Multiple morphologies and their transformation of a polystyrene-block-poly(4-vinylpyridine) block copolymer

We report the multiple morphologies and their transformation of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in low-alkanol solvents. In order to improve the solubility of polystyrene block in alcohol solvents, the solution of block copolymer sample was treated at a higher temperature, and then the influence of rate of decreasing temperature on multiple morphologies (including spheres, rods, vesicles, porous vesicles, large compound vesicles, and large compound micelles) was observed. The transformation of spheres to rods, to tyre-shaped large compound micelles, and to sphere-shaped large compound micelles was also realized. The formation mechanisms of the multiple morphologies and their transformation are discussed briefly.

Multiple morphologies of gold nano-plates by high-temperature polyol syntheses

High-temperature polyol methods were used to fabricate micro- or nano-sized gold plates. 1,2propanediol served as both medium and reducing agent. Triangular plates and polygonal plate shapes derived from triangular prisms as well as pentagonal structured gold particles have been synthesized. Poly(vinylpyrrolidone) (PVP) plays an important role, but is not necessary, for the formation of these structures. These gold plates may have applications in the characterisation of adsorbed proteins or peptides. (C) 2008 Elsevier B. V. All rights reserved.

Hybridization of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine) aggregates in dioxane/water solution

Self-assembly of binary blends of two triblock copolymers of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine), i.e., P4VP(43)-b-PS260-b-P4VP(43) (P1) and P4VP(43)-b-PS366-b-P4VP(43) (P2), in dioxane/water solution was studied. These two triblock copolymers individually tend to form vesicles (P2) and cylindrical micelles (P1) in dilute solution. It was found that copolymer components in the blend, sample preparation method, and annealing time had significant effect on hybridization aggregate morphology. By increasing P1 content in the copolymer blends, fraction of looped and stretched cylinders increased, while fraction of bilayers decreased. Nearly no bilayer was observed when P1 content was above 85 wt%.

Self-assembly of a hydrophobic polypeptide containing a short hydrophilic middle segment: Vesicles to large compound micelles

This report describes a facile route to prepare the vesicles and large compound micelles (LCMs) from a series of poly(epsilon-benzyloxycarbonyl L-lysine)-block-poly[diethylene glycol bis(3-amino propyl) ether]-block-poly(epsilon-benzyloxycarbonyl L-lySine) (PZLL-DGBE-PZLL) in their water solution, depending on molecular weight of the polypeptides. A pyrene probe is used to demonstrate the aggregate formation of PZLL-DGBE-PZLL in solution, and also to measure their critical micelle concentration as a function of molecular weight of the polymer.

Effect of Shear Flow on the Formation of Ring-Shaped ABA Amphiphilic Triblock Copolymer Micelles

We have investigated the effect of Shear flow on the formation of rill.-shaped ABA triblock copolymer (P4VP(43)-b-PS260-b-P4VP(43)) micelles. The results reveal that Shear flow Plays an important role in the formation of the rings Both ring size and its, distribution are found to be dependent sensitively on the stirring rate. Sizable rings are more likely to be formed at moderate stirring rate, Interestingly, the ring formation mechanism is also dependent oil the Shear flow. Copolymers are likely to form rings via end-to-end cylinder connection at low stirring rates, whereas they tend to form rings via the pathway of the rod-sphere-vesicle-ring it high stirring rates.

Self-Assembly of Hyperbranched Multiarmed PEG-PEI-PLys(Z) Copolymer into Micelles, Rings, and Vesicles

Self-assembling of synthesized novel biodegradable hyperbranched amphiphilic poly(ethylene glycol)-polyethylenimine-poly(epsilon-benzyloxycarbonyl-L-lysine) (PEG-PEI-PLys(Z)) in aqueous media is studied. In aqueous media. PLys(Z) is the hydrophobic segment, with PEG and PEI as the hydrophilic segments. It will self-assemble into spherical shape when the selected solvent water is dropped into the common solvent tetrahydrofuran (THF). And when PEG-PEI-PLYS in common solvent is dropped into mixed solvent water and THF, rings will come into King. The spherical and rings are observed by environmental scanning electron microscopy (ESEM) and transmission electron microscopy ITEM). It shows that the size of the sphere is about 100 nm, and the diameter of ring distributes from 400 nm to 10 mu m and bigger with the time roll around.

Study of controllable aggregation morphology of ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.

Fabrication of conductive metallized nanostructures from self-assembled amphiphilic triblock copolymer templates: Nanospheres, nanowires, nanorings

Various metallized nanostructures (such as rings, wires with controllable lengths, spheres) have been successfully fabricated by coating metallic nanolayers onto soft nanotemplates through simple electroless methods. In particular, bimetallic nanostructures have been obtained by using simple methods. The multiple functional polymeric nanostructures, were obtained through the self-assembly of polystyrene/poly(4-vinyl pyridine) triblock copolymer (P4VP-b-PS-b-P4VP) in selective media by changing the common solvent properties. By combining field emission scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) characterization, it was confirmed that polymer/metal and bimetallic (Au@Ag) core-shell nanostructures could be achieved by chemical metal deposition method.

