CN106932392A - A kind of method of cadmium in gold-silver alloy nanoparticles probe visualization detection water based on cysteine modified - Google Patents
A kind of method of cadmium in gold-silver alloy nanoparticles probe visualization detection water based on cysteine modified Download PDFInfo
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- CN106932392A CN106932392A CN201710219202.9A CN201710219202A CN106932392A CN 106932392 A CN106932392 A CN 106932392A CN 201710219202 A CN201710219202 A CN 201710219202A CN 106932392 A CN106932392 A CN 106932392A
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- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 235000018417 cysteine Nutrition 0.000 title claims abstract description 58
- 238000001514 detection method Methods 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 25
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000523 sample Substances 0.000 title claims abstract description 14
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000012800 visualization Methods 0.000 title claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 42
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 39
- 229910052737 gold Inorganic materials 0.000 claims description 39
- 239000010931 gold Substances 0.000 claims description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 31
- 239000004332 silver Substances 0.000 claims description 31
- 239000011780 sodium chloride Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002835 absorbance Methods 0.000 claims description 12
- 229910001254 electrum Inorganic materials 0.000 claims description 12
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 cysteine modified gold-silver Chemical class 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 5
- 235000004237 Crocus Nutrition 0.000 claims description 4
- 241000596148 Crocus Species 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 2
- 229960003067 cystine Drugs 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 29
- 239000000956 alloy Substances 0.000 abstract description 29
- 239000002245 particle Substances 0.000 abstract description 10
- 238000004458 analytical method Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 78
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000151 cysteine group Chemical group N[C@@H](CS)C(=O)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- 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
- G01N21/3151—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 using two sources of radiation of different wavelengths
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Abstract
The invention provides a kind of method of cadmium in gold-silver alloy nanoparticles probe visualization detection water based on cysteine modified, using citrate simultaneously as reducing agent and protective agent, tested by condensing reflux using chemical reduction method, while reducing HAuCl4And AgNO3, particle diameter is prepared for for the gold-silver alloy nanoparticles of 50nm and it is characterized.It is used as identification molecule by alloy nano particle surface modification cysteine, establishes Cd in a kind of quick detection water2+Colorimetric sensing analysis method.Under the experiment condition of optimization, the method is to Cd2+There is preferable selectivity, detect Cd2+Concentration range is 0.4 μM~38.6 μM, and lowest detection is limited to 0.044 μM.The method detection time is short, simple to operate, for detecting the Cd in water2+There is good application prospect.
Description
Technical field
The present invention relates to a kind of method for detecting cadmium in water, more particularly to a kind of electrum based on cysteine modified
The method of cadmium in nanoparticle probes Visual retrieval water.
Background technology
With the development of science and technology, heavy metal pollution has turned into increasingly serious problem.Cadmium is widely present in water, soil and sky
It is one of important composition of heavy metal pollution in gas, it can be entered in human body by food chain, and be possessed 20-30 years
Biological half-life, great damage may be caused to human body and various diseases are induced, therefore a kind of method for detecting cadmium of research has
Significance.Current various analyzing detecting methods have been applied to detection cadmium, including：Atomic fluorescence spectrophotometry, inductively coupled plasma
Mass spectrography, inductively coupled plasma atomic emission spectrometry, graphite oven atomic absorption and flame atomic absorption method etc..These methods
Although with detection sensitivity higher, all having needs technical professional, large-scale instrument, testing cost high, time-consuming
The deficiency such as long, is restricted its application.Nano material due to its special dimensional effect, on catalysis, electricity, optics and surface
All many-sides such as enhancing Ramam effect have good application, especially metal nanoparticle, its unique optics, electricity, catalysis
Property etc. all has potential application value in many fields.Alloy nano particle has the catalytic different from one-component metal
The characteristics such as energy, surface plasma resonance and SERS (SERS), its combination property is far more than each one-component metal,
And gold and silver are due to being easily created gold and silver conjunction with very close lattice parameter, thus when reducing gold and silver in the solution
Gold.The synthetic method of current nano material mainly has photochemical method, electrochemical process, microemulsion method, radiation method and chemical reduction method
Deng wherein chemical reduction method is easy to operate, process is simple, is widely applied.
