Micellar solubilization: structural and conformational changes investigated by 1H and 13C liquid-state NMR

A combination of (1)H self-diffusion measurements and (13)C chemical shift analysis has been used for the study of the solubilization of amphiphilic additives C(n)H(2n+1)X (n=4, 6; X=OH, NH(2)) in cetyltrimethylammonium bromide (CTAB) micelles. This approach, which could be extended to other mixed systems, allows complementary data on structures of micelles and conformations of alkyl chains to be obtained. Previous results on these systems are confirmed and new features emerge. All the additives studied behave as cosurfactants. Their degree of solubilization is determined solely by their alkyl chain length. In the case of cosurfactants with n=6, polar head group differences have been shown to modify micellar structures. This effect has been linked to differences in cosurfactant penetration into micelles. In parallel, the area of CTAB head groups and the length of cetyl chains gradually decrease on average when solubilizing more cosurfactants. Cetyl chain compression is strong in the case of cosurfactants with n=4, whereas it is slightly compensated by an extension below the micellar surface in the case of longer cosurfactants. These conformational changes are related respectively to the formation of smaller spherical micelles and of anisotropic or swollen micelles.     

A role for Thr 252 in cytochrome P450cam oxygen activation

Molecular dynamics simulations of the ferrous dioxygen bound form of wild type cytochrome P450cam were performed and the results analyzed to reveal the time-dependent interactions of T252 with surrounding residues as well as with bound oxygen. The results indicate a time-dependent bimodal interaction of T252 with both G248 and the terminal oxygen of the bound dioxygen. The hydrogen bonding interaction of T252 with these two moieties is "anticorrelated" in the sense that the breaking of the T252-G248 hydrogen bond is concurrent with formation of the T252-dioxygen interaction. These simulations support the probability of a role of T252 in stabilization of the initial dioxygen bound complex and promotion of subsequent formation of compound I previously indicated by several experimental studies.     

Synthesis and antioxidant activity of 3-substituted guaiazulene derivatives

A series of 3-substituted guaiazulene derivatives has been synthesized and their antioxidant properties were evaluated by monitoring their capacity for scavenging the stable free-radical DPPH. 3-Vinylguaiazulene was the most potent, possessing antioxidant activity superior than alpha-tocopherol. These derivatives were also moderate inhibitors of the proliferation of human promyelocytic leukemia cells.     

Studies of polyester fiber as carrier for microbes in a quantitative test method for disinfectants

Tests were conducted by a Task Force on Disinfectant Test Methods that was appointed to investigate controversies regarding the accuracy of AOAC test methods for disinfectants as presented in AOAC's Official Methods of Analysis, Chapter 6. The general principles for new and improved AOAC tests are discussed, and a disinfectant test using microbes labeled onto a polyester fiber surface is described. The quantitative test measures the survival of test microbes as a function of exposure time as well as the exposure conditions required to kill 6 log10 of the test microbes. The time required was similar to that for the kinetics of the kill of Bacillus subtilis-labeled cylinders as tested by methods of the AOAC Sporicidal Test 966.04.     

In situ monitoring of solid-state polymerization reactions in sodium chloroacetate and sodium bromoacetate by 23Na and 13C solid-state NMR spectroscopy

The thermally induced solidstate polymerization reactions in sodium chloroacetate and sodium bromoacetate, leading to poly(hydroxyacetic acid) (polyglycolide) and NaCl and NaBr, respectively, were studied by isothermal in situ solid-state NMR spectroscopy at 120, 130 and 140 degrees C with a time resolution of the order of 5 to 25 min. The nuclei probed were 23Na and 13C, allowing the parent compounds (sodium halogenoacetates) and both reaction products (polymer and alkali halide) to be monitored. For sodium chloroacetate, there is no evidence for the involvement of intermediate phases during the reaction whereas this cannot be excluded for sodium bromoacetate. The crystal structure of sodium bromoacetate was determined directly from powder diffraction data by the Monte Carlo method, and was found to be isostructural with sodium chloroacetate. The topochemical reaction mechanism proposed previously for sodium chloroacetate is thus also applicable for the polymerization reaction in sodium bromoacetate. The mechanistic and kinetic information obtained from our in situ solid-state NMR investigations is compared and contrasted with information obtained from other in situ probes of the polymerization reactions in these materials.     

Hartree-like methods in electronic structure theory

We consider the “Hartree Problem,” here defined as the problem of finding the orthogonal one-electron states which in a single determinant minimize the electronic energy, excluding exchange contributions. These states may provide a useful basis for correlation-energy studies. It is shown how the “Hartree Problem,” although superficially not of pseudoeigenvalue form, can nevertheless be cast in such a form and solved by an iterative diagonalization process.