Hollow capsules prepared from all block copolymer micelle multilayers

We introduce a novel and versatile approach for preparing hollow multilayer capsules containing functional hydrophobic components. Protonated polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and anionic polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films onto polystyrene (PS) colloids. After removing the PS colloids, the stabilities of the formed BCM hollow capsules were found to be strongly dependent on the charge density of the hydrophilic corona segments (i.e., P4VP and PAA block segments) as well as the relative molecular weight ratio of hydrophobic core (i.e., PS segments) blocks and hydrophilic corona shells. Furthermore, in the case of incorporating hydrophobic fluorescent dyes into the PS core blocks of micelles, the hairy/hairy BCM multilayers showed well-defined fluorescent images after colloidal template removal process. These phenomena are mainly caused by the relatively high degree of electrostatic interdigitation between the protonated and anionic corona block shells.     

Study of the ordered structures of poly(styrene-b-vinyl4pyridine) in a solution state by using small-angle X-ray scattering and generalized indirect Fourier transform

The structures of the mesophases and their subunits (micelles) of poly(styrene-b-vinyl4pyridine) (PS-b-P4VP) in a toluene solution were studied by using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and generalized indirect Fourier transform (GIFT) methods. The structures of PS-b-P4VP, such as the individual micelle, the face-centered cubic (fcc) and body-centered cubic (bcc), and the lamellar, were identified. The SAXS from the PS-b-P4VP solution showed a good contrast for the micelle, even in a low concentration of 0.25 wt %. As the concentration increases, the fcc and both fcc and bcc appear for the packing of the micelles of PS(3.3K)-b-P4VP(4.7K) and PS(12K)-b-P4VP(11.8K), respectively. The lamellar structure was also identified, with a further increase in the concentration for PS(3.3K)-b-P4VP(4.7K). These structures were also identified via TEM images.     

pH-Induced antireflection coatings derived from hydrogen-bonding-directed multilayer films

Hydrogen-bonding-directed layer-by-layer assembled films, based on polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles and poly(4-vinylpyridine) (P4VP), were successfully fabricated in methanol. Varying the PAA content in the PS-b-PAA micelles afforded control over the film growth properties, especially the multilayer film thickness. Interestingly, antireflection films with refractive indices that could be tuned between 1.58 and 1.28 were obtained by treatment with an aqueous HCl solution (pH 2.27), and the transmittance obtained was as high as 98.4%. In acid solution, the pyridine group was protonated, destroying the hydrogen bonding between P4VP and PAA. A concomitant pH-induced polymer reorganization in the multilayers resulted in a porous honeycomb-like texture on the substrate.     

Nanoscale elastic modulus variation in loaded polymeric micelle reactors

Tapping mode atomic force microscopy (TM-AFM) enables mapping of chemical composition at the nanoscale by taking advantage of the variation in phase angle shift arising from an embedded second phase. We demonstrate that phase contrast can be attributed to the variation in elastic modulus during the imaging of zinc acetate (ZnAc)-loaded reverse polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock co-polymer micelles less than 100 nm in diameter. Three sample configurations were characterized: (i) a 31.6 μm thick polystyrene (PS) support film for eliminating the substrate contribution, (ii) an unfilled PS-b-P2VP micelle supported by the same PS film, and (iii) a ZnAc-loaded PS-b-P2VP micelle supported by the same PS film. Force-indentation (F-I) curves were measured over unloaded micelles on the PS film and over loaded micelles on the PS film, using standard tapping mode probes of three different spring constants, the same cantilevers used for imaging of the samples before and after loading. For calibration of the tip geometry, nanoindentation was performed on the bare PS film. The resulting elastic modulus values extracted by applying the Hertz model were 8.26 ± 3.43 GPa over the loaded micelles and 4.17 ± 1.65 GPa over the unloaded micelles, confirming that phase contrast images of a monolayer of loaded micelles represent maps of the nanoscale chemical and mechanical variation. By calibrating the tip geometry indirectly using a known soft material, we are able to use the same standard tapping mode cantilevers for both imaging and indentation.     

