1,247 research outputs found
Methyl group dynamics in a confined glass
We present a neutron scattering investigation on methyl group dynamics in
glassy toluene confined in mesoporous silicates of different pore sizes. The
experimental results have been analysed in terms of a barrier distribution
model, such a distribution following from the structural disorder in the glassy
state. Confinement results in a strong decreasing of the average rotational
barrier in comparison to the bulk state. We have roughly separated the
distribution for the confined state in a bulk-like and a surface-like
contribution, corresponding to rotors at a distance from the pore wall
respectively larger and smaller than the spatial range of the interactions
which contribute to the rotational potential for the methyl groups. We have
estimated a distance of 7 Amstrong as a lower limit of the interaction range,
beyond the typical nearest-neighbour distance between centers-of-mass (4.7
Amstrong).Comment: 5 pages, 3 figures. To be published in European Physical Journal E
Direct. Proceedings of the 2nd International Workshop on Dynamics in
Confinemen
A Cladistic Analysis of \u3cem\u3endh\u3c/em\u3eF Sequences from Representative Species of \u3cem\u3eSaintpaulia\u3c/em\u3e and \u3cem\u3eStreptocarpus\u3c/em\u3e Subgenera and \u3cem\u3eStreptocarpella\u3c/em\u3e (Gesneriaceae)
Two African genera of the Gesneriaceae, Saintpaulia and Streptocarpus, are similar in many respects. Both genera have blue to purple flowers, pollen of similar shape and exine sculpting, embryos with one-celled uninucleate chalazal haustoria, shared vegetative structures among some species, and are among the few genera in the Gesneriaceae which include species with chromosome count of n=15. Similarity of these features has indicated that the two genera are likely to be closely related. This study examines the sequences of the chloroplast gene ndhF among several representative Saintpaulia and representatives of Streptocarpus subgenera Streptocarpella and Streptocarpus. The results of this analysis are congruent with those of previous analysis based on the nuclear ribosomal region, ITS. Saintpaulia was found to be nested within Streptocarpus and Streptocarpella. The results raise the possibility of the taxonomic revision of these genera, and this is discussed. Comparisons between the data sets are made regarding utility of the two regions, sample size and outgroup
Effect of nanoparticle loading and magnetic field application on the thermodynamic, optical, and rheological behavior of thermoresponsive polymer solutions
Although processing via external stimuli is a promising technique to tune the structure and properties of polymeric materials, the impact of magnetic fields on phase transitions in thermoresponsive polymer solutions is not well-understood. As nanoparticle (NP) addition is also known to impact these thermodynamic and optical properties, synergistic effects from combining magnetic fields with NP incorporation provide a novel route for tuning material properties. Here, the thermodynamic, optical, and rheological properties of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions are examined in the presence of hydrophilic silica NPs and magnetic fields, individually and jointly, via Fourier-transform infrared spectroscopy (FTIR), magneto-turbidimetry, differential scanning calorimetry (DSC), and magneto-rheology. While NPs and magnetic fields both reduce the phase separation energy barrier and lower optical transition temperatures by altering hydrogen bonding (H-bonding), infrared spectra demonstrate that the mechanism by which these changes occur is distinct. Magnetic fields primarily alter solvent polarization while NPs provide PNIPAM–NP H-bonding sites. Combining NP addition with field application uniquely alters the solution environment and results in field-dependent rheological behavior that is unseen in polymer-only solutions. These investigations provide fundamental understanding on the interplay of magnetic fields and NP addition on PNIPAM thermoresponsivity which can be harnessed for increasingly complex stimuli-responsive materials
Lattice Knots in a Slab
In this paper the number and lengths of minimal length lattice knots confined
to slabs of width , is determined. Our data on minimal length verify the
results by Sharein et.al. (2011) for the similar problem, expect in a single
case, where an improvement is found. From our data we construct two models of
grafted knotted ring polymers squeezed between hard walls, or by an external
force. In each model, we determine the entropic forces arising when the lattice
polygon is squeezed by externally applied forces. The profile of forces and
compressibility of several knot types are presented and compared, and in
addition, the total work done on the lattice knots when it is squeezed to a
minimal state is determined
Synthesis of Mesoporous Silica@Co–Al Layered Double Hydroxide Spheres: Layer-by-Layer Method and Their Effects on the Flame Retardancy of Epoxy Resins
