Block Copolymer Micelles with Inverted Morphologies.

Beyond the crew cut: Highly asymmetric block copolymers self-assemble into microparticles with inverse morphologies far beyond the crew-cut regime. These particles enclose highly ordered channel systems with simple cubic, double diamond, and hexagonally packed hollow-hoop symmetry. The extensive interface and confinement of these particles could enable applications in the storage of cargo, templating, and chemical reactions.

Chemically Synthesized Carbon Nanorods with Dual Polarized Emission.

We realized the synthesis of carbon nanorods-monodisperse colloidal particles with a length of 50 nm and a width of 20 nm-which can be considered an addition to the family of light-emitting carbon-based nanostructures. Their anisotropic shape is determined by the use of the surfactant aminopropylisobutyl polyhedral oligomeric silsesquioxane, and their optical properties originate from domains of polycyclic aromatic hydrocarbons incorporated within an inorganic framework. The nanorods show dual polarized emission with a quantum yield of 15-20% and emission anisotropy of ∼0.3, which changes from blue (460 nm) to yellow (565 nm) depending on the excitation wavelength. These carbon nanorods expand the range of light-emitting carbon nanomaterials available for optoelectronic and biolabeling applications.

A novel wormhole-like mesoporous hybrid MnCoOx catalyst for improved ethanol catalytic oxidation.

A series of wormhole-like mesoporous hybrid MnCoOx catalysts have been successfully prepared using a soft template combining the sol-gel method. The physical and chemical properties of these mesostructured materials are systematically characterized using XRD, BET, Raman, XPS, HRTEM, H2-TPR and O2-TPD and compared with pure MnOx and Co3O4. Their catalytic performances for ethanol oxidation are investigated and carried out on a fixed-bed reactor. It is found that the molar ratio of transition metal precursors has a remarkable influence on the nanoparticle morphology, open-framework structure dispersion, surface element distribution, and redox property. Among the MnCoOx catalysts, Mn1Co1 catalyst composed by uniform worm-like nanoparticles shows the highest BET surface area (208 m2/g), most surface proportion of Co3+ and Mn4+ (18.7%), lowest reducibility potential and best catalytic activity (T50 = 80 °C) as well as an excellent CO2 selectivity (S170 = 100%) with a GHSV of 60,000 mL·(g·h)-1. Based on the structure-function analysis of catalysts, it is deduced that the synergistic effect between Mn and Co in MnxCo1-xOy solid solution and proton scavenger addition in preparation can improve the mesostructured, active sites distribution and catalytic performance. Consequently, it can be expected that the mesoporous hybrid MnCoOx catalysts are promising materials for catalytic removal of VOCs, and the related results in this research would also provide some new insights into the porous composite material design and application exploration for ethanol catalytic oxidation.

Determination of charge carrier concentration in doped nonpolar liquids by impedance spectroscopy in the presence of charge adsorption.

The impedance of dodecane doped with sorbitan trioleate (Span 85), sorbitan monooleate (Span 80) and sorbitan monolaurate (Span 20) was measured as a function of frequency using a 10 mV amplitude sinusoidal voltage applied across a parallel plate cell with a 10 µm spacing. The tested solutions varied in concentration from 1 mM to 100 mM and the frequency range was 10(-2)-10(4) Hz. Nyquist plots of all three surfactants showed the high frequency semicircle characteristic of parallel resistance and capacitance but often exhibited a second semicircle at low frequencies which was attributed to charge adsorption and desorption. The electrical conductivity of each surfactant was proportional to surfactant concentration for concentrations above 10mM. Fitting the data to models for charge migration, differential capacitance, and adsorption allowed extraction of both charge concentration and two kinetic parameters that characterize the rate of adsorption and desorption. Above 10 mM the ratio of charge carriers per surfactant molecule was 22 ppm for Span 20, 3 ppm for Span 80, and 0.2 ppm for Span 85. A higher number of charge carriers per molecule of surfactant was associated with larger micelles. The adsorption rate constants were independent of surfactant concentration while the desorption rate constants were proportional to the surfactant concentration. This dependence indicated that uncharged surfactant, whether in micelles or not, participated in the desorption of charge. Predictions of the adsorption/desorption model for large constant electric fields agreed qualitatively with data from the literature (Karvar et al., 2014).

Yolk@Shell Nanoarchitectures with Bimetallic Nanocores-Synthesis and Electrocatalytic Applications.

In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAuNP@tin-rich ITO (AgAu@ITOTR) yolk@shell nanomaterials. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITOTR yolk@shell can easily be tuned. The conductivity of the ITOTR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAgNP@ITOTR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.

Switching of charged inverse micelles in non-polar liquids.

The electrodynamics of micellar ions in nonpolar liquids are well understood for the case that a voltage is applied or switched off. In this work, the electrodynamics of charged inverse micelles (CIMs) are studied when the applied voltage is switched to the opposite polarity, which is relevant for applications such as electrophoretic displays and liquid toner printing. Transient current measurements are used to characterize the switching of CIMs formed in a solution of surfactant polyisobutylene succinimide in n-dodecane. For reverse voltages with amplitude below 10V the measurements are in good agreement with a drift and diffusion model, confirming the established understanding of CIMs in nonpolar liquids. When the charge content is high, the reversal current shows a characteristic peak which is explained on the basis of dynamic space-charge effects. However, for reverse voltages larger than 10V, the transient currents are influenced by electrohydrodynamic flow in the liquid causing the CIMs to switch faster than predicted by the model. The occurrence of electrohydrodynamic flow is verified by optical tracking of tracer particles. Also, when the polarizing voltage is applied for longer times, an additional current peak emerges which is due to the accumulation of newly generated charges at the electrodes.

Non-ionic amphiphilic block copolymers by RAFT-polymerization and their self-organization.

Water-soluble, amphiphilic diblock copolymers were synthesized by reversible addition fragmentation chain transfer polymerization. They consist of poly(butyl acrylate) as hydrophobic block with a low glass transition temperature and three different nonionic water-soluble blocks, namely, the classical hydrophilic block poly(dimethylacrylamide), the strongly hydrophilic poly(acryloyloxyethyl methylsulfoxide), and the thermally sensitive poly(N-acryloylpyrrolidine). Aqueous micellar solutions of the block copolymers were prepared and characterized by static and dynamic light scattering analysis (DLS and SLS). No critical micelle concentration could be detected. The micellization was thermodynamically favored, although kinetically slow, exhibiting a marked dependence on the preparation conditions. The polymers formed micelles with a hydrodynamic diameter from 20 to 100 nm, which were stable upon dilution. The micellar size was correlated with the composition of the block copolymers and their overall molar mass. The micelles formed with the two most hydrophilic blocks were particularly stable upon temperature cycles, whereas the thermally sensitive poly(N-acryloylpyrrolidine) block showed a temperature-induced precipitation. According to combined SLS and DLS analysis, the micelles exhibited an elongated shape such as rods or worms. It should be noted that the block copolymers with the most hydrophilic poly(sulfoxide) block formed inverse micelles in certain organic solvents.