CN106582860B - Load has noble metal nano particles/metalloporphyrin composite micelle and preparation method - Google Patents
Load has noble metal nano particles/metalloporphyrin composite micelle and preparation method Download PDFInfo
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- CN106582860B CN106582860B CN201611210291.2A CN201611210291A CN106582860B CN 106582860 B CN106582860 B CN 106582860B CN 201611210291 A CN201611210291 A CN 201611210291A CN 106582860 B CN106582860 B CN 106582860B
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- 239000000693 micelle Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 28
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229920001400 block copolymer Polymers 0.000 claims abstract description 24
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 claims abstract description 21
- 239000010970 precious metal Substances 0.000 claims abstract description 12
- 238000000502 dialysis Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910003609 H2PtCl4 Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 15
- 229910052737 gold Inorganic materials 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000004032 porphyrins Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004103 aerobic respiration Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Preparation (AREA)
- Colloid Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods for loading and having noble metal nano particles/metalloporphyrin composite micelle, and the specific steps are synthetic segmented copolymer PEG-b-P4VP；Block copolymer PEG-b-P4VP is dissolved in the hydrochloric acid solution of pH=2.0, alkaline solution is added and adjusts solution ph to neutrality, obtains using P4VP as core, PEG is the core-shell structure micella of shell；Soluble precious-metal salt is added into micella, after stirring and adsorbing 2-6h, adds NaBH4Aqueous solution is restored, and after reacting 72h, is centrifuged, and dialysis obtains micellar solution；Certain density metalloporphyrin is added in micellar solution, is stirred at room temperature for 24 hours, centrifugation, dialysis obtain the composite micelle of core-shell structure.The method of the present invention is simple, easily operated, at low cost, and the composite micelle of preparation can load a plurality of types of metalloporphyrins and metallic, has broad application prospects in the fields such as photocatalysis and photochemistry.
Description
Technical field
The invention belongs to technical field of nano material, have noble metal nano particles/metal porphin more particularly to a kind of load
Composite micelle of quinoline and preparation method thereof.
Background technique
Porphyrin and metal porphyrins are all widely present in natural environment and life entity, such as photosynthetic core
Part chlorophyll, the hemoglobin etc. for participating in aerobic respiration is all Metalloporphyrins.As function important in life entity
Molecule, metalloporphyrin have important application in fields such as life science, medicine and pharmacology.But due to the design feature of its own, cause
There is very big unstability for metalloporphyrin, for example are easy to decompose under illumination, to limit its functional further hair
It waves.Therefore, how the optical stability of metalloporphyrin is improved during application, to expand the application model of metalloporphyrin
It encloses, has very important significance.
In addition one side, noble metal nano particles due to unique physicochemical properties, and catalysis, electronic device,
Information storage, optical device, bio-sensing, microcell imaging and medicine etc. have huge application potential.But due to expensive
The phenomenon that surfaces of metal nanoparticles can be high and unstable, is easy to appear reunion, therefore how to improve noble metal nano particles
Stability is an extremely important problem.
Block copolymer micelle is suffered from multiple fields as a kind of nano particle of special construction and is widely applied, and is led to
Self assembly of the block copolymer in selective solvent is crossed, it is a variety of to have obtained ball-type, vesicle type, rodlike, tubulose and ring-type etc.
The micella of novel form, and the hydrophobic environment that it is constructed can load a variety of pigment moleculars, and be stabilized it.I
Once in Spectroscopic studies on the photostability and photoactivity of
Metallo-tetraphenylporphyrin in micelles, Colloid Polym Sci, 2014,292 (6), 1329-
In 1337, the optical stability and optical activity of block copolymer micelle enhancing metalloporphyrin are utilized.And block copolymer micelle
There is unique advantage in terms of supported precious metal nano-particle, can accurately control the spatial distribution of noble metal nano particles, make
It is with better stability and dispersibility.
Based on this, it is proposed that being loaded metalloporphyrin and noble metal nano simultaneously using block copolymer micelle, mentioning
While the stability of the particle of high metal porphyrin optical stability and noble metal nano, metalloporphyrin and noble metal nano are played
Particle synergistic effect, develop a kind of novel nano material.
Summary of the invention
For the deficiencies in the prior art, the present invention provides one kind, and metalloporphyrin optical stability and expensive can be improved
The preparation method of the polymer composite micelle of metal nanoparticle stability.
