CN106596504A - Method of ultrasensitive detection on cyanide in water body - Google Patents
Method of ultrasensitive detection on cyanide in water body Download PDFInfo
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- CN106596504A CN106596504A CN201611154676.1A CN201611154676A CN106596504A CN 106596504 A CN106596504 A CN 106596504A CN 201611154676 A CN201611154676 A CN 201611154676A CN 106596504 A CN106596504 A CN 106596504A
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- cyanide
- gold
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- 238000001514 detection method Methods 0.000 title claims abstract description 73
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 23
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 29
- 230000035945 sensitivity Effects 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000010931 gold Substances 0.000 claims description 52
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 51
- 229910052737 gold Inorganic materials 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 22
- 238000001069 Raman spectroscopy Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000007689 inspection Methods 0.000 claims description 8
- -1 gold potassium chloride Chemical compound 0.000 claims description 7
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical class OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 108090000526 Papain Proteins 0.000 claims description 4
- 239000004365 Protease Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000019834 papain Nutrition 0.000 claims description 4
- 229940055729 papain Drugs 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical group SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 claims description 3
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WLTCOOBROPAEPO-UHFFFAOYSA-N C1(=CC=CC=C1)S.[F] Chemical compound C1(=CC=CC=C1)S.[F] WLTCOOBROPAEPO-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 claims description 3
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 claims description 3
- 101710088194 Dehydrogenase Proteins 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 3
- 102000016943 Muramidase Human genes 0.000 claims description 3
- 108010014251 Muramidase Proteins 0.000 claims description 3
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims description 3
- 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 claims description 3
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 3
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001922 gold oxide Inorganic materials 0.000 claims description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 3
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 3
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 229960000274 lysozyme Drugs 0.000 claims description 3
- 239000004325 lysozyme Substances 0.000 claims description 3
- 235000010335 lysozyme Nutrition 0.000 claims description 3
- 239000002055 nanoplate Substances 0.000 claims description 3
- SEXOVMIIVBKGGM-UHFFFAOYSA-N naphthalene-1-thiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1 SEXOVMIIVBKGGM-UHFFFAOYSA-N 0.000 claims description 3
- 102000039446 nucleic acids Human genes 0.000 claims description 3
- 108020004707 nucleic acids Proteins 0.000 claims description 3
- 150000007523 nucleic acids Chemical class 0.000 claims description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 claims 1
- XJCPMUIIBDVFDM-UHFFFAOYSA-M nile blue A Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4[O+]=C3C=C(N)C2=C1 XJCPMUIIBDVFDM-UHFFFAOYSA-M 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 13
- 239000000523 sample Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000011896 sensitive detection Methods 0.000 description 3
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- 241000545067 Venus Species 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000011664 signaling Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 208000029039 cyanide poisoning Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to the field of cyanide detection, in particular to a method of ultrasensitive detection on cyanide based on a nanogold substrate SERS technology. The method comprises the following steps: (1) mixing cyanide solutions with different concentrations and aqueous solutions with different concentrations with a nanogold detection substrate respectively to obtain multiple groups of mixed solutions, determining an SERS strength value of each group of the mixed solution, and then drawing a standard curve graph of the cyanide concentrations and the SERS strength value; and (2) mixing the solution to be detected with the nanogold detection substrate to obtain a mixed solution to be detected, determining an SERS strength value of the mixed solution to be detected, and then obtaining the concentration value of the cyanide from the curve graph. The detection method has the advantages that is simple to operate and low in cost, can rapidly and sensitively detect the cyanide, can rapidly detect the cyanide with high specificity and high sensitivity below a lower limit of detection and can still efficiently detect the cyanide to be detected under the condition that the concentration of an interferent reaching up to tens times of the cyanide to be detected.
Description
Technical field
The present invention relates to the detection field of cyanide, is based on nanometer gold substrate SERS technology hypersensitive more particularly to a kind of
The method of detection cyanide.
