection architecture2+When, AuNPs catalysis bridged piperazine derivatives obtain catalysate, occur ultraviolet-visible suction at 340~360nm
Receive peak；When be detected system in contain Hg2+When, bridged piperazine derivatives are by Hg2+It is reduced to Hg atoms, Hg atomic depositions to AuNPs tables
Face forms gold amalgam, occupies the active site on golden nanometer particle surface, it is suppressed that the carrying out of AuNPs catalytic reactions, drops
The low quantity of catalysate, the reduction of its ultraviolet-ray visible absorbing peak intensity.When Hg atoms fully take up the activity on AuNPs surfaces
During site, ultraviolet-ray visible absorbing peak is wholly absent at 340~360nm.According to addition Hg2+Quantity and catalysate absorb strong
The dependence of degree, is capable of achieving Hg2+Quantitative determination.
It is preferred that, golden nanometer particle is 1 with the mol ratio of the bridged piperazine derivatives：(5×104~1 × 109)。
Wherein, the particle diameter of golden nanometer particle be preferably 1~100nm, more preferably 10~40nm, more preferably 13~
30nm, most preferably 15nm.
In the present embodiment, golden nanometer particle be preferably citrate modification golden nanometer particle or carbonate modification
Golden nanometer particle.In some embodiments that the present invention is provided, the golden nanometer particle is preferably the Jenner of citrate modification
Rice corpuscles；In some embodiments that the present invention is provided, the golden nanometer particle is preferably the golden nanometer particle of carbonate modification.
Wherein, the golden nanometer particle of citrate modification refers to make reducing agent using sodium citrate, and reduction gold chloride is obtained
Golden nanometer particle；The golden nanometer particle of carbonate modification refers to make reducing agent using sodium borohydride, and potassium carbonate cooks protective agent, also
The golden nanometer particle that former gold chloride is obtained.Above-mentioned carbonate or citrate are the protective agents on golden nanometer particle surface, with Jenner
The active force of rice corpuscles is weaker, is to realize that piperazine of the gold catalysis containing end position hydroxyl spreads out easily by the ligand substituting of other atoms containing N etc.
Biology obtains the key of catalysate.Therefore, for golden nanometer particle, as long as gold catalysis can be completed containing end position hydroxyl
Bridged piperazine derivatives obtain catalysate, and it is citrate modification or carbonate modification to be not only limited to.
The source of the golden nanometer particle of citrate modification is not particularly limited in the embodiment above, preferred preparation side
Method is：
Gold chloride is added to the water, chlorauric acid solution (presoma of gold) is obtained；
Sodium citrate is added to the water, sodium citrate solution is obtained；
Described chlorauric acid solution is added in described sodium citrate solution, heating carries out hydro-thermal reaction, obtains anti-
Answer mixture；
By mixture centrifugation, the golden nanometer particle of citrate modification is obtained.
The source of the golden nanometer particle of carbonate modification is not particularly limited in the embodiment above, preferred preparation method
For：
Gold chloride is added to the water, chlorauric acid solution (presoma of gold) is obtained；
Potassium carbonate is added to the water, solution of potassium carbonate is obtained；
Described chlorauric acid solution is added in described solution of potassium carbonate, the mixing for obtaining gold chloride and potassium carbonate is molten
Liquid；
Sodium borohydride is added to the water, sodium borohydride solution is obtained；
Described sodium borohydride solution is added in the mixed solution of described gold chloride and potassium carbonate, reaction；
By mixture centrifugation, the golden nanometer particle of carbonate modification is obtained.
Bridged piperazine derivatives are preferably the bridged piperazine derivatives containing end position hydroxyl.Experiment shows：Piperazine derivatives containing end position hydroxyl
Thing can be the catalysate with 340~360nm absorptions by golden nanometer particle surface catalysis.More preferably 4- ethoxys piperazine
Piperazine ethyl sulfonic acid (HEPES) or 3- (hydroxyethyl piperazine) -2- hydroxy-propanesulfonic acids (HEPPSO).
In the present embodiment, there is provided one kind is for detecting Hg in the aqueous solution2+Reagent solution, the reagent solution be based on it is upper
The reagent composition design in embodiment is stated, is made up of above-mentioned any one reagent composition and water.
Mentioned reagent solution is relatively stable, can preserve for a long time at ambient temperature, using convenient.
