A Comparative Study of HBr-Ar and HBr-Cl<Subscript>2</Subscript> Plasma Chemistries for Dry Etch Applications

The effects of HBr/Ar and HBr/Cl₂ mixing ratios in the ranges of 0–100% Ar or Cl₂ on plasma parameters, densities of active species influencing the dry etch mechanisms were analyzed at fixed total gas flow rate of 40 sccm, total gas pressure of 6 mTorr, input power of 700 W and bias power of 300 W. The investigation combined plasma diagnostics by Langmuir probes and the 0-dimensional plasma modeling. It was found that the dilution of HBr by Ar results in maximum effect on the ion energy flux with expected impact on the etch rate in the ion-flux-limited etch regime, while the addition of Cl₂ influences mainly the relative fluxes of Br and Cl atoms on the etched surface with expected impact on the etch rate in the reaction-rate-limited etch regime.     

Efficient Olefin Epoxidation by Robust Re4 Cluster‐Supported MnIII Complexes with Peracids: Evidence of Simultaneous Operation of Multiple Active Oxidant Species,MnVO,MnIVO,and MnIII?OOC(O)R

Two new tetranuclear chalcocyanide cluster complexes, [{Mn(saloph)H₂O}₄Re₄Q₄(CN)₁₂]?4 CH₃OH? 8 H₂O (saloph=N,N′‐o‐phenylenebis(salicylidenaminato), Q=Se ( 1 ‐Se), Te ( 2 ‐Te)), have been synthesized by the diffusion of a methanolic solution of [PPh₄]₄[Re₄Q₄(CN)₁₂] into a methanolic solution of [Mn(saloph)]⁺. The structure of 2 ‐Te has been determined by X‐ray crystallography. These rhenium cluster‐supported [Mn^III(saloph)] complexes have been found to efficiently catalyze a wide range of olefin epoxidations under mild experimental conditions in the presence of meta‐chloroperbenzoic acid (mCPBA). Olefin epoxidation by these catalysts is proposed to involve the multiple active oxidants Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R. Evidence in support of this interpretation has been derived from reactivity and Hammett studies, H₂¹⁸O‐exchange experiments, and the use of peroxyphenylacetic acid as a mechanistic probe. Moreover, it has been observed that the participation of Mn^V?O, Mn^IV?O, and Mn^III? OOC(O)R can be controlled by changing the substrate concentration. This mechanism provides the greatest congruity with related oxidation reactions that employ certain Mn complexes as catalysts.     

Single step synthesis of propionitrile over K/MgO from acetonitrile methylation with methanol

A series of potassium-doped MgO catalysts loaded with KOH up to 15 mol% was prepared and evaluated for a single step synthesis of propionitrile from acetonitrile methylation with methanol. As the amount of potassium dope increased, both the acetonitrile conversion and the selectivity toward propionitrile increased. Based on the activity data coupled with CO₂-TPD and NH₃-IR ones, it was concluded that potassium doping to MgO resulted in the enhancement of both basicity and bifunctionality — methylation and hydrogenation.     

Stimuli sensitive polymers for drug delivery systems

Temperature sensitive and electric field sensitive hydrogels were prepared for use in modulated drug release systems. Crosslinked poly(N-isopropyl-acrylamide) and its networks, modified with hydrophobic components by copolymerization or by interpenetrating polymer networks (IPNs) formation, were utilized as temperature sensitive hydrogels. Indomethacin (a model solute)-release from polymer matrix and permeation through polymer membrane demonstrated “on-off” regulation with temperature fluctuation. This was the result of polymer surface properties rather than bulk swelling, as temperature was changed past the swelling transition temperature range of the polymer. The on-off regulation in an electric field was also obtained with a positively charged solute (Edrophonium chloride) release in distilled-deionized water from a matrix of crosslinked poly(2-acrylamido-2-methylpropanesulfonic acid-co-butyl methacrylate). This was attributed to the ion exchange between Edrophonium ion and protons produced at the anode. The swelling changes produced by local pH or ionic strength changes affected non-charged solute release.