Background technology
In recent years, the timely early warning of environmental pollution and effectively improvement has become particularly important one in national development link
Ring.Due to the fast development of modern industry, many cyanides are entered by the sewage that the industry such as plating, paint, dyestuff, rubber is discharged
Enter in natural water, the serious harm mankind's is healthy.From 2009 so far, China has occurred and that a lot of cyanide poisoning things
Part, has had a strong impact on health of the masses.China is new《Drinking water sanitary standard》In to cyanide in daily drunk water
Content has carried out strict restriction, and puts into effect on April 2nd, 2015《Water prevention and cure of pollution action plan》, in pollution process, work
Industry waste water, the comprehensively many-side such as control pollutant emission carry out strong supervision and start strict system of accountability, and iron hand pollution treatment will be entered
Enter " new normality ".
The method of comparative maturity and conventional detection cyanide has spectrographic method, titrimetry, voltammetry, electrification both at home and abroad at present
Method etc., however, these methods are present, instrument price is expensive, detection time is longer, detection sensitivity is not up to standard, other ions are done
Disturb it is serious, need the defects such as professional operation technical staff.
Therefore, this area is badly in need of a kind of new simple to operation, strong antijamming capability of exploitation, low cost and detects spirit
The method of the high detection cyanide of sensitivity.
The content of the invention
It is an object of the invention to：A kind of new simple to operation, strong antijamming capability, low cost and detection are provided
The method of the high detection cyanide of sensitivity.
To achieve these goals, the present invention provides following technical scheme：
In a kind of super sensitivity detection water body, the method for cyanide, comprises the steps：
(1) variable concentrations cyanide solution and aqueous solution are mixed to get into multigroup mixing with nanometer gold detection substrate respectively
Liquid, determines the SERS intensity levels of every group of mixed liquor, then draws the canonical plotting of concentration of cyanide and SERS intensity levels；
(2) prepare liquid and nanometer gold detection substrate are mixed to get into mixed liquor to be measured, the SERS for determining mixed liquor to be measured is strong
Angle value, then obtains concentration of cyanide value from curve chart.
Preferably, described cyanide be hydrocyanic acid, Cyanogran., potassium cyanide, cyanogen chloride, acrylonitrile, in n-Butyronitrile one
Plant or various.
Preferably, in the liquid to be checked, the concentration limit of cyanide to be checked is 0.01 μm of ol/L.
Preferably, nanometer gold detection substrate is nano gold spherical substrate, nanometer gold bar substrate, nanometer gold satellite-based bottom, receives
One or more in meter Jin Li cube substrates, gold nano-plates substrate.
Preferably, the nanometer gold detection substrate includes cyanide indicator, nanometer gold detection substrate presoma and Raman
Signaling molecule；The concentration of the cyanide indicator is 0.001-100mmol/L；The nanometer gold detects the dense of substrate presoma
Spend for 0.01-100mmol/L；The concentration of the Raman signal molecule is 0.01-100mmol/L.
Preferably, the cyanide indicator is papain, Lysozyme, cytochrome oxidase, thiosulfuric acid
One or more in sodium, peroxidase, lactic acid dehydrogenase；
The nanometer gold detection substrate presoma is gold oxide, gold hydroxide, auric chloride, gold chloride, gold potassium chloride, tetrachloro
Sodium aurate dichloro, (2- pyridine carboxylic acids) gold, tetra chlorauric acid ammonium, one or more of tetra chlorauric acid；
The Raman signal molecule be 4- mercaptopyridines, 4- mercaptobenzoic acids, rhodamine 6G, p-Mercaptoaniline, Nile blue,
Crystal violet mercaptonaphthalene, to one or more in fluorine thiophenol, Graphene.
Preferably, the mixed volume ratio of the liquid to be checked and nanometer gold detection substrate is 1-50：50-1.
Preferably, the nanometer gold detection substrate also includes functionalized reagent.
Preferably, the functionalized reagent be sodium citrate, ascorbic acid, sodium thiosulfate, disodiumedetate,
One or more in tween, polyvinylpyrrolidone, cetyl trimethylammonium bromide, gelatin, polysaccharide, protein, nucleic acid.
Preferably, the concentration of the functionalized reagent in the nanometer gold detection substrate is 0.01-1000 μm of ol/L.