Hierarchical mesoporous silica@Co–Al layered double hydroxide (m-SiO2@Co–Al LDH) spheres were prepared through a layer-by-layer assembly process, in order to integrate their excellent physical and chemical functionalities. TEM results depicted that, due to the electrostatic potential difference between m-SiO2 and Co–Al LDH, the synthetic m-SiO2@Co–Al LDH hybrids exhibited that m-SiO2 spheres were packaged by the Co–Al LDH nanosheets. Subsequently, the m-SiO2@Co–Al LDH spheres were incorporated into epoxy resin (EP) to prepare specimens for investigation of their flame-retardant performance. Cone results indicated that m-SiO2@Co–Al LDH incorporated obviously improved fire retardant of EP. A plausible mechanism of fire retardant was hypothesized based on the analyses of thermal conductivity, char residues, and pyrolysis fragments. Labyrinth effect of m-SiO2 and formation of graphitized carbon char catalyzed by Co–Al LDH play pivotal roles in the flame retardance enhancement
Electrocatalytic oxidation of ascorbic acid on mesostructured SiO2-conducting polymer composites
The conducting self-doping copolymer poly(aniline-co-ABA) preserves its redox activity at pH values as high as 7. This observation was the starting point to synthesize an organic inorganic hybrid composite able to electrochemically oxidize ascorbic acid molecules at that pH. The inorganic part of the catalytic element was an ordered mesoporous electrodeposit of SiO2, which has been used as the template for the electrochemical insertion of the self-doping copolymer. The oxidation of ascorbate ions at a fixed potential on this composite was studied by means of the kinetic model proposed by Bartlett and Wallace (2001). It was observed that the effective kinetic constant K-ME increased significantly but, simultaneously, k'(ME) remained almost constant when the composite was employed as the electrocatalytic substrate. These results were interpreted in the light of two combinations of kinetic constants, which strongly suggested that the increase in K-ME should be ascribed to the improvement in electronic conductivity of the copolymer induced by the highly ordered silica template. (C) 2015 Elsevier Ltd. All rights reserved.Financial support from the Spanish Ministerio de Economia y Competitividad and FEDER funds (MAT2013-42007-P), from the Generalitat Valenciana (PROMETE02013/038) and from the Fundacion Ramon Areces is gratefully acknowledged.Rivero, O.; Huerta, F.; Montilla, F.; Sanchis, C.; Morallón, E. (2015). Electrocatalytic oxidation of ascorbic acid on mesostructured SiO2-conducting polymer composites. European Polymer Journal. 69:201-207. https://doi.org/10.1016/j.eurpolymj.2015.06.004S2012076
Molecular Clusters in Mesoporous Materials as Precursors to Nanoparticles of a New Lacunar Ternary Compound PdxMoyP
Bimetallic clusters of composition Pd2Mo2(g5-C5H5)2(l3-CO)2(l2-CO)4 (PR3)2 (R = ethyl or phenyl) were incorporated by impregnation from solution into two different silica matrices, amorphous xerogels and ordered SBA-15, and a study of their thermal decomposition under a reducing atmosphere is reported. With both matrices, a suitable thermal treatment afforded nanoparticles of a new bimetallic phosphide. Although nanoparticles of composition PdxMoyP, isostructural with Mo3P, were formed in both matrices, they were more uniformly distributed in the SBA-15 framework and showed a narrower size distribution. The samples have been characterized by powder XRD, chemical analysis, FT-IR spectroscopy, TEM and electron tomography (3D TEM)
Probing the Mechanism of Silica Polymerization at Ambient Temperatures using Monte Carlo Simulations
Experimental evidence of the ferroelectric phase transition near the point in liquid water
We studied dielectric properties of nano-sized liquid water samples confined
in polymerized silicates MCM-41 characterized by the porous sizes \sim 3-10nm.
We report the direct measurements of the dielectric constant by the dielectric
spectroscopy method at frequencies 25Hz-1MHz and demonstrate clear signatures
of the second-order phase transition of ferroelectric nature at temperatures
next to the \lambda- point in the bulk supercooled water. The presented results
support the previously developed polar liquid phenomenology and hence establish
its applicability to model actual phenomena in liquid water.Comment: 4 pages, single figur
Self-assembly of highly symmetrical, ultrasmall inorganic cages directed by surfactant micelles
Nanometre-sized objects with highly symmetrical, cage-like polyhedral shapes, often with icosahedral symmetry, have recently been assembled from DNA(1-3), RNA(4) or proteins(5,6) for applications in biology and medicine. These achievements relied on advances in the development of programmable self-assembling biological materials(7-10), and on rapidly developing techniques for generating three-dimensional (3D) reconstructions from cryo-electron microscopy images of single particles, which provide high-resolution structural characterization of biological complexes(11-13). Such single-particle 3D reconstruction approaches have not yet been successfully applied to the identification of synthetic inorganic nanomaterials with highly symmetrical cage-like shapes. Here, however, using a combination of cryo-electron microscopy and single-particle 3D reconstruction, we suggest the existence of isolated ultrasmall (less than 10 nm) silica cages ('silicages') with dodecahedral structure. We propose that such highly symmetrical, self-assembled cages form through the arrangement of primary silica clusters in aqueous solutions on the surface of oppositely charged surfactant micelles. This discovery paves the way for nanoscale cages made from silica and other inorganic materials to be used as building blocks for a wide range of advanced functional-materials applications
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