Transferring the entatic-state principle to copper photochemistry.

The entatic state denotes a distorted coordination geometry of a complex from its typical arrangement that generates an improvement to its function. The entatic-state principle has been observed to apply to copper electron-transfer proteins and it results in a lowering of the reorganization energy of the electron-transfer process. It is thus crucial for a multitude of biochemical processes, but its importance to photoactive complexes is unexplored. Here we study a copper complex-with a specifically designed constraining ligand geometry-that exhibits metal-to-ligand charge-transfer state lifetimes that are very short. The guanidine-quinoline ligand used here acts on the bis(chelated) copper(I) centre, allowing only small structural changes after photoexcitation that result in very fast structural dynamics. The data were collected using a multimethod approach that featured time-resolved ultraviolet-visible, infrared and X-ray absorption and optical emission spectroscopy. Through supporting density functional calculations, we deliver a detailed picture of the structural dynamics in the picosecond-to-nanosecond time range.

Photocontrolled chignolin-derived ß-hairpin peptidomimetics.

The synthesis of novel, chignolin-derived peptides comprising the azobenzene photoswitch [3-(3-aminomethyl)phenylazo]phenylacetic acid (AMPP) is reported. Reversible photoswitching behavior led to folding into ß-hairpin-like structures, as unequivocally demonstrated by CD, FT-IR and NMR spectroscopy.

Improved models of stellar core collapse and still no explosions: what is missing?

Two-dimensional hydrodynamic simulations of stellar core collapse are presented which for the first time were performed by solving the Boltzmann equation for the neutrino transport including a state-of-the-art description of neutrino interactions. Stellar rotation is also taken into account. Although convection develops below the neutrinosphere and in the neutrino-heated region behind the supernova shock, the models do not explode. This suggests missing physics, possibly with respect to the nuclear equation of state and weak interactions in the subnuclear regime. However, it might also indicate a fundamental problem with the neutrino-driven explosion mechanism.

Electron capture rates on nuclei and implications for stellar core collapse.

Supernova simulations to date have assumed that during core collapse electron captures occur dominantly on free protons, while captures on heavy nuclei are Pauli blocked and are ignored. We have calculated rates for electron capture on nuclei with mass numbers A=65-112 for the temperatures and densities appropriate for core collapse. We find that these rates are large enough so that, in contrast to previous assumptions, electron capture on nuclei dominates over capture on free protons. This leads to significant changes in core collapse simulations.

c,T-dependence of the viscosity and the self-diffusion coefficients in some aqueous carbohydrate solutions.

Self-diffusion coefficients for both components are reported for the highly concentrated aqueous solutions of some disaccharides and fructose as a function of temperature and concentration. These data are complemented by viscosity measurements. The disaccharides studied are sucrose, alpha,alpha-trehalose, allosucrose, and leucrose. Up to a sugar concentration of approximately 30% w/w the viscosity and the self diffusion coefficients of the four disaccharides are identical within experimental error for a given concentration and temperature. Water diffusion shows no differences in the four systems studied under these conditions. At higher concentrations significant differences are observed that become more pronounced with increasing temperature. Analysis of the data by the VTF equation yields the result that at a given concentration the self diffusion coefficients of the sugar Dc and the viscosity eta are described by identical ideal glass transition temperatures T0, while the diffusion of the water D(W) molecule decouples from these properties. T0(W) is always lower than T0(c,eta).

EPR, electron spin echo envelope modulation, and electron nuclear double resonance studies of the 2Fe2S centers of the 2-halobenzoate 1,2-dioxygenase from Burkholderia (Pseudomonas) cepacia 2CBS.

The 2-halobenzoate 1,2-dioxygenase from Burkholderia (Pseudomonas) cepacia 2CBS (Fetzner, S., Müller, R., and Lingens, F. (1992) J. Bacteriol. 174, 279-290) contains both a ferredoxin-type and a Rieske-type 2Fe2S center. These two significantly different 2Fe2S clusters were characterized with respect to their EPR spectra, electrochemical properties (Rieske-type cluster with gz = 2.025, gy = 1.91, gx = 1.79, gav = 1.91, Em = -125 +/- 10 mV; ferredoxin-type center with gz = 2.05, gy = 1.96, gx = 1.89, gav = 1.97, Em = -200 +/- 10 mV) and pH dependence thereof. X band electron spin echo envelope modulation and electron nuclear double resonance spectroscopy was applied to study the interaction of the Rieske-type center of the 2-halobenzoate 1,2-dioxygenase with 14N and 1H nuclei in the vicinity of the 2Fe2S cluster. The results are compared to those obtained on the Rieske protein of the cytochrome b6f complex (Em = +320 mV) and the water-soluble ferredoxin (Em = -430 mV) of spinach chloroplasts, as typical representatives of the gav = 1.91 and gav = 1.96 class of 2Fe2S centers. Properties common to all Rieske-type clusters and those restricted to the respective centers in bacterial oxygenases are discussed.