In the present embodiment, there is provided be detection the aqueous solution in Hg2+Reagent solution preparation method, specially：
1) golden nanometer particle is added to the water, obtains the aqueous solution of golden nanometer particle；
2) bridged piperazine derivatives are added to the water, obtain the aqueous solution of bridged piperazine derivatives；
3) by step 1) described in golden nanometer particle the aqueous solution and step 2) described in the aqueous solution of bridged piperazine derivatives mix
Close, obtain Hg in the detection aqueous solution2+Reagent solution.
The concentration of golden nanometer particle is 0.1~20nmol/ in the aqueous solution of golden nanometer particle in wherein, it is preferable that step 1)
l；Step 2) in bridged piperazine derivatives the aqueous solution in bridged piperazine derivatives concentration be 5~100mmol/l, and bridged piperazine derivatives water
Solution ph is 7.0~8.5；Step 3) in the aqueous solution of golden nanometer particle be with the aqueous solution incorporation time of bridged piperazine derivatives
0.5~5min, 5~40 DEG C of mixing temperature.
Wherein, step 2) in bridged piperazine derivatives the aqueous solution pH value regulation, can by add sodium hydrate aqueous solution come
Realize；The regulation for carrying out pH value be in view of the pH of bridged piperazine derivatives solution not only can produce influence to the stability of reagent solution,
Also can be to the quantity of catalysate and Hg2+Detection results produce influence, therefore, to Hg2+During detection, in the reagent solution
PH value to keep appropriate, pH value is too high to be influenceed to Hg2+Concentrations；PH value is too low not only to influence the number of catalysate
Amount, can also influence to detect the stability of AuNPs.Therefore, pH value need to be adjusted to 7.0~8.5, preferably 7.5.
Experiment shows that the reagent solution provided in the embodiment above is to Hg2+Detection is limited to 5.0 × 10-12Mol/l, detection
The range of linearity of concentration is 1.0 × 10-11Mol/l~2.5 × 10-7mol/l。
Hg in the aqueous solution is carried out using mentioned reagent composition and reagent solution2+Detection method be：
1) aqueous solution to be detected is mixed with above-mentioned any one reagent composition or above-mentioned any one reagent solution
Uniformly, mixed solution is obtained；
2) by step 1) described in mixed solution centrifugation, discard precipitation, obtain centrifuged supernatant；
3) absorption spectrum of the centrifuged supernatant is determined, testing result is obtained according to the absorption spectrum.
In the detection method, first, bridged piperazine derivatives as golden catalytic reaction substrate, the nitrogen-atoms in its molecular structure
The part on golden nanometer particle surface can be replaced and golden nanometer particle surface is adsorbed in.Then, gold catalysis bridged piperazine derivatives, obtain
Catalysate with ultraviolet-ray visible absorbing (340~360nm), the catalysate is used as the signal reports molecule for reacting.Its
Secondary, bridged piperazine derivatives also serve as Hg2+Reducing agent, AuNPs presence under conditions of, by Hg2+It is reduced to Hg atoms.When tested
Without Hg in survey system2+When, gold catalysis bridged piperazine derivatives obtain catalysate, ultraviolet-ray visible absorbing occur at (340~360) nm
Peak；When containing Hg in the detection architecture2+When, bridged piperazine derivatives are by Hg2+It is reduced to Hg atoms, Hg atomic depositions to gold nano
Particle surface forms gold amalgam, occupies the active site on golden nanometer particle surface, it is suppressed that the carrying out of golden catalytic reaction,
The quantity of catalysate is reduced, the reduction of its ultraviolet-ray visible absorbing peak intensity.When Hg atoms fully take up the active sites of gold surface
During point, ultraviolet-ray visible absorbing peak is wholly absent at (340~360) nm.Therefore, light is absorbed by observing catalysate in solution
The Strength Changes of spectrum, you can learn and whether contain Hg in test substance2+And contain Hg2+Quantity.Entered using the detection method
During row detection, without being pre-processed to sample, simple to operate, identification sensitivity is high, it is possible to achieve Hg2+Detection.
Due to the reagent composition or reagent solution provided in the embodiment above and other common metal ions, such as
Sodium ion (Na+), potassium ion (K+), magnesium ion (Mg2+), calcium ion (Ca2+), zinc ion (Zn2+), copper ion (Cu2+), manganese from
Son (Mn2+), ferrous ion (Fe2+), cobalt ions (Co2+), nickel ion (Ni2+), iron ion (Fe3+), lead ion (Pb2+), chromium from
Son (Cr3+), cadmium ion (Cd2+) and silver ion (Ag+) etc., in the range of finite concentration all without cause catalysate it is ultraviolet-can
See absorption peak strength reduction phenomenon, therefore, reagent composition, reagent solution and the detection method provided in embodiment can be real
Now to Hg2+Selective enumeration method.