Specifically, provided by the invention load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
Specifically includes the following steps:
S1: synthetic segmented copolymer PEG-b-P4VP, the molecular weight distribution of the block copolymer PEG-b-P4VP is 1.3
Within；
S2: the block copolymer PEG-b-P4VP is dissolved in the hydrochloric acid solution of pH=2.0 at room temperature, is polymerize
Object solution, addition alkaline solution adjust the pH value of the polymer solution to neutrality, obtain using P4VP as core, and PEG is the core of shell
Shell structure micella；
S3: soluble precious-metal salt, the 4- in the block copolymer is added into the micella under the action of stirring
The molar ratio of vinylpyridine and the soluble precious-metal salt is 2-100, after stirring and adsorbing 2-6h, adds NaBH4It is water-soluble
Liquid, NaBH4Molar ratio with the soluble precious-metal salt is 10:1, after reacting 72h, is centrifuged, and dialysis obtains carried noble metal
The micellar solution of nanoparticle.
S4: certain density metalloporphyrin being added in the micellar solution of the supported precious metal nano-particle, described
The molar ratio of 4-vinylpridine and the metalloporphyrin is 5-100 in block copolymer, is stirred at room temperature for 24 hours, centrifugation, dialysis,
Obtain the composite micelle for the core-shell structure that partial size is 100-160nm.
Preferably, the block copolymer PEG-b-P4VP is synthesized using the method for Controlled Living Radical Polymerization.
It is highly preferred that being the CuCl/Me of 1:1 with molar ratio6Tren is catalyst system, butanone/isopropyl of volume ratio 7:3
Alcohol is solvent, PEG114- Br is macromole evocating agent, causes 4-vinylpridine monomer polymerization and obtains block copolymer PEG-b-
P4VP, the molecular weight distribution of block copolymer PEG-b-P4VP is within 1.3.
Preferably, the soluble precious-metal salt is selected from HAuCl4、NaAuCl4、AgNO3、H2PtCl4、H2PtCl6It is any
It is a kind of.
Preferably, the alkaline solution is the sodium hydroxide of 1mol/L.
Preferably, in S3 and S4, the molecular cut off of the dialysis procedure is 3500.
The present invention also provides a kind of loads noble metal nano particles/metalloporphyrin composite micelle, specifically by above-mentioned
Either method is prepared.
Composite micelle provided by the invention assembles shape by amphiphilic diblock copolymer, noble metal nano particles and metalloporphyrin
At nucleocapsid structure, the stratum nucleare of composite micelle can load a plurality of types of metalloporphyrins and metallic, make it have excellent
Stability simultaneously has multifunctionality.Preparation method is simple, easily operated, at low cost, and application easy to spread is especially urged in light
Change and the fields such as photochemistry have broad application prospects.
Detailed description of the invention
Fig. 1 is the optical photograph for the block copolymer micelle load gold nano particle that the embodiment of the present invention 1 provides；
Fig. 2 is the transmission electron microscope photo figure of the composite micelle of carried metal porphyrin and gold nanoparticle in embodiment 1-4；
Fig. 3 is the ultraviolet spectrogram of the composite micelle of carried metal porphyrin and gold nanoparticle in embodiment 1-4；
Fig. 4 is the fluorescence spectra of the composite micelle of carried metal porphyrin and gold nanoparticle in embodiment 1-4；
Fig. 5 is the surface-element analysis chart of the composite micelle of carried metal porphyrin and nano platinum particle in embodiment 5.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
It should be noted that reagent used in following embodiment is unless otherwise noted, and it is conventional reagent, it can be in city
It is commercially available on, the preparation method or detection method of related related compound are unless otherwise noted conventional side
Method.
Embodiment 1
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, the specific steps are as follows:
It is the CuCl/Me of 1:1 with molar ratio using atom transfer radical polymerization (ATRP) method6Tren is catalyst
System, butanone/isopropanol of volume ratio 7:3 are solvent, PEG114- Br is macromole evocating agent, causes 4-vinylpridine activity
Polymerization obtains block copolymer PEG-b-P4VP, and the molecular weight distribution of block copolymer PEG-b-P4VP is within 1.3.
