CN106978160B - Nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof - Google Patents
Nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof Download PDFInfo
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- CN106978160B CN106978160B CN201710105908.2A CN201710105908A CN106978160B CN 106978160 B CN106978160 B CN 106978160B CN 201710105908 A CN201710105908 A CN 201710105908A CN 106978160 B CN106978160 B CN 106978160B
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- nitrogen sulfur
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000000523 sample Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 241000251468 Actinopterygii Species 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 ferric ion compounds compound Chemical class 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000007717 exclusion Effects 0.000 claims abstract description 7
- 239000000284 extract Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001641 gel filtration chromatography Methods 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 4
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 4
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 229920002307 Dextran Polymers 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 37
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 16
- 229930003268 Vitamin C Natural products 0.000 description 16
- 235000019154 vitamin C Nutrition 0.000 description 16
- 239000011718 vitamin C Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 241000209094 Oryza Species 0.000 description 8
- 235000007164 Oryza sativa Nutrition 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- 239000011852 carbon nanoparticle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 6
- 229910001447 ferric ion Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000001576 FEMA 2977 Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 229960003110 quinine sulfate Drugs 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229920005654 Sephadex Polymers 0.000 description 2
- 239000012507 Sephadex™ Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010206 sensitivity analysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
- OJOMAYXJUJFWGZ-UHFFFAOYSA-N 2-formyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC=O OJOMAYXJUJFWGZ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000252233 Cyprinus carpio Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 229920002684 Sepharose Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003539 anti-scorbutic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 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
- 239000003814 drug Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000004280 healthy diet Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
- G01N21/64—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"
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Inorganic Chemistry (AREA)
- Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Biophysics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereofs, comprising the following steps: A, using the fish processing waste rich in protein as raw material, it is 10-100 grams of flesh of fish block that quality is cut into after cleaning；B, the flesh of fish block raw material after stripping and slicing is heat-treated, wherein heat treatment temperature is 100-500 DEG C, and the processing time is 10-60 min；C, it will be soaked in organic solvent and extract by roasted flesh of fish block, wherein extraction time is 2-48 hours, solid-liquid ratio 1:1-1:10；D, after extraction processing, liquid phase is collected, rotary evaporation removes organic solvent；E, it is purified after fat-soluble organic solvent degreasing using volume exclusion gel filtration chromatography, is carbon namo fluorescence probe with containing after ferric ion compounds compound, wherein nano particle and iron ion mass ratio are 20:1-5:1.Nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention, detection process is simple to operate, high sensitivity and selectivity are good, and testing result is intuitive, can quantitative detection.
Description
Technical field
The present invention relates to the preparation of fluorescence probe and applied technical field more particularly to a kind of nitrogen sulfur doping carbon nano fluorescents
Probe environment-friendly preparation method thereof.
Background technique
In the prior art, carbon nano-particle refers to that particle of the diameter less than 100 nanometers, carbon nano-particle have excellent light
Performance is learned, bright fluorescence can be issued under the action of specific wavelength exciting light, in metal ion detection, bio-imaging, medicine
The fields such as object delivering have a wide range of applications, and for preparation method, including top-down cracked by bulk matter is made
The method of standby nano particle and the method for polymerizeing synthesis nano particle by small molecule from bottom to top, top-to-bottom method lead to
More exacting terms is often needed, and the nano-particle fluorescence yield prepared is relatively low, preparation method letter from bottom to top
It is single, it may be convenient to prepare nano particle usually by using the method for doping other elements and obtain high-fluorescence quantum yield
Carbon nano-particle, being usually used in doped chemical is nitrogen, and on the other hand, the recycling of waste is also very important in Green Chemistry
Problem is had not been reported by the method that fish processing waste prepares nitrogen sulfur doping carbon dots at present, vitamin C be it is a kind of oneself
Sugared formylsalicylic acid has antiscorbutic effect, also referred to as ascorbic acid, plays important work in terms of maintaining human health
With, meanwhile, vitamin C or a kind of antioxidant and free radical scavenger can mitigate the oxidative stress of a variety of diseases, be one
The kind organic compound closely related with vital movement, vitamin C is a kind of water soluble vitamin, unstable under normal conditions, is held
It is easily aoxidized by the oxygen in air, the influence vulnerable to temperature, pH value, enzyme, copper ion, iron ion, ultraviolet light and sugar, salt etc.；
Meanwhile for the mankind, vitamin C must be absorbed from food, and therefore, detection Vitamin C content can not only evaluate food
Product quality also all has a very important significance research vitamin C in terms of healthy diet, health care and food fresh keeping.
