CN110026562A - The synthetic method and its application of near infrared fluorescent probe iron nano-cluster - Google Patents
The synthetic method and its application of near infrared fluorescent probe iron nano-cluster Download PDFInfo
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- CN110026562A CN110026562A CN201810028871.2A CN201810028871A CN110026562A CN 110026562 A CN110026562 A CN 110026562A CN 201810028871 A CN201810028871 A CN 201810028871A CN 110026562 A CN110026562 A CN 110026562A
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- cluster
- iron nano
- near infrared
- high purity
- fluorescent probe
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 73
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 40
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 20
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims abstract description 20
- 229940098773 bovine serum albumin Drugs 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 39
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000000523 sample Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 210000004369 blood Anatomy 0.000 claims 1
- 239000008280 blood Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000003223 protective agent Substances 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012888 bovine serum Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 231100000753 hepatic injury Toxicity 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 208000017169 kidney disease Diseases 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004770 neurodegeneration Effects 0.000 description 2
- 208000015122 neurodegenerative disease Diseases 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 1
- 108090000365 Cytochrome-c oxidases Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 208000002972 Hepatolenticular Degeneration Diseases 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007812 deficiency 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
- 108700006189 dopamine beta hydroxylase deficiency Proteins 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- C09K11/60—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing iron, cobalt or nickel
-
- 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"
- 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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- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention discloses the synthetic method and its application of near infrared fluorescent probe iron nano-cluster; it is template and protective agent using bovine serum albumin(BSA); using iron chloride as source of iron; hydrazine hydrate is reducing agent; fluorescence iron nano-cluster is synthesized under conditions of room temperature water phase; again using fluorescence iron nano-cluster as near infrared fluorescent probe, at room temperature using fluorescence intensity change to Cu in solution2+Content carry out it is simple, quickly, highly sensitive and highly selective detection.
Description
Technical field
The invention belongs to bioanalysis detection technique fields, are related to " green " of a kind of near infrared fluorescent probe iron nano-cluster
Synthetic method and the iron nano-cluster of preparation are in actual sample to detection Cu2+Application.
Background technique
Metal nanometre cluster is the semiconductor nanoclusters of luminescence generated by light, mainly there is gold nanoclusters, silver nanoclusters, platinum cluster
And copper nano-cluster etc..Metal nanometer cluster be by the metals such as Au, Ag, Pt several to tens originals it is molecular have fluorescence,
Water-soluble molecular level aggregation.Compared to gold nanoclusters, silver nanoclusters and platinum cluster, iron nano-cluster have it is resourceful, at
The advantages that this is cheap, can be widely applied to enterprise.The diameter of iron nano-cluster is in~2nm or so, since iron nano-cluster is found,
Since it is with unique photoluminescent property, non-toxic, size is smaller and uniform, and good water solubility has been widely used in detecting various
Anion, heavy metal ion and biological micromolecule.However, iron nano-cluster paid close attention to obtained in analysis detection it is less.
After zinc and iron, copper is third metallic element abundant in human body, and is risen in extensive bioprocess
Vital effect.Copper is as cytochrome c oxidase, superoxide dismutase, dopamine-B-hydroxylase and tyrosinase
The co-factor of several important biological enzyme in equal human bodies, playing to the health of the mankind cannot be neglected adjustment effect.But such as
Fruit copper ion can then inhibit the activity of some indispensable enzymes in human body in the intracorporal excessive concentration of people, make associated biomolecule aoxidize or
Reduction process generates exception, thus cause hepatic injury, injury of kidney and neurodegenerative disease, such as Wilson's disease, Alzheimer
Family name's disease and associated oxidative stress illness, constitute great threat to the health of the mankind.Absorption of human body copper coin
The main path of element is the Cu in food and drinking-water2+, therefore must Cu in strict control these substances2+Content is to ensure food
The margin of safety of the copper in drinking water ion set with safe drinking water, American National Environmental Protection Agency (EPA) is 1.3ppm (about 20 μM).
However as the fast development of modern industry, contain plurality of heavy metal ion Cu in industrial wastewater, waste2+If discharge is not
When that will cause to seriously affect to ecological environment, human health is then threatened.Therefore, Cu in quantitative detection water is developed2+Ion
Various technologies be and its necessary.
