A theoretical study of configurational inversion of 1,1′-binaphthyl by molecular mechanics

The molecular mechanics method has been applied to the study of various pathways and transition states for the configurational inversion of 1,1′-binaphthyl. The preferred pathway is found to be one on the anti (“trans”) side involving one point of H?H nonbonded contact in each of two identical transition states, separated by a very shallow minimum. Very satisfactory agreement with available experimental values for the enthalpy of activation is achieved.     

A simple green procedure for the synthesis of 2H-azirines

An efficient and environmentally friendly method preparing 2H-azirines in good yield has been achieved by microwave irradiation of vinyl azides in solvent free conditions.     

Importance of dynamic surface tension to the residual water content of fabrics

At the end of the final spin cycle of the laundry process, the residual moisture content (RMC) of fabric is directly related to the dynamic surface tension of the residual water in the fabric. The LaPlace equation for capillary rise predicts that the capillary rise of solutions in a capillary is proportional to the surface tension at the air-liquid interface. If fabric can be considered to be a large ensemble of capillaries due to interfiber spacing, then the RMC of fabrics will be directly related to the surface tension of residual solution in the fabric. The use of a tailored rinse additive has the potential to decrease the surface tension of solution significantly, thus leading to a decrease in the residual water content of the fabric. It is expected that as the surfactant concentration increases the surface tension decreases. Hence, the RMC of fabrics must decrease with increasing surfactant concentration. However, a peak is observed in the RMC of fabrics before the critical micelle concentration (CMC) is reached. Prior to the CMC, it is proposed that a sudden adsorption of surfactant is occurring on the fabric surface leading to a decrease in bulk monomer concentration. The decrease in free monomer concentration should result in an increase in the equilibrium surface tension of the residual solution leading to a concomitant increase in RMC. Because the dynamic surface tension is measured on a short time scale (on the order of milliseconds), there will be less adsorption of monomer onto the newly created air-liquid interface of the bubbles during the measurement process. This decrease in adsorption should lead to a pronounced increase in the dynamic surface tension. This indeed was observed. The RMC correlates very well with the dynamic surface tension of the residual solution.     

Solid products from thermal decomposition of polyethylene terephthalate: Investigation by CP/MAS 13C-NMR and fourier transform-IR spectroscopy

The solid reaction products from pyrolysis of polyethylene terephthalate in the presence and absence of red phosphorus were characterized by CP/MAS ¹³C-NMR, FR-IR, and MAS ³¹P-NMR spectroscopy. Over the temperature range of 300–400°C, polyethylene terephthalate was converted in a sealed vial to a highly crosslinked polymer of terephthalic acid. Pyrolysis in the presence of red phosphorus, which functions as a flame retardant by increasing the amount of char, yielded an intractible polyaromatic phosphate ester. After thermal cleavage of polyethylene terephthalate with formation of free carboxyl and vinyl ester groups, there are two competing reaction pathways. The smaller molecular weight fragments may enter the vapor phase where they undergo further degradation primarily to CO₂, CO, and acetaldehyde, as described by others. However, if volatilization of the oligomeric fragments is inhibited, an alternate reaction pathway gives rise to the formation of highly crosslinked char. Red phosphorus decreases the volatility of the oligomeric fragments by converting them to phosphates and thereby enhances char formation.     

Olefin oxygenation by the hydroperoxide adduct of a nonheme manganese(IV) complex: epoxidations by a metallo-peracid produces gentle selective oxidations

The reactive intermediates and mechanisms of oxygenation of olefins by manganese complexes were investigated by treating olefins with newly synthesized [MnIV(Me2EBC)(OH)2](PF6)2 in the presence and absence of peroxide and by studying its catalytic epoxidation reaction in normal aqueous solution and, individually, with isotopically labeled H218O, 18O2, and H218O2. The manganese oxo species is not the reactive intermediate for the oxygen transfer process mediated by this manganese complex. A novel manganese(IV) peroxide intermediate, MnIV(Me2EBC)(O)(OOH)+, was captured by mass spectrometry and is proposed as the intermediate that oxygenates olefins in this catalytic system.     

Effects of alloying on the chemistry of CO and H2S on Fe surfaces

Deleterious gases such as CO and H(2)S can cause degradation of steel by reacting with the metal surface. Here we consider whether alloying the steel surface might be able to inhibit these damaging surface reactions by raising the barriers to molecular dissociation. We employ first-principles density functional theory techniques to investigate the elementary reaction pathways and barriers for CO and H(2)S on FeAl and Fe(3)Si surfaces and compare them with pure Fe surfaces (as a model for steel). We find that H(2)S dissociates on iron surfaces much more easily than CO does. Although FeAl surfaces raise the barriers for H(2)S dissociation, they significantly lower the barriers for CO dissociation. On the other hand, Fe(3)Si surfaces raise the barriers for CO dissociation, but they are as vulnerable as Fe surfaces to H(2)S dissociation. Our findings suggest that alloying iron with Al or Si is unlikely to simultaneously increase its resistance to the initial stages of chemical degradation by CO and H(2)S.