Dimensionally and thermally stable polymer,containing disordered graphitic structure and adamantane

In an attempt to develop a low‐k interlayer dielectric, adamantane‐diphenyldiethynyl moiety containing oligomer is prepared. Oligomerization of 1,3,5,7‐tetrakis[3/4‐ethynylphenyl]adamantane ( 4 ) is accomplished by a Glaser–Hay oxidative coupling with 1,3,5‐triethynylbenzene and phenylacetylene end‐capping agent. The CHCl₃ soluble oligomer is then thermally treated by step‐curing at 200, 300, 380, and 450 °C for 30 min at each temperature under nitrogen flow to render a shiny void‐free black polymer. TGA analysis indicates that the polymer is stable under nitrogen up to 500 °C with a marginal decomposition up to 800 °C. Solid‐state ¹³C NMR, Raman scattering, and FTIR are used to characterize the structure of the polymer. The polymer consists of amorphous carbon networks with the adamantane moieties and nanosized graphitic regions (clusters), which are generated from the thermal crosslinking of the diphenyldiethynyl units. It shows a remarkably low linear coefficient of thermal expansion (～25 ppm/°C), presumably due to the presence of the disordered graphitic structure. Its high density (～1.21 g/cm³), refractive index (～1.80 at 632 nm), and Young's modulus (～17.0 GPa) are also consistent with the interpretation. This study reveals important details about the effect of microscopic structure on the macroscopic properties of the highly crosslinked polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6909–6925, 2006     

Spin relaxation of conduction electrons in GaAs

We have used optical spin orientation techniques to measure T₁ of conduction electrons in GaAs (NinA ≈ 10¹⁷ cm^-3) for 4.7 K ? T ? 200 K. From Hall effect measurements we estimated the electron momentum relaxation time τ_p. For 50 K ? T ? 200 K, the product T₁τ_p agrees with our earlier order of magnitude estimate of the D'yakonov-Perel' mechanism, in which band structure induced precession is strongly narrowed by momentum relaxation. The Elliott mechanism is one to two orders of magnitude weaker.     

Coordinated control of distribution supply chains in the presence of fuzzy customer demand

This paper considers a single product inventory control in a Distribution Supply Chain (DSC). The DSC operates in the presence of uncertainty in customer demands. The demands are described by imprecise linguistic expressions that are modelled by discrete fuzzy sets. Inventories at each facility within the DSC are replenished by applying periodic review policies with optimal order up-to-quantities. Fuzzy customer demands imply fuzziness in inventory positions at the end of review intervals and in incurred relevant costs per unit time interval. The determination of the minimum of defuzzified total cost of the DSC is a complex problem which is solved by applying decomposition; the original problem is decomposed into a number of simpler independent optimisation subproblems, where each retailer and the warehouse determine their optimum periodic reviews and order up-to-quantities. An iterative coordination mechanism is proposed for changing the review periods and order up-to-quantities for each retailer and the warehouse in such a way that all parties within the DSC are satisfied with respect to total incurred costs per unit time interval. Coordination is performed by introducing fuzzy constraints on review periods and fuzzy tolerances on retailers and warehouse costs in local optimisation subproblems.     

Bioconjugation of ultrabright semiconducting polymer dots for specific cellular targeting

Semiconducting polymer dots (Pdots) represent a new class of ultrabright fluorescent probes for biological imaging. They exhibit several important characteristics for experimentally demanding in vitro and in vivo fluorescence studies, such as their high brightness, fast emission rate, excellent photostability, nonblinking, and nontoxic feature. However, controlling the surface chemistry and bioconjugation of Pdots has been a challenging problem that prevented their widespread applications in biological studies. Here, we report a facile yet powerful conjugation method that overcomes this challenge. Our strategy for Pdot functionalization is based on entrapping heterogeneous polymer chains into a single dot, driven by hydrophobic interactions during nanoparticle formation. A small amount of amphiphilic polymer bearing functional groups is co-condensed with the majority of semiconducting polymers to modify and functionalize the nanoparticle surface for subsequent covalent conjugation to biomolecules, such as streptavidin and immunoglobulin G (IgG). The Pdot bioconjugates can effectively and specifically label cellular targets, such as cell surface marker in human breast cancer cells, without any detectable nonspecific binding. Single-particle imaging, cellular imaging, and flow cytometry experiments indicate a much higher fluorescence brightness of Pdots compared to those of Alexa dye and quantum dot probes. The successful bioconjugation of these ultrabright nanoparticles presents a novel opportunity to apply versatile semiconducting polymers to various fluorescence measurements in modern biology and biomedicine.     

Parametric resonance of optically trapped aerosols

The Brownian dynamics of an optically trapped water droplet are investigated across the transition from over- to underdamped oscillations. The spectrum of position fluctuations evolves from a Lorentzian shape typical of overdamped systems (beads in liquid solvents) to a damped harmonic oscillator spectrum showing a resonance peak. In this later underdamped regime, we excite parametric resonance by periodically modulating the trapping power at twice the resonant frequency. The power spectra of position fluctuations are in excellent agreement with the obtained analytical solutions of a parametrically modulated Langevin equation.     

Systematic investigation of droplet generation at T-junctions

Droplet microfluidics has attracted much attention in recent years. For many droplet-based applications, researchers want to predict the size of the droplets in a certain experimental condition. To meet this need, van Steijn and colleagues proposed an elegant theoretical model that predicts the volume of droplets generated in a common channel configuration for forming a steady-state, continuous stream of droplets, the T-junction geometry. To determine the accuracy of this model in predicting droplet volume, we performed a systematic experimental study over two orders of magnitude in capillary number. We found that this model, albeit elegant, has a limited range of interfacial tension over which it can predict accurately the droplet volume. Our experimental results, together with fluid dynamic simulations, allowed us to highlight the importance of physical fluid properties when employing theoretical models.     

DYNGA: a general purpose QM-MM-MD program. I. Application to water

We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields.