Polydispersity-induced macrophase separation in diblock copolymer melts

The effect of A-block polydispersity on the phase behavior of AB diblock copolymer melts is examined using a complete self-consistent field theory treatment that allows for fractionation of the parent molecular-weight distribution. In addition to observing the established shift in phase boundaries, we find the emergence of significant two-phase coexistence regions causing, for instance, the disappearance of the complex phase window. Furthermore, we find evidence that polydispersity relieves packing frustration, which will reduce the tendency for long-range order.

The Effects of Stratification on Flow Separation

Separation of stratified flow over a two-dimensional hill is inhibited or facilitated by acceleration or deceleration of the flow just outside the attached boundary layer. In this note, an expression is derived for this acceleration or deceleration in terms of streamline curvature and stratification. The expression is valid for linear as well as nonlinear deformation of the flow. For hills of vanishing aspect ratio a linear theory can be derived and a full regime diagram for separation can be constructed. For hills of finite aspect ratio scaling relationships can be derived that indicate the presence of a critical aspect ratio, proportional to the stratification, above which separation will occur as well as a second critical aspect ratio above which separation will always occur irrespective of stratification.

Energy separation of neutrons scattered at small angles from silicon using time-of-flight techniques

The time-of-flight technique is used on a small-angle neutron scattering instrument to separate the energies of the scattered neutrons, in order to determine the origin of the temperature-dependent scattering observed from silicon at Q > similar to 0.1 angstrom(-1). A quantitative analysis of the results in comparison with the phonon dispersion curves, determined by Dolling using a triple-axis neutron spectrometer, shows that the temperature-dependent scattering can be understood in terms of Umklapp processes whereby neutrons gain energy from phonons.

Born-Oppenheimer failure in the separation of low frequency vibrations

Changes in the effective potential function of a low-frequency large-amplitude molecular vibration, resulting from excitation of a high-frequency vibration, are discussed. It is shown that in some situations a significant contribution to such changes may arise from failure of the Born-Oppenheimer separation of the low-frequency mode. In the particular example of the HF dimer, recent evidence that the tunneling barrier increases on exciting either of the H-stretching vibrations is probably due to this effect.

Effects of solar wind magnetosphere coupling recorded at different geomagnetic latitudes: Separation of directly-driven and storage/release systems

The effect on geomagnetic activity of solar wind speed, compared with that of the strength of the interplanetary magnetic field, differs with geomagnetic latitude. In this study we construct a new index based on monthly standard deviations in the H-component of the geomagnetic field for all geomagnetic latitudes. We demonstrate that for this index the response at auroral regions correlates best with interplanetary coupling functions which include the solar wind speed while mid- and low-latitude regions respond to variations in the interplanetary magnetic field strength. These results are used to isolate the responsible geomagnetic current systems.

The synthesis of chiral N-heterocyclic carbene–borane and –diorganoborane complexes and their use in the asymmetric reduction of ketones

Chiral N-heterocyclic carbene–borane complexes have been synthesised, and have been shown to reduce ketones with Lewis acid promotion. Chiral N-heterocyclic carbene–borane and –diorganoborane complexes can reduce ketones with enantioselectivities up to 75% and 85% ee, respectively.

Lateral phase separation in grafted diblock copolymer films

Tethered films of polystyrene-block-poly(methyl methacrylate) copolymers of varying composition and molecular weight were investigated using atomic force microscopy and the observed structures compared with theoretical predictions. Although the experimental results were in qualitative agreement with the theory, there was significant quantitative variation. This was attributed to the presence of solvent in the films prior to and during annealing, a hypothesis supported by new preliminary calculations reported here. Solvent exchange experiments (where a good solvent for both polymer blocks was gradually replaced by a selective solvent), were also performed on the films. This procedure generated textured films in which the structure was defined by miscibility of the polymer blocks with the second solvent.

1,3-Dipolar cycloadditions to unsymmetrical ketone-derived chiral stabilized azomethine ylides: strategies for the synthesis of highly substituted amino acids

We report herein, the first generation of unsymmetrical ketone-derived chiral stabilized azomethine ylides. Intrairiolecular and intermolecular cycloaddition strategies have been utilized to synthesize both an enantiornerically pure bicyclic proline derivative and an enantionierically pure beta-hydroxy-alpha-amino acid.

Synthesis of the ester side chains of some potently antileukemic harringtonia alkaloids from chiral citrates

The selective reduction of one of the three carboxyl groups of two chiral citric acid derivatives to the corresponding aldehydes, under Rosenmund conditions, are reported together with the application of these aldehydes to the syntheses of the ester side chains of some potently antileukemic Cephalotaxus alkaloids e.g. anhydroharringtonine.

Formation of triple helical nanofibers using self-assembling chiral benzene-1,3,5-tricarboxamides and reversal of the nanostructure's handedness using mirror image building blocks

Intertwining triple helical nanofibers with an overall handedness have been formed from self-assembling chiral benzene-1,3,5-tricarboxamides 1, 2 and 3, whereas the achiralbenzene-1,3,5-tricarboxamide 4 upon self-association gives rise to straight nanofibers without any twist and transmission electron microscopy images of chiral compounds clearly demonstrate that the handedness of the triple helical nanofibers can be reversed by using the enantiomeric benzene-1,3,5-tricarboxamide building blocks.

Separation of Ba-137m from Cs-137 using new ion exchanger Na-2(H2O)(4)(H3O)[Al(OH)(6)Mo6O18]

A new polyoxometalate of chemical formula, Na-2(H2O)(4)(H3O)[Al(OH)(6)Mo6O18] (1) containing Anderson type large anion has been synthesized and characterized by single-crystal X-ray structure determination and IR spectroscopic studies. The crystal of 1 is triclinic, spacegroup P-1 with cell dimensions, a = 6.365(9) angstrom, b = 10.37(1) angstrom, c = 10.44(1) angstrom and alpha = 65.41(1), beta = 77.18(1), gamma = 86.58(1) and Z = 1. The compound 1 behaves as an ion exchanger and is stable in thermal, radiation and chemical environments. Radiochemical separation of the short-lived daughter Ba-137m (t(1/2) = 2.50 min) from its long-lived parent Cs-137 using this newly designed and synthesized ion exchanger has been developed.

Synthesis of enantiopure prolines via exo-stereoselective 1,3-dipolar cycloadditions to acetone-derived chiral stabilised azomethine ylides

The chiral stabilised azomethine ylide formed from condensation of the dimethyl acetal of acetone with (5S)-5-phenylmorpholinone undergoes stereoselective exo-cycloaddition reactions with a range of doubly and singly activated dipolarophiles when generated in the presence of excess (MgBr2OEt2)-O-.. The cycloadducts can be degraded to yield enantiomerically pure proline derivatives.