Metallo-meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrins (metallo-TPPSs), such as ZnTPPS, have been widely used as photosensitizers. However, their vulnerability to photodegradation significantly limits their applications. In this contribution, we demonstrate a method to enhance the photostability of metallo-TPPSs while retaining photoactivity via encapsulation inside cores of complex micelles. Poly(ethylene glycol)-b-poly(4-vinylpyridine) (PEG-b-P4VP) and metallo-TPPSs can form complex micelles in acidic solution through electrostatic interactions and then undergo axial coordination with the pyridine moieties of PEG-b-P4VP when the pH is adjusted to 7.4. In this way, metallo-TPPSs are entrapped in the hydrophobic, compact micellar cores, which effectively prevents photodegradation of the metallo-TPPSs that would otherwise occur in aqueous solution. In addition, the photodebromination of 2,3-dibromo-3-phenylpropionic acid (DPP) sensitized with ZnTPPS has been used as a model reaction to study the photosensitive activity of ZnTPPS entrapped in complex micelles. The entrapped ZnTPPSs exhibit pronounced activity and have much higher efficiency and faster photosensitive reaction rates than free ZnTPPS. 相似文献
A study is presented of the stabilization of gold and palladium nanoparticles (NPs) via a place-exchange reaction. Au and Pd NPs of approximately 3.5 nm were prepared by a conventional method using tetraoctylammonium bromide (TOAB) as the stabilizing agent. The resulting nanoparticles, referred to as Au-TOAB or Pd-TOAB, were later used as templates for the replacement of TOAB ligand with poly(ethylene oxide)- b-polystyrene- b-poly(4-vinylpyridine) (PEO- b-PS- b-P4VP) triblock copolymer. This biamphiphilic triblock copolymer was synthesized by atom transfer radical polymerization (ATRP) with control over the molecular weight and polydispersity. The place-exchange reaction was mediated through strong coordination forces between the 4-vinylpyridine copolymer and the metal species located on the surface of the nanoparticles. In addition, the displacement of the outgoing low molecular weight TOAB ligands by high molecular weight polymers is an entropy-assisted process and is believed to contribute to stabilization. The prepared complex, polymer-NP, exhibits greatly improved stability over the metal-NP complex in common organic solvents for the triblock copolymer. Self-assembly in water after ligand exchange resulted in micellar structures of about approximately 20 nm (electron microscopy) with the metal NP found located on the surface of the micelles. The stability of the nanoparticles in water was shown to depend greatly on the grafting density of the copolymer, with high stability (more than 6 months) at high grafting density and low stability, accompanied with irreversible agglomeration, at relatively low grafting densities. The surprising location of the metal NP (for both Au and Pd) on the surface of the micelles in water is explained by the fact that, upon self-assembly in THF/water system, the most hydrophobic chains (i.e., PS) undergo self-assembly first at low water content forming the core, followed by the P4VP (whether or not associated with the metal) forming a shell, and finally the PEO forming the corona. In lower metal content assemblies, the P4VP chains located in the shell undergo swelling in an acidic medium causing a substantial increase in micellar corona size, as confirmed by dynamic light scattering measurements. The present study offers a simple approach for the stabilization of various metal nanoparticles of catalytic interest, using a unique polymeric support that can be dispersed in organic solvents as well as aqueous solutions. 相似文献
Polymeric micelles with a polystyrene core, poly(acrylic acid)/poly(4-vinyl pyridine) (PAA/P4VP) complex shell and poly(ethylene glycol) & poly(N-isopropylacrylamide) (PEG & PNIPAM) mixed corona were synthesized and used as the supporter for the gold nanoparticles (GNs). It was concluded from the result of 1H NMR characterization that hydrophilic channels formed around PEG chains when PNIPAM collapsed above its lower critical solution temperature. The density of the channels in the corona can be tuned by changing the weight ratios of PEG chains to PNIPAM chains. The GNs were set in the PAA/P4VP complex layer and the catalytic activity of the GNs can be modulated by the channels. The catalytic activity increased with increasing the density of the channels in the corona. Meanwhile, the whole Au/micelle nanoparticles were stabilized by the extended PEG chains. 相似文献
Summary: The complexation between polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles and poly(ethylene glycol)‐block‐poly(4‐vinyl pyridine) (PEG‐b‐P4VP) is studied, and a facile strategy is proposed to prepare core‐shell‐corona micellar complexes. Micellization of PS‐b‐PAA in ethanol forms spherical core‐shell micelles with PS block as core and PAA block as shell. When PEG‐b‐P4VP is added into the core‐shell micellar solution, the P4VP block is absorbed into the core‐shell micelles to form spherical core‐shell‐corona micellar complexes with the PS block as core, the combined PAA/P4VP blocks as shell and the PEG block as corona. A model is suggested to characterize the core‐shell‐corona micellar complexes.
