Contributions to the Optimization of a Caprolactam Production Plant by Radiotracer Techniques

Residence time spectra and material distributions in an operating caprolactam production plant were measured by means of sodium 24, bromine 82 and technetium 99m. The results of the tracerexperiments contributed to an optimization of the plant.     

An Incompressible Fluid in a Weakly Deformable Shell. Part I: Analysis of the Model

We consider the flow of a viscous incompressible fluid in a pipe when the boundary is a deformable shell of Naghdi type. We prove that the corresponding system of partial differential equations has a solution when the deformation of the shell is smooth and small enough. We propose an algorithm that uncouples the unknowns and prove its convergence.     

Beiträge der Radiotracertechnik zur Rationalisierung einer großtechnischen Anlage zur Caprolactamproduktion

This paper reviews ways in which radioactive tracer techniques can he used to improve the efficiency of a caprolactam production plant, Residence time spectra and material distributions in different parts of the plant were measured by application of sodium 24, bromine 82 and technetium 99m. The investigations led to improved cumeneoxidators and gave useful informations on the catalytic decomposition of the phenolic tar and the hydrogenation process of phenol. It could he shown that the construction of the lactam extractor must he varied and the results of the tracerexperiments made in the distillation unit contributed to a higher quality of the final product.     

Scaling equations for a biopolymer in salt solution

The effect of the simultaneous presence of monovalent and divalent cations on the thermodynamics of polyelectrolyte solutions is an incompletely solved problem. In physiological conditions, combinations of these ions affect structure formation in biopolymer systems. Dynamic light scattering measurements of the collective diffusion coefficient D and the osmotic compressibility of semidilute hyaluronan solutions containing different ratios of sodium and calcium ions are compared with simple polyelectrolyte models. Scaling relationships are proposed in terms of polymer concentration and ionic strength J of the added salt. Differences in the effects of sodium and calcium ions are found to be expressed only through J.     

Single‐crystalline gold microplates grown on substrates by solution‐phase synthesis

Chemically synthesized single‐crystalline gold microplates have been attracting increasing interest because of their potential as high‐quality gold films for nanotechnology. We present the growth of tens of nanometers thick and tens of micrometers large single‐crystalline gold plates directly on solid substrates by solution‐phase synthesis. Compared to microplates deposited on substrates from dispersion phase, substrate‐grown plates exhibit significantly higher quality by avoiding severe small‐particle contamination and aggregation. Substrate‐grown gold plates also open new perspectives to study the growth mechanism via step‐growth and observation cycles of a large number of individual plates. Growth models are proposed to interpret the evolution of thickness, area and shape of the plates. It is found that the plate surface remains smooth after regrowth, implying the applicability of regrowth for producing giant plates as well as unique single‐crystalline nano‐structures.     

Controlling Covalent Connection and Disconnection with Light

The on‐going need for feature miniaturization and the growing complexity of structures for use in nanotechnology demand the precise and controlled formation of covalent bonds at the molecular level. Such control requires the use of external stimuli that offer outstanding spatial, temporal, as well as energetic resolution. Thus, photoaddressable switches are excellent candidates for creating a system that allows reversible photocontrol over covalent chemical connection and disconnection. Here we show that the formation of covalent bonds between two reagents and their scission in the resulting product can be controlled exclusively by illumination with differently colored light. A furyl‐substituted photoswitchable diarylethene was shown to undergo a reversible Diels–Alder reaction with maleimide to afford the corresponding Diels–Alder adduct. Our system is potentially applicable in any field already relying on the benefits of reversible Diels–Alder reactions.     

Strong Coupling and Laser Action of Ladder‐Type Oligo(p‐phenylene)s in a Microcavity

We investigate the coupling of ladder‐type quarterphenyl to the photon modes of a dielectric ZrO_x/SiO_x microcavity at ultraviolet wavelengths. For a relatively long cavity (≈10 μm) with high‐reflectivity mirrors (0.998), optically pumped laser action is demonstrated in the weak‐coupling regime. We observe single‐mode operation with a threshold of 0.4 mJ cm^?2. Strong coupling is achieved by using a short λ/2 cavity. We find pronounced anti‐crossing features of the molecular (0,0) and (0,1) vibronic transitions and the cavity mode in angle‐dependent reflectivity measurements providing Rabi splittings of (90±10) meV. All these features occur spectrally resonant to the exciton transition of ZnO demonstrating the potential of ladder‐type oligo(p‐phenylene)s for the construction of inorganic/organic hybrid microcavities.     

Self-Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra-Bay-Acyloxy Perylene Bisimide

A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self-assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen-bond-directed self-assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid-crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo- or heterochiral self-assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self-sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self-assemblies proceeds by dissociation via the monomeric state.