Self-Assembly of Supramolecules Consisting of Octyl Gallate Hydrogen Bonded to Polyisoprene-block-poly(vinylpyridine) Diblock Copolymers

Synchrotron radiation was used to investigate the self-assembly in two comb-shaped supramolecules systems consisting of octyl gallate (OG), i.e., 1-octyl-3,4,5-trihydroxybenzoate, hydrogen bonded to the pyridine groups of polyisoprene-block-poly(vinylpyridine) diblock copolymers. In the case of the 1,2-polyisoprene-block-poly(4-vinylpyridine)(OG)x system, self-assembly was only observed for x ≥0.5, where x denotes the number of OG molecules per pyridine group. For x = 0.5, 0.75, 1.0, and 1.2 the system self-assembled in the form of hexagonally ordered cylinders of P4VP(OG) throughout the entire temperature range of 25-200 °C investigated. For the 1,4-polyisoprene-block-poly(2-vinylpyridine)(OG)x system, on the other hand, a considerably more complex phase behavior was found, including the formation of cubic, hexagonally ordered cylinders and lamellar morphologies. In this case several order-order transitions were observed as a function of temperature, including a lamellar to lamellar transition involving a collapse of the layer thickness. The absence of hydrogen bonding between the octyl gallate molecules and the pyridine groups at elevated temperatures is argued to be a key factor for many of the phenomena observed.

Magnetic nanocomposites at microwave frequencies

Most conventional magnetic materials used in the electronic devices are ferrites, which are composed of micrometer-size grains. But ferrites have small saturation magnetization, therefore the performance at GHz frequencies is rather poor. That is why functionalized nanocomposites comprising magnetic nanoparticles (e.g. Fe, Co) with dimensions ranging from a few nm to 100 nm, and embedded in dielectric matrices (e.g. silicon oxide, aluminium oxide) have a significant potential for the electronics industry. When the size of the nanoparticles is smaller than the critical size for multidomain formation, these nanocomposites can be regarded as an ensemble of particles in single-domain states and the losses (due for example to eddy currents) are expected to be relatively small. Here we review the theory of magnetism in such materials, and we present a novel measurement method used for the characterization of the electromagnetic properties of composites with nanomagnetic insertions. We also present a few experimental results obtained on composites consisting of iron nanoparticles in a dielectric matrix.Comment: 20 pages, 10 figures, 5 table

In-situ SAXS study on the alignment of ordered systems of comb-shaped supramolecules:A shear-induced cylinder-to-cylinder transition

A tooth rheometer, designed to investigate in-situ the influence of large-amplitude oscillatory shear on the macroscopic orientation of complex fluids, is used to study the alignment of two supramolecular systems composed of a polyisoprene-block-poly(2-vinylpyi-idine) block copolymer with octyl gallate (OG) hydrogen bonded to the vinylpyridine block. The molecular ratio x between OG and pyridine groups in these two PI-b-P2VP(OG)(x) systems is 0.50 and 0.75, respectively. In both cases, a hexagonally ordered cylindrical self-assembly was revealed by small-angle X-ray scattering in a broad temperature range. The spacing of the hexagonal structure decreases significantly on heating and reversibly increases on cooling. In in-situ SAXS experiments, performed with the tooth rheometer, a gradual macroscopic alignment of the nanoscale structure is observed on heating for both supramolecular systems. The most striking feature is a shear-induced transition from one hexagonal structure to another, more aligned, hexagonal structure observed for PI-b-P2VP(OG)0.75 in the temperature range 120-140degreesC. The transition is accompanied by an abrupt reduction of the domain spacing and additionally by a decrease of the phase angle measured by the rheometer. In the PI-b-P2V-P(OG)(0.5) system a comparable reduction in the spacing is observed at 90-95degreesC. In this case, it coincides with the most intensive macroscopic alignment of the sample, proceeding in a continuous rather than discontinuous fashion. This behavior is discussed in terms of the breaking of the hydrogen bonds between OG and P2VP being facilitated by shear