The beneficial effects of the present invention is：
(1) high specific under low-detection lower limit, quick detection with sensitivity to cyanide be may be implemented in；
(2) in the case of the concentration decades of times at concentrations up to cyanide to be checked of chaff interference, still efficiently can realize treating
The detection of inspection cyanide；
(3) using the nanometer gold detection substrate qualitative detection on the basis of, based on the nanometer gold detection substrate with
The rapid chemical response of cyanide to be checked, must change the content that can quantitatively detect cyanide to be checked with reference to SERS intensity levels；
(4) detection method is simple to operate, low cost, be capable of achieving rapid sensitive detection cyanide；
(5) detection method is good to measuring samples adaptability, is substantially not present any restriction, easy to utilize；
(6) detection method is capable of achieving to detecting while various cyanides.
Description of the drawings
Cyanide corresponding Raman spectrograms of the Fig. 1 for variable concentrations；
Fig. 2 is the canonical plotting of concentration of cyanide and SERS intensity levels.
Specific embodiment
In a kind of super sensitivity detection water body, the method for cyanide, comprises the steps：
(1) variable concentrations cyanide solution and aqueous solution are mixed to get into multigroup mixing with nanometer gold detection substrate respectively
Liquid, determines the SERS intensity levels of every group of mixed liquor, then draws the canonical plotting of concentration of cyanide and SERS intensity levels, such as schemes
Shown in 1；
(2) prepare liquid and nanometer gold detection substrate are mixed to get into mixed liquor to be measured, the SERS for determining mixed liquor to be measured is strong
Angle value, then obtains concentration of cyanide value from curve chart.
Preferably, described cyanide be hydrocyanic acid, Cyanogran., potassium cyanide, cyanogen chloride, acrylonitrile, in n-Butyronitrile one
Plant or various.
Preferably, in the liquid to be checked, the concentration limit of cyanide to be checked is 0.01 μm of ol/L.
Preferably, nanometer gold detection substrate is nano gold spherical substrate, nanometer gold bar substrate, nanometer gold satellite-based bottom, receives
One or more in meter Jin Li cube substrates, gold nano-plates substrate.
Preferably, the nanometer gold detection substrate includes cyanide indicator, nanometer gold detection substrate presoma and Raman
Signaling molecule；The concentration of the cyanide indicator is 0.001-100mmol/L, and preferred concentration is 0.05-50mmol/L；
The concentration of the nanometer gold detection substrate presoma is 0.01-100mmol/L, and preferred concentration is 0.2-80mmol/L；Institute
The concentration for stating Raman signal molecule is 0.01-100mmol/L, and preferred concentration is 0.2-100mmol/L.
Preferably, the cyanide indicator is papain, Lysozyme, cytochrome oxidase, thiosulfuric acid
One or more in sodium, peroxidase, lactic acid dehydrogenase；
The nanometer gold detection substrate presoma is gold oxide, gold hydroxide, auric chloride, gold chloride, gold potassium chloride, tetrachloro
Sodium aurate dichloro, (2- pyridine carboxylic acids) gold, tetra chlorauric acid ammonium, one or more of tetra chlorauric acid；
The Raman signal molecule be 4- mercaptopyridines, 4- mercaptobenzoic acids, rhodamine 6G, p-Mercaptoaniline, Nile blue,
Crystal violet mercaptonaphthalene, to one or more in fluorine thiophenol, Graphene.
Preferably, the mixed volume ratio of the liquid to be checked and nanometer gold detection substrate is 1-50：50-1.
Preferably, the nanometer gold detection substrate also includes functionalized reagent.
Preferably, the functionalized reagent be sodium citrate, ascorbic acid, sodium thiosulfate, disodiumedetate,
One or more in tween, polyvinylpyrrolidone, cetyl trimethylammonium bromide, gelatin, polysaccharide, protein, nucleic acid.
Preferably, the concentration of the functionalized reagent in the nanometer gold detection substrate is 0.01-1000 μm of ol/L, more preferably
Concentration be 0.1-300 μm of ol/L.