In numerous metal ions, copper ion is especially prominent to the pollution problem of environment, and the excessive copper of human intake then can
Cause serious side effect such as hepatic injury, injury of kidney and neurodegenerative disease.Copper-containing wastewater can be to aquatic life after being discharged into water body
Object generates very big toxicity.It is intended to prepare the iron nano-cluster that high sensitivity, detection limit are low, selectivity is good in this project, is used for
The detection and analysis of environmental contaminants --- copper ion.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of water-soluble, avirulent, room temperature synthesis
, the synthetic method of fluorescence iron nano-cluster easily store, near infrared emission, and at room temperature using fluorescence intensity change to molten
Cu in liquid2+Content carry out it is simple, quickly, highly sensitive and highly selective detection.
Technical purpose of the invention is achieved by following technical proposals: being template using bovine serum albumin(BSA) (BSA)
And protective agent, using iron chloride as source of iron, hydrazine hydrate is reducing agent, and fluorescence iron nano-cluster is synthesized under conditions of room temperature water phase
(BSA-Fe NCs), as probe utilizing fluorescence Strength Changes to Cu in solution2+Content detected.
Based on the bivalent cupric ion detection method of near infrared fluorescent probe iron nano-cluster, dispersed with high purity water, iron nano-cluster
System and sample to be tested form bivalent cupric ion detection architecture, and the fluorescence intensity change before and after sample to be tested, comparison is added in detection
Standard curve obtains the content of bivalent cupric ion in sample to be tested, linear equation F0/ F=1.00+100.15C, F0To be not added
Enter fluorescence intensity detected value when bivalent cupric ion, F is the fluorescence intensity detected value being added after bivalent cupric ion, and C is cupric
Ion concentration, the i.e. concentration of bivalent cupric ion in sample to be tested.
In above-mentioned detection method, the range of linearity of detection is 1.0 × 10-4- 1.0 × 10-2M, detection are limited to 7.23 × 10- 5M。
In above-mentioned detection method, high purity water 2.8mL, iron nano-cluster dispersion 1.0mL and sample to be tested 0.2mL composition two
Valence copper ion detection architecture 4.0mL.
In above-mentioned detection method, after sample to be tested is added into high purity water and iron nano-cluster dispersion, reaction 50-
Its fluorescence intensity is detected after 70s.
Iron nano-cluster dispersion, i.e. near infrared fluorescent probe iron nano-cluster, using bovine serum albumin(BSA) as template and protection
Agent, using iron chloride as source of iron, hydrazine hydrate is reducing agent, fluorescence iron nano-cluster is synthesized under conditions of room temperature water phase, according to following
It is prepared by step:
Step 1,60-120mg of bovine serum albumin(BSA) is weighed to be dispersed in the beaker equipped with 8-10mL high purity waters；
In step 1,80-100mg of bovine serum albumin(BSA) is weighed to be dispersed in the beaker equipped with 10mL high purity water.
Step 2, FeCl is weighed3·6H2O is dispersed in high purity water, forms 0.1M ferric chloride in aqueous solution；
Step 3, under 20-25 degrees celsius of room temperature, 80-100 μ L of ferric chloride in aqueous solution that step 2 synthesizes is added drop-wise to
In Bovine Serum Albumin in Aqueous Solution prepared by step 1, solution becomes hydrogel state from clarifying；300 μ L-1000 μ L are hydrated again
Hydrazine is added drop-wise in hydrogel, and hydrogel is gradually dissolved as yellow transparent clear solution, is finally increased pure water to whole system and is
40-50mL continue to be stirred to react after 2-5h at room temperature to get iron nano-cluster dispersion is arrived.
In step 3, hydrazine hydrate is hydrazine hydrate aqueous solution, and the mass percent of hydrazine hydrate is 80%.
In step 3, the rate of addition of hydrazine hydrate is 0.05-0.1mL/min, and the addition speed of high purity water is 0.5-1mL/
s.Purification condition is that every 4h changes a high purity water, is dialysed for 24 hours, after the completion of dialysing under vacuum conditions by the iron nano-cluster of purifying
35 DEG C of dryings.
It the use of molecular cut off is 6000-8000 after preparation, diameter is that iron nanometer is made to step 3 in 25mm bag filter
Cluster is purified, and every 3-5h changes a high purity water, and dialyse 20-30h, by the iron nano-cluster of purifying in vacuum item after the completion of dialysing
Under part after 30-40 DEG C of drying, near infrared fluorescent probe iron nano-cluster is obtained, maximum excitation wavelength is 284nm, maximum emission wavelength
For 664nm.