Vortex core contribution to textural energy in 3He-B below 0.4Tc

Vortex lines affect the spatial order-parameter distribution in superfluid 3He-B owing to superflow circulating around vortex cores and due to the interaction of the order parameter in the core and in the bulk as a result of superfluid coherence over the whole volume. The step-like change of the latter contribution at 0.6Tc (at a pressure of 29bar) signifies the transition from axisymmetric cores at higher temperatures to broken-symmetry cores at lower temperatures. We extended earlier measurements of the core contribution to temperatures below 0.2Tc, in particular searching for a possible new core transition to lower symmetries. As a measuring tool we track the energy levels of magnon condensate states in a trap formed by the order-parameter texture.Comment: 13 pages, 10 figures, submitted to proceedings of the QFS2010 conferenc

Spectrum of bound fermion states on vortices in 3^3He-B

We study subgap spectra of fermions localized within vortex cores in $^3$He-B. We develop an analytical treatment of the low-energy states and consider the characteristic properties of fermion spectra for different types of vortices. Due to the removed spin degeneracy the spectra of all singly quantized vortices consist of two different anomalous branches crossing the Fermi level. For singular $o$ and $u$ vortices the anomalous branches are similar to the standard Caroli-de Gennes -Matricon ones and intersect the Fermi level at zero angular momentum yet with different slopes corresponding to different spin states. On the contrary the spectral branches of nonsingular vortices intersect the Fermi level at finite angular momenta which leads to the appearance of a large number of zero modes, i.e. energy states at the Fermi level. Considering the $v$, $w$ and $uvw$ vortices with superfluid cores we show that the number of zero modes is proportional to the size of the vortex core.Comment: 6 pages, 1 figur

NMR Experiments on Rotating Superfluid 3He-A : Evidence for Vorticity

Experiments on rotating superfluid 3He-A in an open cylindrical geometry show a change in the NMR line shape as a result of rotation: The amplitude of the peak decreases in proportion to f(T)g(Ω), where Ω is the angular velocity of rotation; at the same time the line broadens. Near Tc, f(T) is a linear function of 1−T/Tc. At small velocities g(Ω)∝Ω. These observations are consistent with the existence of vortices in rotating 3He-A.Peer reviewe

Nanocellulose: Recent Fundamental Advances and Emerging Biological and Biomimicking Applications

In the e'ort toward sustainable advanced functional materials, nanocellu- loses have attracted extensive recent attention. Nanocelluloses range from rod-like highly crystalline cellulose nanocrystals to longer and more entan- gled cellulose nanofibers, earlier denoted also as microfibrillated celluloses and bacterial cellulose. In recent years, they have spurred research toward a wide range of applications, ranging from nanocomposites, viscosity modi- fiers, films, barrier layers, fibers, structural color, gels, aerogels and foams, and energy applications, until filtering membranes, to name a few. Still, nanocelluloses continue to show surprisingly high challenges to master their interactions and tailorability to allow well-controlled assemblies for functional materials. Rather than trying to review the already extensive nanocellulose literature at large, here selected aspects of the recent progress are the focus. Water interactions, which are central for processing for the functional proper- ties, are discussed first. Then advanced hybrid gels toward (multi)stimuli responses, shape-memory materials, self-healing, adhesion and gluing, bio- logical sca'olding, and forensic applications are discussed. Finally, composite fibers are discussed, as well as nanocellulose as a strategy for improvement of photosynthesis-based chemicals production. In summary, selected per- spectives toward new directions for sustainable high-tech functional mate- rials science based on nanocelluloses are described. </div

Self-Assembly of Supramolecular Triblock Copolymer Complexes

Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031<χS,tBOS<0.034 and 0.39<χ4VP,tBOS<0.43, the latter being slightly larger than the known 0.30<χS,4VP≤0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

Self-assembly in solution of a reversible comb-shaped supramolecular polymer

We report a single step synthesis of a polyisobutene with a bis-urea moiety in the middle of the chain. In low polarity solvents, this polymer self-assembles by hydrogen bonding to form a combshaped polymer with a central hydrogen bonded backbone and polyisobutene arms. The comb backbone can be reversibly broken, and consequently, its length can be tuned by changing the solvent, the concentration or the temperature. Moreover, we have proved that the bulkiness of the side-chains have a strong influence on both the self-assembly pattern and the length of the backbone. Finally, the density of arms can be reduced, by simply mixing with a low molar mass bis-urea