Ligand-exchange chemistry of Cr13-polyacrylamide gels

Evidence that ligand-induced de-gelation of Cr(+3)/polyacrylamide (PAAm) gels involves simple extraction of Cr(+3) from the gel matrix has been obtained from rheological studies. Kinetic experiments provide evidence that de-gelation involves dissociative ligand exchange at Cr(+3). On the basis of de-gelation results acetate is suggested to be a poor thermodynamic model for the bonding of PAAm to Cr(+3) and it is hypothesized that Cr(+3)/PAAm complexation may involve bonding to both a polymer carboxylate and a neighboring amide group.     

Kinetic study of the OH + ethylene reaction using frequency-modulated laser absorption spectroscopy

The pressure dependence of the OH + C₂H₄ addition reaction has been investigated using frequency-modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2 to 361 Torr. The pressure-dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high-level ab initio calculations have identified a prereaction complex on the OH + C₂H₄ potential energy surface. The influence of this complex on the OH + C₂H₄ kinetics has been investigated using one-dimensional master equation analyses of the current and previous experimental measurements.     

Indium-mediated regioselective synthesis of ketones from arylstannanes under solvent-free ultrasound irradiation

The solvent-free indium-promoted reaction of alkanoyl chlorides with sterically and electronically diverse arylstannanes is a simple and direct method for the regioselective synthesis of primary, secondary and tertiary alkyl aryl ketones in good to excellent isolated yields (42–84%) under mild and neutral conditions. The protocol is also adequate for the synthesis of aryl vinyl ketones. Reaction times are drastically reduced (from 3–32 h to 10–70 min) under ultrasonic irradiation. Evidences for the involvement of a homolytic aromatic ipso-substitution mechanism, in which indium metal acts as radical initiator, are presented. It is possible the transference of two aryl groups from tin, thus improving effective mass yield, working with diarylstannanes as starting substrates.     

Post-buckling dynamic behavior of periodically supported imperfect shells

A circular cylindrical shell, periodically supported and subjected to step-loading in the form of lateral or hydrostatic pressure, is studied. Using the time-dependent von Kármán-Donnell equations, its imperfection sensitivity is examined and a simple asymptotic expression for the dynamic buckling load, valid for small imperfections, is obtained. There is a simple relation, independent of the imperfection, between the dynamic and static buckling loads.     

Diaryliodonium salts as thermal initiators of cationic polymerization

Diaryliodonium salts (I) undergo efficient thermal decomposition in the presence of copper (II) compounds. Such systems can be employed as a novel class of latent thermal initiators for cationic polymerization. An investigation of the mechanism of the reaction demonstrated that the copper (II) compound is first reduced to the corresponding copper (I) compound, which subsequently reduces the diaryliodonium salt. The cationic polymerization of some typical monomers using these new initiators was carried out to demonstrate the scope of their utility.     

2,6-Dimethylphenylnitrene in low-temperature matrices

Photolysis of 2,6-dimethylphenyl azide in N₂ matrices at 12K gives 2,6-dimethylphenylnitrene; in the presence of CO, the nitrene forms the corresponding isocyanate, while on shorter wavelength irradiation, it undergoes an inefficient rearrangement to an azacycloheptatetraene.     

Simultaneous determination of perhexiline and its monohydroxy metabolites in biological fluids by gas chromatography-electron-capture detection

A rapid and sensitive method for the simultaneous determination of perhexiline and its cis-4-axial and trans-4-equatorial monohydroxy metabolites (M1 and M3, respectively) in human plasma, urine and bile is described. The assay utilises a single diethyl ether extraction, heptafluorobutyric acid anhydride derivatisation and separation and detection by gas chromatography-electron-capture detection. The limits of detection are 0.1 microgram/ml for perhexiline and 0.025 microgram/ml for the M1 and M3 metabolites. This method has been used in a five-day kinetic study of three healthy adult males who ingested a single 300-mg dose of perhexiline maleate. One of these volunteer subjects exhibited elevated plasma perhexiline and markedly reduced plasma and urinary M1 concentrations together with profoundly prolonged plasma and urinary M1 elimination times when compared with the other two subjects. These differences are thought to be of genetic origin. There were also obvious differences in urinary M3 concentrations which were discussed.