CN106596542B - A kind of synthesis of Ultraluminescence molecular probe and its detection to nitrite anions - Google Patents
A kind of synthesis of Ultraluminescence molecular probe and its detection to nitrite anions Download PDFInfo
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- CN106596542B CN106596542B CN201611182739.4A CN201611182739A CN106596542B CN 106596542 B CN106596542 B CN 106596542B CN 201611182739 A CN201611182739 A CN 201611182739A CN 106596542 B CN106596542 B CN 106596542B
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- indoles
- ultraluminescence
- pyridine
- nitrite anions
- pyridine diformamide
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- -1 nitrite anions Chemical class 0.000 title claims abstract description 42
- 239000003068 molecular probe Substances 0.000 title claims abstract description 26
- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 150000002475 indoles Chemical class 0.000 claims abstract description 94
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 75
- 239000000523 sample Substances 0.000 claims abstract description 33
- 238000010189 synthetic method Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 238000000862 absorption spectrum Methods 0.000 claims description 17
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007995 HEPES buffer Substances 0.000 claims description 14
- 238000002189 fluorescence spectrum Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- ZCBIFHNDZBSCEP-UHFFFAOYSA-N 1H-indol-5-amine Chemical compound NC1=CC=C2NC=CC2=C1 ZCBIFHNDZBSCEP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000000295 emission spectrum Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 3
- 230000012447 hatching Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims 2
- 238000001556 precipitation Methods 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 3
- MUXMPBYMARNJDR-UHFFFAOYSA-N C(=O)N.C(=O)N.N1=CC=CC=C1 Chemical compound C(=O)N.C(=O)N.N1=CC=CC=C1 MUXMPBYMARNJDR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007811 spectroscopic assay Methods 0.000 abstract 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 238000005259 measurement Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 229940005654 nitrite ion Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000017897 Carcinoma of esophagus Diseases 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 208000000461 Esophageal Neoplasms Diseases 0.000 description 1
- 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 1
- YKLFSQROPDRLQF-UHFFFAOYSA-N NCCN.C1=CC=CC2=CC=CC=C21 Chemical compound NCCN.C1=CC=CC2=CC=CC=C21 YKLFSQROPDRLQF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000007698 birth defect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 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
- 238000011835 investigation Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 208000000995 spontaneous abortion Diseases 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- G01N21/75—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
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- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The present invention relates to a kind of synthetic method of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- for detecting nitrite anions and its applications in the nitrite detection of all kinds of actual samples.This using double indoles as fluorogen, pyridine diformamide is the synthesis of two indoles -2,6- pyridine diformamide of both arms cryptate N, N ' -5- of bracket, realizes the specific recognition to nitrite anions.Probe is stablized with optical property, and specific good, high sensitivity is easily prepared, feature at low cost, and (2 ~ 5) can detect nitrite anions under the pH value condition of milder.With N, two indoles -2 of N ' -5-, 6- pyridine diformamide measures the content of the nitrite anions in all kinds of actual samples, can be by whether containing nitrite anions in the qualitative judgement sample of variation of color, while can pass through the nitrite anions content of Ultraluminescence spectroscopic assay sample.
Description
Technical field
The present invention relates to a kind of conjunctions of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-
At and its to nitrite anions detection, belong to luminous organic material field.
Background technique
Nitrite refers mainly to sodium nitrite (NaNO2) and potassium nitrite (KNO2), it is crystallization white or yellowish or particle
Sprills, referred to as industrial table salt.Nitrite is distributed widely in nature, be distributed in nature most wide nitrogenous compound it
One, since nitrite easily acts on forming carcinogen N- nitrosamine compound with protein in human body, took in
The nitrite of amount is easy to cause a variety of diseases, such as: cancer of the esophagus, the methemoglobinemia of baby, spontaneous abortion and maincenter mind
Birth defect of warp etc. disease.Therefore the measurement of content of nitrite is just particularly important in water quality monitoring.Currently, lattice
In this reagent (Griess) colorimetric method and 2,3- diaminonaphthalene reagent fluorescence method be most common two kinds of nitrite ion of detection
Method.But when both methods detection nitrite ion, plurality of reagents combination is required, wherein the reagent of Ge Lisi method
It is to be mixed to prepare by the phosphoric acid solution of P-aminobenzene-sulfonamide aqueous solution and naphthodiamide, detecting step is cumbersome, complicated, needs to keep away
Light stored under refrigeration, is finished in half an hour, and reagent storage is difficult, and time-consuming, and needs to react under strong acid effect.Therefore one is established
The method of easy, mild, the highly sensitive detection nitrite anions of kind has safely important application value for guarantee human life.
