Sulfur heterocycles. I. Use of 4,4-dimethyl-1,3-oxathiolane-3,3-dioxide as a carbonyl anion equivalent

The title heterocycle is used as a carbonyl anion equivalent in the preparation of aldehydes and α-silyl ketones; the key step is the thermal demasking of the heterocycle by loss of isobutylene and sulfur dioxide.     

The crystalline core of the row structures in isotactic polystyrene. I. Nucleation and growth

The nucleation and growth of the crystalline core in the row structures of isotactic polystyrene were investigated by transmission electron microscopy. The number of core crystals, nucleated at a specific temperature, depends on the external strain. Their length was found to increase with time if the sample is kept at the straining temperature. If a strained sample is cooled to room temperature and subsequently reheated, no further growth of the core crystals is observed. Obstacles in the path of growth were circumvented by local changes of the growing direction. Melt-soluble noncrystallizable molecules are rejected by the growing core into the surrounding melt. The observations suggest a growth mechanism of the cores based on the successive self-induced alignment of molecules at the tip of the growing cores.     

Coal Handleability — A good or a bad coal?

The avalanching behaviour of two coal types was determined, one of good and the other of poor handleability characteristics. This revealed significant differences in the nature of flow of the coals. Analysis of the strange attractors of the weight series of avalanches enabled quanitification of this difference, and the establishment of practical, relative criteria for the measurement of coal handleability. These criteria will now enable a structured study of the variables that affect handleability, for example proportion of fines and moisture content, and industrial consumers of coal to specify minimum acceptable limits for its transport characteristics.     

Viscous scattering of a pressure wave: calculation of the fluid tractions on a biomimetic acoustic velocity sensor

In the paper we give a method for calculating the tractions (local forces) of the fluid motion determined by an incoming plane pressure wave on an artificial hair cell transducer structure. The sensing element of the transducer is a standing high aspect ratio cilium in the shape of a narrow thin curved beam (tape-like), which can be easily fabricated in micro-/nanotechnology. The method is based on considering the system of partial differential equations describing the motion of the compressible viscous fluid in an acoustic linearized approximation, and representation of the velocity field as a viscous acoustic single-layer potential. The boundary conditions, stating the cancellation of the velocity components on the solid beam, yield a two-dimensional (2-D) system of three integral equations over the beam's surface for the traction components. In the case of a narrow cilium, the system of integral equations furnishes a system of two 1-D integral equations over the symmetry curve of the structure for obtaining the tangential and normal components of the traction. This system is solved numerically by a finite (boundary) element method. The numerical code written for solving the problem was applied to some particular structures. The last structure is similar to the trichobothrium of a spider Cupiennius salei. The results obtained show that the curvature of the hair is enhancing sensitivity to flows directed normal to the main shaft of the hair confirming the assertion of Barth et al. [Philos. Trans. R. Soc. London, Ser. B 340, 445-461 (1993)].     

An optically driven pump for microfluidics

We demonstrate a method for generating flow within a microfluidic channel using an optically driven pump. The pump consists of two counter rotating birefringent vaterite particles trapped within a microfluidic channel and driven using optical tweezers. The transfer of spin angular momentum from a circularly polarised laser beam rotates the particles at up to 10 Hz. We show that the pump is able to displace fluid in microchannels, with flow rates of up to 200 microm(3) s(-1) (200 fL s(-1)). The direction of fluid pumping can be reversed by altering the sense of the rotation of the vaterite beads. We also incorporate a novel optical sensing method, based upon an additional probe particle, trapped within separate optical tweezers, enabling us to map the magnitude and direction of fluid flow within the channel. The techniques described in the paper have potential to be extended to drive an integrated lab-on-chip device, where pumping, flow measurement and optical sensing could all be achieved by structuring a single laser beam.     

Growth of polymer crystals during annealing

Observations by transmission electron microscopy are reported on the processes involved in polymer crystal growth during annealing. The observations suggest that crystal growth occurs by two processes. One process involves the melting of those regions of the crystals in which the melting point is lower than the annealing temperature. The polymer melt due to the melting process gradually becomes incorporated into the unmolten crystals, resulting in crystal growth. The alternative process is solid-state crystal growth by the migration of the amorphous region between crystallites.     

Parallel distributed-memory simplex for large-scale stochastic LP problems

We present a parallelization of the revised simplex method for large extensive forms of two-stage stochastic linear programming (LP) problems. These problems have been considered too large to solve with the simplex method; instead, decomposition approaches based on Benders decomposition or, more recently, interior-point methods are generally used. However, these approaches do not provide optimal basic solutions, which allow for efficient hot-starts (e.g., in a branch-and-bound context) and can provide important sensitivity information. Our approach exploits the dual block-angular structure of these problems inside the linear algebra of the revised simplex method in a manner suitable for high-performance distributed-memory clusters or supercomputers. While this paper focuses on stochastic LPs, the work is applicable to all problems with a dual block-angular structure. Our implementation is competitive in serial with highly efficient sparsity-exploiting simplex codes and achieves significant relative speed-ups when run in parallel. Additionally, very large problems with hundreds of millions of variables have been successfully solved to optimality. This is the largest-scale parallel sparsity-exploiting revised simplex implementation that has been developed to date and the first truly distributed solver. It is built on novel analysis of the linear algebra for dual block-angular LP problems when solved by using the revised simplex method and a novel parallel scheme for applying product-form updates.     

Optimisation of a key cross-coupling reaction towards the synthesis of a promising antileishmanial compound

During the course of a research program aimed at identifying novel antileishmanial compounds, a multi-gram synthesis of N-(trans-4-((4-methoxy-3-((R)-3-methylmorpholino)-1H-pyrazolo[3,4-d]pyrimidin-6-yl)amino)cyclohexyl)-2-methylpropane-1-sulfonamide ((R)-1) was required. This letter describes optimisation of the reaction conditions and protecting group strategy for a key Buchwald-Hartwig coupling, delivering the required quantities of (R)-1, as well as further compounds in the series.     

Polarization singularities in 2D and 3D speckle fields

The 3D structure of randomly polarized light fields is exemplified by its polarization singularities: lines along which the polarization is purely circular (C lines) and surfaces on which the polarization is linear (L surfaces). We visualize these polarization singularities experimentally in vector laser speckle fields, and in numerical simulations of random wave superpositions. Our results confirm previous analytical predictions [M. R. Dennis, Opt. Commun. 213, 201 (2002)] regarding the statistical distribution of types of C points and relate their 2D properties to their 3D structure.