1 accuracy of embodiment is detected
Deionized water is added to make the aqueous solution of known cyanide ion concentration the cryanide ion of various dose：C0-C6, wherein C0
For blank.
Configuration nanometer Venus detection substrate：Take in the aqueous solution of chloraurate 3mL addition 50mL deionized waters of 5mmol/L, so
Add 1mL0.1M CTAB, stirring after ten minutes, to add 50mM silver nitrate solutions afterwards, gold is made after stirring half an hour and plants solution.Take
5mL gold is planted solution and rapidly joins 5mL 20mg/mL ascorbic acid solutions, and after stirring 30 seconds, lucifuge is aged 2 hours.Take what is prepared
Nano-Au solution 10mL adds the papain solution of 100 μ L 0.1mM, rapidly joins 50 μ L40mM's after stirring half an hour
4- mercaptobenzoic acid solution, continues stirring and obtains within ten minutes a nanometer Venus detection substrate.
The liquid to be checked of 200 μ L difference cyanide ion concentrations is separately added in the matched somebody with somebody detection substrates of 800 μ L, using Raman spectrum
Instrument measures SERS intensity levels.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity (being shown in Table 1).
Table 1
As it can be seen from table 1 using measured concentration obtained by the inventive method and liquid to be checked concentration known closely, return
(wherein, the response rate refers to and adds quantitative reference material in the blank sample substrate for not having measured matter yield between 90～96
Matter, analyzes according to the process step of sample, the ratio of the result for obtaining and theoretical value), even if at very low concentrations, still may be used
The highly sensitive detection to cryanide ion to be checked is realized, this shows high to realize to be checked precisely, with sensitivity using the inventive method
The measurement of cryanide ion.
2 specific detection of embodiment
Other interfering ions (F is added in the cryanide ion aqueous solution of the variable concentrations of configuration in the present embodiment-, Cl-,Br-,
I-,NO3 -,NO2 -,CO3 2-,SCN-,S2-,SO4 2-) (adding in the form of salts, the total concentration of added interfering material is 10 μm of ol/L),
Repeat the method used by embodiment 1 to measure the aqueous solution of concentration known.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity (being shown in Table 2).
Table 2
From table 2 it can be seen that using measured concentration obtained by the inventive method and liquid to be checked concentration known closely, return
Even if yield at very low concentrations, is still capable of achieving the highly sensitive detection to cryanide ion to be checked, this table between 86～103
Bright use the inventive method can the high measurement realized precisely, with sensitivity to cryanide ion to be checked.
Additionally, further comparing with the testing result of embodiment 1, it is known that even if in the situation that there are a large amount of interfering materials
Under, gained testing result still very accurately, is differed with 1 gained testing result of embodiment also less, shows the inventive method
Strong antijamming capability, with very strong specificity.
The detection of cryanide ion in 3 river of embodiment, lake water water sample
Gather water sample S3.1～S3.4 to be detected：The same depth in different location in river, lake is gathered with water sampling bottle
Water sample, places to be checked.Repeat the method used by embodiment 1 to measure the aqueous solution of concentration known.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity (being shown in Table 3).
Table 3
The detection of cryanide ion in 4 plant chimney stalk of embodiment
Gather water sample S4.1-S4.4 to be detected：Different time collection same volume is in the discharge of wastewater mouth of factory
Water sample, after be mixed uniform, obtain water sample to be detected.Remaining method is with embodiment 3.Repeat the method pair used by embodiment 1
The aqueous solution of concentration known is measured.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity (being shown in Table 4).
Table 4
The detection of dicyanogen in 5 air of embodiment
Collection detected sample S5.1-S5.2：By specific impinger, one is extracted with constant speed detection zone is needed
Determine the air of volume, suspended particulate substance of the air particle diameter less than 100 μm is trapped within specific filter membrane, by the suspension collected
Particulate matter is acidified with the hydrochloric acid of 0.1mol/L so as to dissolved.Remaining method is with embodiment 3.Repeat the method pair used by embodiment 1
The aqueous solution of concentration known is measured.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity (being shown in Table 5).
