CN106318375A - Preparing method of reinforced gold nanoparticle cluster fluorescence system based on surface plasma - Google Patents
Preparing method of reinforced gold nanoparticle cluster fluorescence system based on surface plasma Download PDFInfo
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- CN106318375A CN106318375A CN201610681630.9A CN201610681630A CN106318375A CN 106318375 A CN106318375 A CN 106318375A CN 201610681630 A CN201610681630 A CN 201610681630A CN 106318375 A CN106318375 A CN 106318375A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 83
- 239000010931 gold Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002105 nanoparticle Substances 0.000 title abstract 7
- 239000000243 solution Substances 0.000 claims abstract description 126
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000007853 buffer solution Substances 0.000 claims abstract description 14
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims abstract description 8
- 229940098773 bovine serum albumin Drugs 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 102000008100 Human Serum Albumin Human genes 0.000 claims abstract description 5
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 5
- 229960003180 glutathione Drugs 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 29
- 125000003368 amide group Chemical group 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 238000005034 decoration Methods 0.000 claims description 3
- 235000003969 glutathione Nutrition 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000008280 blood Substances 0.000 claims 1
- 210000004369 blood Anatomy 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 13
- 108091006905 Human Serum Albumin Proteins 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract 2
- 108010024636 Glutathione Proteins 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 description 40
- 229910052906 cristobalite Inorganic materials 0.000 description 40
- 229910052682 stishovite Inorganic materials 0.000 description 40
- 229910052905 tridymite Inorganic materials 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 31
- 238000001514 detection method Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 101150113720 aunc gene Proteins 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 15
- 238000005424 photoluminescence Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 sulfur alcohol compound Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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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
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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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
- C09K11/582—Chalcogenides
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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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a preparing method of a reinforced gold nanoparticle cluster fluorescence system based on surface plasma. The preparing method comprises the steps of conducting contact reaction of gold nanoparticle solution and modified gold nanorod solution with buffer solution to prepare the reinforced gold nanoparticle cluster fluorescence system based on surface plasma; among them, modified gold nanorod in the gold nanorod solution comprises gold nanorod, a silicon dioxide layer and an amine modified layer, wherein the silicon dioxide layer is covered outside the gold nanorod, and the amine modified layer is distributed on the outer surface of the silicon dioxide layer; the outer protecting group of the gold nanoparticle in the gold nanoparticle solution is chosen from one kind or multiple kinds of BSA (Bovine Serum Albumin), HAS (human serum albumin) and glutathione. The gold nanoparticle cluster fluorescence system prepared from the method has excellent fluorescence quantum yield.
Description
Technical field
The present invention relates to gold nano cluster, in particular it relates to the gold nano cluster fluorescence strengthened based on surface plasma
The preparation method of system.
Background technology
Gold nano cluster (AuNCs) is by several to dozens of coelectrones, organic supramolecular such as sulfur alcohol compound or
The molecule aggregate that person's protein etc. combines as blocking group.AuNCs becomes due to preferable optical property and electrical property
One of current study hotspot.Research shows, (the usual ＜ when Fermi's wavelength that AuNCs gradually decreases to electronics is suitable
1.5nm), due to two word size effects, can present with semiconductor type as feature, produce discrete energy levels, and can inspire glimmering
Light.
For traditional fluorescent marker, AuNCs has many advantages, such as: have the highest biocompatibility,
Toxicity is low, light stability, just can be able to be synthesized under conditions of as mild as a dove, and glow color is along with cluster size
Adjustable；But it is low to have fatal defect, i.e. photoluminescence quantum yield, will be typically less than 10%, and this defect is greatly just
Limit the application of AuNCs.
Summary of the invention
It is an object of the invention to provide the preparation of a kind of gold nano cluster fluorescence system strengthened based on surface plasma
Method, the gold nano cluster fluorophor cording prepared by the method has the photoluminescence quantum yield of excellence.