Summary of the invention
In view of above-mentioned, the purpose of the present invention is intended to provide a kind of two indoles -2,6- pyrrole of Ultraluminescence molecular probe N, N ' -5-
The synthesis of pyridine diformamide.
Another object of the present invention is to provide Ultraluminescence molecular probes to the detection method of nitrite anions.
The purpose of the present invention is be achieved through the following technical solutions:
A kind of synthesis of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-
661 mg 5- amino indoles are placed in 250 mL round-bottomed flasks, are dissolved in 100 mL anhydrous acetonitriles, room temperature
It stirs, under nitrogen protection, 7.5 mL triethylamines and 18 mg 4-dimethylaminopyridine is added.By 510 mg 2,6- pyridine diformazans
Acyl chlorides is dissolved in anhydrous acetonitrile, and is instilled in above-mentioned solution, there is white cigarette generation immediately, is stirred at room temperature 12 hours, Zhi Daoyou
Solid is precipitated, and solvent is evaporated off after the reaction was completed, solid is washed with water, and continues to be washed three times with acetonitrile after filtering, 30 DEG C of vacuum
It is dry, obtain two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-.
The composite structure formula of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- is as follows:
The physicochemical property of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-:
Two indoles -2,6- pyridine diformamide (C of N, N ' -5-24H21N5O3) it is in dark brown solid, molecular weight is
395.1462 fusing point is 324-325 degrees Celsius.
The mechanism of Ultraluminescence molecular probe measurement nitrite anions.
Two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, since the p- of amido bond is pi-conjugated, electricity
In sub- cloud delocalization to C-N key, so that its property for having partial double bond, conjugation range expands, molecular rigidity enhancing, has relatively strong
Fluorescence.And the hydrogen in two indoles -2,6- pyridine diformamide of N, N ' -5- on amido bond nitrogen is easy to pass through hydrogen as hydrogen bond donor
Key is in conjunction with nitrite-anion, therefore, in acid condition, nitrite anions and N, two indoles -2,6- pyridine diformazan of N ' -5-
Hydrogen in amide on amido bond nitrogen has interrupted the big pi bond of conjugation, and due to hydrogen bond action, make molecule no longer by Hydrogenbond
In same plane, fluorescent quenching is eventually led to.Pass through the line between the change and nitrite ion concentration of system fluorescence signal
Sexual intercourse is realized to Huanghe water, lake water and the originally fast qualitative quantitative detection of water sample Nitrite.Meanwhile N, N ' -5- two
Indoles -2,6- pyridine diformamide and NO2 ﹣After effect, red shift is had occurred in UV absorption, occurs new absorption peak in visual field,
Cause its color to become pale pink, illustrates that N, two indoles -2,6- pyridine diformamide probe of N ' -5- can pass through color change pair
NO2 ﹣Realize qualitatively identification.
Advantages of the present invention and generate the utility model has the advantages that
The present invention overcomes in place of the deficiencies in the prior art.Utilize 5- amino indole, 2,6- pyridine diformamides, three second
Amine, 4-dimethylaminopyridine have synthesized two indoles -2,6- pyridine of Ultraluminescence molecular probe N, N ' -5- using One-step Reaction At Room Temperature
Diformamide, the synthesis of probe is very simple and mild condition, strong operability.The operating procedure of present invention measurement nitrite anions
Simply, the conventional method of complex steps is compared advantageously.The present invention can detect water with two methods of ultraviolet and fluorescence simultaneously
Nitrite anions content in sample, probe and nitrite anions by after hydrogen bond action, UV absorption maximum wavelength at 270 nm,
Most hyperfluorescence emits at 360 nm.The present invention is used for the assay of all kinds of natural water Nitrites, can detecte out
Huanghe water, lake water and the originally content of water sample Nitrite, minimum detection limit is respectively 166 nM and 100 nM, for monitoring
Harmful nitrite anions content in natural water, so that prevention and guarantee human health generate positive effect.Present invention synthesis
Two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, optical property stablize, storage time is long, specifically
Property good, high sensitivity, be a kind of method of simply and effectively detection nitrite anions.
Detailed description of the invention
Fig. 1 is N synthesized by the present invention, two indoles -2,6- pyridine diformamide of N ' -5-1H spectrum.
