Kinetics and mechanism of the general-acid-catalyzed ring-closure of the malondialdehyde-DNA adduct, N2-(3-oxo-1-propenyl)deoxyguanosine (N2OPdG-), to 3-(2'-Deoxy-beta-D-erythro-pentofuranosyl)pyrimido[1,2-alpha]purin- 10(3H)-one (M1dG)

3-(2'-Deoxy-beta-D-erythro-pentofuranosyl)pyrimido[1,2-alpha]purin-10(3H)-one (M1dG) is the major product of the reaction of deoxyguanosine with malondialdehyde (MDA). M1dG blocks replication by DNA polymerases in vitro and is mutagenic in vivo. M1dG reacts with hydroxide to form the N2-(3-oxo-1-propenyl)deoxyguanosine anion (N2OPdG-). This reaction is pH-dependent and reverses under neutral and acidic conditions to form M1dG. Here we describe the kinetics and mechanism of the ring-closure reaction in both the nucleoside and oligonucleotides. Kinetic analysis of absorbance and fluorescence changes demonstrates that ring-closure is biphasic, leading to the rapid formation of an intermediate that slowly converts to M1dG in a general-acid-catalyzed reaction. The dependence of the rate of the rapid phase on pH reveals the pKa for protonated N2OPdG is 6.9. One-dimensional 1H NMR and DQF-COSY experiments identified two distinct intermediates, N2OPdG-H and 8-hydroxy-6,7-propenodeoxyguanosine (HO-Prene-dG), that are formed upon acidification of N2OPdG-. Characterization of ring-closure in single-stranded and in melted duplex oligonucleotides shows M1dG formation is also acid-catalyzed in single-stranded oligonucleotides and that the denaturation of an oligonucleotide duplex enhances ring-closure. This work details the complexity of ring-closure in the nucleoside and oligonucleotides and provides new insight into the role of duplex DNA in catalyzing ring-opening and ring-closing of M1dG and N2OPdG.     

Biaryl sulfonamides from O‐acetyl amidoximes: 1,2,4‐Oxadiazole cyclization under acidic conditions

A series of 4‐cyanobenzenesulfonamides ( 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h ) was converted to the corresponding O‐acetylated amidoximes ( 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h ). The reaction of 1a was exemplarily investigated with respect to the formation of a byproduct, which was identified as 1,2,4‐oxadiazole derivative 3a . This observation led to the development of an improved procedure for the preparation of 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h . Compounds 2 could be transformed to 1,2,4‐oxadiazoles 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h in high yields and purity upon heating in acetic acid. J. Heterocyclic Chem., (2011).     

Magnetically induced electric field gradients

Several investigations of the Mössbauer spectrum of Fe₂As have yielded results which do not agree with those obtained by neutron diffraction studies. We report here a new investigation, and we show that the earlier disagreement is caused by a lack of appreciation of several factors. These include fluctuating hyperfine magnetic fields (relaxation) and an asymmetry of the electric field gradient produced by the spontaneous magnetization.On leave of absence at Laboratoire de Spectroscopie Hertzienne de l'Ecole Normale Superieure, 24 Rue Lhomond, 75005 Paris, France     

Localized transverse bursts in inclined layer convection

We investigate a novel bursting state in inclined layer thermal convection in which convection rolls exhibit intermittent, localized, transverse bursts. With increasing temperature difference, the bursts increase in duration and number while exhibiting a characteristic wave number, magnitude, and size. We propose a mechanism which describes the duration of the observed bursting intervals and compare our results to bursting processes in other systems.     

Statistics of defect motion in spatiotemporal chaos in inclined layer convection

We report experiments on defect-tracking in the state of undulation chaos observed in thermal convection of an inclined fluid layer. We characterize the ensemble of defect trajectories according to their velocities, relative positions, diffusion, and gain and loss rates. In particular, the defects exhibit incidents of rapid transverse motion which result in power law distributions for a number of quantitative measures. We examine connections between this behavior and Levy flights and anomalous diffusion. In addition, we describe time-reversal and system size invariance for defect creation and annihilation rates.     

Pattern formation in inclined layer convection

We report experiments on thermally driven convection in an inclined layer of large aspect ratio in a fluid of Prandtl number sigma approximately 1. We observed a number of new nonlinear, mostly spatiotemporally chaotic, states. At small angles of inclination we found longitudinal rolls, subharmonic oscillations, Busse oscillations, undulation chaos, and crawling rolls. At larger angles, in the vicinity of the transition from buoyancy- to shear-driven instability, we observed drifting transverse rolls, localized bursts, and drifting bimodals. For angles past vertical, when heated from above, we found drifting transverse rolls and switching diamond panes.     

Bestimmung von optischen Konstanten an Palladium und Silber aus Energieverlustmessungen im Energiebereich von 2 bis 90 eV

The energy loss functions Im (?1/?) of Silver and Palladium are determined from energy loss experiments with 60 keV electrons. The influence of surface effects and multiple losses is discussed and the values of Im (?1/?) are corrected for them. By means of Kramers-Kronig analysis the optical constants? ₁ and? ₂ are calculated from the energy loss function and found to be in good agreement with data derived from optical experiments by various authors.