Table 5
The detection of cryanide ion in 6 food of embodiment
Acquisition testing liquid：Sample (about 2 grams) is obtained from food, mixed solution acidification is used, then with 2% hydrochloric acid
Dissolving, then adjusts pH to neutrality, obtains liquid to be detected.Remaining method is with embodiment 3.Repeat the method pair used by embodiment 1
The aqueous solution of concentration known is measured.
As a result
Substitute into correspondence mark curve (X-SERS intensity levels) respectively to be treated after eight times measured SERS values are averaged
Inspection liquid in cyanide containing numerical quantity, do not contain in as a result illustrating food samples to be detected cryanide ion or only contain micro cryanide ion.
The all documents for referring in the present invention are all incorporated as reference in this application, just as each document coverlet
Solely it is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned teachings for having read the present invention, those skilled in the art
The present invention can be made various changes or modifications, these equivalent form of values equally fall within the model limited by the application claims
Enclose.
Claims (10)
1. in a kind of super sensitivity detection water body cyanide method, it is characterised in that：Comprise the steps：
(1) variable concentrations cyanide solution and aqueous solution are mixed to get into multigroup mixed liquor with nanometer gold detection substrate respectively, are surveyed
The SERS intensity levels of fixed every group of mixed liquor, then draw the canonical plotting of concentration of cyanide and SERS intensity levels；
(2) prepare liquid and nanometer gold detection substrate are mixed to get into mixed liquor to be measured, determine the SERS intensity levels of mixed liquor to be measured,
Then concentration of cyanide value is obtained from curve chart.
2. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：
Described cyanide be hydrocyanic acid, Cyanogran., potassium cyanide, cyanogen chloride, acrylonitrile, one or more in n-Butyronitrile.
3. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：
In the liquid to be checked, the concentration limit of cyanide to be checked is 0.01 μm of ol/L.
4. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：
The nanometer gold detection substrate is nano gold spherical substrate, nanometer gold bar substrate, nanometer gold satellite-based bottom, nanometer gold cube base
One or more in bottom, gold nano-plates substrate.
5. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：
The nanometer gold detection substrate includes cyanide indicator, nanometer gold detection substrate presoma and Raman signal molecule；Institute
The concentration for stating cyanide indicator is 0.001-100mmol/L；The concentration of the nanometer gold detection substrate presoma is 0.01-
100mmol/L；The concentration of the Raman signal molecule is 0.01-100mmol/L.
6. in super sensitivity detection water body according to claim 5 cyanide method, it is characterised in that：
The cyanide indicator is papain, Lysozyme, cytochrome oxidase, sodium thiosulfate, peroxide
One or more in enzyme, lactic acid dehydrogenase；
The nanometer gold detection substrate presoma is gold oxide, gold hydroxide, auric chloride, gold chloride, gold potassium chloride, tetra chlorauric acid
Sodium dichloro, (2- pyridine carboxylic acids) gold, tetra chlorauric acid ammonium, one or more of tetra chlorauric acid；
The Raman signal molecule is 4- mercaptopyridines, 4- mercaptobenzoic acids, rhodamine 6G, p-Mercaptoaniline, Nile blue, crystallization
Purple mercaptonaphthalene, to one or more in fluorine thiophenol, Graphene.
7. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：The liquid to be checked and
The mixed volume ratio of the nanometer gold detection substrate is 1-50：50-1.
8. in super sensitivity detection water body according to claim 1 cyanide method, it is characterised in that：The nanometer gold inspection
Survey substrate and also include functionalized reagent.
9. in super sensitivity detection water body according to claim 8 cyanide method, it is characterised in that：
The functionalized reagent is sodium citrate, ascorbic acid, sodium thiosulfate, disodiumedetate, tween, polyethylene
One or more in ketopyrrolidine, cetyl trimethylammonium bromide, gelatin, polysaccharide, protein, nucleic acid.
10. in super sensitivity detection water body according to claim 8 cyanide method, it is characterised in that：The nanometer gold
The concentration of the functionalized reagent in detection substrate is 0.01-1000 μm of ol/L.
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