Summary of the invention
The object of the present invention is to provide a kind of traditional preparation method of breakthrough, it is low to reduce production cost, realize process it is simple, can
The nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of control.
Present invention technical solution used for the above purpose is: a kind of nitrogen sulfur doping carbon namo fluorescence probe green
Preparation method, comprising the following steps:
A, using the fish processing waste rich in protein as raw material, the flesh of fish that quality is 10-100 grams is cut into after cleaning
Block；
B, the flesh of fish block raw material after stripping and slicing is heat-treated, wherein heat treatment temperature be 100-500 DEG C, processing the time be
10-60 min；
C, it will be soaked in organic solvent and extract by roasted flesh of fish block, wherein extraction time is 2-48 hours, feed liquid
Than for 1:1-1:10；
D, after extraction processing, liquid phase is collected, rotary evaporation removes organic solvent；
E, it is purified after fat-soluble organic solvent degreasing using volume exclusion gel filtration chromatography, is compounded with containing ferric ion compounds
It is afterwards carbon namo fluorescence probe, wherein nano particle and iron ion mass ratio are 20:1-5:1.
The step A Mesichthyes is freshwater fish.
The maximum gauge of flesh of fish block is 0.1-10 centimetres in the step A.
Organic solvent in the step C is one or more of ethyl alcohol, methanol, ether, ethyl acetate.
In the step E fat-soluble organic solvent be one of chloroform, methylene chloride, n-hexane, isopropanol or
It is several.
Volume exclusion gel column is cross-link dextran, Ago-Gel, one in polyacrylamide gel in the step E
Kind is several.
In the step E containing ferric ion compounds be iron chloride, ferric nitrate, ferric acetate, ferric sulfate molysite and they
Hydrate.
A kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention, detection process are simple to operate, clever
Sensitivity is high and selectivity is good, and testing result is intuitive, can quantitative detection.
Detailed description of the invention
Fig. 1 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The particle diameter distribution schematic diagram of rice fluorescence probe.
Fig. 2 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The x-ray photoelectron spectroscopy scanning figure of rice fluorescence probe.
Fig. 3 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The fine spectrogram of C1s of rice fluorescence probe.
Fig. 4 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The fine spectrogram of N1s of rice fluorescence probe.
Fig. 5 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The fine spectrogram of O1s of rice fluorescence probe.
Fig. 6 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The fine spectrogram of S2p of rice fluorescence probe.
Fig. 7 is that a kind of carbon prepared by the embodiment one of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention is received
The infrared spectrogram of rice fluorescence probe.
Fig. 8 is the Fe in a kind of embodiment two of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention3+It is dense
Spend the influence schematic diagram to fluorescence intensity.
Fig. 9 is the vitamin in a kind of embodiment five of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof of the present invention
Influence schematic diagram of the C concentration to fluorescence intensity.