The content of the invention
The purpose of the present invention is directed to the deficiencies in the prior art, there is provided a kind of electrum based on cysteine modified is received
The method of cadmium in rice corpuscles probe visualization detection water, the method selectively good, simple to operate, detection time is short, instrument is inexpensive,
Sensitivity is higher, disclosure satisfy that Cd in water2+Detection.
The present invention is achieved through the following technical solutions：
A kind of method of cadmium in gold-silver alloy nanoparticles probe visualization detection water based on cysteine modified, including
Following steps：
(1) preparation of cysteine modified gold-silver alloy nanoparticles
Accurately pipette 48 μ L 1.0%AgNO3Solution and 47 μ L 1.0%HAuCl4Solution is added separately to super equipped with 15mL
In the flask of pure water, the μ L of 0.4mM citric acid three sodium solutions 250 are added simultaneously after condensing reflux heating 5min, reheat 2min, so
Mix and continue agitating heating 15min immediately afterwards, obtain the solution of crocus clarification and stable and uniform, as electrum is molten
Liquid；
Add 0.7mL 1.0mM cysteine solutions at the uniform velocity to stir 2h in the electrum solution of above-mentioned new synthesis, obtain
To the gold and silver Nanoalloy solution of cysteine modified, the gold and silver Nanoalloy solution addition NaCl wrapped up to cysteine；
(2) Cd in colorimetric detection water2+
NaCl is added to the gold and silver Nanoalloy solution of cysteine modified, makes its concentration for 0.024M, respectively by concentration
For 0.40,1.34,2.23,4.44,6.65,8.85,11.00,13.2,15.40,17.50,21.80,26.10,30.30,
34.50、38.60μM Cd2+The gold and silver Nanoalloy that standard liquid is added to the above-mentioned cysteine modifieds containing NaCl of 2mL is molten
In liquid, hatch 15min, after question response is complete, it can be observed that obvious color change, the face of solution is shot with digital camera
Color, makes standard color comparison card；Meanwhile, suction of the solution at 435nm and at 600nm is determined using UV-VIS spectrophotometry
Luminosity, with solution absorbance ratio (A600/A435) it is ordinate, Cd2+Concentration is abscissa, drawing curve, linear fit
Obtain a linear equation with one unknown；10 μ L are taken through precipitation, filtering, the regulation pretreated water samples of pH to 6.0, is added on 2mL
State in the gold and silver Nanoalloy solution of the cysteine modified containing NaCl, hatch 15min, after question response is complete, use digital phase
Machine shoots the color of solution, and the color of solution is contrasted with standard color comparison card in the photo that will be shot, i.e., to the Cd in water sample2+Content
Carry out half-quantitative detection；Meanwhile, determine solution 435nm locate with 600nm at absorbance and calculate solution absorbance ratio
(A600/A435), substitute into linear equation with one unknown, you can try to achieve Cd in water2+Content.
The gold and silver Nanoalloy solution of cysteine modified obtained in step (1) using before need to solution in add
NaCl, makes NaCl concentration in the solution be 0.024M；
1.0%AgNO described in step (1)3Solution and 1.0%HAuCl4Solution is mass fraction.
Semicystinol concentration concentration is 23.33 μ in the gold and silver Nanoalloy solution of cysteine modified described in step (2)
M；
The pH of the gold and silver Nanoalloy solution of cysteine modified described in step (2) is 6.0.
The present invention is by controlling suitable condition, while reducing HAuCl4And AgNO3Gold-silver alloy nanoparticles have been obtained,
And being capable of Cd in specific recognition water by its surface modification cysteine, establishing one kind2+Method for quick.The party
Method detection time is short, simple to operate, to Cd in water2+Detection be limited to 0.044 μM, detection range is 0.4 μM~38.6 μM.
Brief description of the drawings
(A) is nm of gold (a), Nano Silver (b), electrum (c) and nm of gold and Nano Silver physical mixed (d) in Fig. 1
Ultraviolet-visible absorption spectroscopy figure；(B) be different gold and silver ratios alloy maximum absorption peak and alloy in gold molar ratio line
Sexual intercourse figure.
Fig. 2 is 10 μM of Cd of addition2+Before (a) afterwards (c) alloy uv-vis spectra change and add 10 μM of Cd2+Before (b)
The change of (d) cysteine modified alloy uv-vis spectra and solution colour afterwards, left side test tube is 10 μM of addition in illustration
Cd2+Before (b) cysteine modified alloy solution color, the right test tube for add 10 μM of Cd2+(d) cysteine modified is closed afterwards
The color of gold solution.
