THE KINETICS OF DISSOCIATION OF FIVE-COORDINATE TRANSITION METAL COMPLEXES IN NONAQUEOUS AND MIXED MEDIA

Five-coordinate complexes of nickel (II), cobalt (II), and copper (II), were prepared from the quadridentate ligand tris-(2-dimethylaminoethyl)-amine, a ligand which forms high-spin trigonal bipyramidal complexes. Previous studies of the dissociation of these complexes in aqueous perchloric acid revealed a single step kinetic process. Dissociation of the cobalt (II) complex was undertaken in acetonitrile, in dimethyl sulfoxide, and in N,N-dimethylformamide, with monochloroacetic acid as the dissociating agent. Multi-step kinetic behavior was observed. The rate-determining step was considerably faster in dimethyl sulfoxide and in N,N-dimethylformamide than in acetonitrile and in water. Possible mechanisms for the dissociation reaction are described and discussed in terms of solvent properties and crystal field energetics. Further studies were undertaken in mixed solvents such as dimethyl sulfoxide/water and N,N-dimethylformamide/water mixtures, to determine the effect of the presence of water on the mechanism of the dissociation reaction. Kinetic measurements were obtained with a Durrum-Gibson stopped-flow spectrophotometer

Comparison of the ultrafast to slow time scale dynamics of three liquid crystals in the isotropic phase

The dynamics of three liquid crystals, 4'(pentyloxy)-4-biphenylcarbonitrile (5-OCB), 4'-pentyl-4-biphenylcarbonitrile (5-CB), and 1-isothiocyanato-(4-propylcyclohexyl)benzene (3-CHBT), are investigated from very short time (~1 ps) to very long time (>100 ns) as a function of temperature using optical heterodyne detected optical Kerr effect experiments. For all three liquid crystals, the data decay exponentially only on the longest time scale (>several ns). The temperature dependence of the long time scale exponential decays is described well by the Landau-de Gennes theory of the randomization of pseudonematic domains that exist in the isotropic phase of liquid crystals near the isotropic to nematic phase transition. At short time, all three liquid crystals display power law decays. Over the full range of times, the data for all three liquid crystals are fit with a model function that contains a short time power law. The power law exponents for the three liquid crystals range between 0.63 and 0.76, and the power law exponents are temperature independent over a wide range of temperatures. Integration of the fitting function gives the empirical polarizability-polarizability (orientational) correlation function. A preliminary theoretical treatment of collective motions yields a correlation function that indicates that the data can decay as a power law at short times. The power law component of the decay reflects intradomain dynamics

Liquid crystal dynamics in the isotropic phase

The dynamics in the isotropic phase of the liquid crystal 1-isothiocyanato-(4-propylcyclohexyl) benzene (3-CHBT) are investigated from very short time (~1 ps) to very long time (>100 ns) as function of temperature. The data decay exponentially only on the longest time scale (>10 ns). The temperature dependence of the long time scale exponential decays is described well by the Landau-de Gennes theory of the randomization of pseudo-nematic domains that exist in the isotropic phase of liquid crystals near the isotropic to nematic phase transition. Over the full range of times, the data are fit with a model function that contains a short time power law. The power law exponent is temperature independent over a wide range of temperatures. Integration of the function gives the empirical polarizability-polarizability (orientational) correlation function. A preliminary theoretical treatment of collective motions yields a correlation function that indicates that the data can decay as a power law at short times. The power law component of the decay reflects intradomain dynamics

Acoustic and relaxation processes in supercooled o-ter-phenyl by optical-heterodyne transient grating experiment

The dynamics of the fragile glass-forming o-ter-phenyl is investigated by time-resolved transient grating experiment with an heterodyne detection technique in a wide temperature range. We investigated the dynamics processes of this glass-former over more then 6 decades in time with an excellent signal/noise. Acoustic, structural and thermal relaxations have been clearly identify and measured in a time-frequency window not covered by previous spectroscopic investigations. A detailed comparison with the density response function, calculated on the basis of generalized hydrodynamics model, has been worked out

Mucin Dynamics in Intestinal Bacterial Infection

Bacterial gastroenteritis causes morbidity and mortality in humans worldwide. Murine Citrobacter rodentium infection is a model for gastroenteritis caused by the human pathogens enteropathogenic Escherichia coli and enterohaemorrhagic E. coli. Mucin glycoproteins are the main component of the first barrier that bacteria encounter in the intestinal tract.Using Immunohistochemistry, we investigated intestinal expression of mucins (Alcian blue/PAS, Muc1, Muc2, Muc4, Muc5AC, Muc13 and Muc3/17) in healthy and C. rodentium infected mice. The majority of the C. rodentium infected mice developed systemic infection and colitis in the mid and distal colon by day 12. C. rodentium bound to the major secreted mucin, Muc2, in vitro, and high numbers of bacteria were found in secreted MUC2 in infected animals in vivo, indicating that mucins may limit bacterial access to the epithelial surface. In the small intestine, caecum and proximal colon, the mucin expression was similar in infected and non-infected animals. In the distal colonic epithelium, all secreted and cell surface mucins decreased with the exception of the Muc1 cell surface mucin which increased after infection (p<0.05). Similarly, during human infection Salmonella St Paul, Campylobacter jejuni and Clostridium difficile induced MUC1 in the colon.Major changes in both the cell-surface and secreted mucins occur in response to intestinal infection

Liquid crystal dynamics in the isotropic phase

The dynamics in the isotropic phase of the liquid crystal 1-isothiocyanato-(4-propylcyclohexyl) benzene (3-CHBT) are investigated from very short time (~1 ps) to very long time (>100 ns) as function of temperature. The data decay exponentially only on the longest time scale (>10 ns). The temperature dependence of the long time scale exponential decays is described well by the Landau–de Gennes theory of the randomization of pseudo-nematic domains that exist in the isotropic phase of liquid crystals near the isotropic to nematic phase transition. Over the full range of times, the data are fit with a model function that contains a short time power law. The power law exponent is temperature independent over a wide range of temperatures. Integration of the function gives the empirical polarizability–polarizability (orientational) correlation function. A preliminary theoretical treatment of collective motions yields a correlation function that indicates that the data can decay as a power law at short times. The power law component of the decay reflects intradomain dynamics