Schematic formation of core‐shell‐corona (CSC) micellar complexes by adsorption of PEG‐b‐P4VP into core‐shell PS‐b‐PAA micelles. 相似文献
In acidic solution, complex micelles were formed by diblock copolymers of poly (ethylene glycol)-b-poly (ε-caprolactone) (PEG-b-PCL) and folate-poly (2-(dimethylamino) ethyl methylacrylate)-b-poly (ε-caprolactone) (Fol-PDMAEMA-b-PCL) with a PCL core, a mixed PEG/Fol-PDMAEMA shell. The surface charge of the complex micelles was positive at acidic surroundings for the protonated PDMAEMA. With increasing pH value to 7.4 (above pKa of PDMAEMA), these micelles could convert into a core-shell-corona (CSC) structure composing a hydrophobic PCL core, a collapsed PDMAEMA shell, and a soluble PEG corona. Compared to core-shell micelles formed by PEG-b-PCL, micelles with CSC structure can prolong degradation by enzyme. Doxorubicin was physically loaded into the PCL core. The drug release rate was pH-dependent. At pH 5.5, complex micelles with core-shell structure showed faster drug release rate, while at pH 7.4, complex micelles gained CSC structure which control the drug release at a lower rate. The multifunctional complex micelles were prepared for enhanced tumor therapy. 相似文献
Poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymers and poly(acrylic acid) (PAA) have been mixed in organic solvents. Complexation via hydrogen bonding occurs between the P4VP and PAA blocks. Those insoluble complexes aggregate to form the core of micelles surrounded by a corona of PS chains. Reorganization of these structures occurs upon addition of acidic or basic water, which results in the breaking of the hydrogen bonds between the P4VP and PAA blocks. After transfer of the initial complexes in acidic water, micelles consisting of a PS core and a protonated P4VP corona are observed. In basic water, well-defined nanoparticles formed by the PS-b-P4VP copolymers are obtained. It is demonstrated that these nanoparticles are stabilized by the negatively charged PAA chains. Finally, thermally induced disintegration of the micelles is investigated in organic solvents. 相似文献
The pyranine-induced micellization of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG114-b-P4VP61) in aqueous solutions and pH-triggered release of pyranine from the complex micelles were studied by dynamic and static light scattering, transmission electron microscopy, 1H NMR spectroscopy, and UV-vis spectroscopy. At pH 2, the ionized pyranine can ionically cross-link the protonated P4VP block and result in well-defined spherical complex micelles with a P4VP/pyranine core surrounded by a PEG corona. The ratio of pyranine to pyridyl units can influence the structure and the properties of the resultant complex micelles. The complex micelles are stable upon dilution and heating but are sensitive to pH changes. pH-triggered release of the incorporated pyranine from the complex micelles demonstrates that the release behavior is pH-tunable and displays good controlled-release characteristics at pH approximately 4. 相似文献
We report here on the formation of hybrid compound block copolymer micelles encapsulating gold nanoparticles, utilizing a direct and general preparation method. The giant hybrid compound micelles are structured with micelles of PS‐b‐P2VP with gold nanoparticles in their P2VP core and PI‐b‐PS chains as the outer part of the compound micelles. The gold nanoparticles were produced using gold ion‐loaded PS‐b‐P2VP micelles as a nanoreactor, in a PS selective solvent (toluene), by the subsequent reduction of gold ions. The synthesis of the gold nanoparticles was monitored by UV‐vis spectroscopy. The gold containing micelles were then encapsulated in larger micelles of PI‐b‐PS copolymer, by successive utilization of toluene and heptane with the intermediate evaporation of toluene. The nanoassembly of the compound materials comprised a PI corona and a PS compound core, with P2VP/Au0 domains, and was characterized using UV‐vis spectroscopy, dynamic light scattering and transmission electron microscopy.
