Summary: Amphiphilic cylindrical brush‐coil block copolymers consisting of a polystyrene coil and a cylindrical brush block with poly(acrylic acid) side chains are prepared by ATRP of t‐butylacrylate from a block comacroinitiator. Upon acidolysis of the poly(t‐butylacrylate), water‐soluble polymers were obtained that were observed to form micelles consisting of 4–5 block copolymers on average in aqueous solution. The star‐like nature of such micelles was clearly visualized by scanning force microscopy.
Schematic of coil‐cylindrical brush block copolymer PS‐b‐(PiBEMA‐g‐PAA), its AFM image clearly showing the main chain and the PAA corona of the cylindrical brush block. 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.
Summary: A novel way to prepare polymer hair/polysilsesquioxane core hybrid nanospheres is presented based on a self‐assembly and gelation process of a reactive block copolymer, poly(ethylene oxide)‐block‐poly[3‐(trimethoxysilyl)propyl methacrylate] (PEO113‐b‐PTMSPMA206). Nanospheres of uniform size were obtained. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and static light scattering (SLS) were employed to characterize the products.
Schematic of the PEO‐b‐PTMSPMA nanospheres formed here, the light gray part represents the PEO hairs, the dark parts are the polysilsesquioxane from the gelation of the PTMSPMA blocks of the self‐assembled sphere. 相似文献
An amphiphilic metallo‐supramolecular poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide) diblock copolymer containing a bis(2,2′:6′,2″‐terpyridine)ruthenium(II) complex as a supramolecular connection between the two constituting blocks was used to prepare stable aqueous micelles. The micelles were characterized by dynamic light scattering and atomic force microscopy. Individual micelles were observed together with aggregates of micelles. Only the addition of a large excess of competitive ligand caused the cleavage of the very stable ruthenium complex. 相似文献
MH, a semisynthetic tetracycline antibiotic with promising neuroprotective properties, was encapsulated into PIC micelles of CMD‐PEG as a potential new formulation of MH for the treatment of neuroinflammatory diseases. PIC micelles were prepared by mixing solutions of a Ca2+/MH chelate and CMD‐PEG copolymer in a Tris‐HCl buffer. Light scattering and 1H NMR studies confirmed that Ca2+/MH/CMD‐PEG core‐corona micelles form at charge neutrality having a hydrodynamic radius ≈100 nm and incorporating ≈ 50 wt.‐% MH. MH entrapment in the micelles core sustained its release for up to 24 h under physiological conditions. The micelles protected the drug against degradation in aqueous solutions at room temperature and at 37 °C in the presence of FBS. The micelles were stable in aqueous solution for up to one month, after freeze drying and in the presence of FBS and BSA. CMD‐PEG copolymers did not induce cytotoxicity in human hepatocytes and murine microglia (N9) in concentrations as high as 15 mg·mL?1 after incubation for 24 h. MH micelles were able to reduce the inflammation in murine microglia (N9) activated by LPS. These results strongly suggest that MH PIC micelles can be useful in the treatment of neuroinflammatory disorders.
Controlling the orientation and long‐range order of nanostructures is a key issue in the self‐assembly of block copolymer micelles. Herein, a versatile strategy is presented to transform one‐component oxime‐based block copolymer micelles into long‐range ordered dense nanopatterns. Photoisomerization provides a straightforward and versatile approach to convert the hydrogen‐bonding association from inward dimerization (E‐type oxime motifs, slightly desolvated in ethyl acetate) into outward interchain association (Z‐type ones, highly desolvated in ethyl acetate). This increases the glass transition temperature in bulk and converts swollen micelles into compact spherical micelles in solution. The reconstruction of these micelles on various substrates demonstrates that the phase transformation enables reconstruction of spherical micelles into mesoscopic sheets, nanorods, nanoworms, nanowires, networks, and eventually into long‐range ordered and densely packed textile‐like and lamellar nanopatterns on a macroscopic scale by adjusting E/Z‐oxime ratio and solvent‐evaporation rate.
Precise control over the morphology and dimensions of block copolymer (BCP) micelles has attracted interest due to the potential of this approach to generate functional nanostructures. Incorporation of liquid crystalline (LC) block can provide additional ways to vary micellar morphologies, but the formation of uniform micelles with controllable dimensions from LC BCPs has not yet been realized. Herein, we report the preparation of monodisperse cylindrical micelles with a LC poly(2‐(perfluorooctyl)ethyl methacrylate (PFMA) core via a fragmentation‐thermal annealing (F‐TA) process, resembling the “self‐seeding” process of crystalline BCP micelles. The average length of the cylinders increases with annealing temperature, with a narrow length distribution (Lw/Ln<1.1). We also demonstrate the potential application of the cylinders with LC cores as a cargo‐carrier by the successful incorporation of a hydrophobic fluorescent dye tagged with a fluorooctyl group. 相似文献
Although biodegradable amphiphilic block copolymer micelles have been widely applied in the clinical applications as drug delivery nanocarriers, low‐efficiency cellular internalization frequently reduces therapeutic efficacy of the loaded drugs. Here, photothermal effect‐promoted cellular internalization of finely tuned thermo‐responsive amphiphilic biodegradable block copolymer nanocarriers via noninvasive stimuli of near‐infrared (NIR) light irradiation is demonstrated. Amphiphilic block copolymers, poly(ε‐caprolactone)‐block‐poly(N‐isopropylacrylamide‐co‐N,N‐dimethylacrylamide) (PCL‐b‐P(NIPAM‐co‐DMA)), are prepared with finely tuned compositions of P(NIPAM‐co‐DMA) for desirable lower critical solution temperature of the block copolymer micelles in aqueous solution. The block copolymers are then used to co‐encapsulate doxorubicin and indocyanine green, which show high encapsulation efficiency and significant photothermal effect upon exposure to NIR light irradiation. The photothermal effect‐induced collapse and hydrophilic‐to‐hydrophobic transition of P(NIPAM‐co‐DMA) shells significantly enhance the interactions between drug‐loaded micelles and cell membranes, which dramatically promote the cellular internalization of the micelles and therapeutic efficacy of loaded anticancer drugs.