Fig. 3 is 10 μM of Cd of addition2+Before (A) (B) gold-silver alloy nanoparticles afterwards Electronic Speculum and grain-size graph.
(A) is alloy nano particle EDX spectrograms in Fig. 4；(B) it is cysteine (a) and cysteine modified alloy nano
Particle (b) infrared spectrogram.
Fig. 5 is the influence figure of semicystinol concentration (A), detection time (B), pH (C) and NaCl concentration (D) to detection.Fig. 6
In (A) be different Cd2+Cysteine modified electrum nano-solution abosrption spectrogram under concentration；(B) it is electrum nanometer
Solution absorbance ratio (A600/A435) and Cd2+Concentration relationship figure.
Fig. 7 is the influence schematic diagram (A) of pairing gold nano solution absorption p-ratio in the presence of different metal ions；Half Guang ammonia
Acid modification alloy nano solution stability schematic diagram (B), illustration be cysteine modified alloy in different time in 435nm
The absorption peak at place.
Specific embodiment
Embodiment 1：Cadmium in a kind of gold-silver alloy nanoparticles probe visualization detection water based on cysteine modified
Method, comprises the following steps：
(1) preparation of cysteine modified gold-silver alloy nanoparticles
Accurately pipette 48 μ L 1.0%AgNO3Solution and 47 μ L 1.0%HAuCl4Solution is added separately to super equipped with 15mL
In the flask of pure water, the μ L of 0.4mM citric acid three sodium solutions 250 are added simultaneously after condensing reflux heating 5min, reheat 2min, so
Mix and continue agitating heating 15min immediately afterwards, obtain the solution of crocus clarification and stable and uniform, as electrum is molten
Liquid；
Add 0.7mL 1.0mM cysteine solutions at the uniform velocity to stir 2h in the electrum solution of above-mentioned new synthesis, obtain
To the gold and silver Nanoalloy solution of cysteine parcel, the gold and silver Nanoalloy solution addition NaCl wrapped up to cysteine；
(2) Cd in colorimetric detection water2+
NaCl is added to the gold and silver Nanoalloy solution of cysteine modified, makes its concentration for 0.024M, respectively by concentration
For 0.40,1.34,2.23,4.44,6.65,8.85,11.00,13.20,15.40,17.50,21.80,26.10,30.30,
34.50、38.60μM Cd2+The gold and silver Nanoalloy that standard liquid is added to the above-mentioned cysteine modifieds containing NaCl of 2mL is molten
In liquid, hatch 15min, after question response is complete, it can be observed that obvious color change, the face of solution is shot with digital camera
Color, makes standard color comparison card；Meanwhile, suction of the solution at 435nm and at 600nm is determined using UV-VIS spectrophotometry
Luminosity, with solution absorbance ratio (A600/A435) it is ordinate, Cd2+Concentration is abscissa, drawing curve, linear fit
Obtain a linear equation with one unknown；10 μ L are taken through precipitation, filtering, the regulation pretreated water samples of pH to 6.0, is added on 2mL
State in the gold and silver Nanoalloy solution of the cysteine modified containing NaCl, hatch 15min, after question response is complete, use digital phase
Machine shoots the color of solution, and the color of solution is contrasted with standard color comparison card in the photo that will be shot, i.e., to the Cd in water sample2+Content
Carry out half-quantitative detection；Meanwhile, determine solution 435nm locate with 600nm at absorbance and calculate solution absorbance ratio
(A600/A435), substitute into linear equation with one unknown, you can try to achieve Cd in water2+Content.
1.0%AgNO described in step (1)3Solution and 1.0%HAuCl4Solution is mass fraction.
Semicystinol concentration concentration is 23.33 μ in the gold and silver Nanoalloy solution of cysteine modified described in step (2)
M；
The pH of the gold and silver Nanoalloy solution of cysteine modified described in step (2) is 6.0.
