On the coherent description of diffusion-influenced fluorescence quenching experiments

The fluorescence quenching by electron transfer of a fluorophore, 2,5-bis(dimethylamino)-1,3-benzenedicarbonitrile, to 1,3-dimethyl-2-nitrobenzene, has been studied by means of time-resolved and steady-state experiments at different viscosities and up to large quencher concentrations. Differential Encounter Theory (DET) has been used to rationalize the results, in combination with electron transfer modelled by the Marcus theory. Additionally, the solvent structure and the hydrodynamic effect on the diffusion coefficient have been taken into account. Any simpler model failed to simultaneously fit all the results. The large number of quencher concentrations used is crucial to unambiguously extract the electron transfer parameters.     

Flow-driven orientation dynamics of semiflexible fiber systems

We study the flow-induced orientation dynamics of semiflexible fibers in dilute fiber suspensions. Starting from the equations of motion for a two-rod model of flexible fibers in Stokes flow, the Smoluchowski equation for a connected monomer orientation distribution function is derived. We then obtain a set of equations for the time dependence of the first and second moments of the orientation distribution function, thus extending the Folgar Tucker equations for short rigid fiber suspensions to flexible fiber suspensions. The resulting generalized equations for the orientation dynamics of a suspension of flexible fibers are solved for simple channel flow. It is shown that all qualitative effects of bending and straightening of fibers and their influence on the orientation of flexible fibers are captured within our model. A scalar measure for the distribution of bending in a flow is introduced, which allows to detect the degree of bending of fibers. Paper was presented at the 3rd Annual Rheology Conference, AERC 2006, April 27–29, 2006, Crete, Greece.     

Convergence of the Stochastic Euler Scheme for Locally Lipschitz Coefficients

Stochastic differential equations are often simulated with the Monte Carlo Euler method. Convergence of this method is well understood in the case of globally Lipschitz continuous coefficients of the stochastic differential equation. However, the important case of superlinearly growing coefficients has remained an open question. The main difficulty is that numerically weak convergence fails to hold in many cases of superlinearly growing coefficients. In this paper we overcome this difficulty and establish convergence of the Monte Carlo Euler method for a large class of one-dimensional stochastic differential equations whose drift functions have at most polynomial growth.     

Comparative numerical study of two concentrated fiber suspension models

We consider two rheological models for concentrated fiber suspensions. In both models the equations for orientation and flow are fully coupled, i.e., the orientation influences the flow via a constitutive relation for the viscosity and the orientation of the fibers is determined by the flow field. The orientation state of the fibers is characterized by the Advani–Tucker orientation tensor. We are investigating suspensions of fibers in which the kinetic energies of the fibers are large compared to the thermal energies, i.e., the influence of Brownian motion may be neglected. The first model is the Folgar–Tucker model with backcoupling to the flow (FT model). The second model is an extension of Folgar–Tucker, which models phenomenologically the topological exclusion interaction in dense suspensions (FTMS model). As test cases for the simulation are considered channel flow, 8:1 contraction flow and flow around a cylinder.     

Symmetry and Rigidity for Boosting Erbium-Based Molecular Light-Upconversion in Solution

Previously limited to highly symmetrical homoleptic triple-helical complexes [Er( Lk )₃]³⁺, where Lk are polyaromatic tridentate ligands, single-center molecular-based upconversion using linear optics and exploiting the excited-state absorption mechanism (ESA) greatly benefits from the design of stable and low-symmetrical [ Lk Er(hfa)₃] heteroleptic adducts (hfa⁻=hexafluoroacetylacetonate anion). Depending on (i) the extended π-electron delocalization, (ii) the flexibility and (iii) the heavy atom effect brought by the bound ligand Lk , the near-infrared (801 nm) to visible green (542 nm) upconversion quantum yield measured for [ Lk Er(hfa)₃] in solution at room temperature can be boosted by up to three orders of magnitude.     

Ueber Ammoniak und salpetrige Säure in der atmosphärischen Luft und ihre Nachweisung,sowie über das Verhalten verdünnter Ammonnitritlösungen beim Kochen

Analytical and Bioanalytical Chemistry -