Radiation-damage investigation of a DNA 16-mer.

In macromolecular crystallography, a great deal of effort has been invested in understanding radiation-damage progression. While the sensitivity of protein crystals has been well characterized, crystals of DNA and of DNA-protein complexes have not thus far been studied as thoroughly. Here, a systematic investigation of radiation damage to a crystal of a DNA 16-mer diffracting to 1.8 Šresolution and held at 100 K, up to an absorbed dose of 45 MGy, is reported. The RIDL (Radiation-Induced Density Loss) automated computational tool was used for electron-density analysis. Both the global and specific damage to the DNA crystal as a function of dose were monitored, following careful calibration of the X-ray flux and beam profile. The DNA crystal was found to be fairly radiation insensitive to both global and specific damage, with half of the initial diffraction intensity being lost at an absorbed average diffraction-weighted dose, D1/2, of 19 MGy, compared with 9 MGy for chicken egg-white lysozyme crystals under the same beam conditions but at the higher resolution of 1.4 Å. The coefficient of sensitivity of the DNA crystal was 0.014 Å2 MGy-1, which is similar to that observed for proteins. These results imply that the significantly greater radiation hardness of DNA and RNA compared with protein observed in a DNA-protein complex and an RNA-protein complex could be due to scavenging action by the protein, thereby protecting the DNA and RNA in these studies. In terms of specific damage, the regions of DNA that were found to be sensitive were those associated with some of the bound calcium ions sequestered from the crystallization buffer. In contrast, moieties farther from these sites showed only small changes even at higher doses.

Calibration of rotation axes for multi-axis goniometers in macromolecular crystallography.

The installation of multi-axis goniometers such as the ESRF/EMBL miniKappa goniometer system has allowed the increased use of sample reorientation in macromolecular crystallography. Old and newly appearing data collection methods require precision and accuracy in crystal reorientation. The proper use of such multi-axis systems has necessitated the development of rapid and easy to perform methods for establishing and evaluating device calibration. A new diffraction-based method meeting these criteria has been developed for the calibration of the motors responsible for rotational motion. This method takes advantage of crystal symmetry by comparing the orientations of a sample rotated about a given axis and checking that the magnitude of the real rotation fits the calculated angle between these two orientations. Hence, the accuracy and precision of rotational motion can be assessed. This rotation calibration procedure has been performed on several beamlines at the ESRF and other synchrotrons. Some resulting data are presented here for reference.

Water-induced changes in the charge-transport dynamics of titanate nanowires.

The temperature dependence of dielectric processes in humid titanate nanowires was investigated via broadband dielectric spectroscopy under quasi-isosteric conditions in the temperature range of 150-350 K. It was found that the dynamic parameters obtained from low-temperature measurements cannot describe the dielectric behavior of the system above 273 K, implying changes in the dynamics of the corresponding dielectric processes. The calculated activation energies and pre-exponential factors counterintuitively increase linearly with the amount of adsorbed water, and a compensation effect was also found to apply to all contributions in the TiONW spectra.

Water types and their relaxation behavior in partially rehydrated CaFe-mixed binary oxide obtained from CaFe-layered double hydroxide in the 155-298 K temperature range.

Heat-treated CaFe-layered double hydroxide samples were equilibrated under conditions of various relative humidities (11%, 43% and 75%). Measurements by FT-IR and dielectric relaxation spectroscopies revealed that partial to full reconstruction of the layered structure took place. Water types taking part in the reconstruction process were identified via dielectric relaxation measurements either at 298 K or on the flash-cooled (to 155 K) samples. The dynamics of water molecules at the various positions was also studied by this method, allowing the flash-cooled samples to warm up to 298 K.

Superoxide dismutase mimicking Cu(II)-mixed amino acid complexes covalently grafted onto silica gel--an FT-IR study.

Our recent work concerning the synthesis, characterisation and testing of bioinspired electron transfer catalysts is described in this contribution. The catalysts were various Cu(II) complexes having mixed C- or N-protected amino acids (L-histidine and L-tyrosine) as ligands covalently grafted onto surface-modified silica gel. The resulting materials were structurally characterised by FT-IR spectroscopy, and their superoxide dismutase activities were tested. The covalently anchored Cu(II) complexes displayed appreciable activities in the test reaction; thus, they may be considered as promising candidates as durable electron transfer catalysts approaching the efficiency of the enzyme mimicked.