PORPHYRIN-INDUCED PHOTODAMAGE TO ISOLATED HUMAN NEUTROPHILS

Abstract— Human neutrophils were irradiated with light at 340–380 nm in the presence of low concentrations of protoporphyrin or uroporphyrin. At increasing light doses or increasing concentrations of protoporphyrin, the neutrophils rapidly lost the ability of locomotion. Also, neutrophil chemiluminescence and hexose-monophosphate shunt activity rapidly declined. An early event was leakage of endogenous K⁺ followed by lactate dehydrogenase and at a later stage leakage of particle-bound acid phosphatase. A number of cellular enzymes were inactivated, the susceptibility to inactivation decreased in the order: succinate dehydrogenase > lactate dehydrogenase > glutamate dehydrogenase > acid phosphatase. Uroporphyrin had no effect on neutrophil functions, leakage of K⁺, or cellular enzymes. The results suggest that photodamage to the plasma membrane and the mitochondria are earlier events than photodamage to lysosomes.     

C−H Bond Activation by an Imido Cobalt(III) and the Resulting Amido Cobalt(II) Complex

The 3d‐metal mediated nitrene transfer is under intense scrutiny due to its potential as an atom economic and ecologically benign way for the directed amination of (un)functionalised C?H bonds. Here we present the isolation and characterisation of a rare, trigonal imido cobalt(III) complex, which bears a rather long cobalt–imido bond. It can cleanly cleave strong C?H bonds with a bond dissociation energy of up to 92 kcal mol^?1 in an intermolecular fashion, unprecedented for imido cobalt complexes. This resulted in the amido cobalt(II) complex [Co(hmds)₂(NH^tBu)]^?. Kinetic studies on this reaction revealed an H atom transfer mechanism. Remarkably, the cobalt(II) amide itself is capable of mediating H atom abstraction or stepwise proton/electron transfer depending on the substrate. A cobalt‐mediated catalytic application for substrate dehydrogenation using an organo azide is presented.     

Polypropylene Copolymers Designed for Fused Filament Fabrication 3D‐Printing

Several chemical properties which influence the printability for fused filament fabrication 3D‐printing are derived from analyses of commercially available filaments. In preliminary experiments, polymerization conditions are optimized and suitable monomers and selectivity control agents (donors) are selected. An experimental series in which propene is copolymerized with the comonomers 1‐butene and 1‐hexene with an industrial Ziegler–Natta catalyst will be discussed here. The experiments are planned using design of experiments. Based on a split‐plot design, the design is adapted for mixtures and the combination of homo‐ and copolymerization. The observed factors, besides the mixture composition, are hydrogen partial pressure and the amount of donor. The obtained polymers are analyzed by means of high‐temperature size exclusion chromatography, differential scanning calorimetry, and rheology. 1‐Butene copolymers show good printing results and promising properties almost matching the desired ones. The targeted polymer properties are achieved within certain limits. 1‐Hexene copolymers result in lower molecular masses while crystallinity remains slightly higher, which does not match with the desired profile. Beneficial properties are likely to be achieved within a wider factor range, for example, higher comonomer amount and lower hydrogen partial pressure.     

Algorithm engineering for optimal alignment of protein structure distance matrices

Protein structural alignment is an important problem in computational biology. In this paper, we present first successes on provably optimal pairwise alignment of protein inter-residue distance matrices, using the popular dali scoring function. We introduce the structural alignment problem formally, which enables us to express a variety of scoring functions used in previous work as special cases in a unified framework. Further, we propose the first mathematical model for computing optimal structural alignments based on dense inter-residue distance matrices. We therefore reformulate the problem as a special graph problem and give a tight integer linear programming model. We then present algorithm engineering techniques to handle the huge integer linear programs of real-life distance matrix alignment problems. Applying these techniques, we can compute provably optimal dali alignments for the very first time.     

Aspects of ground effect modeling

A recently published one-parameter ground model based on Darcy's law is here generalized into a two-parameter model which depends on an effective flow resistivity and an effective layer depth. Extensive field measurements of the acoustic impedance of various ground types have been carried out for frequencies in the range from 200 Hz to 2.5 kHz. The model based on Darcy's law gives an improved fit to the measurements compared to the Delany-Bazley model. It is, in addition, argued on purely theoretical grounds that the suggested model is preferable. In contrast to the Delany-Bazley model it corresponds to a proper causal time-domain model. This is particularly relevant for extrapolation of the models to lower frequencies and for the recently developed harmonized methods intended for use in the implementation of the European Union directive on the assessment and management of environmental noise. The harmonized methods include frequencies down to the 25 Hz third octave band and have the Delany-Bazley ground impedance model as the default choice. The arguments presented here suggest that this default choice should be replaced by the more physically based model from the law of Darcy.