Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV5-b-P2VP44), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV5-b-P2VP44 with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV5-b-PNIPAM49 and OPV5-b-P2VP44 to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities. 相似文献
With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (block ratio=1:5) and P3HT44‐b‐P2VP115 (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH<iPrOH<nBuOH). Very long (>3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain‐extended P3HT blocks. The crystallinity and π‐conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide‐angle X‐ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23‐b‐P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23‐b‐P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (Lw/Ln <1.11) and lengths from about 100‐300 nm, that were dependent on the unimer‐to‐seed micelle ratio. 相似文献
Linear poly(4‐tert‐butoxystyrene)‐b‐poly(4‐vinylpyridine) (PtBOS‐b‐P4VP) diblock copolymers are synthesized using reversible addition–fragmentation chain transfer polymerization. The self‐assembly of four different PtBOS‐b‐P4VP diblock copolymers is studied using small‐angle X‐ray scattering and transmission electron microscopy and a number of interesting observations are made. A tBOS62‐b‐4VP28 diblock copolymer with a weight fraction P4VP of 0.21 shows a disordered morphology of P4VP spheres with liquid‐like short‐range order despite an estimated value of of the order of 50. Increasing the length of the 4VP block to tBOS62‐b‐4VP199 results in a diblock copolymer with a weight fraction P4VP of 0.66. It forms a remarkably well‐ordered lamellar structure. Likewise, a tBOS146‐b‐4VP120 diblock copolymer with a weight fraction P4VP of 0.33 forms an extremely well‐ordered hexagonal structure of P4VP cylinders. Increasing the P4VP block of this block copolymer to tBOS146‐b‐4VP190 with a weight fraction P4VP of 0.44 results in a bicontinuous gyroid morphology despite the estimated strong segregation of . These results are discussed in terms of the architectural dissimilarity of the two monomers, characterized by the presence of the large side group of PtBOS, and the previously reported value of the interaction parameter, , for this polymer pair.
Stable colloidal dispersions of polyaniline (PAni) nanofibers with controlled lengths from about 200 nm–1.1 μm and narrow length distributions (Lw/Ln<1.04; Lw=weight average micelle length, Ln=number average micelle length) were prepared through the template‐directed synthesis of PAni using monodisperse, solution‐self‐assembled, cylindrical, block copolymer micelles as nanoscale templates. These micelles were prepared through a crystallization‐driven living self‐assembly method from a poly(ferrocenyldimethylsilane)‐b‐poly(2‐vinylpyridine) block copolymer (PFS25‐b‐P2VP425). This material was initially self‐assembled in iPrOH to form cylindrical micelles with a crystalline PFS core and a P2VP corona and lengths of up to several micrometers. Sonication of this sample then yielded short cylinders with average lengths of 90 nm and a broad length distribution (Lw/Ln=1.32). Cylindrical micelles of PFS25‐b‐P2VP425 with controlled lengths and narrow length distributions (Lw/Ln<1.04) were subsequently prepared using thermal treatment at specific temperatures between 83.5 and 92.0 °C using a 1D self‐seeding process. These samples were then employed in the template‐directed synthesis of PAni nanofibers through a two‐step procedure, where the micellar template was initially stabilised by deposition of an oligoaniline coating followed by addition of a polymeric acid dopant, resulting in PAni nanofibers in the emeraldine salt (ES) state. The ES–PAni nanofibers were shown to be conductive by scanning conductance microscopy, whereas the precursor PFS25‐b‐P2VP425 micelle templates were found to be dielectric in character. 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
A variety of sub‐10 nm nanoparticles are successfully prepared by crosslinking of polystyrene‐b‐poly(1,3‐butadiene) (PS‐b‐PB) and polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) block copolymer micelles and inverse micelles. Among them, the core‐crosslinked PS‐b‐PB micelles can self‐assemble into ultrathin (< 10 nm) macroporous (pore size <1 µm) membranes in a facile way, i.e., by simply drop‐coating the particle solution onto a mica surface. No continuous/porous membranes are produced from shell‐crosslinked PS‐b‐PB micelles and both forms of PS‐b‐P4VP micelles. This suggests that the unique structure of the block copolymer precursor, including the very flexible core‐forming block and the glassy corona‐forming block and the specific block length ratio, directly determines the formation of the macroporous membrane.
Here we report a facile method for the preparation of a PEO113‐b‐P4VP93 brush on gold surface with a grafting density as high as 1.32 chains/nm2; the P4VP blocks were physically adsorbed on gold surface forming an inner layer while the PEO blocks stretched towards the solution forming PEO brush. PEO113‐b‐P4VP93 micelles with P4VP core and PEO shell formed in methanol/water mixed solvents were used as the precursor. By adsorbing PEO113‐b‐P4VP93 micelles from pure water, in which the density of the micelles is the largest, maximum amount of the micelles was adsorbed onto gold surface, and the adsorbed micelles existed as individual domains on the surface. To prepare the polymer brush with a density as high as possible, we annealed the adsorbed micelles by methanol/water mixed solvent at the volume fraction of methanol (VF) of 20%, which was the proper proportion at which the core‐forming P4VP chains began to be flexible but the integrity of the micelles was remained. At this volume fraction, almost all the adsorbed micelles originally existing as individual domains were transformed into a dense polymer brush. 相似文献
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
Complex micelles with a P4VP core surrounded by a mixed PNIPAM/PEG shell were prepared by comicellization of PNIPAM93‐b‐P4VP58 and PEG114‐b‐P4VP58 in aqueous solutions. Increasing the temperature above the LCST of the PNIPAM induced a phase separation of the mixed shell due to the collapse of the PNIPAM block. The morphology of the collapsed PNIPAM was dependent on the composition of the mixed shell; a lower content of the PNIPAM resulted in separately distributed domains on the surface of the P4VP core, while a higher content of the PNIPAM led to the formation of continuous membrane around the P4VP core. When the continuous membrane was formed, the hydrophilic PEG block could connect the inner P4VP core and the outer milieu to form channels across the PNIPAM membrane for water and other small molecules to pass through.
Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross‐linkable nanostructured materials via Diels–Alder reactions. Here, the use of FGE for the mid‐chain functionalization of a P2VP‐b‐PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68‐FGE‐b‐PEO390, which can be subsequently addressed in Diels–Alder reactions using maleimide‐functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero‐grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68‐FGE‐b‐PEO390, a powerful tool for selective functionalization reactions, including the modification of surfaces.