To achieve these goals, the invention provides a kind of gold nano cluster fluorescence strengthened based on surface plasma
The preparation method of system, including: gold nano cluster solution, modified gold nanorods solution and buffer solution are carried out haptoreaction with
Prepare the gold nano cluster fluorescence system strengthened based on surface plasma；
Wherein, the modified gold nanorods in modified gold nanorods solution includes that gold nanorods, silicon dioxide layer and amino are repaiied
Decorations layer, silicon dioxide layer is coated on the outside of gold nanorods, and amido modified layer is distributed in the outer surface of silicon dioxide layer；Described gold
The outer layer protection group of nanocluster GOLD FROM PLATING SOLUTION nanocluster is selected from bovine serum albumin, human serum albumin and glutathion
In one or more.
Present invention also offers a kind of gold nano cluster fluorescence system strengthened based on surface plasma, this gold nano group
Bunch fluorescence system is prepared from by above-mentioned method.
By technique scheme, the present invention is by utilizing modified gold nanorods (AuNR@SiO2@NH2, AuNR refers to gold
Nanometer rods) and gold nano cluster (AuNCs) between carry out compound preparing AuNR@SiO2@NH2@AuNCs structure, this structured particles energy
Enough realizing the resonance of surface plasma, and then achieve the enhancing of fluorescence, the luminescent quantum that i.e. improve gold nano cluster is produced
Rate.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is the preparation principle figure of embodiment 1；
Fig. 2 is the transmission electron microscope picture of gold nanorods in detection example 1；
Fig. 3 is AuNR@SiO in detection example 22The transmission electron microscope picture of solution A 1；
Fig. 4 is AuNR@SiO in detection example 22The transmission electron microscope picture of solution A 2；
Fig. 5 is AuNR@SiO in detection example 22The transmission electron microscope picture of solution A 3；
Fig. 6 is the transmission electron microscope picture under low power of D3 in detection example 3；
Fig. 7 is the transmission electron microscope picture under high power of D3 in detection example 3；
Fig. 8 is the transmission electron microscope picture of AuNCs in detection example 4；
Fig. 9 is the fluorescence spectrum figure of D6, D7, E1, E3 in detection example 7；
Figure 10 is the fluorescence spectrum figure of D1, D2, D3, D4, D5, E1 and E2 in detection example 5；
Figure 11 is the ultraviolet spectrogram of F1, E1, A2, B2, G12 in detection example 6；
Figure 12 is the fluorescence spectrum figure of D8, D9, D10, E1, E4 in detection example 8；
Figure 13 is the fluorescence spectrum figure of E1, E6-E11 in detection example 12；
Figure 14 is the fluorescence spectrum figure of E2, E12-E17 in detection example 11；
Figure 15 is the fluorescence spectrum figure of D3, D11-D16 in detection example 10；
Figure 16 is the fluorescence spectrum figure of E7, D17-D24 in detection example 12.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of gold nano cluster fluorescence system strengthened based on surface plasma, bag
Include: gold nano cluster solution, modified gold nanorods solution and buffer solution are carried out haptoreaction with prepare based on surface etc. from
The gold nano cluster fluorescence system that daughter strengthens；
Wherein, the modified gold nanorods in modified gold nanorods solution includes that gold nanorods, silicon dioxide layer and amino are repaiied
Decorations layer, silicon dioxide layer is coated on the outside of gold nanorods, and amido modified layer is distributed in the outer surface of silicon dioxide layer；Described gold
The outer layer protection group of nanocluster GOLD FROM PLATING SOLUTION nanocluster is selected from bovine serum albumin, human serum albumin and glutathion
In one or more.
In the present invention, gold nano cluster can select with the consumption of modified gold nanorods in wide scope, but is
The photoluminescence quantum yield of further raising gold nano cluster fluorescence system, it is preferable that relative to 1 in gold nano cluster solution
The gold nano cluster of μm ol, the consumption of modified gold nanorods is 0.0327-0.0607 μm ol.
In the present invention, gold nano cluster solution can select with the concentration of modified gold nanorods solution in wide scope
Select, but in order to improve the photoluminescence quantum yield of gold nano cluster fluorescence system further, it is preferable that in gold nano cluster solution
The concentration of gold nano cluster is 6.87 × 10-11-7.41×10-11mol/L-1, the concentration of modified gold nanorods solution is 2.43 ×
10-12-4.50×10-12mol/L-1。
On the premise of this above-mentioned gold nano cluster solution with the concentration of modified gold nanorods solution, gold nano cluster solution
Can select in wide scope with the concrete consumption of modified gold nanorods solution, but in order to improve gold nano cluster further
The photoluminescence quantum yield of fluorescence system, it is preferable that relative to the buffer solution of 100 μ L, the consumption of gold nano cluster solution is
100-120 μ L, the consumption of modified gold nanorods solution is 30-100 μ L.
In the present invention, the thickness of the silicon oxide layer in modified gold nanorods can select in wide scope, but is
The further photoluminescence quantum yield improving gold nano cluster fluorescence system, it is preferable that in modified gold nanorods, dioxy
The thickness of SiClx layer is 5-27nm.
In the present invention, concrete structure and the composition of modified gold nanorods can select in wide scope, but in order to
Improve the photoluminescence quantum yield of gold nano cluster fluorescence system further, it is preferable that relative to the gold nanorods of 1 μm ol,
In silicon dioxide layer, the content of silicon dioxide is 0.801-0.874 μm ol, and in amido modified layer, the content of amido modified group is
0.0422-0.0461μmol.In the present invention, the concrete structure of gold nano cluster and composition can select in wide scope,
But in order to improve the photoluminescence quantum yield of gold nano cluster fluorescence system further, it is preferable that described gold nano cluster
Including gold atom core, described outer layer protection group is coated on the outside of described gold atom core, the grain of described gold atom core
Footpath is 46-53nm, and the thickness of described outer layer protection group is 5-27nm.
It addition, the concrete kind of the amido modified group of modified gold nanorods can select in wide scope, but it is
The photoluminescence quantum yield of the gold nano cluster fluorescence system that further raising prepares, it is preferable that amido modified group is for for such as
The group (slough ethyl by APTES i.e. 3-aminopropyl triethoxysilane and obtain) of structure shown in formula (I),
Meanwhile, the pH of buffer solution can select in wide scope, but in order to improve prepared gold nano further
The photoluminescence quantum yield of cluster fluorescence system, it is preferable that the pH of buffer solution is 5.8-6.4.
Additionally, the pH of buffer solution can select in wide scope, but in order to improve prepared gold nano further
The photoluminescence quantum yield of cluster fluorescence system, it is preferable that buffer solution is selected from PBS buffer solution.
On the basis of the above, catalytic actual conditions can select in wide scope, but in order to enter
One step improves the photoluminescence quantum yield of the gold nano cluster fluorescence system prepared, it is preferable that haptoreaction at least meets following bar
Part: reaction temperature is 25-30 DEG C, the response time is 55-65min.
Present invention also offers a kind of gold nano cluster fluorescence system strengthened based on surface plasma, this gold nano group
Bunch fluorescence system is prepared from by above-mentioned method.
Present invention provides the preparation method of modified gold nanorods solution, the method includes:
1) gold nanorods solution is adjusted to alkalescence, is subsequently added into the methanol solution containing tetraethyl orthosilicate (TEOS) and contacts
Reaction, reaction is centrifugal after terminating, washing, is then scattered in product in aqueous isopropanol to obtain AuNR@SiO2Solution；
2) APTES (3-aminopropyl triethoxysilane) solution is added to AuNR@SiO2Solution carries out haptoreaction,
Reaction is centrifugal after terminating, washing, is then dispersed in water product to obtain AuNR@SiO2@NH2Solution.