Polyelectrolyte multilayers of diblock copolymer micelles with temperature-responsive cores

We report on assembly and stimuli-response behavior of layer-by-layer (LbL) films of pH- and temperature-responsive cationic diblock copolymer micelles (BCMs) of poly(2-(dimethylamino)ethyl methacrylate)-block-poly(N-isopropylacrylamide) (PDMA-b-PNIPAM) and a linear polyanion polystyrene sulfonate (PSS). As a function of solution pH at temperatures above lower critical solution temperature (LCST) of PNIPAM, PDMA-b-PNIPAM micelles have been demonstrated earlier to exhibit an abrupt change in micellar aggregation number and hydrodynamic size between larger and smaller BCMs (LBCMs and SBCMs, respectively). Here, LBCMs or SBCMs were included within LbL films through self-assembly with a polyanion, and film pH and temperature responses were studied using ellipsometry and atomic force microscopy (AFM). Both types of micelle preserved their micellar morphology when adsorbed at the surface of oxidized silicon wafers coated with PSS-terminated precursor layer at a constant pH. Response of adsorbed BCMs to temperature and pH variations was strongly dependent on whether or not BCMs were coated with the PSS layer. While monolayers of LBCMs lost their original dry morphology in response to pH or temperature variations, depositing a PSS layer atop LBCMs inhibited such irreversible restructuring. As a result of wrapping around and strong binding of PSS chains with LBCM micelles, BCM/PSS assemblies preserved their original dry state morphology despite the application of pH and temperature triggers. However, the wet-state film response to pH and temperature stimuli was drastically different. Swelling of BCM/PSS multilayers was strongly affected by temperature but was almost independent of pH due to neutralization of BCM PDMA's coronal charge with PSS. Cycling the temperature below and above PNIPAM's LCST caused PNIPAM chains within BCM cores to swell or collapse, resulting in reversible swelling transitions in the entire BCM/PSS assemblies. Temperature-controlled switching between the hydrophobic and hydrophilic state of assembled micellar cores was also used to regulate the release of a micelle-loaded hydrophobic pyrene dye, whose release rate increased at temperatures below PNIPAM's LCST.     

Influence of metalation on the morphologies of poly(ethylene oxide)-block-poly(4-vinylpyridine) block copolymer micelles

Micellization of a poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO45-b-P4VP28) copolymer in water during metalation (incorporation of gold compounds and gold nanoparticle formation) with three types of gold compounds, NaAuCl4, HAuCl4, and AuCl3, was studied using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The transformations of the PEO45-b-P4VP28 block copolymer micelles in water were found to depend on a number of parameters including the thermal history of the as-prepared block copolymer, the type of the metal compound, and the metal loading. For the HAuCl4-filled PE045-b-P4VP28 micelles, the subsequent reduction with hydrazine hydrate results in a significant fraction of rodlike micelles, suggesting that slow nucleation (confirmed by the formation of the large gold nanoparticles) and facilitated migration of gold ions yields the ideal conditions for sphere-to-rod micellar transition.     

Intelligent reversible nanoporous antireflection film by solvent-stimuli-responsive phase transformation of amphiphilic block copolymer

An erasure-reconstruction porous structure with reversible antireflection (AR) property at near-infrared region (NIR) was prepared for the first time based on solvent-stimuli-responsive phase transformation of polystyrene-block-poly(4-vinypyridine) (PS-b-P4VP). The inhomogeneous porous structure with a dense skin and porous underneath, which was obtained by the nonsolvent-induced phase separation of PS-b-P4VP film from micelle solution with mixed solvents (tetrahydrofuran and dimethylformamide), was used as starting porous film. Then, the film was annealed by PS-selective solvent to erase the nanopores because the PS block was swollen effectively by its selective solvent. Afterward, the nonporous film was immersed in linear aliphatic acid to reconstruct the nanoporous structure (loosely packed micelles) by the combination of the hydrogen bond interaction and the positively charge-induced repulsion between each chain. Thus, an intelligent reversible AR property in the NIR region between a high-transmittance porous state (～99.0%) and a low-transmittance nonporous state (～90.0%) was realized by alternate treatments of PS-selective solvent and linear aliphatic acids. This reversible erasure-reconstruction porous structure for switching between AR (98.0%) and non-AR (90.0%) properties could be recycled by at least four times.     