Specific embodiment
As shown in figs. 1-9, nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof, comprising the following steps:
A, using the fish processing waste rich in protein as raw material, the flesh of fish that quality is 10-100 grams is cut into after cleaning
Block, wherein maximum gauge is 0.1-10 centimetres, and Mesichthyes is the freshwater fishes such as crucian, carp；B, by the flesh of fish block after stripping and slicing
Raw material is heat-treated, and wherein heat treatment temperature is 100-500 DEG C, and the processing time is 10-60 min；C, roasted fish will be passed through
Meat piece is soaked in organic solvent and extracts, and wherein extraction time is 2-48 hours, solid-liquid ratio 1:1-1:10, organic solvent packet
One or more of ethyl alcohol, methanol, ether, ethyl acetate are included,；D, after extraction processing, liquid phase is collected, rotary evaporation removing has
Solvent；E, it is purified after fat-soluble organic solvent degreasing using volume exclusion gel filtration chromatography, is compounded with containing ferric ion compounds
It is afterwards carbon namo fluorescence probe, wherein nano particle and iron ion mass ratio are 20:1-5:1, there is fat-soluble organic solvent packet
One or more of chloroform, methylene chloride, n-hexane, isopropanol are included, volume exclusion gel column includes: Sephadex
One or more of cross-link dextran, Sepharose Ago-Gel, Bio-Gel P polyacrylamide gel, iron content from
Sub- compound includes: the molysite such as iron chloride, ferric nitrate, ferric acetate, ferric sulfate and their hydrate, which visits
Needle is detected applied to reducing substances, especially ascorbic detection, and excitation optical range is 250-400 nanometers in detection, transmitting
Optical range is 400-600 nanometers, and ascorbic detection is emitted based on " On-Off-On " tri-state.
Embodiment one: crucian is cleaned in the preparation of the carbon nano-particle of nitrogen sulfur doping, 10-20 g meat piece is cut into, 400
DEG C 30 min of baking, extract nano particle, solid-liquid ratio 1:5 by alcohol steep after natural cooling, extraction time is 15 hours；
The ethyl alcohol in alcohol extracts is removed by vacuum rotary evaporator；Residue uses chloroform extraction after redissolving using water
The volume ratio of degreasing, water and chloroform is 1:1, (is repeated 5 times) until aqueous phase solution clear；Water phase is slightly mentioned into solution
G-25 sephadex column chromatography is crossed, fluorescence intensity is collected and is higher than 80(excitation wavelength=340 nm, launch wavelength=410 nm) portion
Point, the powdered carbon nano-particle obtained after freeze-drying finds that its is spherical in shape by transmission electron microscope observing, and average grain diameter is
16.7 nm, carbon nano fluorescent yield are measured by known formula, Φ 1=Φ 2I1A2 η 21/I2A1 η 22, it is desirable that absorbance
A1, A2 are less than 0.1, to reduce error, using quinine sulfate as reference substance, the integral area of I2- quinine sulfate fluorescence intensity
Value, the integrated area value of I1- nano-particle fluorescence intensity, the ultraviolet absorption value of A2- quinine sulfate, A1- nano-particle fluorescence are strong
The ultraviolet absorption value of degree, the refractive index of η 2- quinine sulfate solvent, the refractive index of η 1- nano particle.Prepare carbon Nano quantum fluorescence
Quantum yield is 12.6%, and by X-ray photoelectron spectroscopic analysis, nano particle obtained is made of carbon, nitrogen, oxygen and sulphur, ratio
Example is 57.15%, 15.64%, 26.1% and 1.11%, meanwhile, X-ray photoelectron spectroscopic analysis and FTIR spectrum analytical table
Bright its surface functional group rich in, including hydroxyl, carbonyl, amino etc..
Embodiment two: the preparation of the carbon namo fluorescence probe for vitamin C detection, by nanometer obtained in embodiment one
Particle is configured to the aqueous solution that concentration is 0.1 mg mL-1, and iron chloride is added thereto, its final concentration is made to distinguish 10,20,
40,60,80,100,150,300,400,500 μm of ol L-1, it is rear to stand 2 min after being sufficiently mixed, using detection
Wave-length coverage covers the fluorescence intensity F1 in the fluophotometer examination criteria solution of 280-700nm, and testing conditions are excitation wave
A length of 340 nm, 410 nm of launch wavelength, the fluorescence intensity of blank control group (not plus iron ion) are that (excitation wavelength is F0
340 nm, 410 nm of launch wavelength), draw out the standard between fluorescent quenching intensity ((F0- F1)/F0) and Fe3+ concentration
Curve, Fig. 8 are sensitivity analysis figure of the carbon namo fluorescence probe to Fe3+, it is seen that with the increase of Fe3+ concentration, carbon nanometer
Grain fluorescence intensity gradually decreases, and illustrates that the carbon nano-particle is very sensitive to the concentration of Fe3+；But as [Fe3+] >=100 μm ol
When L-1, the reduction of the fluorescence intensity of carbon nano-particle and the raising of iron concentration no longer have linear relationship；It is molten with Fe3+
Liquid concentration range is that abscissa can with fluorescent quenching intensity ((F0- F1)/F0) for ordinate in 10-100 μm of ol L-1
Equation of linear regression y=0.00378x+0.01998, coefficient R 2=0.9948 is made, by nanometer made from 1 in embodiment
Grain is configured to the aqueous solution that concentration is 0.1 mg mL-1, and ferric chloride solution is added, is allowed to final concentration of 40 μm of ol L-1, stands
After ten minutes, fluorescence probe can be obtained after nano particle and iron ion cooperation, under 340 nanometers of exciting lights, at 410 nanometers
Lower fluorescence intensity, fluorescence intensity can be used for ascorbic detection because the presence of iron ion is quenched.