Hereinafter will be described the present invention by embodiment.
Preparation example 1
The preparation of gold nanorods (AuNR) solution:
1) preparation that gold is planted: weigh the CTAB (CTAB) of 0.3645g in 50mL conical flask, add
Enter bis-water dissolutioies of 10mL, be sequentially added into the HAuCl that concentration is 0.01M of 250 μ L wherein4Solution and the NaBH of 600 μ L4
Solution (frozen water is now joined), after the uniform 2min of Quick shaking, the color from yellow of solution becomes light brown, by solution in 30 DEG C of water-baths
Stand and place 2h with prepared gold kind solution.
2) preparation of growth-promoting media: weigh the CTAB of 5.4675g in 250mL volumetric flask, adds bis-water dissolutioies of 150mL
After, add the HAuCl of the 0.01M of 7.5mL4, after shaking uniformly, add the AgNO of the 0.01M of 1.2mL3Solution；Add after shaking uniformly
The HCl of the 1M of 3mL, adds the AA (ascorbic acid) of 0.1M of 1.2mL with prepared growth-promoting media after shaking uniformly.
3), after homoepitaxial liquid is shaken in mixing, take 210 μ L seed liquor and be rapidly injected above-mentioned gold and plant in solution and shake up and be placed on
In 30 DEG C of thermostat water baths, 12h is to obtain gold nanorods solution.
4) purification gold nanorods solution: take above-mentioned 10ml gold nanorods solution in centrifuge with the speed of 8000r/min
Centrifugal 10min, takes out the supernatant carefully with liquid-transfering gun, with secondary water, lower sediment is diluted to 10mL, repeats above-mentioned
Centrifugally operated, after water-dispersible for lower sediment secondary, obtain gold nanorods solution F1, put in refrigerator stand-by.Its concentration root
Calculate according to langbobier law.
Preparation example 2
AuNR@SiO2@NH2The preparation of solution:
1)AuNR@SiO2The preparation of solution: the gold nanorods solution taking the above-mentioned purification of 20mL good is placed in 50mL round-bottomed flask
In, adjust pH after 10-11, stirring 1h by the NaOH solution of 0.1M, be sequentially added into the 10 μ L TEOS containing 20 weight % every 30min
Methanol solution (adding three times, 30 μ L altogether), at 25 DEG C stirring reaction 36h.Take 14ml solution with methanol solution 6500r,
After 10min washes three times, it is dispersed in aqueous isopropanol, available SiO2Layer thickness is the AuNR@SiO of 7nm2Solution, separately takes 6ml
Solution centrifugal is scattered in 6mL water and prepares AuNR@SiO2Solution A 1 is stand-by.
2)AuNR@SiO2@NH2The preparation of solution: under the conditions of 80 DEG C of oil baths, to the AuNR@SiO of 10mL2Solution adds
APTES (3-aminopropyl triethoxysilane) solution of 3 μ L, stirring reaction 4h, the product with methylalcohol solution 6000r obtained,
10min washes three times, is dispersed in secondary water and prepares AuNR@SiO2@NH2Solution B 1, is placed in refrigerator stand-by.
Preparation example 3
Carry out preparing AuNR@SiO according to the method for embodiment 22Solution A 2, AuNR@SiO2@NH2Solution B 2, wherein SiO2
The thickness of layer is 15nm, and except for the difference that the consumption of the methanol solution of TEOS is 45 μ L.
Preparation example 4
Carry out preparing AuNR@SiO2 solution A 3, AuNR@SiO according to the method for embodiment 22@NH2Solution B 3, wherein SiO2
The thickness of layer is 24nm, and except for the difference that the consumption of the methanol solution of TEOS is 60 μ L.