Embodiment 2：Detailed investigation is carried out to the performance of this method below in conjunction with specific embodiment, and it is attached to combine specification
Figure is illustrated, and is comprised the following steps that：
1.1 instruments and reagent
UV -2450 is ultraviolet-visible spectrophotometer (Japanese Shimadzu Corporation), Instrument working parameter：Scanning wavelength 300~
800nm；JEM -2100 high resolution transmission electron microscopes (Jeol Ltd.)；Nicomp 380ZLS nano particle sizes
Instrument (PSS particle size analyzers company of the U.S.)；PHS -3C types acidometer (Shanghai Lei Ci instrument plants)；Bidirectional magnetic agitator (China of Changzhou state
Electrical Appliances Co., Ltd)；Millipore Simplicity water purification systems.
HAuCl4(purity >=99.9%), Shanghai Yuan Ye bio tech ltd) and AgNO3(purity >=99.8%), on
The factory of extra large reagent one) it is configured to 1.0% storing solution with ultra-pure water；Cysteine ultra-pure water is configured to 1.0mM solution, citric acid three
The ultrapure water dissolves of sodium, are configured to 0.4mM solution；Cd2+Standard liquid caddy (purity >=99%, the chemistry examination of Shanghai examination one
Agent Co., Ltd) it is configured to the standard liquid of 1.0mM；Running water, lake water are taken from University Of Nanchang campus.
1.2 test methods
1.2.1 the preparation of cysteine modified gold-silver alloy nanoparticles
Accurately pipette 48 μ L 1.0%AgNO3Solution and 47 μ L 1.0%HAuCl4Solution is added separately to super equipped with 15mL
In the flask of pure water, the μ L of 0.4mM citric acid three sodium solutions 250 are added simultaneously after condensing reflux heating 5min, reheat 2min, so
Mix and continue agitating heating 15min immediately afterwards, obtain the solution of crocus clarification and stable and uniform.
Add 0.7mL 1.0mM cysteine solutions at the uniform velocity to stir 2h in the electrum solution of above-mentioned new synthesis, obtain
To the gold and silver Nanoalloy solution of cysteine modified.
1.2.2 the optimization of testing conditions
The Cd in water is detected2+During, different can the generation to final testing result of testing conditions significantly affects.For
Detection sensitivity and accuracy higher is obtained, in the case of other conditions identical is controlled, this experiment has successively been investigated partly
The influence of cystine concentration, detection time, pH value and NaCl concentration to testing result.
1.2.3 Cd in colorimetric detection water2+
NaCl is added to the gold and silver Nanoalloy solution of cysteine modified, makes its concentration for 0.024M, respectively by concentration
For 0.40,1.34,2.23,4.44,6.65,8.85,11.00,13.20,15.40,17.50,21.80,26.10,30.30,
34.50、38.60μM Cd2+The gold and silver Nanoalloy that standard liquid is added to the above-mentioned cysteine modifieds containing NaCl of 2mL is molten
In liquid, hatch 15min, after question response is complete, it can be observed that obvious color change, using ultraviolet-visible spectrophotometry
Determine the absorbance of solution.
1.2.4 the detection of actual water sample
Running water and lake water in collection University Of Nanchang campus, by the conventional pre- place such as precipitation, filtering, regulation pH to 6.0
After reason, Cd in water is determined2+Content simultaneously carries out mark-on reclaims analysis using standard addition method.
2 results and discussion
The synthesis of 2.1 cysteine modified gold-silver alloy nanoparticles
Figure 1A is the ultraviolet-visible absorption spectra of synthetic gold-silver alloy nanoparticles, it can be seen that in Detection wavelength
In the range of the alloy nano particle only have an absworption peak at 435nm, the absworption peak is located at silver
Between (400nm) and golden (520nm) nano-particle maximum absorption band, show to have successfully synthesized electrum nanometer
Particle.And with the increase of the molar ratio of gold in alloy, its maximum absorption peak is presented with the molar ratio of gold in alloy
Outlet sexual intercourse (Figure 1B).
The sign of 2.2 gold-silver alloy nanoparticles
2.2.1 the spectral characterization of alloy nano particle
Fig. 2 curves d shows, adds Cd2+Afterwards, there is a new absworption peak in 600nm vicinity in nano-particle solution, and
And there is obvious change in the color of solution.