Fig. 2 is N synthesized by the present invention, two indoles -2,6- pyridine diformamide of N ' -5-13C spectrum.
Fig. 3 is N synthesized by the present invention, the high resolution mass spectrum figure of two indoles -2,6- pyridine diformamide of N ' -5-.Spectrogram
In 395.1462 [M+H+] it is N, the molecular ion peak of two indoles -2,6- pyridine diformamide of N ' -5-.
Fig. 4 is N of the present invention, the high-resolution of product after two indoles -2,6- pyridine diformamide of N ' -5- is reacted with nitrite anions
Mass spectrogram, 515.1516 [M+H in spectrogram+] it is N, two indoles -2,6- pyridine diformamide of N ' -5- produces after reacting with nitrite anions
The molecular ion peak of object.
Fig. 5 is N of the present invention, the ultra-violet absorption spectrum of two indoles -2,6- pyridine diformamide of N ' -5-.
Fig. 6 is N of the present invention, the ultraviolet suction of product after two indoles -2,6- pyridine diformamide of N ' -5- is reacted with nitrite anions
It receives spectrum (b), test system is 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, pH=3
HEPES buffer solution.
Fig. 7 is N of the present invention, the fluorescence emission spectrum of two indoles -2,6- pyridine diformamide of N ' -5-.
Fig. 8 is N of the present invention, the fluorescence hair of product after two indoles -2,6- pyridine diformamide of N ' -5- is reacted with nitrite anions
Spectrum is penetrated, test system is 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, the HEPES of pH=3
Buffer solution.
Fig. 9 is N of the present invention, two indoles -2,6- pyridine diformamide of N ' -5- and NO2 ﹣Fluorescence under the different role time
Strength Changes, test system are 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, pH=3
HEPES buffer solution.
Figure 10 is N of the present invention, two indoles -2,6- pyridine diformamide of N ' -5- and NO2 ﹣Before and after effect at various ph values
Fluorescence intensity change, test system are 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, pH=0
~ 12 HEPES buffer solutions.
Figure 11 is N of the present invention, and two indoles -2,6- pyridine diformamide of N ' -5- and the ultraviolet of various analytes effect can
See that absorption spectrum, test system are 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, pH=3
HEPES buffer solution.
Figure 12 is N of the present invention, the fluorescence hair of two indoles -2,6- pyridine diformamide of N ' -5- and the effect of various analytes
Spectrum is penetrated, test system is 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, 200 μM of NaNO2, the HEPES of pH=3
Buffer solution.
Figure 13 is N of the present invention, the NO of N ' -5- two indoles -2,6- pyridine diformamide and various concentration2 ﹣Purple after effect
Outside-visible absorption spectra variation
Figure 14 is N of the present invention, the NO of N ' -5- two indoles -2,6- pyridine diformamide and various concentration2 ﹣It is ultraviolet after effect
Absorption maximum intensity and NO2 ﹣The linear relationship of concentration, test system are 10 μM of N, two indoles -2,6- pyridine of N ' -5-, two formyl
Amine, the HEPES buffer solution of pH=3, NO2 ﹣: 0, 0.1, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0,
8.0, 9.0, 10 μM。
Figure 15 is N of the present invention, the NO of N ' -5- two indoles -2,6- pyridine diformamide and various concentration2 ﹣Fluorescence after effect
Emission spectrum variation
Figure 16 is N of the present invention, the NO of N ' -5- two indoles -2,6- pyridine diformamide and various concentration2 ﹣Maximum after effect
Fluorescence intensity and NO2 ﹣The linear relationship of concentration, test system are 10 μM of N, two indoles -2,6- pyridine diformamide of N ' -5-, pH
=3 HEPES buffer solutions, NO2 ﹣: 0, 0.1, 1.0, 2.0, 3.0, 4.0, 5.0, 7.0, 8.0, 9.0, 10,
12, 15, 20, 50, 100 μM。
Specific embodiment
With reference to the accompanying drawings and examples and experimental example is described further technical solution of the present invention again:
Embodiment 1
661 mg 5- amino indoles are placed in 250 mL round-bottomed flasks, are dissolved in 100 mL anhydrous acetonitriles, room temperature
It stirs, under nitrogen protection, 7.5 mL triethylamines and 18 mg 4-dimethylaminopyridine is added.By 510 mg 2,6- pyridine diformazans
Acyl chlorides is dissolved in anhydrous acetonitrile, and is instilled in above-mentioned solution, there is white cigarette generation immediately, is stirred at room temperature 12 hours, Zhi Daoyou
Solid is precipitated, and solvent is evaporated off after the reaction was completed, solid is washed with water, and continues to be washed three times with acetonitrile after filtering, 30 DEG C
Vacuum drying, obtains two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, yield 72%.