The silica/polymer hybrid hollow nanoparticles with channels and gatekeepers were successfully fabricated with a facile strategy by using thermoresponsive complex micelles of poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) and poly(N-isopropylacrylamide)-b-poly(4-vinylpyridine) (PNIPAM-b-P4VP) as the template. In aqueous solution, the complex micelles (PEG-b-PNIPAM/PNIPAM-b-P4VP) formed with the PNIPAM block as the core and the PEG/P4VP blocks as the mixed shell at 45 °C and pH 4.0. After shell cross-linking by 1,2-bis(2-iodoethoxyl)ethane (BIEE), tetraethylorthosilicate (TEOS) selectively well-deposited on the P4VP block and processed the sol-gel reaction. When the temperature was decreased to 4 °C, the PNIPAM block became swollen and further soluble, and the PEG-b-PNIPAM block copolymer escaped from the hybrid nanoparticles as a result of swelled PNIPAM and weak interaction between PEG and silica at pH 4.0. Therefore, the hybrid hollow silica nanoparticles with inner thermoresponsive PNIPAM as gatekeepers and channels in the silica shell were successfully obtained, which could be used for switchable controlled drug release. In the system, the complex micelles, as a template, could avoid the formation of larger aggregates during the preparation of the hybrid hollow silica nanoparticles. The thermoresponsive core (PNIPAM) could conveniently control the hollow space through the stimuli-responsive phase transition instead of calcination or chemical etching. In the meantime, the channel in the hybrid silica shell could be achieved because of the escape of PEG chains from the hybrid nanoparticles. 相似文献
Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)-b-poly(Nisopropylacrylamide) (PDMAEMA-b-PNIPAM) in aqueous solutions.The resultant complex micelles had a complex P4VP/ PDMAEMA/TPPS core and a mixed PEG/PNIPAM shell.Different noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the ... 相似文献
Template synthesis of various morphological gold colloidal nanoparticles using a thermoresponsive and pH-responsive coordination triblock copolymer of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) is studied. The template morphology of the thermoresponsive and pH-responsive coordination triblock copolymer, which can be tuned by simply changing the pH or temperature of the triblock copolymer aqueous solution, ranges from single chains to core-corona micelles and further to micellar clusters. Various morphological gold colloidal nanoparticles such as discrete gold nanoparticles, gold@polymer core-shell nanoparticles, and gold nanoparticle clusters are synthesized on the corresponding template of the triblock copolymer by first coordination with gold ions and then reduction by NaBH4. All three resultant gold colloidal nanoparticles are stable in aqueous solution, and their sizes are 2, 10, and 7 nm, respectively. The gold@polymer core-shell nanoparticles are thermoresponsive. The gold nanoparticle cluster has a novel structure, and each one holds about 40 single gold nanoparticles. 相似文献
Thermo- and pH-sensitive graft copolymers, hydroxypropylcellulose-graft-poly(4-vinyl pyridine) (HPC-g-P4VP), were synthesized via atom transfer radical polymerization (ATRP) and characterized. The thermo- and pH-induced micellization and stimuli-responsive properties of HPC-g-P4VP graft copolymers in aqueous solution were investigated by transmittance, (1)H NMR, dynamic light scattering (DLS), and so on. For the pH-induced micellization, the P4VP side chains collapse to form the core of the micelles, and the HPC backbones stay in the shell to stabilize the micelles. In the case of thermoinduced micellization, the HPC backbones collapse to form the core of the micelles that was stabilized by the P4VP side chains in the shell upon heating. What's more, the cloud point of the HPC-g-P4VP copolymers in the aqueous solution could be finely tuned by changing the length of P4VP side chains or the pH values. In acidic water, the longer the side chains, the higher the cloud point. For those HPC-g-P4VP copolymers with short side chains, for example, HPC0.05-g-P4VP(3), the lower pH correlates a higher cloud point. The thermo- or pH-induced micelles also have the pH- or thermosensitivity due to their P4VP or HPC shells. 相似文献