2.2.2 the Electronic Speculum and diameter characterization of alloy nano particle
Transmission electron microscope (TEM) image shows (Fig. 3) that alloy nano particle particle diameter is smaller, in spherical, the particle diameter distribution of rule
More uniform (Fig. 3 A)；Add Cd2+Afterwards there is obvious aggregation (Fig. 3 B) in alloy nano particle.Diameter characterization shows, alloy nano
The particle diameter of particle is about 50nm (illustration, Fig. 3 A), adds 10 μM of Cd2+Particle diameter is increased to 500nm (illustration, Fig. 3 B) afterwards, shows
Cd2+Addition cause cysteine modified gold-silver alloy nanoparticles aggregation so that its particle diameter increases, and causes solution
The change of color.2.2.3 the EDX and IR Characterization of alloy nano particle
The analysis of constituent obtains (Fig. 4 A) by EDX in alloy, and analysis can obtain the ratio of silver and gold in alloy from figure
About 0.7:0.3, this matches with silver gold ratio initial in solution.Infrared spectrum characterization result such as Fig. 4 B, 2500-
2600cm-1The characteristic peak for locating-SH weakens, and illustrates cysteine by sulfydryl modification in alloy nano particle surface.
The optimization of 2.3 experiment conditions
2.3.1 the optimization of semicystinol concentration
The aggregation of gold-silver alloy nanoparticles is by Cd in the aqueous solution2+It is special in the cysteine of alloy surface with modifying
Property combine and realize, therefore the concentration of cysteine has a great impact to the detection sensitivity of the detection method.Half Guang ammonia
Acid the concentration easier aggregation of more high alloy, but semicystinol concentration it is too high when, unnecessary cysteine can cause alloy
Self aggregation between particle, causes the reduction of detection sensitivity.In 13.2 μM of Cd2+In the presence of, with the increasing of this semicystinol concentration
Plus, p-ratio increase is absorbed, Detection results are more obvious (Fig. 5 A), but when concentration is more than 23.33 μM, Detection results substantially drop
It is low, therefore, 23.33 μM of selection is used as optimal semicystinol concentration.
2.3.2 the selection of detection time
Fig. 5 B are influence of the detection time to testing result under the conditions of normal temperature (25 DEG C).As can be seen from the figure half Guang ammonia
The gold-silver alloy nanoparticles of acid modification are to Cd2+Detection react completion in very short time, 15min basically reaches stabilization, because
This, 15min is chosen for the follow-up reaction time.
2.3.3 the influence of alloy solution pH value
Investigated pH between 5-11 alloy nano particle to Cd2+Detection sensitivity influence.Fig. 5 C show, identical
Cd2+Under concentration, the absorption p-ratio of maximum can be obtained as pH=6.0, therefore, selection pH=6.0 is detected.
2.3.3NaCl the influence of concentration
Ionic strength in alloy solution has larger influence to detection, to make detection sensitivity higher, have studied molten
Influence (Fig. 5 D) of the NaCl concentration to testing result in liquid, it can be seen that with NaCl concentration increase sensitivity not
It is disconnected to improve, but when NaCl concentration is 0.024M, solution starts to produce aggregation, therefore NaCl concentration is that 0.024M is optimum concentration.
Cd in 2.4 colorimetric detection water2+
With optimal conditions, detection Cd is depicted2+Working curve.As shown in Figure 6A, with Cd2+The increase of concentration, it is molten
Absworption peak of the liquid at 435nm constantly reduces, and the new absworption peak occurred at 600nm constantly strengthens.Cd2+The work of detection
Curve as shown in Figure 6B, works as Cd2+When concentration is 0.4~38.6 μM (Fig. 6 B), linear equation is Y=0.0142C+0.0858 (R2
=0.9985)；Lowest detection is limited to 0.044 μM.2.5 selectivity experiments
Cd is determined respectively2+, toluene (Met), parachloronitrobenzene (4-Nc), dimethylbenzene (Xyl), diphenylamines (Dpl), Ni2 +、K+、Ba2+、Al3+、Zn2+、Co2+、Cu2+、Mg2+、Hg2+、Mn2+、Na+、Fe3+、Pb2+Gold and silver is closed under same concentrations (21.6 μM)
The absorption p-ratio (Fig. 7 A) of solution of gold nanoparticles, as a result shows and only adding Cd2+When solution have obvious absorbance ratio
Change, and other chaff interferences are substantially unchanged, show the method to Cd2+Detection has good selectivity.
The stability of 2.6 gold-silver alloy nanoparticles
The gold-silver alloy nanoparticles solution for preparing still keeps clear in longer time, its absorption spectrum and
Absorption peak strength had almost no change (Fig. 7 B) in 15 days, shows the gold-silver alloy nanoparticles solution of synthesis and has preferably steady
It is qualitative.
