Near-infrared spectroscopy of PKS 1549-79: a protoquasar revealed?

We present a near-infrared (near-IR) spectrum of the nearby radio galaxy PKS 1549-79 (z = 0.153). These data were taken with the aim of testing the idea that this object contains a quasar nucleus that is moderately extinguished, despite evidence that its radio jet points close to our line of sight. We detect broad Paalpha emission (FWHM 1745 +/- 40 km s(-1)), relatively bright continuum emission, and a continuum slope consistent with a reddened quasar spectrum (3.1 <A(V) <7.3), all emitted by an unresolved point source. Therefore we conclude that we have, indeed, detected a hidden quasar nucleus in PKS 1549-79. Combined with previous results, these observations are consistent with the idea that PKS 1549-79 is a young radio source in which the cocoon of debris left over from the triggering events has not yet been swept aside by circumnuclear outflows.

Porphyrin and tetrabenzoporphyrin dendrimers: Tunable membrane-impermeable fluorescent pH nanosensors

The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended pi-conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar4TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar4P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar(4)Ps and Ar(4)TBPs become water soluble and can serve as pH indicators, with pKs adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H2P-Glu(4)OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H2TBP-Nw(1)OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pKs of the encapsulated porphyrins (pK(H2P-Glu)(OH)(4) = 6.2 and pK(H2TBP)-Nw(1)OH = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.

Synthesis and characterization of amphiphilic star copolymers of 2-(dimethylamino) ethyl methacrylate and methyl methacrylate: Effects of architecture and composition

Six amphiphilic star copolymers comprising hydrophilic units of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic units of methyl methacrylate (MMA) were prepared by the sequential group transfer polymerization (GTP) of the two comonomers and ethylene glycol dimethacrylate (EGDMA) cross-linker. Four star-block copolymers of different compositions, one miktoarm star, and one statistical copolymer star were synthesized. The molecular weights (MWs) and MW distributions of all the star copolymers and their linear homopolymer and copolymer precursors were characterized by gel permeation chromatography (GPC), while the compositions of the stars were determined by proton nuclear magnetic resonance (H-1 NMR) spectroscopy. Tetrahydrofuran (THF) solutions of all the star copolymers were characterized by static light scattering to determine the absolute weight-average MW ((M) over bar (w)) and the number of arms of the stars. The R, of the stars ranged between 359,000 and 565,000 g mol(-1), while their number of arms ranged between 39 and 120. The star copolymers were soluble in acidic water at pH 4 giving transparent or slightly opaque solutions, with the exception of the very hydrophobic DMAEMA(10)-b-MMA(30)-star, which gave a very opaque solution. Only the random copolymer star was completely dispersed in neutral water, giving a very opaque solution. The effective pKs of the copolymer stars were determined by hydrogen ion titration and were found to be in the range 6.5-7.6. The pHs of precipitation of the star copolymer solutions/dispersions were found to be between 8.8-10.1, except for the most hydrophobic DMA-EMA(10)-b-MMA(30)-Star, which gave a very opaque solution over the whole pH range. (c) 2006 Elsevier Ltd. All rights reserved.

Process simulation of co-firing torrefied biomass in a 220 MWe coal-fired power plant

Torrefaction based co-firing in a pulverized coal boiler has been proposed for large percentage of biomass co-firing. A 220 MWe pulverized coal-power plant is simulated using Aspen Plus for full understanding the impacts of an additional torrefaction unit on the efficiency of the whole power plant, the studied process includes biomass drying, biomass torrefaction, mill systems, biomass/coal devolatilization and combustion, heat exchanges and power generation. Palm kernel shells (PKS) were torrefied at same residence time but 4 different temperatures, to prepare 4 torrefied biomasses with different degrees of torrefaction. During biomass torrefaction processes, the mass loss properties and released gaseous components have been studied. In addition, process simulations at varying torrefaction degrees and biomass co-firing ratios have been carried out to understand the properties of CO₂ emission and electricity efficiency in the studied torrefaction based co-firing power plant. According to the experimental results, the mole fractions of CO ₂ and CO account for 69-91% and 4-27% in torrefied gases. The predicted results also showed that the electrical efficiency reduced when increasing either torrefaction temperature or substitution ratio of biomass. A deep torrefaction may not be recommended, because the power saved from biomass grinding is less than the heat consumed by the extra torrefaction process, depending on the heat sources. 

Chiral dienamides-substrates for asymmetric synthesis of amido cyclohexenes

Chiral dienamides, derived from chiral amines and oxazolidinones, react with electron deficient dienophiles Eo give amino-cyclohexanes with good to excellent de's.