Synthesis of O-unprotected glycosyl selenoureas. A new access to bicyclic sugar isoureas

β-d-Gluco and mannopyranosyl selenoureas have been prepared by coupling of the corresponding glycosylamines with phenyl isoselenocyanate in aqueous pyridine. Alkyl and aryl isoselenocyanates, and 1,4-phenylene diisoselenocyanate have been obtained from the corresponding formamides with an excess of triphosgene, black selenium and triethylamine. Treatment of the O-unprotected β-d-glucopyranosyl selenourea with aqueous oxygen peroxide afforded a 1,2-trans-fused bicyclic isourea.     

Equilibrium of the reaction between dissolved sodium sulfide and biologically produced sulfur

The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, K_x, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pK_x = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pK_x value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pK_x = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, K_x.     

A comparison of phototautomerism in different sites of free-base porphin (H2P) in n-alkane crystals

Selective laser-induced phototautomerism of free-base porphin in different n-alkanes (n-hexane, n-heptane, n-octane, nnonane, n-decane, n-undecane and n-dodecane) has been used to identify tautomer splittings in a number of sites in polycrystalline samples at 2 K. Pairs or lines arising from the two molecular orientations in each site can be reversibly transformed into each other. In the odd n-alkanes the occupation of different sites was not dependent on the rate at which the samples were frozen, but in the even n-alkanes metastable sites were only occupied following rapid quenching.     

Enantioselective oxidation of sulfides with hydrogen peroxide catalyzed by vanadium complex of sterically hindered chiral Schiff bases

Sterically hindered chiral Schiff base ligands 4a-d were prepared from an aldehyde derived from BINOL. The vanadium complexes of the ligands catalyze an efficient, enantioselective H₂O₂-promoted sulfoxidation of alkyl aryl sulfides, and enantioselectivities as high as 98-99% ee are observed in the sulfoxidation of benzyl aryl sulfides.     

Transference Numbers and Activity Coefficients of Some Alkali Metal Halide Solutions in Ethylene Glycol,Using Concentration Cells

Abstract

The reliability of the concentration cell method for determining cation transference numbers has been tested using solutions of LiCl, NaCl, KCl, NaBr and LiBr in ethylene glycol at 25°C. Concentrations in the range 0.0005 to 0.5 mol dm^?3 were used. Our transference numbers have been compared with those deduced from previous data on moving boundary and conductivity experiments. Good agreement between both sets of values has been found in most of the solutions, but significant discrepancies appear in the cases of NaBr and LiCl. The mean activity coefficients have been calculated from the EMF data and the transference numbers.     

Electrochemical investigations of stable cavitation from bubbles generated during reduction of water

Megasonic cleaning is traditionally used for removal of particles from wafer surfaces in semiconductor industry. With the advancement of technology node, the major challenge associated with megasonic cleaning is to be able to achieve high cleaning efficiency without causing damage to fragile features. In this paper, a method based on electrochemistry has been developed that allows controlled formation and growth of a hydrogen bubbles close to a solid surface immersed in an aqueous solution irradiated with ∼1 MHz sound field. It has been shown that significant microstreaming from resonating size bubble can be induced by proper choice of transducer duty cycle. This method has the potential to significantly improve the performance of megasonic cleaning technology through generation of local microstreaming, interfacial and pressure gradient forces in close vicinity of conductive surfaces on wafers without affecting the transient cavitation responsible for feature damage.     

Hydrogen dissociation on high-temperature tungsten

H₂ dissociation on polycrystalline tungsten is measured from 1700 to 3000 K using the filament temperature (T) change and a normalized H-atom density at the chamber surface. The dissociation probability per H₂ filament collision (P_diss) saturates at 0.40 at high T and has a 2.25 ± 0.05 eV apparent activation energy when P_diss ? 1. This activation energy is consistent with prior data and models, but the H₂ pressure dependence is not. P_diss is independent of the H₂ pressure for this entire T range and the 1-85 mTorr pressure range studied, contradicting the primary model that has been used to explain H₂ dissociation on tungsten and other metals. We show that some apparently contradictory prior measurements are actually consistent with our observations and with each other, once this pressure dependence of P_diss is recognized.     

Structural effects on water formation from coadsorbed H + O on Rh(100)

The effect of adsorbate coverage, adsorption sequence and temperature on the structure, composition and reactivity of coadsorbed layers, produced by dissociative adsorption of O₂ and H₂ at 200 K on a Rh(100) surface, has been studied by combined TPD, XPS and LEED measurements. The emphasis is on the impact of the structure and composition of the mixed O + H layers on the synthesis of hydroxyl and water as a result of the O + H surface reaction. The difference in the O 1s binding energies of adsorbed O (529.9 eV) and OH species (530.8 eV) was used as a fingerprint to monitor the formation of the OH species. The H₂O TPD spectra show substantial variations of the desorption temperature range and the amount of water evolved with coadsorbate coverage and structure: from 270 to 350 K and from 0 to 0.08 ML, respectively. It has been found that dense O + H adlayers, where the O coverage is in the range 0.25-0.4 ML, favor the formation of stable OH species. The maximum amount of stable hydroxyl OH species ( 0.16 ML) can be produced by heating of these dense adlayers to 260 K. This results in reordering of the adspecies to form a new O + OH − (2 × 6) structure, where hydroxyls react readily to evolve 0.08 ML of water in a sharp desorption peak at 280 K. The effect of the adlayer density and restructuring on the production of OH and H₂O is discussed.     

Organic contaminants removal by oxygen ECR plasma

Recently electron cyclotron resonance (ECR) plasma have been explored for wafer cleaning applications, since it is known to do less damage to silicon surface than conventional plasma. Organic contaminants removal efficiency and plasma radiation damage of the ECR plasma cleaning have been investigated. In oxygen ECR plasma cleaning, the plasma exposure time needed to remove the organic contaminants on the silicon surface down to the detection limit is 40 s, but the one to reach the lowest surface roughness is 10 s. The leakage current level of the MOS capacitor made using the Si substrate exposed to oxygen ECR plasma for 40 s is 8 × 10⁻⁹ A. The optimum exposure time determined by considering the contaminants removal efficiency and the plasma radiation damage (or the leakage current level) is 40 s. Organic contaminants seem to be removed through both sputter-off mechanism by oxygen ion bombardment and evaporation mechanism by chemical reactions with excited oxygen atoms.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.