The detection of 2.7 actual water samples
The pretreated actual water samples of 10 μ L are taken respectively, and Cd is carried out according to the method described above2+Determine, and carry out 0.8,5.0,
15.0 μM of three horizontal Cd2+The recovery testu of concentration, spectra re-recorded data simultaneously carry out Mathematical treatment, the mark-on being calculated
The rate of recovery is 102.9%~110.0% (table 1), and experimental result is satisfactory.
The sample analysis result of table 1 and the rate of recovery
Table 1Recovery test of the assay in tap and lake samples with spiked
Cd2+
3 conclusions
HAuCl is reduced using chemical reduction method simultaneously4And AgNO3, successfully synthesize the gold-silver alloy nanoparticles of stabilization.
Based on Cd2+Can cause the gold-silver alloy nanoparticles of cysteine modified that aggregation occurs causes solution colour to change, and sets up
It is a kind of to Cd in water2+The method of quick detection, the method selectively good, simple to operate, detection time is short, instrument is inexpensive, spirit
Sensitivity is higher, disclosure satisfy that Cd in water2+Detection.
Claims (2)
1. a kind of method that gold-silver alloy nanoparticles probe visualization based on cysteine modified detects cadmium in water, its feature
It is：Comprise the following steps：
(1) preparation of cysteine modified gold-silver alloy nanoparticles
Accurately pipette 48 μ L 1.0%AgNO3Solution and 47 μ L 1.0%HAuCl4Solution is added separately to equipped with 15mL ultra-pure waters
Flask in, add the μ L of 0.4mM citric acid three sodium solutions 250 simultaneously after condensing reflux heating 5min, reheat 2min, Ran Houli
Mix and continue agitating heating 15min, obtain the solution of crocus clarification and stable and uniform, as electrum solution；
Add 0.7mL 1.0mM cysteine solutions at the uniform velocity to stir 2h in the electrum solution of above-mentioned new synthesis, obtain half
The gold and silver Nanoalloy solution of cystine modification；
(2) Cd in colorimetric detection water2+
NaCl is added to the gold and silver Nanoalloy solution of cysteine modified, makes its concentration for 0.024M, be by concentration respectively
0.40、1.34、2.23、4.44、6.65、8.85、11.00、13.20、15.40、17.50、21.80、26.10、30.30、
34.50、38.60μM Cd2+The gold and silver Nanoalloy that standard liquid is added to the above-mentioned cysteine modifieds containing NaCl of 2mL is molten
In liquid, hatch 15min, after question response is complete, it can be observed that obvious color change, the face of solution is shot with digital camera
Color, makes standard color comparison card；Meanwhile, suction of the solution at 435nm and at 600nm is determined using ultraviolet-visible spectrophotometry
Luminosity, with solution absorbance ratio (A600/A435) it is ordinate, Cd2+Concentration is abscissa, drawing curve, linear fit
Obtain a linear equation with one unknown；10 μ L are taken through precipitation, filtering, the regulation pretreated water samples of pH to 6.0, is added on 2mL
State in the gold and silver Nanoalloy solution of the cysteine modified containing NaCl, hatch 15min, after question response is complete, use digital phase
Machine shoots the color of solution, and the color of solution is contrasted with standard color comparison card in the photo that will be shot, i.e., to the Cd in water sample2+Content
Carry out half-quantitative detection；Meanwhile, determine solution 435nm locate with 600nm at absorbance and calculate solution absorbance ratio
(A600/A435), substitute into linear equation with one unknown, you can try to achieve Cd in water2+Content.
2. a kind of gold-silver alloy nanoparticles probe visualization based on cysteine modified as claimed in claim 1 detects water
The method of middle cadmium, it is characterised in that：Cysteine is dense in the gold and silver Nanoalloy solution of cysteine modified described in step (1)
Degree concentration is 23.33 μM；The pH of the gold and silver Nanoalloy solution of cysteine modified described in step (1) is 6.0.
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| CN109807344A (en) * | 2019-01-22 | 2019-05-28 | 天津大学 | The gold nanoparticle and the preparation method and application thereof of Norvancomycin modification |
| CN111965118A (en) * | 2020-08-13 | 2020-11-20 | 中国海洋大学 | Method for detecting cadmium ions by assembling gold nanoparticle array |
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