Photoakustische Messung der Absorption an einem Ensemble dichtgepackter kugelförmiger Absorber

Photoacoustic Measurement of Absorption in an Ensemble of Close-Packed Absorbing Spheres Using the Rosencwaig-Gersho-model the photoacoustic absorption signal from an ensemble of tightly packed absorbing spheres was calculated taking into account the light scattering of the sample. Theoretical results were compared with experimental data, obtained from high refracting glass beads (so called Ballotini).     

Smoothness Properties of Semiflows for Differential Equations with State-Dependent Delays

Differential equations with state-dependent delay can often be written as (t)=f(x_t) with a continuously differentiable map f from an open subset of the space C¹=C¹([-h,0], {}^n), {h>0}, into {}^n. In a previous paper we proved that under two mild additional conditions the set is a continuously differentiable n-codimensional submanifold of C ¹, on which the solutions define a continuous semiflow F with continuously differentiable solution operators F_t=F(t,·), t 0. Here we show that under slightly stronger conditions the semiflow F is continuously differentiable on the subset of its domain given by {t> h}. This yields, among others, Poincaré return maps on transversals to periodic orbits. All hypotheses hold for an example which is based on Newton's law and models automatic position control by echo.     

Electronic substituent effects on the cleavage specificity of a non-heme Fe(2+)-dependent beta-diketone dioxygenase and their mechanistic implications

Acinetobacter johnsonii acetylacetone dioxygenase (Dke1) is a non-heme Fe(II)-dependent dioxygenase that cleaves C-C bonds in various beta-dicarbonyl compounds capable of undergoing enolization to a cis-beta-keto enol structure. Results from 18O labeling experiments and quantitative structure-reactivity relationship analysis of electronic substituent effects on the substrate cleavage specificity of Dke1 are used to distinguish between two principle chemical mechanisms of reaction: one involving a 1,2-dioxetane intermediate and another proceeding via Criegee rearrangement. Oxygenative cleavage of asymmetrically substituted beta-dicarbonyl substrates occurs at the bond adjacent to the most electron-deficient carbonyl carbon. Replacement of the acetyl group in 1-phenyl-1,3-butanedione by a trifluoro-acetyl group leads to a complete reversal of cleavage frequency from 83% to only 8% fission of the bond next to the benzoyl moiety. The structure-activity correlation for Dke1 strongly suggests that enzymatic bond cleavage takes place via nucleophilic attack to generate a dioxetane, which then decomposes into the carboxylate and alpha-keto-aldehyde products.     

Solidification of gold nanoparticles in carbon nanotubes

The structure and the solidification of gold nanoparticles in a carbon nanotube are investigated using molecular dynamics simulations. The simulations indicate that the predicted solidification temperature of the enclosed particle is lower than its bulk counterpart, but higher than that observed for clusters placed in vacuum. A comparison with a phenomenological model indicates that, in the considered range of tube radii (R(CNT)) of 0.5 < R(CNT) < 1.6 nm, the solidification temperature depends mainly on the length of the particle with a minor dependence on R(CNT).     

Guest-Editorial

Editorial Introduction

Guest-Editorial     

Measurement of the phase of few-cycle laser pulses

For the shortest pulses generated to date, the amplitude of the electromagnetic wave changes almost as rapidly as the field oscillates. The temporal variation of the field, which directly governs strong-field interactions, therefore depends on whether the maximum of the pulse amplitude coincides with that of the wave cycle or not, i.e., on the phase of the field with respect to the pulse envelope. It is demonstrated that the direction of electron emission from photoionized atoms can be controlled by varying the phase of the field, providing for the first time a tool for its accurate determination. Directing fast electron emission to the right or to the left with the light phase constitutes a new kind of coherent control.     

COAL TAR PHOTOTOXICITY: ACTIVE COMPOUNDS AND ACTION SPECTRA*

Abstract Eight compounds present in crude coal tar were tested for phototoxicity on guinea-pig skin. Four concentrations (5 μM to 5 mM) of each compound in ethanol were applied to the dorsal surface of 6 guinea-pigs. Each animal received 1.0 x 10⁵ j/m² of UVA radiation. The erythematous (phototoxic) response was evaluated after 20 h. Pyrene, anthracene and fluoranthene were strongly phototoxic. Acridine was markedly less phototoxic. Action spectra based on erythema as an endpoint were determined in guinea-pigs for anthracene, pyrene and fluoranthene. Each compound was applied to 5 animals which received irradiations from 274 to 502 nm in 12 nm bands for 3, 6, 9, 12 and 15 min. The maximum erythema response to anthracene was observed between 346 and 382 nm, to fluoranthene between 322 and 382 nm and to pyrene between 322 and 358 nm.     

Determination of chain stiffness and polydispersity from static light-scattering

Chain stiffness is often difficult to distinguish from molecular polydisperity. Both effects cause a downturn of the angular dependence at large q² (q = (4π/λ)sin θ/2) in a Zimm plot. A quick estimation of polydisperity becomes possible from a bending rod (BR) plot in which lim (c → 0) qRθ/Kc is plotted against q(〈S²〉_z)^1/2 = u. Flexible and semiflexible chains show a maximum whose position is shifted from u_max = 1.41 for monodisperse chains towards larger values as polydispersity is increased, while simultaneously, the maximum height is lowered. Stiff chains display a constant plateau at large q, its value is πM_L where M_L is the linear mass density. Using Koyama's theory, the number of Kuhn segments can be determined from the ratio of the maximum height to the plateau height, if the polydispersity index z = (M_w/M_n ? 1)^?1 is known. Thus, if the weight-average molecular weight M_w, is known, the contour length L_w, the number of Kuhn segments (N_k)_w, the Kuhn segment length l_k and the polydispersity of the stiff chains can be determined. The influence of excluded volume is shown to have no effect on this set of data. The reliability of this set can be cross-checked with the mean-square radius of gyration 〈s²〉_z which can be calculated from the Benoit-Doty equation for polydisperse chains. Rigid and slightly bending rods exhibit no maximum in the BR plot, and the effect of polydispersity can no longer be distinguished from a slight flexibility if only static scattering techniques are applied.