The iron nanocluster size of preparation concentrates on 1.8-2nm, the copper nanocluster size size uniformity of synthesis and distribution is equal
It is even；Iron nano-cluster is distributed on bovine serum albumin(BSA) matrix, i.e., the functional groups such as the amino of iron ion and protein surface, hydroxyl into
Row coordination realizes that in-situ reducing forms Nanoscale Iron cluster under hydrazine hydrate effect.
Application of the iron nano-cluster dispersion prepared by the present invention in detection bivalent cupric ion, Cu2+It is filled with iron nano-cluster
It is allocated as after using, so that system fluorescence occurs to quench and detects fluorescence emission spectrum, passes through the changing value of fluorescence emission spectral intensity
Iron nano-cluster dispersion can be realized to Cu2+Detection.
When being detected, copper chloride related solution is configured as follows:
(1) preparation of copper chloride mother liquor: 1.705g CuCl is weighed2·2H2O is dissolved in 100mL volumetric flask with high purity water
In, it is made into 0.1M CuCl2High standard solution saves stand-by.
(2) preparation of copper ion standard solution:
Pipette a series of CuCl of different volumes2High standard solution is diluted in 10mL colorimetric cylinder, be configured to concentration according to
Secondary is 1.0 × 10-4M、5.0×10-4M、1.0×10-3M、2.0×10-3M、6.0×10-3M、8.0×10-3M、1.0×10-2M's
Copper ion standard solution.
Compared with prior art, the present invention is template and protective agent using bovine serum albumin(BSA) (BSA), using iron chloride as iron
Source, hydrazine hydrate are reducing agent, synthesize fluorescence iron nano-cluster (BSA-Fe NCs) under conditions of room temperature water phase, as probe benefit
With fluorescence intensity change to Cu in solution2+Content carry out it is simple, quickly, highly sensitive and highly selective detection.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture (TEM) based on the iron nano-cluster that bovine serum albumin is template.
Fig. 2 is the iron nanocluster fluorescence launching light spectrogram based on bovine serum albumin for template.
Fig. 3 is to detect Cu based on the iron nano-cluster that bovine serum albumin is template2+Range of linearity figure.
Specific embodiment
Technical solution of the present invention is further illustrated below with reference to specific embodiment, and features described above and advantage will become
It is more clear and is readily appreciated that.Agents useful for same is that analysis is pure, and agents useful for same and manufacturer are as follows: bovine serum albumin, Beijing
Prosperity Bioisystech Co., Ltd, ancient cooking vessel state；Fine Chemical Co., Ltd is recovered in hydrazine hydrate, Tianjin；Iron chloride (99%), Tianjin light
Multiple Fine Chemical Co., Ltd.
Embodiment 1
0.1M FeCl3The preparation of solution: 1.3515g FeCl is weighed3It is dissolved in appropriate high purity water, is transferred to 50mL capacity
Constant volume in bottle, labelling are stand-by；
The preparation of bovine serum albumen solution: it weighs 0.1000g bovine serum albumin and is dissolved in 10mL high purity water, under stirring condition
Sufficiently dissolution；
The synthesis of iron nano-cluster: prepared FeCl is added under stirring condition into above-mentioned bovine serum albumen solution3Solution
90 μ L sufficiently after reaction, are added 300 μ L of hydrazine hydrate, 5h are reacted under stirring condition, obtain fluorescence iron and receive in Xiang Shangshu mixed solution
Rice cluster.
Embodiment 2
0.1M FeCl3The preparation of solution: 1.3515g FeCl is weighed3It is dissolved in appropriate high purity water, is transferred to 50mL capacity
Constant volume in bottle, labelling are stand-by；
The preparation of bovine serum albumen solution: it weighs 0.1000g bovine serum albumin and is dissolved in 10mL high purity water, under stirring condition
Sufficiently dissolution；
The synthesis of iron nano-cluster: prepared FeCl is added under stirring condition into above-mentioned bovine serum albumen solution3Solution
90 μ L sufficiently after reaction, are added 500 μ L of hydrazine hydrate, 5h are reacted under stirring condition, obtain fluorescence iron and receive in Xiang Shangshu mixed solution
Rice cluster.
Embodiment 3
Cu2+Detection: take 2 empty centrifuge tubes respectively, 1., 2. number, pipettes high purity water 2.8mL respectively and is added to 1., 2.
In number centrifuge tube, then pipette 1.0mL iron nano-cluster solution and be added in above-mentioned centrifuge tube, after mixing, continue to 1. number from
200 μ L high purity waters are added in heart pipe as blank control group, 200 μ L Cu are added into 2. number centrifuge tube2+Solution reacts 1min,
So that fluorescence occurs quenching and detects fluorescent emission intensity with fluophotometer, the detection for bivalent cupric ion can be realized.
Embodiment 4
Cu2+Detection: take 2 empty centrifuge tubes respectively, 1., 2. number, pipettes high purity water 2.6mL respectively and is added to 1., 2.
In number centrifuge tube, then pipette 1.2mL iron nano-cluster solution and be added in above-mentioned centrifuge tube, after mixing, continue to 1. number from
200 μ L high purity waters are added in heart pipe as blank control group, 200 μ L Cu are added into 2. number centrifuge tube2+Solution reacts 1min,
So that fluorescence occurs quenching and detects fluorescent emission intensity with fluophotometer, the detection for bivalent cupric ion can be realized.
Embodiment 5-detects the determination of the linear detection range of bivalent cupric ion
Into 4mL centrifuge tube be added 2.8mL high purity water, be added 1.0mL iron nano-cluster solution, after mixing, respectively plus
Enter the Cu of 0.2mL various concentration2+Standard solution detects its fluorescence intensity after reacting 1min, is measured in parallel three times.According to different dense
Spend Cu2+To the Quenching of fluorescence degree of iron nano-cluster, iron nano-cluster and Cu are obtained2+Between linear relationship, and in this, as according to
Quantitative detection is carried out according to copper ion, the range of linearity of detection is 1.0 × 10-4- 1.0 × 10-2M, detection are limited to 7.23 × 10- 5M。
The detection processing of 6-actual sample of embodiment
(1) processing of actual sample: taking three parts of volumes is the originally water sample of 4.0mL, is added respectively into every part of sample
The Cu of the known concentration of certain volume2+The standard solution volume of standard solution (be added minimum), so that Cu in sample after mark-on2+
Concentration successively are as follows: 5.0 × 10-4M、1.0×10-3M、2.0×10-3M, it is stand-by that solution prepares rear labeling；
2,4 empty centrifuge tubes are taken, 1., 2., 3., 4. number, pipettes high purity water 2.8mL respectively and is added to 1., 2., 3., 4.
In number centrifuge tube, then pipette 1.0mL iron nano-cluster solution and be added in above-mentioned centrifuge tube, after mixing, continue to 1. number from
200 μ L high purity waters are added in heart pipe as blank control group, 200 μ L Cu are added into 2. number centrifuge tube2+Concentration be 5.0 ×
10-4200 μ L Cu are added into 3. number centrifuge tube for the actual sample solution of M2+Concentration be 1.0 × 10-3The actual sample of M is molten
200 μ L Cu are added into number centrifuge tube for liquid2+Concentration be 2.0 × 10-3The actual sample solution of M reacts 1min, then surveys
Its Quenching of fluorescence degree to iron nano-cluster is measured, the rate of recovery is calculated, as shown in the table:
Wherein spiked levels are the bivalent cupric ion concentration (concentration determined according to sample preparation) in system to be detected,
Cu2+Detectable concentration is the bivalent cupric ion concentration detected according to the present invention program to obtain, and the rate of recovery is the ratio of the two
Example.
" highly sensitive fluorescence iron nanometer aggregate probe is in environment dirt for project by Tianjin Normal University's " big wound plan " for this patent
Application in dye object selective enumeration method " (No.201522), state natural sciences fund general project 21375095, Tianjin are certainly
Right science fund youth project (No.17JCQNJC05800) and Tianjin Normal University's doctor's fund project (No.52XB1510)
It subsidizes.
It is adjusted using the technological parameter of the content of present invention, the preparation of iron nano-cluster can be achieved, and realize and be directed to two
The detection of valence copper ion.Illustrative description is done to the present invention above, it should which explanation is not departing from core of the invention
In the case where, any simple deformation, modification or other skilled in the art can not spend being equal for creative work
Replacement each falls within protection scope of the present invention.
Claims (10)
1. near infrared fluorescent probe iron nano-cluster, which is characterized in that iron nanocluster size concentrates on 1.8-2nm, iron nano-cluster point
For cloth on bovine serum albumin(BSA) matrix, maximum excitation wavelength is 284nm, maximum emission wavelength 664nm；As steps described below into
Row preparation:
Step 1,60-120mg of bovine serum albumin(BSA) is weighed to be dispersed in the beaker equipped with 8-10mL high purity waters；
Step 2, FeCl is weighed3·6H2O is dispersed in high purity water, forms 0.1M ferric chloride in aqueous solution；
Step 3, under 20-25 degrees celsius of room temperature, 80-100 μ L of ferric chloride in aqueous solution that step 2 synthesizes is added drop-wise to step
In the Bovine Serum Albumin in Aqueous Solution of 1 preparation, solution becomes hydrogel state from clarifying；300 μ L-1000 μ L hydrazine hydrates are dripped again
It is added in hydrogel, hydrogel is gradually dissolved as yellow transparent clear solution, and finally increasing pure water to whole system is 40-
50mL continues to be stirred to react after 2-5h at room temperature to get iron nano-cluster dispersion is arrived.
2. near infrared fluorescent probe iron nano-cluster according to claim 1, which is characterized in that in step 1, weigh ox blood
Pure 80-100mg of albumen is dispersed in the beaker equipped with 10mL high purity water.
3. near infrared fluorescent probe iron nano-cluster according to claim 1, which is characterized in that in step 3, hydrazine hydrate is
Hydrazine hydrate aqueous solution, the mass percent of hydrazine hydrate are 80%；The rate of addition of hydrazine hydrate is 0.05-0.1mL/min, high purity water
Addition speed be 0.5-1mL/s.
4. the synthetic method of near infrared fluorescent probe iron nano-cluster, which is characterized in that prepared as steps described below:
Step 1,60-120mg of bovine serum albumin(BSA) is weighed to be dispersed in the beaker equipped with 8-10mL high purity waters；
Step 2, FeCl is weighed3·6H2O is dispersed in high purity water, forms 0.1M ferric chloride in aqueous solution；
Step 3, under 20-25 degrees celsius of room temperature, 80-100 μ L of ferric chloride in aqueous solution that step 2 synthesizes is added drop-wise to step
In the Bovine Serum Albumin in Aqueous Solution of 1 preparation, solution becomes hydrogel state from clarifying；300 μ L-1000 μ L hydrazine hydrates are dripped again
It is added in hydrogel, hydrogel is gradually dissolved as yellow transparent clear solution, and finally increasing pure water to whole system is 40-
50mL continues to be stirred to react after 2-5h at room temperature to get iron nano-cluster dispersion is arrived.
5. the synthetic method of near infrared fluorescent probe iron nano-cluster according to claim 2, which is characterized in that in step 1
In, it weighs 80-100mg of bovine serum albumin(BSA) and is dispersed in the beaker equipped with 10mL high purity water.
6. the synthetic method of near infrared fluorescent probe iron nano-cluster according to claim 2, which is characterized in that in step 3
In, hydrazine hydrate is hydrazine hydrate aqueous solution, and the mass percent of hydrazine hydrate is 80%；The rate of addition of hydrazine hydrate is 0.05-
0.1mL/min, the addition speed of high purity water are 0.5-1mL/s.
7. application of the near infrared fluorescent probe iron nano-cluster in detection bivalent cupric ion as described in one of claim 1-3,
It is characterized in that, Cu2+After sufficiently being acted on iron nano-cluster, so that system fluorescence occurs to quench and detects fluorescence emission spectrum, lead to
Iron nano-cluster dispersion can be realized to Cu in the changing value for crossing fluorescence emission spectral intensity2+Detection.
8. the bivalent cupric ion detection method based near infrared fluorescent probe iron nano-cluster, which is characterized in that with high purity water, Tie Na
Rice cluster dispersion and sample to be tested form bivalent cupric ion detection architecture, and the fluorescence intensity change before and after sample to be tested is added in detection
To change, contrast standard curve obtains the content of bivalent cupric ion in sample to be tested, linear equation F0/F=1.00+100.15C,
F0 is fluorescence intensity detected value when being added without bivalent cupric ion, and F is the fluorescence intensity detected value being added after bivalent cupric ion, C
For bivalent cupric ion concentration, the i.e. concentration of bivalent cupric ion in sample to be tested；The range of linearity of detection is 1.0 × 10-4- 1.0
×10-2M, detection are limited to 7.23 × 10-5M。
9. the bivalent cupric ion detection method according to claim 8 based near infrared fluorescent probe iron nano-cluster, special
Sign is that high purity water 2.8mL, iron nano-cluster dispersion 1.0mL and sample to be tested 0.2mL form bivalent cupric ion detection architecture
4.0mL。
10. the bivalent cupric ion detection method according to claim 8 based near infrared fluorescent probe iron nano-cluster, special
Sign is, it is strong to detect its fluorescence after sample to be tested is added into high purity water and iron nano-cluster dispersion, after 50-70s of reaction
Degree.
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