Self-assembly of tetrahedral and trigonal antiprismatic clusters [Fe4(L4)4] and [Fe6(L5)6] on the basis of trigonal tris-bidentate chelators

In a one-pot reaction, the tetranuclear iron chelate complex [Fe4(L4)4] 6 was generated from benzene-1,3,5-tricarboxylic acid trichloride (4), bis-tert-butyl malonate (5a), methyllithium, and iron(II) dichloride under aerobic conditions. Alternatively, hexanuclear iron chelate complex [Fe(L5)6] 7 was formed starting from bis-para-tolyl malonate (5b) by employing identical reaction conditions to those applied for the synthesis of 6. The clusters 6 and 7 are present as racemic mixtures of homoconfigurational (delta,delta,delta,delta)/(lambda,lambda,lambda,lambda)-fac or (delta,delta,delta,delta,delta,delta)/(lambda,lambda,lambda,lambda,lambda,lambda)-fac stereoisomers. The structures of 6 and 7 were unequivocally resolved by single-crystal X-ray analyses. The all-iron(III) character of 6 and 7 was determined by M?ssbauer spectroscopy.     

Topochemical Reactions in Langmuir-Blodgett Multilayers

Abstract

The topochemical polymerization of diacetylenes and.the dimerization of cinnamic acid derivatives have been studied in Langmuir-Blodgett-multilayers. The resulting polymer films are of controlled thickness and morphology and exhibit excellent stability. Structure, morphology and phase changes occuring in monomer and polymer films have been investigated using spectroscopic methods, electron and x-ray diffraction. Possible applications of the polymer films are discussed.     

Numerical methods for the simulation of a coalescence-driven droplet size distribution

The droplet size distribution in a turbulent flow field is considered and modeled by means of a population balance system. This paper studies different numerical methods for the 4D population balance equation and their impact on an output of interest, the time-space-averaged droplet size distribution at the outlet, which is known from experiments. These methods include different interpolations of the experimental data at the inlet, various discretizations in time and space, and different schemes for computing the coalescence integrals. It will be shown that noticeable changes in the output of interest might occur. In addition, the computational efficiency of the studied methods is discussed.     

Absorption coefficient measurements of particle-laden filters using laser heating: Validation with nigrosin

A laser-heating technique, referred as the laser-driven thermal reactor, was used in conjunction with laser transmissivity measurements to determine the absorption coefficient of particle-laden substrates (e.g., quartz-fiber filters). The novelty of this approach is that it analyzes a wide variety of specific samples (not just filtered samples) and overcomes measurement issues (e.g., absorption enhancement) associated with other filter-based particle absorption techniques. The absorption coefficient was determined for nigrosin-laden, quartz-fiber filters and the effect of the filter on the absorption measurements was estimated when compared to the isolated nigrosin results. The isolated nigrosin absorption coefficient compared favorably with Lorenz–Mie calculations for an idealized polydispersion of spherical particles (based on a measured nigronsin/de-ionized water suspension size distribution) dispersed throughout a volume equivalent to that of the nigrosin-laden filter. To validate the approach, the absorption coefficient of a nigrosin/de-ionized water suspension was in good agreement with results obtained from an ultraviolet/visible spectrometer. In addition, the estimated imaginary part of the refractive index from the Lorenz–Mie calculations compared well with literature values and was used to estimate the absorption coefficient of optically opaque packed nigrosin.     

An algebraic variational multiscale–multigrid method for large-eddy simulation of turbulent variable-density flow at low Mach number

An algebraic variational multiscale–multigrid method is proposed for large-eddy simulation of turbulent variable-density flow at low Mach number. Scale-separating operators generated by level-transfer operators from plain aggregation algebraic multigrid methods enable the application of modeling terms to selected scale groups (here, the smaller of the resolved scales) in a purely algebraic way. Thus, for scale separation, no additional discretization besides the basic one is required, in contrast to earlier approaches based on geometric multigrid methods. The proposed method is thoroughly validated via three numerical test cases of increasing complexity: a Rayleigh–Taylor instability, turbulent channel flow with a heated and a cooled wall, and turbulent flow past a backward-facing step with heating. Results obtained with the algebraic variational multiscale–multigrid method are compared to results obtained with residual-based variational multiscale methods as well as reference results from direct numerical simulation, experiments and LES published elsewhere. Particularly, mean and various second-order velocity and temperature results obtained for turbulent channel flow with a heated and a cooled wall indicate the higher prediction quality achievable when adding a small-scale subgrid-viscosity term within the algebraic multigrid framework instead of residual-based terms accounting for the subgrid-scale part of the non-linear convective term.