Functional nanostructures of self‐assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two‐dimensional self‐assembly of anisotropic titanium dioxide (TiO2) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) copolymer inverse micelles. The independent position‐selective assembly of TiO2 NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin‐coating a mixture solution of PS‐b‐P4VP and ex situ synthesized TiO2 NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO2 NCs with a diameter and length of approximately 3 nm and 20–30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high‐temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO2 NCs into connected nanoparticles, thus leading to a two‐dimensionally ordered TiO2 network in which AgNPs were also self‐organized. The enhanced photocatalytic activity of the AgNP‐decorated TiO2 networks by approximately 27 and 44 % over that of Ag‐free TiO2 networks and randomly deposited TiO2 nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue. 相似文献
In this work, a novel type of block copolymer micelles with K+‐responsive characteristics for targeted intracellular drug delivery is developed. The proposed smart micelles are prepared by self‐assembly of poly(ethylene glycol)‐b‐poly(N‐isopropylacry‐lamide‐co‐benzo‐18‐crown‐6‐acrylamide) (PEG‐b‐P(NIPAM‐co‐B18C6Am)) block copolymers. Prednisolone acetate (PA) is successfully loaded into the micelles as the model drug, with loading content of 4.7 wt%. The PA‐loaded micelles display a significantly boosted drug release in simulated intracellular fluid with a high K+ concentration of 150 × 10−3m , as compared with that in simulated extracellular fluid. Moreover, the in vitro cell experiments indicate that the fluorescent molecules encapsulated in the micelles can be delivered and specifically released inside the HSC‐T6 and HepG2 cells responding to the increase of K+ concentration in intracellular compartments, which confirms the successful endocytosis and efficient K+‐induced intracellular release. Such K+‐responsive block copolymer micelles are highly potential as new‐generation of smart nanocarriers for targeted intracellular delivery of drugs. 相似文献
We report a combined experimental and theoretical study of micellization of block copolymer with hydrophilic nonionic corona‐forming blocks and weak polyelectrolyte (wPE) core‐forming blocks with pH‐triggered solubility in aqueous solutions. We demonstrate that in addition to micelles with neutral cores, there exist two other types of micelles with PE‐ or ionomer‐like cores, in which monovalent counterions are released or condensed on core wPE block, respectively. The transition between the two types of micelles occurred upon changes in ionization of the PE core block and resulted in nonmonotonous changes of aggregation number as a function of pH. Such micelles with stimulus responsive cores represent promising nanocarriers for controlled delivery applications.
Well‐defined ABC triblock copolymers based on two hydrophilic blocks, A and C, and a hydrophobic block B are synthesized and their self‐assembly behavior is investigated. Interestingly, at the same solvent, concentration, pH, and temperature, different shape micelles are observed, spherical and worm‐like micelles, depending on the preparation method. Specifically, spherical micelles are observed with bulk rehydration while both spherical and worm‐like micelles are observed with film rehydration.
We present a morphological study of the micellization of an asymmetric semicrystalline block copolymer, poly(butadiene)‐block‐poly(ethylene oxide), in the selective solvent n‐heptane. The molecular weights of the poly(butadiene) (PB) and poly(ethylene oxide) (PEO) blocks are 26 and 3.5 kg · mol−1, respectively. In this solvent, micellization into a liquid PEO‐core and a corona of PB‐chains takes place at room temperature. Through a thermally controlled crystallization of the PEO core at −30 °C, spherical micelles with a crystalline PEO core and a PB corona are obtained. However, crystallization at much lower temperatures (−196 °C; liquid nitrogen) leads to the transition from spherical to rod‐like micelles. With time these rod‐like micelles aggregate and form long needles. Concomitantly, the degree of crystallinity of the PEO‐cores of the rod‐like micelles increases. The transition from a spherical to a rod‐like morphology can be explained by a decrease of solvent power of the solvent n‐heptane for the PB‐corona chains: n‐Heptane becomes a poor solvent at very low temperatures leading to a shrinking of the coronar chains. This favors the transition from spheres to a morphology with a smaller mean curvature, that is, to a cylindrical morphology.
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