Synthesis of unsymmetrically substituted pyrene derivatives through (6-bromo-3,8-dibutylpyren-1-yl)trimethylsilane

A straightforward route to unsymmetrically functionalized pyrene derivatives is described involving the synthesis of key precursor (6-bromo-3,8-dibutylpyren-1-yl)trimethylsilane 1. In a first step bromide 1 was successful in Suzuki-Miyaura, Sonogashira, and Buchwald-Hartwig cross-coupling reactions. Subsequent transformation of the trimethylsilyl group to bromide enabled the introduction of a second variable functional group onto the pyrene skeleton.     

Light-induced conformational change and product release in DNA repair by (6-4) photolyase

Proteins of the cryptochrome/photolyase family share high sequence similarities, common folds, and the flavin adenine dinucleotide (FAD) cofactor, but exhibit diverse physiological functions. Mammalian cryptochromes are essential regulatory components of the 24 h circadian clock, whereas (6-4) photolyases recognize and repair UV-induced DNA damage by using light energy absorbed by FAD. Despite increasing knowledge about physiological functions from genetic analyses, the molecular mechanisms and conformational dynamics involved in clock signaling and DNA repair remain poorly understood. The (6-4) photolyase, which has strikingly high similarity to human clock cryptochromes, is a prototypic biological system to study conformational dynamics of cryptochrome/photolyase family proteins. The entire light-dependent DNA repair process for (6-4) photolyase can be reproduced in a simple in vitro system. To decipher pivotal reactions of the common FAD cofactor, we accomplished time-resolved measurements of radical formation, diffusion, and protein conformational changes during light-dependent repair by full-length (6-4) photolyase on DNA carrying a single UV-induced damage. The (6-4) photolyase by itself showed significant volume changes after blue-light activation, indicating protein conformational changes distant from the flavin cofactor. A drastic diffusion change was observed only in the presence of both (6-4) photolyase and damaged DNA, and not for (6-4) photolyase alone or with undamaged DNA. Thus, we propose that this diffusion change reflects the rapid (50 μs time constant) dissociation of the protein from the repaired DNA product. Conformational changes with such fast turnover would likely enable DNA repair photolyases to access the entire genome in cells.     

Elongation of carbonyl compounds by utilizing electroreduction as a key step

The transformation of aldehydes, ketones and esters to the next higher homologous aldehydes was accomplished by utilizing electroreductive 1,2-elimination as a key step.     

The oldest mid-oceanic carbonate buildup complex: Setting and lithofacies of the Vendian (Late Neoproterozoic) Baratal limestone in the Gorny Altai Mountains,Siberia

The Baratal limestone in the Gorny Altai Mountains, southern Siberia, occurs as large allochthonous blocks within a Cambrian accretionary complex that developed around the Siberia craton. Before the final accretion to Siberia in the Cambrian, the terrigenous clastic-free Baratal limestone was deposited directly upon a basaltic basement with a geochemical signature identical to that of modern oceanic plateau. The Baratal limestone with 598 ± 25 Ma (Early Vendian) Pb-Pb isochron age consists of three distinct facies; 1) massive lime mudstone with ooids and stromatolites, 2) bedded lime mudstone, and 3) limestone conglomerate/breccia dominated by ooid-bearing lime mudstone clasts. The first represents a shallow marine environment on top of an ancient oceanic plateau, while the latter two represent the deeper slope to bottom-of-slope facies of a plateau. The Vendian Baratal limestone provides the oldest example of a reconstructed shallow marine carbonate buildup complex developed on a plateau/seamount in a mid-ocean.     

Behavior and process of background signal formation of hydrogen,carbon, nitrogen,and oxygen in silicon wafers during depth profiling using dual-beam TOF-SIMS

The behavior and mechanism of background signals during depth profiling of atmospheric elements using dual-beam time-of-flight secondary ion mass spectrometry (TOF-SIMS) have been experimentally investigated for silicon wafers. The background signals of atmospheric elements were found to be inversely proportional to the sputtering rate. Most of the background signals are largely attributable to the accumulation of components through adsorption and ion bombardment in the pre-equilibrium state. On the other hand, the contribution of real-time adsorption during the instant after the last sputtering in the equilibrium state is negligible under the present experimental conditions. H₂O is dominant in the background formation process of hydrogen and oxygen, which is supported by the higher adsorption coefficients. The background levels of carbon and nitrogen are lower than those of hydrogen and oxygen. Furthermore, the background signal of carbon with respect to the sputtering rate shows a different trend than the other elements. This could be attributed to accumulation in the pre-equilibrium state. These results indicate that the background levels can be lowered close to those of dynamic-SIMS by using an extremely high sputtering rate in dual-beam TOF-SIMS.     

In silico modeling of PAX8–PPARγ fusion protein in thyroid carcinoma: influence of structural perturbation by fusion on ligand-binding affinity

Journal of Computer-Aided Molecular Design - Paired box 8 (PAX8)–peroxisome proliferator-activated receptor γ (PPARγ) rearrangement is believed to play an important role in...     

Exfoliation of graphite by dry ball milling with cellulose

Dry ball milling of graphite with cellulose and related polysaccharides was found effective for exfoliation-dispersion of graphene-like carbon. The exfoliation behavior was found to depend strongly on the polymer species; namely, polysaccharides are much more effective than thermoplastic polymers. The compression-molded slabs from co-milled powder with cellulose and carboxymethylcellulose showed an electrical percolation threshold of 1.0 % (w/w) or lower. The carbon fraction isolated from milling with carboxymethylcellulose was water-dispersible, containing single- to few-layer graphenes. This method can provide facile and solventless graphene exfoliation and mechanical alloying with polymers.     

Analysis of Cu segregation to oxide–metal interface of Ni‐based alloy in a metal‐dusting environment

Hard X‐ray photoelectron spectroscopy (HX‐PES) has been realized using high‐brilliance synchrotron radiation. High‐energy photon excitation enables us to probe photoelectrons with larger escape depth compared to conventional PES. This allows us to conduct, without destruction, a study of the embedded interface of materials as the oxide‐ metal interface. We apply HX‐PES to investigate for Cu segregation in the oxide–metal interface during metal‐dusting corrosion. The effective concentration of Cu in the segregation was estimated a few times higher than the bulk concentration. These results on the interface layer can explain the variation in the corrosion resistance. Copyright © 2008 John Wiley & Sons, Ltd.