带有可调通道的嵌段共聚物胶束对药物的控制释放

用聚丙烯酸叔丁酯-b-聚乙二醇(PtBA45-b-PEG114)和聚丙烯酸叔丁酯-b-聚4-乙烯基吡啶(PtBA60-b-P4VP80)制备了复合胶束. 该胶束在pH=2.5的酸性水溶液中形成以PtBA为核, PEG和P4VP为壳的稳定球型结构. 在pH=12时, 壳层的P4VP链段变为疏水, 塌缩在PtBA的核上形成内壳, PEG链段继续保持溶解状态, 与成核的PtBA连接并穿过塌陷的P4VP内壳, 形成胶束的冠, 由于PEG处于溶解状态, 其分子链间有比较大的空隙, 可以控制一些小分子通过, 在胶束的表面形成通道. 该通道类似于生物膜的蛋白通道, 可以控制PtBA核与外界进行能量或物质交换的速度. 以布洛芬为模型分子, 负载在胶束内进行药物控制释放研究的结果表明, 胶束表面的通道可以起到明显控制布洛芬释放速度的作用, 并且药物的释放速度与通道在胶束表面的比例成正比.     

Temperature-triggered micellization of block copolymers on an ionic liquid surface

In situ neutron reflectivity was used to study thermally induced structural changes of the lamellae-forming polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films floating on the surface of an ionic liquid (IL). The IL, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, is a nonsolvent for PS and a temperature-tunable solvent for P2VP, and, as such, micellization can be induced at the air-IL interface by changing the temperature. Transmission electron microscopy and scanning force microscopy were used to investigate the resultant morphologies of the micellar films. It was found that highly ordered nanostructures consisting of spherical micelles with a PS core surrounded by a P2VP corona were produced. In addition, bilayer films of PS homopolymer on top of a PS-b-P2VP layer also underwent micellization with increasing temperature but the micellization was strongly dependent on the thickness of the PS and PS-b-P2VP layers.     

含pH敏感聚(4-乙烯基吡啶)的嵌段共聚物成核胶束化过程的NMR研究

利用NMR技术研究了聚乙二醇-b-聚(4-乙烯基吡啶)(PEG114-b-P4VP107)和聚(N-异丙烯基丙烯酰胺)-b-聚(4-乙烯基吡啶)(PNIPAM53-b-P4VP260)在逐步降低聚(4-乙烯基吡啶)链段质子化程度时嵌段共聚物的胶束化过程.在开始形成胶束时,吡啶环上氢原子的自旋-晶格弛豫时间(T1)急剧减小.结果表明,PEG114-b-P4VP107在质子化程度降为0.54时已有胶束生成;PNIPAM53-b-P4VP260在质子化程度降为0.58时也能观测到胶束生成的信号.将两个嵌段共聚物各自制得胶束的溶液相混合,观测到了发生在高分子链间的2DNOE信号,这表明所制得溶液中胶束与高分子链间有链交换的动态平衡.     

Temperature tunable micellization of polystyrene-block-poly(2-vinylpyridine) at Si-ionic liquid interface

Highly ordered and stable micelles formed from both symmetric and asymmetric block copolymers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) at the Si-ionic liquid (IL) interface have been investigated by scanning force microscopy (SFM) and transmission electron microscopy (TEM). The 1-butyl-3-methylimidazolium trifluoromethanesulfonate IL, a selective and temperature-tunable solvent for the P2VP block, was used and gave rise to block copolymer micelles having different morphologies that strongly depended on the annealing temperature. The effects of film thickness, molecular weight of block copolymers, and experimental conditions, such as preannealing, rinsing, and substrate properties, on the morphologies of block copolymer micelles were also studied. In addition, spherical micelles consisting of PS core and P2VP shell could also be obtained by core-corona inversion by annealing the as-coated micellar film in the IL at high temperatures. The possible mechanism for micelle formation is discussed.     

Hierarchical Nanoporous Structures by Self‐Assembled Hybrid Materials Based on Block Copolymers

Hierarchical nanoporous structures are fabricated by adsorption of micelles of diblock copolymer‐templated Au‐nanoparticles onto a hydrophilic solid substrate. Gold nanoparticles are prepared using micelles (19 nm) of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) as nanoreactors. Deposition of thin films of the micellar solution, modified with a non‐selective solvent (THF), on hydrophilic surfaces leads to the formation of hierarchical nanoporous morphologies. The thin films exhibit two different pore diameters and a total pore density of 15 × 10⁸ holes per cm². The structure was analyzed in terms of topography and chemical composition using AFM, TEM and XPS measurements. The PS‐b‐P4VP template was subsequently removed by oxygen plasma etching, to leave behind metallic nanopores that mimic the original thin film morphology.