For a further understanding of the present invention, further details of theory is carried out to the present invention with reference to specific embodiment
It is bright.
Embodiment 1
The golden nanometer particle of citrate modification is prepared according to following steps：100ml redistilled waters are added to 250ml
In volumetric flask, boiling is heated to；The chlorauric acid solution that 2ml mass percents are 1% is added in the distilled water, chlorine gold is obtained
Aqueous acid, is heated to boiling；The gold chloride that the sodium citrate solution that 4ml mass percents are 2% is added into the boiling is molten
In liquid, agitating heating, solution colour is changed into black-and-blue from light yellow, eventually becomes claret；Continue agitating heating 1 hour.Room
The lower cooling of temperature, is centrifuged 15 minutes under 9400rpm revolutions, obtains the golden nanometer particle that the citrate that particle diameter is 15nm is modified.
The golden nanometer particle that citrate is modified is dissolved into water, is saved backup.
Golden nanometer particle to prepared citrate modification is analyzed, referring to Fig. 1 and Fig. 2, Fig. 1 for the present invention is real
The golden nanometer particle UV-visible absorption spectrum in aqueous of the citrate modification of example offer is provided；Fig. 2 is the present invention
The transmission electron microscope picture of the golden nanometer particle of the citrate modification that embodiment is provided.
Embodiment 2
The golden nanometer particle of carbonate modification is prepared according to following steps：100ml redistilled waters are added into 250ml to burn
In cup；The chlorauric acid solution that 375 μ l mass percents are 4% is added in the distilled water；By 500 μ l substance withdrawl syndromes
For the potassium carbonate of 0.2mol/l is added in described chlorauric acid solution, the mixed solution of gold chloride and potassium carbonate is obtained, at 4 DEG C
Stirring；By 5ml concentration for the sodium borohydride solution of 0.5mg/ml is added in described gold chloride and potassium carbonate mixed solution, instead
Should, solution colour is orange red by livid purple discoloration；Continue to react 10 minutes, be centrifuged 15 minutes under 12000rpm revolutions, obtain
The golden nanometer particle of carbonate modification.The golden nanometer particle that carbonate is modified is dissolved into water, is saved backup.
Golden nanometer particle to prepared carbonate modification is analyzed, and referring to Fig. 3, Fig. 3 is carried for the embodiment of the present invention
The golden nanometer particle of the carbonate modification of confession UV-visible absorption spectrum in aqueous.
Embodiment 3
According to following steps reagent preparation solution：
3- (hydroxyethyl piperazine) -2- hydroxy-propanesulfonic acids (HEPPSO) is dissolved in redistilled water, using the amount of material
Concentration is the sodium hydroxide solution regulation pH of 6mol/l, obtains concentration for 100mmol/l, and pH value is 7.5 HEPPSO solution；Will
The solution of gold nanoparticles of certain volume is added in described HEPPSO solution, obtains reagent solution, wherein, golden nanometer particle
Substance withdrawl syndrome is 2.5nmol/l, and the substance withdrawl syndrome of HEPPSO is 25mmol/l.
Prepared reagent solution is analyzed, referring to Fig. 4, Fig. 4 is HEPPSO provided in an embodiment of the present invention and lemon
The UV-visible absorption spectrum of the golden nanometer particle mixed solution of lemon acid group modification.
Embodiment 4
According to following steps reagent preparation solution：
3- (hydroxyethyl piperazine) -2- hydroxy-propanesulfonic acids (HEPPSO) is dissolved in redistilled water, using the amount of material
Concentration is the sodium hydroxide solution regulation pH of 6mol/l, obtains concentration for 100mmol/l, and pH value is 7.5 HEPPSO solution；Take
The solution of gold nanoparticles of the carbonate modification of certain volume is added in described HEPPSO solution, obtains reagent solution.
Prepared reagent solution is analyzed, referring to Fig. 5, Fig. 5 is HEPPSO provided in an embodiment of the present invention and carbon
The UV-visible absorption spectrum of the golden nanometer particle mixed solution of acid group modification.
