Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

Enhanced Photoelectrochemistry in CdS/Au Nanoparticle Bilayers

Three different configurations of Au‐nanoparticle/CdS‐nanoparticle arrays are organized on Au/quartz electrodes for enhanced photocurrent generation. In one configuration, Au‐nanoparticles are covalently linked to the electrode and the CdS‐nanoparticles are covalently linked to the bare Au‐nanoparticle assembly. The resulting photocurrent, φ = 7.5 %, is ca. 9‐fold higher than the photocurrent originating from a CdS‐nanoparticle layer that lacks the Au‐nanoparticles, φ = 0.8 %. The enhanced photocurrent in the Au/CdS nanoparticle array is attributed to effective charge separation of the electron–hole pair by the injection of conduction‐band electrons from the CdS‐ to the Au‐nanoparticles. Two other configurations involving electrostatically stabilized bipyridinium‐crosslinked Au/CdS or CdS/Au nanoparticle arrays were assembled on the Au/quartz crystal. The photocurrent quantum yields in the two systems are φ = 10 % and φ = 5 %, respectively. The photocurrents in control systems that include electrostatically bridged Au/CdS or CdS/Au nanoparticles by oligocationic units that lack electron‐acceptor units are substantially lower than the values observed in the analogous bipyridinium‐bridged systems. The enhanced photocurrents in the bipyridinium‐crosslinked systems is attributed to the stepwise electron transfer of conduction‐band electrons to the Au‐nanoparticles by the bipyridinium relay bridge, a process that stabilizes the electron–hole pair against recombination and leads to effective charge separation.     

Development of a Continuous Segmented Flow Tubular Reactor and the “Scale‐out” Concept – In Search of Perfect Powders

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.     

Panchromatic Chromophore Mixtures in an AlPO4‐5 Molecular Sieve: Spatial Separation Effects and Energy Transfer Cascades

Dye‐loaded AlPO₄‐5 single crystals were prepared by microwave‐assisted hydrothermal synthesis from a batch, containing a mixture of three chromophores (Coumarin 40, Rhodamine BE50, and Oxazine 1) differing in their absorption range, molecular dimensions, and solubilities. Confocal fluorescence images reveal a spatial separation effect of the dye molecules, where the slimmer, more‐soluble dye molecule (Coumarin 40) is uniformly distributed in the body of the single crystal, and the bulky and/or less‐soluble ones (Rhodamine BE50, Oxazine 1) are situated in distinct domains. Visible spectra show good panchromatic absorption of visible light. Fluorescence lifetime measurements indicate the presence of an energy transfer cascade of the entirely fixed dye molecules from Coumarin 40 to Oxazine 1. The transfer mechanism is predominantly radiative.     

D-AKAP2, a novel protein kinase A anchoring protein with a putative RGS domain

Subcellular localization directed by specific A kinase anchoring proteins (AKAPs) is a mechanism for compartmentalization of cAMP-dependent protein kinase (PKA). Using a two-hybrid screen, a novel AKAP was isolated. Because it interacts with both the type I and type II regulatory subunits, it was defined as a dual specific AKAP or D-AKAP1. Here we report the cloning and characterization of another novel cDNA isolated from that screen. This new member of the D-AKAP family, D-AKAP2, also binds both types of regulatory subunits. A message of 5 kb pairs was detected for D-AKAP2 in all embryonic stages and in all adult tissues tested. In brain, skeletal muscle, kidney, and testis, a 10-kb mRNA was identified. In testis, several small mRNAs were observed. Therefore, D-AKAP2 represents a novel family of proteins. cDNA cloning from a mouse testis library identified the full length D-AKAP2. It is composed of 372 amino acids which includes the R binding fragment, residues 333-372, at its C-terminus. Based on coprecipitation assays, the R binding domain interacts with the N-terminal dimerization domain of RIalpha and RIIalpha. A putative RGS domain was identified near the N-terminal region of D-AKAP2. The presence of this domain raises the intriguing possibility that D-AKAP2 may interact with a Galpha protein thus providing a link between the signaling machinery at the plasma membrane and the downstream kinase.     

Filter matrix estimation in automated DNA sequencing

In four-color fluorescence-based automated DNA sequencing, a 4×4 filter matrix parameterizes the relationship between the dye-intensity signals of interest and the data collected by an optical imaging system. The filter matrix is important because the estimated DNA sequence is based on the dye intensities that can only be recovered via inversion of the matrix. Here, the authors present a calibration method for the estimation of the columns of this matrix, using data generated through a special experiment in which DNA samples are labeled with only one fluorescent dye at a time. Simulations and applications of the method to real data are provided, with promising results     

Evaluation of a compound probability model with tower-mountedscatterometer data

Six months of data from the YSCAT94 experiment conducted at the CCIW WAVES research platform on Lake Ontario, Canada, are analyzed to evaluate a compound probability model. YSCAT was an ultrawideband small footprint (≈1 m) microwave scatterometer that operated at frequencies of 2-18 GHz, incidence angles from 0° to 60°, both h-pol and v-pol, and which tracked the wind using simultaneous weather measurements. The probability distribution function of the measured instantaneous backscattered amplitude (p(a)) is compared to theoretical distributions developed from-the composite model and a simple wave spectrum. Model parameters of the resulting Rayleigh/generalized lognormal distribution probability density function (pdf) (C, a₁ , and a₂) are derived directly from the data and are found to demonstrate relationships with wind speed, incidence angle, and radar frequency