Preparation example 5
The preparation of gold nano cluster (AuNCs) solution:
The HAuCl that concentration is 0.01M of 5ml is added in BSA (bovine serum albumin) solution of the 50mg/ml of 5ml4Molten
Liquid, adjusts pH to be 11-12 by the NaOH solution of 1M, stands growth 12h in 37 DEG C of water-baths；Finally with 100kDa dialyzer in secondary water
Middle dialysis 24h, changes a water every 8h, and gold nano cluster (AuNCs) solution obtained is placed in refrigerator stand-by.
Embodiment 1
Take 100 μ L above-mentioned AuNCs solution, add the PBS solution of the 0.1M of the pH=6 of 100 μ L, the most successively
Add the AuNR@SiO of 30 μ L2@NH2Solution B 2 is settled to 2mL, obtains AuNR@SiO2@NH2@AuNCs composite construction G1,25 DEG C
Lower standing and reacting 1h obtains gold nano cluster fluorescence system D1 strengthened based on surface plasma；Concrete preparation principle and
Step can be found in Fig. 1, forms coated with silica layer the most before this on the surface of AuNR, and amino is modified on the surface of clad the most again
Group is to obtain AuNR@SiO2@NH2, then by AuNCs Yu the AuNR@SiO of bovine serum albumin modification2@NH2Compound prepared
AuNR@SiO2@NH2@AuNCs。
Embodiment 2
Carry out obtaining fluorescence system D2, except for the difference that AuNR SiO according to the method for embodiment 12@NH2The consumption of solution B 2
Change 50 μ L into.
Embodiment 3
Carry out obtaining fluorescence system D3, except for the difference that AuNR SiO according to the method for embodiment 12@NH2The consumption of solution B 2
Change 70 μ L into.
Embodiment 4
Carry out obtaining fluorescence system D4, except for the difference that AuNR SiO according to the method for embodiment 12@NH2The consumption of solution B 2
Change 90 μ L into.
Embodiment 5
Carry out obtaining fluorescence system D5, except for the difference that AuNR SiO according to the method for embodiment 12@NH2The consumption of solution B 2
Change 110 μ L into.
Embodiment 6
Carry out obtaining gold nano cluster fluorescence system D6 according to the method for embodiment 2, except for the difference that, by AuNR SiO2@NH2
Solution B 2 is changed to AuNR@SiO2@NH2Solution B 1.
Embodiment 7
Carry out obtaining gold nano cluster fluorescence system D7 according to the method for embodiment 3, except for the difference that, by AuNR SiO2@NH2
Solution B 2 is changed to AuNR@SiO2@NH2Solution B 1.
Embodiment 8
Carry out obtaining gold nano cluster fluorescence system D8 according to the method for embodiment 1, except for the difference that, by AuNR SiO2@NH2
Solution B 2 is changed to AuNR@SiO2@NH2Solution B 3.
Embodiment 9
Carry out obtaining gold nano cluster fluorescence system D9 according to the method for embodiment 2, except for the difference that, by AuNR SiO2@NH2
Solution B 2 is changed to AuNR@SiO2@NH2Solution B 3.
Embodiment 10
Carry out obtaining gold nano cluster fluorescence system D10 according to the method for embodiment 3, except for the difference that, by AuNR SiO2@
NH2Solution B 2 is changed to AuNR@SiO2@NH2Solution B 3.
Embodiment 11
Carry out obtaining fluorescence system D11 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 4.
Embodiment 12
Carry out obtaining fluorescence system D12 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 5.
Embodiment 13
Carry out obtaining fluorescence system D13 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 7.
Embodiment 14
Carry out obtaining fluorescence system D14 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 8.
Embodiment 15
Carry out obtaining fluorescence system D15 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 9.
Embodiment 16
Carry out obtaining fluorescence system D16 according to the method for embodiment 3, except for the difference that the pH of PBS solution is changed to 10.
Embodiment 17
Carrying out obtaining fluorescence system D15 according to the method for embodiment 3, except for the difference that the standing and reacting time is 10min.
Embodiment 18
Carrying out obtaining fluorescence system D18 according to the method for embodiment 3, except for the difference that the standing and reacting time is 20min.
Embodiment 19
Carrying out obtaining fluorescence system D19 according to the method for embodiment 3, except for the difference that the standing and reacting time is 30min.
Embodiment 20
Carrying out obtaining fluorescence system D20 according to the method for embodiment 3, except for the difference that the standing and reacting time is 40min.
Embodiment 21
Carrying out obtaining fluorescence system D21 according to the method for embodiment 3, except for the difference that the standing and reacting time is 45min.
Embodiment 22
Carrying out obtaining fluorescence system D22 according to the method for embodiment 3, except for the difference that the standing and reacting time is 50min.
Embodiment 23
Carrying out obtaining fluorescence system D23 according to the method for embodiment 3, except for the difference that the standing and reacting time is 60min.
Embodiment 24
Carrying out obtaining fluorescence system D24 according to the method for embodiment 3, except for the difference that the standing and reacting time is 120min.
Comparative example 1
Carry out obtaining gold nano cluster fluorescence system E1 according to the method for embodiment 1, except for the difference that, by AuNR SiO2@NH2
The consumption of solution B 2 changes 0 μ L into.
Comparative example 2
Carry out obtaining fluorescence system E2 according to the method for embodiment 3, except for the difference that, by the AuNR SiO of 70 μ L2@NH2Solution
B2 is changed to the AuNR@SiO of 70 μ L2Solution A 2.
Comparative example 3
Carry out obtaining fluorescence system E3 according to the method for comparative example 2, except for the difference that, by AuNR SiO2Solution A 2 changes into
AuNR@SiO2Solution A 1.
Comparative example 4
Carry out obtaining fluorescence system E4 according to the method for comparative example 2, except for the difference that, by AuNR SiO2Solution A 2 changes into
AuNR@SiO2Solution A 3.
Comparative example 5
Carrying out obtaining fluorescence system E5 according to the method for embodiment 2, except for the difference that the standing and reacting time is 0min.
Comparative example 6
Carry out obtaining fluorescence system E6 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 4.
Comparative example 7
Carry out obtaining fluorescence system E7 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 5.
Comparative example 8
Carry out obtaining fluorescence system E8 according to the method for comparative example 1, except for the difference that the pH of PBS solution is changed to 7.
Comparative example 9
Carry out obtaining fluorescence system E9 according to the method for comparative example 1, except for the difference that the pH of PBS solution is changed to 8.
Comparative example 10
Carry out obtaining fluorescence system E10 according to the method for comparative example 1, except for the difference that the pH of PBS solution is changed to 9.
Comparative example 11
Carry out obtaining fluorescence system E11 according to the method for comparative example 1, except for the difference that the pH of PBS solution is changed to 10.
Comparative example 12
Carry out obtaining fluorescence system E12 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 4.
Comparative example 13
Carry out obtaining fluorescence system E13 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 5.
Comparative example 14
Carry out obtaining fluorescence system E14 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 7.
Comparative example 15
Carry out obtaining fluorescence system E15 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 8.
Comparative example 16
Carry out obtaining fluorescence system E16 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 9.
Comparative example 17
Carry out obtaining fluorescence system E17 according to the method for comparative example 2, except for the difference that the pH of PBS solution is changed to 10.
Detection example 1
By the transmission electron microscope of Tecnai G2 20ST (FEI), gold nanorods (AuNR) solution carried out transmission electricity
Microscopy is surveyed, and concrete outcome is shown in Fig. 2, and the particle diameter of gold nanorods is between 40-70nm as shown in Figure 2, predominantly 46-53nm.
