Synthesis of substituted thiacrown ethers via a bromoalkoxylation reaction

A variety of alkyl- or phenyl-substituted thia-crown ethers were prepared in two or three steps via bromoalkoxylation reactions of olefins. Dialkyl- and phenyl-substituted mono-and dithia-crown ethers were obtained as single compounds, whereas monoalkyl-substituted derivatives were a mixture of two positional isomers reflecting the isomeric mixture formation in the bromoalkoxylation reaction.     

Properties of reactively sputtered Mo1−x O x films

Molybdenum oxide (Mo_1–xO_x) films were prepared by reactive rf sputtering of a Mo target in O₂/Ar plasma. The dependence of film properties on various sputtering parameters is investigated. The atomic percentage of oxygen (x) in the Mo_1–xO_x films decreases with sputtering power and increases with the partial pressure of oxygen. Mo_1–xO_x films that exhibit metallic conductivities can be obtained over a wide range of sputtering conditions. The intrinsic film stress of conducting Mo_1–xO_x is compressive. Such M_1–xO_x films were shown by backscattering spectrometry to be excellent diffusion barriers between Al and Si up to 600 °C annealing for 30 min.     

Low-Reynolds-number modelling of flows over a backward-facing step

The complex turbulent flow behind a backward-facing step is modelled using a full Reynolds stress closure. In order to develop a closure model that can resolve the complex near-wall flow in the recirculation region and in the recovery region downstream of the reattachment point, the performance of a low and a high Reynolds number version of the full Reynolds stress closure is examined and compared. Furthermore, the effects of redistribution modelling on the calculated flow is studied by comparing the performance of three redistribution models: one return-to-isotropy model and two with mean-strain effects. The results are grid independent and show that the flow downstream of the step is best described by a low-Reynolds-number model that does not depend on the conventional wall function assumption. However, the skin friction behavior is correctly predicted by the stipulation of a wall function. Of the three redistribution models examined, the return-to-isotropy model gives results that are in excellent agreement with measurements. Finally, the calculated results are adversely affected by refining the redistribution models to include meanstrain effects.     

A probable hydrogen-bonded Meisenheimer complex: an unusually high S(N)Ar reactivity of nitroaniline derivatives with hydroxide ion in aqueous media

Observations show that nitroanilines exhibit an unusually high S(N)Ar reactivity with OH(-) in aqueous media in reactions that produce nitrophenols. S(N)Ar reaction of 4-nitroaniline (2a) in aqueous NaOH for 16 h yields 4-nitrophenol (4a) quantitatively, whereas a similar reaction of 4-nitrochlorobenzene (1a) gave 4a in 2% yield together with recovered 1a in 97%, suggesting that the leaving ability of the NH(2) group far surpasses that of Cl under these conditions. An essential feature of S(N)Ar reactions of nitroanilines is probably that the NH(2) leaving group participates in a hydrogen-bonding interaction with H(2)O. Density functional theory (DFT) calculations for a set of 4-nitroaniline, OH(-), and H(2)O suggest a possible formation of a Meisenheimer complex stabilized by hydrogen-bonding interactions and a six-membered ring structure. The results obtained here contrast with conventional S(N)Ar reactivity profiles in which nitroanilines are nearly unreactive with nucleophiles in organic solvents.     

A novel pH-responsive polysaccharidic ionic complex for proapoptotic D-(KLAKLAK)2 peptide delivery

We report charge-switching ionic nanocomplexes comprised of glycol chitosan grafted with 2,3-dimethylmaleic acid (DMA) (denoted as 'GCS-g-DMA' hereafter) and a proapoptotic peptide. This system allowed for improved peptide delivery to tumor sites via a mechanism of selective peptide release when the pH was dropped from 7.4 to 6.8.     

Efficient and stable panchromatic squaraine dyes for dye-sensitized solar cells

A new series of stable, unsymmetrical squaraine near-IR sensitizers (JK-216 and JK-217), which are assembled using both thiophenyl pyrrolyl and indolium groups, exhibit a panchromatic light harvesting up to 780 nm. The JK-216 based cell exhibited a record efficiency of 6.29% for near-IR DSSCs. In addition, the JK-217 device showed an excellent stability under a light soaking test at 60 °C for 1000 h.