This experiment nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize Ultraluminescence molecular probe
The structure of two indoles -2,6- pyridine diformamide of N, N ' -5-.
Product is tested with nuclear magnetic resonance chemical analyser after probe synthesis, obtains its hydrogen spectrogram 1, it was demonstrated that there are 17 hydrogen originals
Son, chemical shift data are as follows:
1H NMR (400 MHz,d6-DMSO) δ 10.95 (s, 2H), 10.88 (s, 2H ), 8.37 (d, J
= 7.7 Hz, 2H), 8.24 (t, J = 7.7 Hz, 1H), 8.06 (s, 2H), 7.51 (dd, J = 8.6, 1.0
Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H), 7.32 (s, 2H), 6.45 (s, 2H)。
Obtain its carbon spectrogram 2, it was demonstrated that there are 23 carbon atom its chemical shift datas are as follows:
13C NMR (101 MHz, ) δ 162.02 (s), 150.07 (s), 140.08 (s), 134.07 (s),
130.41 (s), 128.12 (s), 126.58 (d, J = 14.8 Hz), 125.21 (s), 117.44 (s),
113.85 (s), 111.64 (s), 101.81 (d, J = 9.1 Hz)。
High resolution mass spectrum Fig. 3 shows that its molecular weight is ESI-MSm/z (M + H+) =395.1462。
The above characterization demonstrates compound N, and two indoles -2,6- pyridine diformamide of N ' -5- synthesizes successfully.
In the following, the present invention is by high resolution mass spectrum, ultra-violet absorption spectrum, fluorescence emission spectrum experiment to Ultraluminescence molecule
Two indoles -2,6- pyridine diformamide of probe N, N ' -5- tests the detection performance of nitrite anions.
1. high resolution mass spectrum is tested
After the success of two indoles -2,6- pyridine diformamide molecule synthesis of N, N ' -5-, the present invention has studied N, N ' -5- first
The mechanism of action of two indoles -2,6- pyridine diformamide molecules and nitrite anions.
To N, 200 μM of NO is added in two indoles -2,6- pyridine diformamide of N ' -5-2 ﹣, hatch 30 points in 37 DEG C of water-baths
After clock (pH=3, HEPES), occurring at m/z:515.1516 molecular ion peak (Fig. 4), the appearance of molecular ion peak proves N,
Two indoles -2,6- pyridine diformamide of N ' -5- is had an effect with nitrite anions, and the reaction mechanism of this and supposition is consistent.
2. Ultraluminescence is tested
N is measured respectively, and NO is added in two indoles -2,6- pyridine diformamide of N ' -5-2 -The ultraviolet-ray visible absorbing light of front and back
Spectrum and fluorescence emission spectrum.
N, two indoles -2,6- pyridine diformamide of N ' -5- and NO are measured in the HEPES buffer solution of pH=32 ﹣Before effect
Ultraviolet and photoluminescent property variation afterwards.The present invention determines N, two indoles -2,6- pyridine diformamide of N ' -5- and NO first2 ﹣Make
With the uv-visible absorption spectra of front and back, as shown in figure 5, two indoles -2,6- pyridine diformamide of N, N ' -5- is at 270 nm
There is a strong UV absorption, and two indoles -2,6- pyridine diformamide of N, N ' -5- and NO2 ﹣After effect, Fig. 6 is shown in 520 nm
There is new ultraviolet absorption peak in place.
The present invention also measured were N, two indoles -2,6- pyridine diformamide of N ' -5- and NO2 ﹣Act on the fluorescence emission of front and back
Spectrum, Fig. 7 show that N, two indoles -2,6- pyridine diformamide of N ' -5- have strong fluorescent emission at 360 nm, as addition NO2 -
Afterwards, quenching (such as Fig. 8) occurs for fluorescence.