Embodiment 5
According to following steps reagent preparation solution：
4- HEPESs (HEPES) are dissolved in redistilled water, are 6mol/ using substance withdrawl syndrome
The sodium hydroxide solution regulation pH of l, obtains concentration for 100mmol/l, and pH value is 7.5 HEPES solution；Take the gold of certain volume
Nano-particle solution is added in described HEPES solution, obtains reagent solution, wherein, golden nanometer particle substance withdrawl syndrome
It is 2.5nmol/l, the substance withdrawl syndrome of HEPES is 25mmol/l.
Prepared reagent solution is analyzed, referring to Fig. 6, Fig. 6 is HEPES provided in an embodiment of the present invention and lemon
The UV-visible absorption spectrum of the golden nanometer particle mixed solution of acid group modification.
Embodiment 6
Catalysate is prepared and characterized according to following steps：
The reagent solution 50ml that will be obtained in embodiment 3 is incubated 24 hours at room temperature, and 9400rpm turns lower centrifugation 15 minutes,
Reject supernatant, the golden nanometer particle for precipitating is re-dissolved in the HEPPSO storing solutions that the pH value of 50ml is 7.5, is obtained
The concentration of HEPPSO is 25mmol/l in reagent solution, and pH value of solution is 7.5.Room temperature catalysis is incubated 3 days.Produced to collect the catalysis
Thing, lower centrifugation 25 minutes is turned by reagent solution 11500rpm, is taken in supernatant to rotary evaporation flask, is concentrated by evaporation to about
5ml.By concentrate freeze-drying, yellowish-brown oily thick liquid is obtained.The thick liquid is divided into three parts, portion is used in water
Its uv-visible absorption spectra is determined in solution, portion carries out the sign of molecular weight for liquid chromatography-mass spectrography, and a
Structural characterization is carried out for carbon-13 nmr spectra.
Prepared catalysate is analyzed, referring to Fig. 7~Figure 11.Fig. 7 is HEPPSO provided in an embodiment of the present invention
The UV-visible absorption spectrum of the catalysate that the aqueous solution and gold catalysis HEPPSO are obtained, Fig. 8 is provided for the embodiment of the present invention
HEPPSO samples and the gold catalysis catalysate sample photo figures that obtain of HEPPSO, Fig. 9 is gold provided in an embodiment of the present invention
The liquid chromatogram of the catalysate that catalysis HEPPSO is obtained, Figure 10 is obtained for gold catalysis HEPPSO provided in an embodiment of the present invention
Catalysate electrospray ionization mass spectrum figure, Figure 11 is the gold catalysis catalysates that obtain of HEPPSO provided in an embodiment of the present invention
Carbon-13 nmr spectra figure.
Embodiment 7
Hg is detected according to following steps2+：
By Hg (NO3)2It is dissolved in redistilled water, is made into the Hg of 0.01mol/l2+Stock solution, while adding same concentration
Hydrochloric acid solution be used for prevent Hg2+Hydrolysis；With redistilled water by the Hg2+Storing solution is diluted to 1.0 × 10 respectively-11, 5.0
×10-11,1.0×10-10,5.0×10-10,1.0×10-9,5.0×10-9,1.0×10-8,5.0×10-8,1.0×10-7,5.0
×10-7,1.0×10-6,2.5×10-6,1.0×10-5, 2.0.5 is dilute-5, 3.0 are diluted to-5It is dilute with 1.0.0-4mol/l.Take 17 parts
Reagent solution prepared by embodiment 3, every part of 180 μ l；To 20 μ l redistilled waters are added in the 1st part of reagent solution, to the 2nd~17
The Hg of 20 above-mentioned each concentration of μ l is separately added into part reagent solution2+Solution, is mixed after placing 4 hours, and each solution is existed
11500rpm turns lower centrifugation 15 minutes, takes supernatant, the absorption spectrum of each supernatant is determined, as a result referring to Figure 12.Figure 12 is this
Hg is added in the reagent solution that inventive embodiments are provided2+The UV-visible absorption spectrum of centrifuged supernatant afterwards.