Embodiment three: the preparation of the carbon namo fluorescence probe for vitamin C detection, by nanometer obtained in embodiment one
Particle is configured to the aqueous solution that concentration is 0.1 mg mL-1, and ferric chloride solution is added, is allowed to final concentration of 100 μm of ol L-1,
It stands after ten minutes, fluorescence probe can be obtained after nano particle and iron ion cooperation, under 340 nanometers of exciting lights, 410
The lower fluorescence intensity of nanometer, can be used for ascorbic detection.
Example IV: the preparation of the carbon namo fluorescence probe for vitamin C detection, by nanometer obtained in embodiment one
Particle is configured to the aqueous solution that concentration is 0.1 mg mL-1, and ferric chloride solution is added, is allowed to final concentration of 150 μm of ol L-1.It is quiet
It sets after ten minutes, fluorescence probe can be obtained after nano particle and iron ion cooperation.Under 340 nanometers of exciting lights, received 410
The lower fluorescence intensity of rice, can be used for ascorbic detection.
Embodiment five: ascorbic detection is used for carbon namo fluorescence probe obtained in embodiment three to detect vitamin
The content of C takes the above-mentioned carbon namo fluorescence probe solution of 1.9 mL, and vitamin C, which is added, makes its final concentration be respectively 10,40,80,
150,250,400,500 μm of ol L-1, it is rear to stand 30 min after being sufficiently mixed, 280- is covered using Detection wavelength range
Fluorescence intensity F1 in the fluophotometer examination criteria solution of 700nm, testing conditions are that excitation wavelength is 340 nm, transmitted wave
Long 410 nm, the fluorescence intensity of blank control group (not plus iron ion) are that (excitation wavelength is 340 nm, launch wavelength 410 to F0
Nm), the standard curve between fluorescent quenching intensity ((F1- F0)/F0) and vitamin C concentration is drawn out, Fig. 9 is carbon nanometer
Fluorescence probe is to ascorbic sensitivity analysis figure, it is seen that increase of the carbon namo fluorescence probe with vitamin C concentration, fluorescence
Intensity gradually rises, and illustrates the carbon namo fluorescence probe to ascorbic concentration sensitive；But work as vitamin C concentration >=250 μ
When mol L-1, the raising of the fluorescence intensity of carbon nanometer and the raising of vitamin C concentration no longer have linear relationship；With vitamin
C concentration range 10-250 μm of ol L-1 be abscissa, with fluorescent quenching intensity ((F0- F1)/F0) be ordinate, can make
Equation of linear regression y=0.000862x+0.01505, coefficient R 2=0.9108 are obtained, by carbon nanometer obtained in embodiment three
Fluorescence probe takes the above-mentioned carbon namo fluorescence probe solution of 1.9 mL, 0.1 mL 0.8 is added for detecting ascorbic content
The vitamin c solution of mmol L-1, under 340 nanometers of exciting lights, reproducibility is being added in the fluorescence intensity under 410 nanometers
After substance, iron ion is reduced into ferrous ion, because iron ion exist cause fluorescence intensity be quenched obtain to a certain extent it is extensive
Multiple, recovery extent is directly proportional to reducing substances additional amount, realizes the response of " On-Off-On " of fluorescence, reaches measurement mesh
, in this example, being calculated according to standard curve and obtaining its concentration is 0.84 mmol L-1, the rate of recovery 105%.
