Rate constants for the gas-phase reactions of OH radicals and Cl atoms with n-alkyl nitrites at atmospheric pressure and 298 K

Rate constants for the reactions of OH radicals and Cl atoms with CH₃ONO, C₂H₅ONO, n-C₃H₇ONO, n-C₄H₉ONO, and n-C₅H₁₁ONO have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute rate technique of pulse radiolysis combined with kinetic spectroscopy and a relative rate method involving simultaneous measurement of the loss of the nitrite and the reference compound. The Cl rate constants were measured using the relative rate method. Values of the rate constants in units of 10^?13 cm³ molecule^?1 s^?1 are:

Non-trivial solution chemistry between amido-pyridylcalix[4]arenes and some metal salts

Mercury ion complexation reactions were carried out between 3 and various mercury(II) salts. (1)H NMR studies showed that the role of solvent, the anion chosen and the initial reaction conditions were critical and that the formation of a "simple" mercury(II) complex was non-trivial. The mercury(II) ion can cause either (i) the formation of an ion-pair system, which have a characteristic doubling of all signals in the (1)H NMR spectrum, (ii) a cleavage reaction to occur resulting in the reformation of the calix[4]arene diester compound 2, but only when the reaction is heated and (iii) "simple" mercury binding to the pyridine rings when the binding studies are carried out using NMR titration techniques. The electrochemistry results, on the same systems, show that the initial reaction involves the removal of the phenoxide protons followed by the resulting catalysis of the mercury species. This proton removal is not observed in the NMR spectra of any of the mercury reactions. It was also found that 3 could bind silver and zinc salts and was not selective for mercury(II) as was previously described.     

Protein directed assembly of lipids

Highly ordered ring-like structures are formed via the directed assembly of lipid domains in supported bilayers, using the extracellular matrix protein fibronectin. The ability of biological molecules to guide nanoscale assembly suggests potential biomimetic approaches to nanoscale structures.