Synthesis, structure, and dynamics of nickelacarboranes incorporating the [nido-7,9-C(2)B(9)H(11)](2)(-) ligand

The nickelacarboranes [NEt(4)][2-(eta(3)-C(3)H(4)R)-closo-2,1,7-NiC(2)B(9)H(11)] (R = H (1a), Ph (1b)) have been synthesized via reaction between [Na](2)[nido-7,9-C(2)B(9)H(11)] and [Ni(2)(micro-Br)(2)(eta(3)-C(3)H(4)R)(2)] in THF (THF = tetrahydrofuran), followed by addition of [NEt(4)]Cl. Protonation of 1a in the presence of a donor ligand L affords the complexes [2,2-L(2)-closo-2,1,7-NiC(2)B(9)H(11)] (L = CO (2), CNBu(t) (3)). Addition of PEt(3) (1 equiv) to 2 produces quantitative conversion to [2-CO-2-PEt(3)-closo-2,1,7-NiC(2)B(9)H(11)], 4. Species 2-4 exhibit in solution hindered rotation of the NiL(2) fragment with respect to the eta(5)-C(2)B(9) cage unit. Protonation of 1a in the presence of a diene affords the neutral complexes [2-(eta(2):eta(2)-diene)-closo-2,1,7-NiC(2)B(9)H(11)] (diene = C(5)Me(5)H (5), dcp (6), cod (7), nbd (8), chd (9), and cot (10a); dcp = dicyclopentadiene, cod = 1,5-cyclooctadiene, nbd = norbornadiene, chd = 1,3-cyclohexadiene, and cot = cyclooctatetraene). Variable temperature (1)H NMR experiments show that the [Ni(diene)] fragments are freely rotating even at 193 K. A small quantity of the di-cage species [2,2'-micro-(1,2:5,6-eta-3,4:7,8-eta-cot)-(closo-2,1,7-NiC(2)B(9)H(11))(2)] (10b) is formed as a coproduct in the synthesis of 10a. This species can be rationally synthesized by protonation of 1a and subsequent addition of 10a.     

One-pot synthesis of 3-arylaminomaleimides from terminal alkynes and isocyanates

The reaction of aryl acetylide anions with phenyl isocyanate and subsequent addition of a protonating agent such as ethanol affords good yields of 3-aminomaleimides, formed by the cyclization of one molecule of alkyne with two isocyanates. When the reaction is quenched with water instead, cyclopentadienone imines are formed as the major products.     

All-optical switching in silicon photonic crystal waveguides by use of the plasma dispersion effect

Silicon photonic crystals offer new ways of controlling the propagation of light as well as new tools for the realization of high-density optical integration on monolithic substrates. However, silicon does not possess the strong nonlinearities that are commonly used in the dynamic control of optical devices. Such dynamic control is nevertheless essential if silicon is to provide the higher levels of functionality that are required for optical integration. We demonstrate that the combination of the refractive index change caused by the presence of photoexcited carriers, or so-called plasma dispersion, and photonic crystal properties such as photonic bandgaps, constitutes a powerful tool for active control of light in silicon integrated devices. We show close to 100% modulation depth near the photonic crystal band edge.     

High-throughput manual parallel synthesis using SynPhase crowns and lanterns

The high-throughput manual solid-phase parallel synthesis of libraries comprising thousands of discrete samples using pellicular supports (i.e. SynPhase crowns and lanterns) and a suite of novel tools and techniques is described. Key aspects of this approach include the combination of a split-split-split synthesis strategy with spatial encoding to differentiate thousands of crowns, the rapid washing and filtration of up to 48 reaction vessels in parallel, the application of an inexpensive and environmentally friendly technique to remove trifluoroacetic acid from sixteen 96-well plates in parallel, and a high-throughput method for removing cleaved crowns from reusable pin racks. Tens of thousands of discrete samples have been produced in-house using this conceptually and operationally straightforward strategy.     

The analyses of alkyllead compounds in fish and environmental samples in Ontario,Canada (1981–1987)

Analyses of fish and other environmental samples (clams, macrophytes, sediments and waters) from areas upstream and downstream from two alkyllead manufactures beside the St Lawrence and St Clair Rivers, Ontario, show a clear indication of elevated alkyllead levels in samples near the industries. Most species of fish contained alkyllead compounds with tetraethyllead and triethyllead as the predominant forms. Most fish from the contaminated areas contained 50–75% of total lead as alkylleads. Carp, yellow perch and white sucker were generally the most contaminated species while pike, alewife and rock bass were the least contaminated. Average alkyllead levels varied from year to year but declined steadily after 1981. For example, the geometric mean of alkyllead compounds in carp from the St Lawrence River decreased from 4207 μg kg^?1 in 1981 to 2000 μg kg^?1 in 1982 and to 49 μg kg^?1 in 1987, reflecting the reduction of alkylleads in the effluents and the closure of one of the manufactures in 1985. Alkyllead levels were consistently lower in muscle and carcass samples in comparison with whole fish containing fatty intestines. However, muscle levels were generally equal to carcass levels. The concentrations of alkyllead compounds were generally low in clams, macrophytes, sediments and waters except from the immediate vicinity of the manufactures' final effluent discharges.     

Shock-bubble interactions : Generation and evolution of vorticity in two-dimensional supersonic flows

We present high resolution simulations with the PPM code of shock-bubble interactions coresponding to the recent Haas-Sturtevant experiments. VCR cinemas show and diagnostic interpretations quantify the variety of shock-vortex interactions     

Visualization of turbulent spots and unsteady wake-induced boundary-layer transition with thermochromic liquid crystals

A method of using thermochromic liquid crystals has been developed to visualize the thermal footprints of turbulent spots convecting downstream in an otherwise laminar boundary layer over a heated surface. This technique has been employed to visualize the development of turbulent spots under the influence of adverse pressure gradients. It has also been used to visualize the transitional events that occur during unsteady wake-induced boundary layer transition typically of those occurring in multi-stage turbomachines. The results show that liquid crystal is not only capable of providing quantitative information about the growth and development of individual spots but also allows a detailed study of formation of turbulent spots occurring naturally during a complicated transition process.