Referring to Figure 12, the curve in Figure 12 is respectively the supernatant of Reagent blank solutions from top to bottom, containing 1.0 × 10- 12mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-12mol/l Hg2+Reagent solution supernatant, containing 1.0 ×
10-11mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-11mol/l Hg2+Reagent solution supernatant, containing 1.0
×10-10mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-10mol/l Hg2+Reagent solution supernatant, contain
1.0×10-9mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-9mol/l Hg2+Reagent solution supernatant, contain
1.0×10-8mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-8mol/l Hg2+Reagent solution supernatant, contain
1.0×10-7mol/l Hg2+Reagent solution supernatant, containing 2.5 × 10-7mol/l Hg2+Reagent solution supernatant, contain
1.0×10-6mol/l Hg2+Reagent solution supernatant, containing 2.0 × 10-6mol/l Hg2+Reagent solution supernatant, contain
3.0×10-6mol/l Hg2+Reagent solution supernatant and containing 1.0 × 10-5mol/l Hg2+Reagent solution supernatant
UV-visible absorption spectrum.As seen from the figure, Hg is worked as2+Concentration reaches 5.0 × 10-12During mol/l, catalysate absorption spectrum
Intensity starts to reduce；With Hg2+The increase of concentration, the intensity decreases degree of catalysate absorption spectrum is more obvious；Work as concentration
Reach 1.0 × 10-5During mol/l, absorption spectrum is almost wholly absent.To Hg2+Detection be limited to 5.0 × 10-12mol/l。
Therefore, the reagent solution detection Hg that the present invention is provided2+Sensitivity it is higher, referring to Figure 13, as shown in Figure 13, this hair
The reagent solution detection Hg of bright offer2+The concentration range of linearity be 1.0 × 10-11Mol/l~2.5 × 10-7mol/l。
Embodiment 8
Hg is detected according to following steps2+：
By Hg (NO3)2It is dissolved in redistilled water, is made into the Hg of 0.01mol/l2+Stock solution, while adding same concentration
Hydrochloric acid solution be used for prevent Hg2+Hydrolysis；With redistilled water by the Hg2+Storing solution is diluted to 1.0 × 10 respectively-9, 5.0
×10-8,1.0×10-8,5.0×10-7,1.0×10-7,5.0×10-7,1.0×10-6,5.0×10-5,1.0×10-5,5.0×
10-5With 1.0 × 10-4mol/l.Take reagent solution prepared by 12 parts of embodiments 5, every part of 180 μ l；Add in the 1st part of reagent solution
Enter 20 μ l redistilled waters, to the Hg that 20 above-mentioned each concentration of μ l are separately added into the 2nd~12 part of reagent solution2+Solution, mixes
After placing 16 hours, each solution is turned into lower centrifugation 15 minutes in 11500rpm, take supernatant, determine the absorption light of each supernatant
Spectrum, as a result referring to Figure 14.Figure 14 be reagent solution provided in an embodiment of the present invention in add Hg2+Afterwards centrifuged supernatant it is ultraviolet-
Visible absorption spectra figure.
Referring to Figure 14, the curve in Figure 14 is respectively the supernatant of Reagent blank solutions from top to bottom, containing 1.0 × 10- 10mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-10mol/l Hg2+Reagent solution supernatant, containing 1.0 ×
10-9mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-9mol/l Hg2+Reagent solution supernatant, containing 1.0 ×
10-8mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-8mol/l Hg2+Reagent solution supernatant, containing 1.0 ×
10-7mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-7mol/l Hg2+Reagent solution supernatant, containing 1.0 ×
10-6mol/l Hg2+Reagent solution supernatant, containing 5.0 × 10-6mol/l Hg2+Reagent solution supernatant and containing 1.0
×10-5mol/l Hg2+Reagent solution supernatant UV-visible absorption spectrum.As seen from the figure, Hg is worked as2+Concentration reaches
5.0×10-10During mol/l, the intensity of catalysate absorption spectrum is substantially reduced；With Hg2+The increase of concentration, catalysis is produced
The reduction degree of thing absorption spectrum intensity is more obvious；When concentration reaches 1.0 × 10-5During mol/l, absorption spectrum intensity decreases are extremely
Minimum.
Embodiment 9
According to following steps identification, detection Hg2+：
By Na+It is dissolved in redistilled water, is made into the stock solution of 0.01mol/l, then with redistilled water by its point
It is not diluted to 1.0 × 10-11, 5.0 × 10-11,1.0×10-10,5.0×10-10,1.0×10-9,5.0×10-9,1.0×10-8,
5.0×10-8,1.0×10-7,5.0×10-7With 1.0 × 10-6The solution of mol/l；Reagent solution prepared by 11 parts of embodiments 4 is taken,
Every part of 180 μ l, to adding 20 μ l redistilled waters in the 1st part of reagent solution, to being separately added into 20 in the 2nd~13 part of reagent solution
The Na of above-mentioned each concentration of μ l+The aqueous solution, is mixed after placing 4 hours, and each solution is centrifuged 15 minutes under 11500 turns, is taken
Clear liquid, determines the absorption spectrum of each supernatant.Result shows that concentration is less than or equal to 1.0 × 10-6The Na of mol/l+Examination can not be made
There is absorption intensity reduction phenomenon in agent solution.
Embodiment 10
The identification of the step of according to embodiment 9, detection K+, as a result show that concentration is less than or equal to 1.0 × 10-6The K of mol/l+
Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 11
The identification of the step of according to embodiment 9, detection Mg2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Mg2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 12
The identification of the step of according to embodiment 9, detection Ca2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Ca2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 13
The identification of the step of according to embodiment 9, detection Zn2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Zn2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 14
The identification of the step of according to embodiment 9, detection Cu2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Cu2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 15
The identification of the step of according to embodiment 9, detection Mn2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Mn2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 16
The identification of the step of according to embodiment 9, detection Fe2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Fe2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 17
The identification of the step of according to embodiment 9, detection Co2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Co2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 18
The identification of the step of according to embodiment 9, detection Ni2+, as a result show that concentration is 1.0 × 10-6The Ni of mol/l2+Can not make
There is absorption intensity reduction phenomenon in reagent solution.
Embodiment 19
The identification of the step of according to embodiment 9, detection Fe3+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Fe3+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 20
The identification of the step of according to embodiment 9, detection Cd2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Cd2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 21
The identification of the step of according to embodiment 9, detection Cr3+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Cr3+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 22
The identification of the step of according to embodiment 9, detection Pb2+, as a result show that concentration is less than or equal to 1.0 × 10-6Mol/l's
Pb2+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 23
The identification of the step of according to embodiment 9, detection Ag+, as a result show that concentration is less than or equal to 1.0 × 10-6The Ag of mol/l+Can not make reagent solution that absorption intensity reduction phenomenon occurs.
Embodiment 24
By Hg2+、Na+、K+、Mg2+、Ca2+、Zn2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Pb2+、Ag+、Fe3+、Cd2+And Cr3+
It is dissolved in redistilled water respectively, is made into 1.0 × 10-5Each metal ion solution of mol/l；The reagent that Example 4 is provided is molten
17 parts of liquid, every part of 180 μ l, to 20 μ l redistilled waters are added in the 1st part of reagent solution, in the 2nd~17 part of reagent solution points
The above-mentioned each aqueous metallic ions of 20 μ l are not added, and concentration of metal ions is 1.0 × 10 in making each system-6mol/l；Mix and place
After 4 hours, each solution is turned into lower centrifugation 15 minutes in 11500rpm, take supernatant, determine the absorption spectrum of each supernatant, as a result
Referring to Figure 15.Figure 15 is to be catalyzed when reagent solution provided in an embodiment of the present invention is detected to the aqueous solution containing each metal ion
The block diagram of product absorption values at 340nm, as shown in Figure 15, other metal ions reach 1.0 × 10 in concentration-6mol/
Absorption intensity during l on catalysate in reagent solution is not influenceed substantially, and the detection identification system that the present invention is provided can be selected
The detection Hg of selecting property2+。
Embodiment 25
By Hg2+、Na+、K+、Mg2+、Ca2+、Zn2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Pb2+、Ag+、Fe3+、Cd2+And Cr3+
It is dissolved in redistilled water respectively, is made into 1.0 × 10-5Each metal ion solution of mol/l；The reagent that Example 5 is provided is molten
17 parts of liquid, every part of 180 μ l, to 20 μ l redistilled waters are added in the 1st part of reagent solution, in the 2nd~17 part of reagent solution points
The above-mentioned each aqueous metallic ions of 20 μ l are not added, and concentration of metal ions is 1.0 × 10 in making each system-6mol/l；Mix and place
After 4 hours, each solution is turned into lower centrifugation 15 minutes in 11500rpm, take supernatant, determine the absorption spectrum of each supernatant.Experiment
Show, other metal ions reach 1.0 × 10 in concentration-6Absorption intensity during mol/l to catalysate in reagent solution is basic
Without influence, the detection identification system that the present invention is provided is capable of the detection Hg of selectivity2+。
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (14)
1. a kind of for detecting Hg in the aqueous solution2+Reagent composition, it is characterised in that：Including golden nanometer particle and piperazine derivatives
Thing.
