Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Compositionally modulated Fermi surfaces, structured diffuse scattering and ternary derivatives of 1T-TaS2

Ternary derivatives of 1T-TaS₂ have been synthesized and the variation in the highly structured diffuse intensity distributions characteristic of such materials carefully monitored to investigate the effect that such substitution has upon the band structures and Fermi surfaces (FSs) of the materials. Removal of d electrons via the replacement of Ta ions with lower valent transition metal ions leads to a systematic increase in the radii of the characteristic structured diffuse intensity distribution. Extended Hückel tight binding calculations of the FSs of the doped samples are carried out and used to predict possible nesting wave-vectors. The results are in reasonably good agreement with the radii of the experimentally observed diffuse intensity distributions.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Unified theory of bound and scattering molecular Rydberg states as quantum maps

Using a representation of multichannel quantum defect theory in terms of a quantum Poincaré map for bound Rydberg molecules, we apply Jung's scattering map to derive a generalized quantum map, that includes the continuum. We show that this representation not only simplifies the understanding of the method, but moreover produces considerable numerical advantages. Finally we show under what circumstances the usual semi-classical approximations yield satisfactory results. In particular we see that singularities that cause problems in semi-classics are irrelevant to the quantum map.     

Unified nomenclature for chromatography

The background of the new Unified Nomenclature for Chromatography just accepted by the International Union of Pure and Applied Chemistry (IUPAC) is explained and selected highlights of the new rules are elaborated.     

Investigation of the reaction order for nucleophilic substitution of dialkyl methylphosphonates by alkoxides

The rate of nucleophilic substitution at the phosphorus centre of dialkyl methylphosphonates by methoxide and ethoxide has been studied to investigate the possible involvement of hexacoordinated phosphorus species in this reaction. For alkoxide concentrations less than ca. 1.5 M the rate increases with the square of alkoxide concentration. However, consideration of the activity of the alkoxides, represented by an appropriate acidity function, reveals that only one equivalent of alkoxide is involved in the rate-determining step. Thus, there is no requirement to invoke the intermediacy of a hexacoordinated species in the reaction pathway. © John Wiley & Sons, Inc.     

A phloroglucinol derivative with a new carbon skeleton from Hypericum perforatum (Guttiferae)

Examination of the aerial parts of a Chinese herbal medicine yielded a novel metabolite, perforatumone 1, which is characterized by its unique carbon skeleton. Its structure was determined by detailed spectroscopic analysis.     

Fractional commensurate, composition, and adding schemes: Learning trajectories of Jason and Laura: Grade 5

A case study of two 5th-Grade children, Jason and Laura, is presented who participated in the teaching experiment, Children’s Construction of the Rational Numbers of Arithmetic. The case study begins on the 29th of November of their 5th-Grade in school and ends on the 5th of April of the same school year. Two basic problems were of interest in the case study. The first was to provide an analysis of the concepts and operations that are involved in the construction of three fractional schemes: a commensurate fractional scheme, a fractional composition scheme, and a fractional adding scheme. The second was to provide an analysis of the contribution of interactive mathematical activity in the construction of these schemes. The phrase, “commensurate factional scheme” refers to the concepts and operations that are involved in transforming a given fraction into another fraction that are both measures of an identical quantity. Likewise, “fractional composition scheme” refers to the concepts and operations that are involved in finding how much, say, 1/3 of 1/4 of a quantity is of the whole quantity, and “fractional adding scheme” refers to the concepts and operations involved in finding how much, say, 1/3 of a quantity joined to 1/4 of a quantity is of the whole quantity. Critical protocols were abstracted from the teaching episodes with the two children that illustrate what is meant by the schemes, changes in the children’s concepts and operations, and the interactive mathematical activity that was involved. The body of the case study consists of an on-going analysis of the children’s interactive mathematical activity and changes in that activity. The last section of the case study consists of an analysis of the constitutive aspects of the children’s constructive activity, including the role of social interaction and nonverbal interactions of the children with each other and with the computer software we used in teaching the children.