     

Fabrication of an open Au/nanoporous film by water-in-oil emulsion-induced block copolymer micelles

Water-in-oil (W/O) emulsion-induced micelles with narrow size distributions of approximately 140 nm were prepared by sonicating the polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer in the toluene/water (50:1 vol %). The ordered nanoporous block copolymer films with the hydrophilic P2VP interior and the PS matrix were distinctly fabricated by casting the resultant solution on substrates, followed by evaporating the organic solvent and water. The porous diameter was estimated to be about 70 nm. Here, we successfully prepared the open nanoporous nanocomposites, the P2VP domain decorated by Au (5+/-0.4 nm) nanoparticles based on the methodology mentioned. We anticipate that this novelty enhances the specific function of nanoporous films.     

Pyranine-induced micellization of poly(ethylene glycol)-block-poly(4-vinylpyridine) and pH-triggered release of pyranine from the complex micelles

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.     

中间嵌段为亲水性的BAB型三嵌段共聚物水溶液中初级聚集体的二次聚集行为研究

采用TEM和AFM研究了PS(聚苯乙烯)₄₃-b-PEO(聚氧乙烯)₄₅-b-PS₄₃和PS₃₉-b-P4VP(聚4-乙烯基吡啶)₉₈-b-PS₃₉三嵌段共聚物在水介质中的球形胶束、囊泡和蠕虫状胶束之间的二次聚集行为.实验发现,初级聚集体的二次聚集具有不同的复杂程度.对称性的初级聚集体,如球形胶束和囊泡,其二次聚集表现出球形对称性;而非对称性初级聚集体(如蠕虫状胶束)二次聚集开始倾向于非对称性.BAB型的嵌段设计有利于初级聚集体的二次聚集发生.     

Formation of a highly ordered dot array of surface micelles of a block copolymer via liquid crystal-hybridized self-assembly

A highly ordered dot array pattern of surface micelles on water is formed by a spread monolayer of an amphiphilic block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-4VP), via hybridization with a liquid crystal molecule, 4'-pentyl-4-cyanobiphenyl (5CB), on water. Simple co-spreading of PS-4VP with 5CB provides a flat homogeneous monolayer of PS-4VP on water without the aggregation of PS blocks. With increasing surface pressure, well-defined dots of the PS blocks start to grow and are arrayed in a highly ordered hexagonal structure. The exact coincidence of the surface pressure-area curves for the hybrid monolayer in the compression and expansion processes confirms that the flat spread monolayer and the dot array are formed on water in the equilibrium state by a self-assembly process.     

Thermally stable antireflective coatings based on nanoporous organosilicate thin films

Thermally stable nanoporous organosilicate thin films were realized by the microphase separation of pore-generating polymers mixed with an organosilicate matrix to be antireflective coatings (ARCs), for which a thin film with a refractive index (n) of 1.23 for zero reflection is required. The refractive index of such nanoporous organosilicate films can be tuned from 1.39 down to 1.23 by incorporating nanopores within the films. With a nanoporous single layer with n approximately 1.23, the light transmittance of the glass above 99.8% was achieved in the visible range (lambda approximately 550 nm). To overcome the limitation on the narrow wavelength for high transmittance imposed by a single antireflective nanoporous thin film, bilayer thin films with different refractive indices were prepared by placing a high refractive index layer with a refractive index of 1.45 below the nanoporous thin film. UV-vis transmittance of a glass coated with the bilayer films was compared with nanoporous single-layer films and it is demonstrated that the novel broadband antireflection coatings in a wide range of visible wavelength can be easily obtained by the organosilicate bilayer thin films described in this study. Also, ARCs developed in this study demonstrate excellent AR durability owing to the hydrophobic nature of the organosilicate matrix.     

Effect of micelle composition on the formation of surfactant-templated polymer films

Surfactant-templated polymer films prepared from polyethylenimine (PEI), cetyltrimethylammonium bromide (CTAB), and octaethylene glycol monohexadecyl ether (C(16)E(8)) were examined and the effect of increasing the percentage of nonionic surfactant in the micelles measured using both surface and bulk-sensitive techniques. It was found that there is a strong interaction between CTAB and C(16)E(8), although no interaction between the C(16)E(8) and PEI was observed. Generally, increasing the percentage of C(16)E(8) in the micelles decreases both the thickness and degree of order in the films; however, it was observed, depending on the conditions, that films could still be formed with as little as 20% cationic surfactant. Experiments on the CTAB/Brij56/PEI system were also performed and these indicate that it is similar to the CTAB/C(16)E(8)/PEI system.     

Micellar structures of poly(styrene-b-4-vinylpyridine)s in THF/toluene mixtures and their functionalization with gold

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