Self-assembly of crystalline-coil diblock copolymer in solvents with varying selectivity: From spinodal-like aggregates to spheres, cylinders, and lamellae

We have investigated systematically the morphology of thin films spin-coated from solutions of a semicrystalline diblock copolymer, poly(L-lactic acid)-block-polystyrene (PLLA-b-PS), in solvents with varying selectivity. In neutral solvents (chloroform and tetrahydrofuran (THF)), a spinodal-like pattern was obtained and the pattern boundary was sharpened by diluting the solution. Meanwhile, loose spherical associates, together with larger aggregates composed of these associates by unimer bridges, formed partly due to crystallization of the PLLA blocks in relatively concentrated solutions. In slightly PS-selective solvent (e.g., benzene), both loose and compact spherical micelles were obtained, depending on the polymer concentration, coexisting with unimers. When enhancing the selectivity with mixed solvents, for example, mixing the neutral solvent and the slightly selective solvent with a highly PS-selective solvent, CS2, loose assemblies (nanorods in CS2/THF mixtures and polydisperse aggregates in CS2/benzene mixtures) and well-developed lamellar micelles were obtained.

A Monte Carlo simulation for the micellization of ABC 3-miktoarm star terpolymers in a selective solvent

We have used Monte Carlo simulation to study the micellization of ABC 3-miktoarm star terpolymers in a selective solvent (good to A segment, bad to B and C segments). The simulation results reveal that the self-assembled morphology is determined by the block length, molecular architecture, terpolymer concentration and insolubility of insoluble block in the solvent. In dilute solution, symmetric terpolymers (N-B = N-C = 30) tend to aggregate into a novel wormlike pearl-necklace structure linked by an alternating arrangement of B and C spheres, whereas the asymmetric terpolymers (NB = 10, NC = 50) are likely to aggregate into spherical or cylindrical micelles (formed by C blocks) connected with some small B spheres, when the concentration of terpolymer is relatively low (chain number is 100). However, when the concentration of terpolymer is relatively high (chain number is 250), the symmetric terpolymers tend to aggregate into a netlike structure linked by an alternation of B and C spheres, whereas the asymmetric terpolymers are likely to aggregate into wormlike micelles (formed by C blocks) connected with some of small spheres (formed by B blocks). Moreover, when the insolubility of insoluble block in the solvent is weak, the insoluble blocks aggregate into some incompact micelles.

Multiple vesicular morphologies in AB/AC diblock copolymer complexes through hydrogen bonding interactions

We report for the first time multiple vesicular morphologies in block copolymer complexes formed in aqueous media via hydrogen bonding interactions. A model AB/AC diblock copolymer system consisting of polystyrene-block- poly(acrylic acid) (PS-b-PAA) and polystyrene-block-poly(ethylene oxide) (PS-b-PEO) was examined using transmission electron microscopy, small-angle X-ray scattering, and dynamic light scattering. The complexation and morphological transitions were driven by the hydrogen bonding between the complementary binding sites on PAA and PEO blocks of the two diblock copolymers. Upon the addition of PS-b-PEO, a variety of bilayer aggregates were formed in PS-b-PAA/PS-b-PEO complexes including vesicles, multilamellar vesicles (MLVs), thick-walled vesicles (TWVs), interconnected compound vesicles (ICCVs), and irregular aggregates. Among these aggregates, ICCVs were observed as a new morphology. The morphology of aggregates was correlated with respect to the molar ratio of PEO to PAA. At [EO]/[AA] = 0.5, vesicles were observed, while MLVs were obtained at [EO]/[AA] = 1. TWVs and ICCVs were formed at [EO]/[AA] = 2 and 6, respectively. When [EO]/[AA] reached 8 and above, only irregular aggregates appeared. These findings suggest that complexation between two amphiphilic diblock copolymers is a viable approach to prepare polymer vesicles in aqueous media.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.

The role of hierarchical morphologies in the superior gas sensing performance of CuO-based chemiresistors

The development of gas sensors with innovative designs and advanced functional materials has attracted considerable scientific interest given their potential for addressing important technological challenges. This work presents new insight towards the development of high-performance p-type semiconductor gas sensors. Gas sensor test devices, based on copper (II) oxide (CuO) with innovative and unique designs (urchin-like, fiber-like, and nanorods), are prepared by a microwave-assisted synthesis method. The crystalline composition, surface area, porosity, and morphological characteristics are studied by X-ray powder diffraction, nitrogen adsorption isotherms, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. Gas sensor measurements, performed simultaneously on multiple samples, show that morphology can have a substantial influence on gas sensor performance. An assembly of urchin-like structures is found to be most effective for hydrogen detection in the range of parts-per-million at 200 °C with 300-fold larger response than the previously best reported values for semiconducting CuO hydrogen gas sensors. These results show that morphology plays an important role in the gas sensing performance of CuO and can be effectively applied in the further development of gas sensors based on p-type semiconductors. High-performance gas sensors based on CuO hierarchical morphologies with in situ gas sensor comparison are reported. Urchin-like morphologies with high hydrogen sensitivity and selectivity that show chemical and thermal stability and low temperature operation are analyzed. The role of morphological influences in p-type gas sensor materials is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.