We have synthesized copper-gold, core-shell nanoparticles by the microemulsion method. The particles were prepared in two steps, by first reducing copper ions and then gold ions in the aqueous domains of anionic microemulsions. Two surfactants have been used as emulsifiers, AOT and Cu(AOT)2. The latter is the source of copper ions. Gold ions come from aqueous solutions of HAuCl4. Ultraviolet-visible spectroscopy experiments show that copper nanoparticles are created in the first step of the synthesis, and that a gold layer covers them in the second step. Transmission electron microscopy and related techniques confirm the formation of copper (core)-gold (shell) nanocrystals. 相似文献
The effects of the block copolymer composition and the solvent selectivity on the micellar morphologies of poly(styrene- b-4-vinylpyridine)s (PS- b-P4VPs) and their functionalizations with gold were studied in 10 mg/mL solutions using small-angle X-ray scattering and transmission electron microscopy (TEM). The solvent selectivity for the PS block was controlled by toluene/tetrahydrofuran (THF) mixtures in which toluene and THF are selective for PS and nonselective, respectively. The micellar structure was strongly dependent on phi (wt % toluene in toluene/THF mixture) and the composition of the block copolymers. PS(12K)- b-P4VP(11.8K) (symmetric) showed spherical micelles in the entire range of phi except phi = 0 (THF, nonselective solvent). PS(3.3K)- b-P4VP(18.7K) (asymmetric, longer P4VP) showed multiple morphologies with transitions from spheres to cylinders and finally to vesicles with an increase in phi. PS(19.6K)- b-P4VP(5.1K) (asymmetric, longer PS) showed spherical micelles only at the narrow ranges of 90 wt % 相似文献
Gold nanoparticles were employed to prepare shell cross-linked Pluronic micelles that exhibit a reversibly thermosensitive swelling/shrinking behavior. Two terminal hydroxyl groups of Pluronic F127 were thiol-functionalized to form self-assembling Pluronic micelles in aqueous solution with exposed -SH groups in an outer shell layer. The thiol groups present in the outer shell were cross-linked by gold nanoparticles synthesized through NaBH4 reduction of gold precursor anions. The resultant shell cross-linked gold-Pluronic micelles exhibited a temperature-dependent volume transition: their hydrodynamic diameter was changed from 157.1 +/- 15.6 nm at 15 degrees C to 53.4 +/- 5.5 nm at 37 degrees C as determined by dynamic light scattering. The critical micelle temperature measured by a pyrene solubilization technique suggested that the reversible swelling/shrinking behavior of the micelles was caused by hydrophobic interactions of cross-linked or grafted Pluronic copolymer chains in the micelle structure with increasing temperature. Transmission electron microscopy directly revealed that the shell cross-linked micelles were indeed produced by gold nanoparticles covalently clustered on the surface. These novel self-assembled organic/inorganic hybrid micelles would hold great potential for diagnostic and therapeutic applications. 相似文献
Inspired by natural photosynthesis, we employed polymeric micelles to enhance the water solubility and photostability of hydrophobic metallo-tetraphenylporphyrin (metallo-TPP) by complexation with poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP) via axial coordination. The structure and photochemical properties of the complex micelles were characterized by UV-visible spectroscopy, fluorescence spectroscopy, and laser light scatting. The photostability and electron transfer ability of metalloporphyrins in the micelles were investigated under continuous irradiation. The results show that metallo-TPPs entrapped in the micellar cores possess higher photostability and better electron transfer ability. The hydrophobic metalloporphyrins remains active inside the micelles which is reminiscent of chlorophyll protein complex in photosynthesis. The use of micelle thus may provide a promising system on designing photocatalysts for targeting applications in solar energy conversion and photodynamic tumor therapy (PDT). 相似文献