3. the response time tests
N, two indoles -2,6- pyridine diformamide of N ' -5- and NO has been determined2 ﹣Act on the Absorption and emission spectra property of front and back
Afterwards, the present invention is to N, two indoles -2,6- pyridine diformamide of N ' -5- and NO2 ﹣Action time studied.Fig. 9 shows N,
Two indoles -2,6- pyridine diformamide of N ' -5- can be in 30 minutes and NO2 -Reach reaction balance, the fluorescence at 360 nm
Quenching (λ completelyex=270 nm).
4. the selection of pH value
N in pH=0 ~ 12 ranges, two indoles -2,6- pyridine diformamide of N ' -5- and NO are determined respectively2 -Effect front and back
Fluorescence intensity change (such as Figure 10).The experimental results showed that when in pH=7 ~ 12 ranges, two indoles -2,6- pyridine diformazan of N, N ' -5-
Amide and NO2 -Effect front and back almost unstressed configuration, and probe N when pH is 3, two indoles -2,6- pyridine diformamide fluorescence of N ' -5-
Intensity reaches maximum value, this moment as addition NO2 -Afterwards, fluorescence quenches substantially, therefore, selects the HEPES buffer solution in pH=3.0
In tested.
5. selectivity experiment
In order to study N, two indoles -2,6- pyridine diformamide probe of N ' -5- is to NO2 ﹣Recognition capability, the present invention by N,
Two indoles -2,6- pyridine diformamide of N ' -5- respectively with analyte F-, Cl-, Br-, I-, HCO3 -, SO4 2-, SO3 2-,
H2PO4 -, P2O7 4-, CH3COO-, ClO4 -, NO3 -, NO2 ﹣Hatch 30 min in 37 DEG C of water-baths, after the completion of hatching, measures respectively
N, the ultra-violet absorption spectrum and fluorescence emission spectrum of N ' -5- two indoles -2,6- pyridine diformamide and various analytes.Such as
Shown in Figure 11, ultra-violet absorption spectrum is recorded with ultraviolet-visible spectrophotometer, works as N, two indoles -2,6- pyridine of N ' -5-, two formyl
Amine and NO2 ﹣When effect, there is new absorption peak at 520 nm in ultra-violet absorption spectrum, and after being acted on other analytes,
There is no large changes for its ultraviolet spectra, and do not occur new absorption peak in the visible region of 520 nm.As shown in figure 12,
N is recorded with sepectrophotofluorometer, two indoles -2,6- pyridine diformamide of N ' -5- is under 270 nm excitation wavelengths, in 360 nm
The fluorescence emission spectrum at place works as N, two indoles -2,6- pyridine diformamide of N ' -5- and NO2 ﹣When effect, fluorescence emission spectrum exists
Fluorescence at 360 nm quenches, and with after the effect of other analytes, there is no any variations for fluorescence emission spectrum.
This is the results show that two indoles -2,6- pyridine diformamide of N, N ' -5- can be to NO2 -Realize the identification of specificity.
6. concentration titrations are tested
The present invention has studied N, and two indoles -2,6- pyridine diformamide of N ' -5- is for NO2 ﹣Quantitative detection ability.This hair
It is bright that quantitative investigation can be carried out to its with UV absorption and fluorescence emission spectrum respectively.To 10 mmol/L of different volumes
NaNO2In be separately added into the N of 20.0 μ L, 1 mM, two indoles -2,6- pyridine diformamide of N ' -5-, with pH=3 of 10 mol/L
HEPES buffer solution be settled to 2 mL, hatch 30 min in 37 DEG C of water-baths.After the completion of hatching, spectrophotometry is used
Meter record N, two indoles -2,6- pyridine diformamide of N ' -5- and its after react with sodium nitrite product ultra-violet absorption spectrum, use
Ultraviolet-uisible spectrophotometer records N, UV absorption of the two indoles -2,6- pyridine diformamide of N ' -5- under 270 nm wavelength
Spectrum.As seen from Figure 13, with NO2 ﹣The increase of concentration, two indoles -2,6- pyridine diformamide of N, N ' -5- is in 270 nm
The UV absorption at place enhances, and occurs new ultraviolet absorption peak at 520 nm, and gradually increase, in addition, the suction at 270 nm
Receive intensity and NO2 ﹣The concentration of (0-4 μm of ol/L) present good linear relationship (regression equation y=0.0687+
0.552 × [NO2 -], R=0.994), detection limit (LOD, S/N=3) can achieve 166 nM (σ=0.00144)
(Figure 14).