Obtained block copolymer PEG-b-P4VP is dissolved in the hydrochloric acid solution of pH=2.0 at room temperature, is polymerize
The pH value of sodium hydroxide adjusting polymer solution of 1mol/L is added to neutrality, since P4VP is in neutral conditions in object solution
Therefore insoluble block is obtained using P4VP as core, PEG is the core-shell structure micella of shell.
HAuCl is added into micella under the action of stirring4Solution, after stirring and adsorbing 6h, 4- ethylene in block copolymer
Yl pyridines and HAuCl4Molar ratio be R=2, add NaBH4Aqueous solution, NaBH4Molar ratio with nanogold is 10, reaction
It after 72h, is centrifuged, dialysis obtains the micellar solution of load gold nano particle to remove the reducing agent of dereaction.
Certain density metalloporphyrin (ZnTPPS) is added in the micellar solution of gold nanoparticle, in block copolymer
The molar ratio of 4-vinylpridine and the metalloporphyrin is 25, is made using the axial coordination between pyridine groups and metalloporphyrin
With, be stirred at room temperature for 24 hours, centrifugation, dialysis, obtain partial size be 100-160nm supported nano-gold and metalloporphyrin core-shell structure
Composite micelle.
Embodiment 2
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, specific steps and reality
It is identical to apply example 1, the difference is that only, 4-vinylpridine and HAuCl in block copolymer4Molar ratio be R=10.
Embodiment 3
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, specific steps and reality
It is identical to apply example 1, the difference is that only, 4-vinylpridine and HAuCl in block copolymer4Molar ratio be R=25.
Embodiment 4
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, specific steps and reality
It is identical to apply example 1, the difference is that only, 4-vinylpridine and HAuCl in block copolymer4Molar ratio be R=100.
The optical photograph of the micellar solution of load gold nano particle made from embodiment 1- embodiment 4 is as shown in Figure 1, by scheming
As can be seen that the increase of the concentration with gold nanoparticle, solution colour is deeper and deeper, and it is compound to illustrate that gold nanoparticle loads to
On micella.
Transmissioning electric mirror test, the preparation of transmission electron microscope sample are carried out to composite micelle obtained by embodiment 1 specifically:
Under room temperature, it is coated with one side of carbon film copper mesh with tweezers clamping, tilts copper mesh plane slightly with horizontal plane.One drop was diluted
Polymer micelle solution drip to copper mesh surface, suck most solutions with filter paper in a moment, after natural drying to copper mesh, vacuum
Lower drying at room temperature 12h or more is saved, is then characterized with form of the transmission electron microscope to composite micelle.It transmits electricity
The result of mirror is as shown in Fig. 2, gold nanoparticle more uniformly loads to micellar surface, since the title degree of metalloporphyrin is smaller,
Therefore only load of the display to nanogold in transmission electron microscope photo.
It is right respectively in order to verify whether the metalloporphyrin of embodiment 1- embodiment 4 load successfully to nano Au particle
The composite micelle sample of embodiment 1-4 carries out ultraviolet spectra and the characterization of fluorescence spectrum can see by the ultraviolet spectra of Fig. 3,
The characteristic absorption peak of nanogold and metalloporphyrin is shown in picture, and passes through metalloporphyrin in the ultraviolet characteristic peak of Soret band
From the point of view of red shift, certain interaction is had occurred with metalloporphyrin in gold, by the fluorescence spectrum of Fig. 4 it can also be seen that with gold
The fluorescence intensity of the increase of nanoparticle concentration, metalloporphyrin is substantially reduced, and produces apparent fluorescent quenching, the hair of the phenomenon
Life demonstrates gold nanoparticle, and there are very strong interactions with metalloporphyrin.
Embodiment 5
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, specific steps and reality
It is identical to apply example 1, the difference is that only, by HAuCl4Replace H2PtCl6, while H2PtCl6Solution is in micella when stirring and adsorbing
Between be 2h, obtain the composite micelle of supporting Pt nanoparticle and metalloporphyrin.In order to which whether the metalloporphyrin for verifying embodiment 5 is right
Nano Pt particles load successfully, surface-element analysis have been carried out to the composite micelle of load nano Pt particles, as a result such as Fig. 5
It is shown, it can be seen that have the presence of Pt element, so proving to load successfully.
Embodiment 6
It is a kind of to load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, specific steps and reality
It is identical to apply example 1, the difference is that only, by HAuCl4Replace AgNO3, while AgNO3Solution stirring and adsorbing time in micella is
2h obtains the composite micelle of loaded Ag nanoparticle and metalloporphyrin.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, and protection scope is unlimited
In this.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in protection of the invention
Within the scope of, protection scope of the present invention is subject to claims.