2. according to being used to detect Hg in the aqueous solution described in claim 12+Reagent composition, it is characterised in that：The gold nano
Particle is 1 with the mol ratio of the bridged piperazine derivatives：(5×104~1 × 109)。
3. according to being used to detect Hg in the aqueous solution described in claim 12+Reagent composition, it is characterised in that：The gold nano
The particle diameter of particle is 1~100nm.
4. according to being used to detect Hg in the aqueous solution described in claim 12+Reagent composition, it is characterised in that：The gold nano
Particle is the golden nanometer particle of citrate modification or the golden nanometer particle of carbonate modification.
5. according to being used to detect Hg in the aqueous solution described in claim 12+Reagent composition, it is characterised in that：The piperazine spreads out
Biology is the bridged piperazine derivatives containing end position hydroxyl.
6. according to being used to detect Hg in the aqueous solution described in claim 12+Reagent composition, it is characterised in that：The piperazine spreads out
Biology is 4- HEPESs or 3- (hydroxyethyl piperazine) -2- hydroxy-propanesulfonic acids.
7. according to being used to detect Hg in the aqueous solution described in claim 42+Reagent composition, it is characterised in that the citric acid
The golden nanometer particle of root modification is prepared from accordance with the following methods：
The presoma of gold, sodium citrate and water Hybrid Heating are carried out into hydro-thermal reaction, Jenner's grain of rice of citrate modification is obtained
Son.
8. according to being used to detect Hg in the aqueous solution described in claim 42+Reagent composition, it is characterised in that the carbonate
The golden nanometer particle of modification is prepared from accordance with the following methods：
The presoma of gold, potassium carbonate, sodium borohydride are mixed with water, is reacted, obtain the golden nanometer particle of carbonate modification.
9. a kind of for detecting Hg in the aqueous solution2+Reagent solution, it is characterised in that：The reagent solution is by claim 1~8
In any one reagent composition and water composition.
10. it is used to detect Hg in the aqueous solution described in a kind of claim 92+Reagent solution preparation method, it is characterised in that bag
Include following steps：
1) golden nanometer particle is added to the water, obtains the aqueous solution of golden nanometer particle；
2) bridged piperazine derivatives are added to the water, obtain the aqueous solution of bridged piperazine derivatives；
3) by step 1) described in golden nanometer particle the aqueous solution and step 2) described in the aqueous solution of bridged piperazine derivatives mix, obtain
The Hg in the detection aqueous solution2+Reagent solution.
11. are used to detect Hg in the aqueous solution according to claim 102+Reagent solution preparation method, it is characterised in that：
Step 1) described in golden nanometer particle the aqueous solution in golden nanometer particle concentration be 0.1~20nmol/l.
12. are used to detect Hg in the aqueous solution according to claim 102+Reagent solution preparation method, it is characterised in that：
Step 2) described in bridged piperazine derivatives the aqueous solution in the concentration of bridged piperazine derivatives be 5~100mmol/l, and piperazine derivatives
The pH value of water solution of thing is 7.0~8.5.
13. are used to detect Hg in the aqueous solution according to claim 102+Reagent solution preparation method, it is characterised in that：
Step 3) described in golden nanometer particle the aqueous solution and the bridged piperazine derivatives aqueous solution incorporation time be 0.5~5min, mix
Close 5~40 DEG C of temperature.
Hg in a kind of 14. detection aqueous solution2+Method, it is characterised in that：
1) by any one reagent composition in the aqueous solution to be detected and claim 1~8 or claim 9 any one
Reagent solution is well mixed, and obtains mixed solution；
2) by step 1) in mixed solution centrifugation, discard precipitation, obtain centrifuged supernatant；
3) absorption spectrum of the centrifuged supernatant is determined, testing result is obtained according to the absorption spectrum.
Priority Applications (1)
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| CN110044885A (en) * | 2019-04-18 | 2019-07-23 | 桂林理工大学 | One kind exempting from instrument Hg2+Quantitative detecting method |
| CN111234569A (en) * | 2018-11-29 | 2020-06-05 | 内蒙古东盛硅藻土科技创新产业园有限公司 | Diatomite coating, preparation method thereof and decorative plate made of diatomite coating |
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