Meanwhile the present invention also records N, two indoles -2,6- pyridine diformamide of N ' -5- and its and nitrous with fluophotometer
The fluorescence emission spectrum of product, records N, two indoles -2,6- pyridine of N ' -5-, two formyl with sepectrophotofluorometer after sour sodium reaction
Fluorescence emission spectrum of the amine under 270 nm excitation wavelengths, as shown in figure 15, with NO2 ﹣The increase of concentration, two Yin of N, N ' -5-
Fluorescent emission intensity of diindyl -2,6- pyridine diformamide at 360 nm gradually decreases, and and NO2 ﹣(0-10 μm of ol/L's)
Concentration presents good linear relationship (regression equation y=- 0.00124+0.05721 × [NO2 -], R =
0.993), detection limit (LOD, S/N=3) can achieve 100 nM (σ=0.428) (Figure 16).This result shows that, N,
Two indoles -2,6- pyridine diformamide of N ' -5- can be under ultraviolet-ray visible absorbing and fluorescent emission both of which to NO2 ﹣It carries out
Quantitative analysis.
7. the measurement experiment of Huanghe water, lake water and tap water Nitrite content
After systematic research N, the optical property of two indoles -2,6- pyridine diformamide of N ' -5-, the present invention by its
Applied to actual sample --- NO in sample in Huanghe water, lake water and tap water2 ﹣The measurement of content.For this purpose, the present invention directly surveys
NO in Yellow River water samples is determined2 ﹣Content, and Huanghe water determined using the method for mark-on reclaims, Lanzhou University gives birth elegant lake lake water
Originally NO in water sample2 ﹣Content.Test NO in the different actual samples of three kinds measured2 ﹣Content and the traditional side Griess
The result of method measurement is close (table 1,2), it was demonstrated that two indoles -2,6- pyridine diformamide of N, N ' -5- can be applied to actual sample
Middle NO2 ﹣Quantitative test.Method particularly includes:
A. sample treatment
Yellow River water samples are derived from Lanzhou Huanghe section, 0.45 μm of filtering with microporous membrane of acquired water sample；Pipette 50 μ L
NaNO2(10 mM) is settled to 10 mL with filtered Huanghe water.
Lake water water sample is derived from Lanzhou University and gives birth elegant lake, and 0.45 μm of filtering with microporous membrane of acquired water sample pipettes 25 μ L
NaNO2(10 mM) is settled to 10 mL with filtered lake water.
Originally water sample is derived from use for laboratory water, pipettes 25 μ L NaNO2(10 mM), tap water is settled to 10 mL.
B. NO in ultraviolet method measurement actual sample2 ﹣Content
The above-mentioned actual sample handled well of 1980 μ L is taken, adjusting pH value with the HCl of 1 mol/L is 3.0, is separately added into 20
Two indoles -2,6- pyridine diformamide of the N of μ L, N ' -5-, shakes up, hatches 30 min at 37 DEG C, use spectrophotometry
Meter records its ultra-violet absorption spectrum.
C. NO in fluorescence spectrometry actual sample2 ﹣Content
The above-mentioned actual sample handled well of 1980 μ L is taken, adjusting pH value with the HCl of 1 mol/L is 3.0, is separately added into 20
Two indoles -2,6- pyridine diformamide of the N of μ L, N ' -5-, shakes up, hatches 30 min at 37 DEG C, with sepectrophotofluorometer point
Intensity of emission spectra at 360 nm (270 nm excitation) is not acquired.
D. NO in Griess method measurement actual sample2 ﹣Content
Griess preparation of reagents:
50 mg P-aminobenzene-sulfonamide are weighed, are settled to the P-aminobenzene-sulfonamide that 50 mL obtain 1% with ultrapure water；It weighs
500 mg naphthodiamides are settled to 50 mL with 5% phosphoric acid and obtain 1% naphthodiamide.By 1% P-aminobenzene-sulfonamide and 1% naphthalene
Ethylenediamine is mixed according to volume ratio 1:1, is obtained Griess reagent, is protected from light stored under refrigeration, is finished in half an hour.
Standard curve is established, into the Griess reagent of 100 μ L, be separately added into (0,15,30,75,150,225,
300.0 μ L, 1 mM) NaNO2, it is settled to 1 mL with ultrapure water, is shaken up, after 30 min of incubation at room temperature, recording it in wavelength is
Absorption values at 548 nm.And standard curve is drawn according to the relationship of concentration and absorbance.