Detection example 2
By the transmission electron microscope of Tecnai G2 20ST (FEI) to AuNR@SiO2Solution A 1-A3 carries out transmission electricity
Microscopy is surveyed, and concrete outcome is shown in Fig. 3, Fig. 4 and Fig. 5, and as seen from the figure, Fig. 3 shows AuNR@SiO2AuNR@SiO in solution A 12Dioxy
The thickness of SiClx layer is that 7nm, Fig. 4 show AuNR@SiO2AuNR@SiO in solution A 22The thickness of silicon dioxide layer be 15nm, figure
5 display AuNR@SiO2AuNR@SiO in solution A 32The thickness of silicon dioxide layer be 24nm, and silicon dioxide layer thickness is uniform,
Favorable dispersibility.
Detection example 3
By the transmission electron microscope of Tecnai G2 20ST (FEI), gold nano cluster fluorescence system D3 is carried out transmission
Electronic Speculum detects, and concrete outcome is shown in Fig. 6-7, as seen from the figure, and AuNR@SiO2@NH2The most compound with AuNCs.
The AuNR@SiO in D1-D2, D4-D24 detected in the same manner2@NH2The most multiple with AuNCs
Close.
Detection example 4
By the transmission electron microscope of Tecnai G2 20ST (FEI), gold nano cluster AuNCs is carried out transmission electron microscope
Detecting, concrete outcome is shown in Fig. 8, and as seen from the figure, the particle diameter of AuNC is mainly at 2-4nm.
Detection example 5
By spectrofluorophotometer, D1, D2, D3, D4, D5, E1 and E2 being carried out fluoroscopic examination, concrete outcome is shown in Figure 10,
Gold nanorods can cause gold nano cluster fluorescent quenching after modifying silicon dioxide as seen from the figure, but, carry out at silicon dioxide layer
After modification amino makes itself and gold nano cluster effect, make the Fluorescence Increasing of gold nano cluster, and amido modified along with add
Increasing of the amount of the gold nanorods of silicon dioxide, the effect of enhancing is the best, until the concentration ratio of gold nanorods with gold nano cluster
Suitably, the most no longer change.
Detection example 6
By ultraviolet-visible spectrophotometer (U-3010, Hitachi), above-mentioned F1, E1, A2, B2, G1 are carried out ultraviolet suction
Receiving detection, concrete outcome is shown in Figure 11, modifies the uv absorption figure of gold nanorods A2 of silicon dioxide as seen from the figure compared to Jenner
There is red shift about 5nm in rice rod F1, it was demonstrated that silicon dioxide is coated with gold nanorods really；And the gold nanorods B2 phase of modified amino
Do not change for modifying the uv absorption figure of the gold nanorods A2 of silicon dioxide；And the uv absorption of E1 after finally acting on
There is red shift in the peak position on the figure uv absorption figure relative to G1, and observes absworption peak at 270nm, and gold nano group is described
Bunch the most successfully use with modified gold nanorods.
Detection example 7
By spectrofluorophotometer, above-mentioned fluorescence system D6, D7, E1, E3 being carried out fluoroscopic examination, concrete outcome is shown in figure
9, as seen from the figure, SiO2The AuNR@SiO that thickness is 7nm of layer2@NH2Make the fluorescent quenching of Aurum clusters.
Detection example 8
By spectrofluorophotometer, above-mentioned fluorescence system D8, D9, D10, E1, E4 are carried out fluoroscopic examination, concrete outcome
See Figure 12, as seen from the figure, SiO2The AuNR@SiO that thickness is 24nm of layer2@NH2Make the Fluorescence Increasing of Aurum clusters, but strengthen effect
Fruit is weaker than SiO2The AuNR@SiO that thickness is 15nm of layer2@NH2Fluorescence system.
Detection example 9
Detecting fluorescence system E7, the fluorescence intensity of D17-D24 by spectrofluorophotometer, concrete outcome is shown in Figure 16, by
Figure understands, and fluorescence system D3 is that fluorescence intensity during 60min is optimal in the response time.
Detect that D1-D16, E1-E4, E6, E8-E17 are also glimmering when the response time is 60min in the same manner
Light intensity is optimal.