Claims (7)
1. a kind of load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle, which is characterized in that specific packet
Include following steps:
S1: the molecular weight distribution of synthetic segmented copolymer PEG-b-P4VP, the block copolymer PEG-b-P4VP 1.3 with
It is interior；
S2: the block copolymer PEG-b-P4VP is dissolved in the hydrochloric acid solution of pH=2.0 at room temperature, it is molten to obtain polymer
Liquid, addition alkaline solution adjust the pH value of the polymer solution to neutrality, obtain using P4VP as core, and PEG is the nucleocapsid knot of shell
Structure micella；
S3: soluble precious-metal salt, the 4- ethylene in the block copolymer is added into the micella under the action of stirring
The molar ratio of yl pyridines and the soluble precious-metal salt is 2-100, after stirring and adsorbing 2-6h, adds NaBH4Aqueous solution,
NaBH4Molar ratio with the soluble precious-metal salt is 10:1, after reacting 72h, is centrifuged, and dialysis obtains carried noble metal and receives
The micellar solution of rice corpuscles；
S4: certain density metalloporphyrin being added in the micellar solution of the supported precious metal nano-particle, the block
The molar ratio of 4-vinylpridine and the metalloporphyrin is 5-100 in copolymer, is stirred at room temperature for 24 hours, and centrifugation, dialysis obtain
Partial size is the composite micelle of the core-shell structure of 100-160nm.
2. according to claim 1 load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
It is characterized in that, the block copolymer PEG-b-P4VP is synthesized using the method for Controlled Living Radical Polymerization.
3. according to claim 2 load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
It is characterized in that, is the CuCl/Me of 1:1 with molar ratio6Tren is catalyst system, and butanone/isopropanol of volume ratio 7:3 is molten
Agent, PEG114- Br is macromole evocating agent, causes 4-vinylpridine monomer polymerization and obtains block copolymer PEG-b-P4VP.
4. according to claim 1 load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
It is characterized in that, the soluble precious-metal salt is selected from HAuCl4、NaAuCl4、AgNO3、H2PtCl4、H2PtCl6Any one.
5. according to claim 1 load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
It is characterized in that, the alkaline solution is the sodium hydroxide of 1mol/L.
6. according to claim 1 load the preparation method for having noble metal nano particles/metalloporphyrin composite micelle,
It is characterized in that, in S3 and S4, the molecular cut off in the dialysis procedure is 3500.
7. a kind of load has noble metal nano particles/metalloporphyrin composite micelle, which is characterized in that appointed by claim 1-6
Method described in one is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611210291.2A CN106582860B (en) | 2016-12-24 | 2016-12-24 | Load has noble metal nano particles/metalloporphyrin composite micelle and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611210291.2A CN106582860B (en) | 2016-12-24 | 2016-12-24 | Load has noble metal nano particles/metalloporphyrin composite micelle and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN106582860A CN106582860A (en) | 2017-04-26 |
| CN106582860B true CN106582860B (en) | 2019-05-07 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1834955A1 (en) * | 2006-03-10 | 2007-09-19 | Humboldt Universität zu Berlin | Porphyrin derivates and their use as photosensitizers in photodynamic therapy |
| CN104861172A (en) * | 2015-04-28 | 2015-08-26 | 同济大学 | Preparation method of porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1834955A1 (en) * | 2006-03-10 | 2007-09-19 | Humboldt Universität zu Berlin | Porphyrin derivates and their use as photosensitizers in photodynamic therapy |
| CN104861172A (en) * | 2015-04-28 | 2015-08-26 | 同济大学 | Preparation method of porphyrin core star copolymer with fluorescence effect, PH responsiveness and temperature responsiveness |
Non-Patent Citations (2)
| Title |
|---|
| Enhanced stability of ZnTPPS by polymeric gold nanoparticles in acidic aqueous solutions--complex micelle metalloporphyrin gold;Zhihua Chai等;《JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY》;20160406;第53卷(第5期);第2节及图1 |
| 嵌段共聚物/金属卟啉复合胶束的功能化;柴志华;《中国博士学位论文全文数据库（电子期刊）》;20150415(第4期);第2.2.4，2.2.3.4节 |
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