After establishing curve, the above-mentioned actual sample handled well of 2.9 mL is taken, the Griess reagent of 100 μ L is added, shakes up,
30 min of incubation at room temperature, recording it in wavelength is the absorption values at 548 nm.It is calculated in actual sample according to standard curve
Nitrite anions content.
The comparison of Griess method and present invention measurement Yellow River water samples Nitrite content:
NO in 1. Griess method of table and present invention measurement Yellow River water samples2 ﹣Content is contrasted
Griess method and standard samples recovery of the present invention measurement Huanghe water, lake water and originally nitre radical content in the water sample Central Asia is contrasted
As a result:
2 Griess method of table and standard samples recovery of the present invention measure Huanghe water, lake water and originally NO in water sample2 ﹣The ratio of content
According to
By anti-to two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- and its with nitrite anions
Answer the optical Quality Research in front and back, it was demonstrated that Ultraluminescence molecular probe N, N ' -5- two indoles -2, the 6- pyridine of the invention synthesized
Diformamide can be realized by the analysis mode of uv-visible absorption spectra and fluorescence emission spectrum to NO2 ﹣Measurement, compare
Traditional Griess method, present invention synthesis is very simple, and optical property is stablized, specific good, high sensitivity, it is only necessary to which a step is
The detection to nitrite anions can be completed, probe is easier to save, and operates simpler nitrite anions in detection Natural Water
Undoubtedly a kind of short-cut method.
Claims (2)
1. a kind of synthetic method of two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, the steps include:
5- amino indole is placed in 250 mL round-bottomed flasks, is dissolved in anhydrous acetonitrile, is stirred at room temperature, under nitrogen protection,
Triethylamine and 4-dimethylaminopyridine is added, 2,6- pyridine dimethyl chloride is dissolved in anhydrous acetonitrile, and is instilled above-mentioned mixed
It closes in solution, has white cigarette generation immediately, be stirred at room temperature 12 hours, until there is solid precipitation, solvent is evaporated off after the reaction was completed, Gu
Body is washed with water, and continues to be washed three times with anhydrous acetonitrile after filtering, and 30 DEG C of vacuum drying obtain Ultraluminescence molecular probe N,
Two indoles -2,6- pyridine diformamide of N ' -5-.
2. the two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- synthesized by claim 1 is to the Yellow River
Water, lake water and originally the nitrite anions in water sample is detected, the steps include:
A. by two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, it is dissolved in the HEPES of 10 mM, pH=3
In buffer solution, two indoles of Ultraluminescence molecular probe N, N ' -5--is measured respectively with ultra-violet absorption spectrum and fluorescence emission spectrum
The Absorption and emission spectra of 2,6- pyridine diformamides, after measured, UV absorption maximum wavelength are most hyperfluorescence at 270 nm
Transmitting is at 360 nm；Nitrite anions is added thereto, is put in after hatching 30 minutes in 37 DEG C of waters bath with thermostatic control, UV absorption
Maximum wavelength still in 270 nm at, while there is a new absorption peak in 520 nm visible regions, result in solution face
Color becomes pink colour from colourless, and therefore, two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- can be used for pair
Nitrite anions carries out Glassless identification；After nitrite anions is added, most hyperfluorescence emits at still in 360 nm, while fluorescence is sent out
Raw quenching；Two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5- can be in ultraviolet-ray visible absorbing and glimmering
Quantitative analysis is carried out to nitrite anions under light emitting both of which；
B. by two indoles -2,6- pyridine diformamide of Ultraluminescence molecular probe N, N ' -5-, it is dissolved in the HEPES of 10 mM, pH=3
In buffer solution, the nitrite anions that concentration is 0-100 μM is added into solution, is put in 37 DEG C of waters bath with thermostatic control and hatches 30 minutes
Afterwards, solution colour becomes pink colour from colourless, while being detected with ultra-violet absorption spectrum and fluorescence emission spectrum, records it in 270 nm
The UV absorption intensity and the fluorescent emission intensity at 360 nm at place, according to the strong of the concentration of nitrite anions and ultra-violet absorption spectrum
Degree establishes standard curve, and equation is y=0.0687+0.552 × [NO2 ﹣], R=0.994, detection limit can achieve
0.166 μM, meanwhile, standard curve is established according to the intensity of the concentration of nitrite anions and fluorescence emission spectrum, equation be y=
-0.00124 + 0.0572 × [NO2 -], R=0.994, detection limit can achieve 0.10 μM.
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