Detection example 10
Detecting fluorescence system D3, the fluorescence intensity of D11-D16 by spectrofluorophotometer, concrete outcome is shown in Figure 15, by
Figure understands, and it is Fluorescence Increasing best results when 6 that the fluorophor that the present invention provides ties up to pH.
Detection example 11
Detecting fluorescence system E2, the fluorescence intensity of E12-E17 by spectrofluorophotometer, concrete outcome is shown in Figure 14, by
Figure understands, and it is fluorescent quenching best results when 6 that above-mentioned fluorophor ties up to pH.
Detection example 12
Detecting fluorescence system E1, the fluorescence intensity of E6-E11 by spectrofluorophotometer, concrete outcome is shown in Figure 13, by scheming
Understanding, above-mentioned fluorophor ties up to the fluorescent stabilization that pH is 4-10.
Detecting in the same manner, D1-D10, E1-E5 are also to be that fluorescence intensity when 6 is optimal at pH.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of the gold nano cluster fluorescence system strengthened based on surface plasma, it is characterised in that including:
Gold nano cluster solution, modified gold nanorods solution and buffer solution are carried out haptoreaction with prepare described based on surface etc. from
The gold nano cluster fluorescence system that daughter strengthens；
Wherein, the modified gold nanorods in described modified gold nanorods solution includes that gold nanorods, silicon dioxide layer and amino are repaiied
Decorations layer, described silicon dioxide layer is coated on the outside of described gold nanorods, and described amido modified layer is distributed in described silicon dioxide
The outer surface of layer；The outer layer protection group of described gold nano cluster GOLD FROM PLATING SOLUTION nanocluster is selected from bovine serum albumin, human blood
One or more in pure albumen and glutathion.
Preparation method the most according to claim 1, wherein, relative to the gold of 1 μm ol in described gold nano cluster solution
Nanocluster, the consumption of described modified gold nanorods is 0.0327-0.0607 μm ol.
Preparation method the most according to claim 2, wherein, the concentration of described gold nano cluster GOLD FROM PLATING SOLUTION nanocluster is
6.87×10-11-7.41×10-11mol/L-1, the concentration of described modified gold nanorods solution is 2.43 × 10-12-4.50×10- 12mol/L-1。
Preparation method the most according to claim 3, wherein, relative to the described buffer solution of 100 μ L, described gold nano group
The consumption of bunch solution is 100-120 μ L, and the consumption of described modified gold nanorods solution is 30-100 μ L.
5. according to the preparation method described in any one in claim 1-4, wherein, in described modified gold nanorods, described
The thickness of silicon oxide layer is 5-27nm.
Preparation method the most according to claim 5, wherein, relative to the described gold nanorods of 1 μm ol, described silicon dioxide
In Ceng, the content of silicon dioxide is 0.801-0.874 μm ol, and in described amido modified layer, the content of amido modified group is
0.0422-0.0461μmol；
Preferably, described gold nano cluster includes that gold atom core, described outer layer protection group are coated on described gold atom core
Outside, the particle diameter of described gold atom core is 46-53nm, and the thickness of described outer layer protection group is 5-27nm.
Preparation method the most according to claim 6, wherein, described amido modified group is the base of structure as shown in formula (I)
Group,
8. according to the preparation method described in claim 6 or 7, wherein, the pH of described buffer solution is 5.8-6.4；
Preferably, described buffer solution is selected from PBS buffer solution.
Preparation method the most according to claim 8, wherein, described haptoreaction at least meets following condition: reaction temperature
For 25-30 DEG C, the response time is 55-65min.
10. the gold nano cluster fluorescence system strengthened based on surface plasma, it is characterised in that described gold nano cluster
Fluorescence system is prepared from by the method described in any one in claim 1-9.
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| CN114309633A (en) * | 2021-12-16 | 2022-04-12 | 杭州电子科技大学 | Preparation method of oleophylic gold nanorods |
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