Embodiment six: ascorbic detection is used for carbon namo fluorescence probe obtained in embodiment three to detect vitamin
The content of C takes the above-mentioned carbon namo fluorescence probe solution of 1.9 mL, and the vitamin c solution of 0.1 mL, 1.6 mmol L-1 is added,
Under 340 nanometers of exciting lights, the fluorescence intensity under 410 nanometers, after reducing substances are added, iron ion is reduced into
Ferrous ion is restored to a certain extent because iron ion presence causes fluorescence intensity to be quenched, recovery extent and reproducibility
Substance additional amount is directly proportional, realizes the response of " On-Off-On " of fluorescence, reaches measurement purpose, in this example according to standard curve
Calculating and obtaining its concentration is 1.82 mmol L-1, the rate of recovery 114%.
Embodiment 7: ascorbic detection is used for carbon namo fluorescence probe obtained in embodiment three to detect vitamin C
Content, take the above-mentioned carbon namo fluorescence probe solution of 1.9 mL, the vitamin c solution of 0.1 mL, 5.0 mmol L-1 be added,
Under 340 nanometers of exciting lights, the fluorescence intensity under 410 nanometers, after reducing substances are added, iron ion is reduced into Asia
Iron ion is restored to a certain extent because iron ion presence causes fluorescence intensity to be quenched, recovery extent and reproducibility object
Matter additional amount is directly proportional, realizes the response of " On-Off-On " of fluorescence, reaches measurement purpose, in this example, according to standard curve
Calculating and obtaining its concentration is 5.2 mmol L-1, the rate of recovery 104%, nitrogen sulfur doping carbon namo fluorescence probe green system of the present invention
Preparation Method, raw material is easy to get, is at low cost, process is simply controllable, i.e., to grilled fish carry out simple organic solvent extraction, revolving, extraction,
Gel chromatography, gained carbon nanometer are chondritic of the diameter less than 20 nanometers, quantum efficiency height long with fluorescence lifetime,
As a result reproducible feature.
Claims (7)
1. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof, which comprises the following steps:
A, using the fish processing waste rich in protein as raw material, the flesh of fish block that quality is 10-100 grams is cut into after cleaning；
B, the flesh of fish block raw material after stripping and slicing is baked, wherein baking temperature is 100-500 DEG C, the processing time is 10-60
min；
C, it will be soaked in organic solvent and extract by roasted flesh of fish block, wherein extraction time is 2-48 hours, and solid-liquid ratio is
1:1-1:10；
D, after extraction processing, liquid phase is collected, rotary evaporation removes organic solvent；
E, after fat-soluble organic solvent degreasing using volume exclusion gel filtration chromatography purify, with containing ferric ion compounds compound after i.e.
For carbon namo fluorescence probe, wherein nano particle and iron ion mass ratio are 20:1-5:1.
2. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
Stating step A Mesichthyes is freshwater fish.
3. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
State flesh of fish block in step A with a thickness of 0.1-10 centimetres.
4. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
Stating the organic solvent in step C is one or more of ethyl alcohol, methanol, ether, ethyl acetate.
5. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
Stating fat-soluble organic solvent in step E is one or more of chloroform, methylene chloride, n-hexane, isopropanol.
6. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
Stating volume exclusion gel column in step E is one or more of cross-link dextran, Ago-Gel, polyacrylamide gel.
7. a kind of nitrogen sulfur doping carbon namo fluorescence probe environment-friendly preparation method thereof according to claim 1, it is characterised in that: institute
State in step E containing ferric ion compounds be iron chloride, ferric nitrate, ferric acetate, ferric sulfate molysite and their hydrate.
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| CN108084997A (en) * | 2017-12-28 | 2018-05-29 | 大连工业大学 | The preparation method of N doping fluorescent carbon quantum dots |
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