A photocontrolled beta-hairpin peptide

Beta-hairpins constitute the smallest beta-type structures in peptides and proteins. The development of highly stable, yet monomeric beta-hairpins based on the tryptophan zipper motif was therefore a remarkable success [A. G. Cochran, N. J. Skelton, M. A. Starovasnik, Proc. Natl. Acad. Sci USA 2001, 98, 5578-5583]. We have been able to design, synthesize and characterize a hairpin based on this motif which incorporates an azobenzene-based photoswitch, that allows for time-resolved folding studies of beta-structures with unprecedented time resolution. At room temperature the trans-azo isomer exhibits a mostly disordered structure; however, light-induced isomerization to the cis-azo form leads to a predominantly extended and parallel conformation of the two peptide parts, which are linked by the novel photoswitch, [3-(3-aminomethyl)phenylazo]phenylacetic acid (AMPP). While in the original sequence the dipeptide Asn-Gly forms a type I' beta-turn which connects the two strands of the hairpin, this role is adopted by the AMPP chromophore in our photoresponsive beta-hairpin that can apparently act as a beta I'-turn mimetic. The beta-hairpin structure was determined and confirmed by NMR spectroscopy, but the folding process can be monitored by pronounced changes in the CD, IR and fluorescence spectra. Finally, incorporation of the structurally and functionally important beta-hairpin motif into proteins by chemical ligation might allow for the photocontrol of protein structures and/or functions.     

Mechanism of UV-induced formation of Dewar lesions in DNA

The importance of a backbone: The mechanism of formation of Dewar lesions has been investigated by using femtosecond IR spectroscopy and ab?initio calculations of the exited state. The 4π?electrocyclization is rather slow, occurs with an unusual high quantum yield, and--surprisingly--is controlled by the phosphate backbone.     

Local coarsening of simplicial finite element meshes generated by bisections

A simple criterion that allows the efficient local coarsening of simplicial finite element meshes generated by bisections is devised and analyzed. Under a mild condition on the initial triangulation the proposed criterion allows to gradually reverse the entire refinement without employing its history explicitly. Numerical experiments underline the efficiency of the resulting algorithm.     

Spin dynamics in the reentrant spin glass ( Fe0.65 Ni0.35)1-x Mnx

The spin dynamics in the reentrant spin glass ( Fe_0.65 Ni_0.35)_1-x Mn_x has been studied by zero, longitudinal and transverse field μSR. In the ferromagnetic reentrant and pure spin glass regimes (x\leqslant 0.175), zero field experiments reveal a stretched exponential muon relaxation with a universal behaviour of the dynamic exponent \beta above the spin glass transition. There are no qualitative differences between the ferromagnetic and paramagnetic phases. In transversal field μSR experiments the divergence of the relaxation rate close to the spin glass transition is suppressed for manganese doping up to x=0.113 but enhanced for slightly higher doping (x\geqslant 0.12). We understand this behaviour as a crossover from an itinerant to a more localized state of the 3d electron system. This is also supported by the fact that in the highly doped regime with dominant antiferromagnetic interactions the muon relaxation rate diverges above the antiferromagnetic transition temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Radio frequency digital-to-analog converter

Dynamic performance of high-speed high-resolution digital-to-analog converters (DACs) is limited by distortion at the data switching instants. Inter-symbol interference (ISI), imperfect timing synchronization, and clock jitter are all culprits. A DAC output controlled by an oscillating waveform is proposed to mitigate the effects of switching distortion and clock jitter. This architecture has the additional benefit of mixing the DAC impulse response energy to a higher frequency, allowing a high-frequency image of the input to be used as the output. This has the potential for better noise performance and power and hardware savings relative to a conventional DAC+mixer architecture. A narrow-band sigma-delta (/spl Sigma//spl Delta/) DAC with eight unit elements is chosen to demonstrate the radio frequency digital-to-analog converter (RF DAC) concept in a 1.8-V 0.18-/spl mu/m CMOS technology. Measured single-tone SFDR is -75 dBc, SNR is 53 dB, and two-tone IMD3 is -70.8 dBc for a 17.5-MHz band centered at 942 MHz. SNR performance is shown to have the predicted dependence on the phase alignment of the data clock and oscillating pulse.     

Veränderungen der Baumwollzellulose durch Färbevorgänge

Ohne Zusammenfassung 8. Mitteilung von K. Brass, Untersuchungen über das Zustandekommen von F?rbungen [7. Mitteilung siehe K. Brass und R. Smrček, Ber. Dtsch. chem. Ges.75, 1680 (1942)].     

Competition between H and CO for Active Sites Governs Copper‐Mediated Electrosynthesis of Hydrocarbon Fuels

The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO₂. Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface‐affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH₄ and H₂ production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate‐limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis.     

Cardiac anisotropy: is it negligible regarding noninvasive activation time imaging?

The aim of this study was to quantify the effect of cardiac anisotropy in the activation-based inverse problem of electrocardiography. Differences of the patterns of simulated body surface potential maps for isotropic and anisotropic conditions were investigated with regard to activation time (AT) imaging of ventricular depolarization. AT maps were estimated by solving the nonlinear inverse ill-posed problem employing spatio-temporal regularization. Four different reference AT maps (sinus rhythm, right-ventricular and septal pacing, accessory pathway) were calculated with a bidomain theory based anisotropic finite-element heart model in combination with a cellular automaton. In this heart model a realistic fiber architecture and conduction system was implemented. Although the anisotropy has some effects on forward solutions, effects on inverse solutions are small indicating that cardiac anisotropy might be negligible for some clinical applications (e.g., imaging of focal events) of our AT imaging approach. The main characteristic events of the AT maps were estimated despite neglected electrical anisotropy in the inverse formulation. The worst correlation coefficient of the estimated AT maps was 0.810 in case of sinus rhythm. However, all characteristic events of the activation pattern were found. The results of this study confirm our clinical validation studies of noninvasive AT imaging in which cardiac anisotropy was neglected.     

On the trapping of SOx on CaO-Al2O3-based novel high capacity sorbents

Calcium-aluminum mixed oxide based materials doped with Na and Mn were explored as sulfur trapping materials. The materials showed a three times higher total storage capacity and a higher time on stream with complete SO2 removal compared to a second generation SOx trapping material which was mesoporous with calcium mainly present in oxidic form. Combining in situ XANES at the S K-edge and IR spectroscopy the key properties of the storage materials and the affiliated storage processes were identified. CaO-Al2O3 acts as the primary support and storage component, while Na+ cations adjust the base strength and enhances the storage capacity. Manganese cations provide the appropriate oxidation capacity in absence and presence of up to 10% water. The transport into the bulk phase, which is markedly influenced by a layer of sorbed water, is the rate-limiting step in presence of Mn cations. In the absence of manganese cations the oxidation step appears controlling the rate. The overall reaction network, identified by in situ IR spectroscopy and the 2D Correlation Analysis, is similar on all materials.