Crude glycerol – a by‐product of the large scale production of diesel oil from rape – is examined for its possible use as a cheap feedstock for the biotechnological synthesis of poly(3‐hydroxybutyrate) (PHB). The glycerol samples of various manufacturers differ in their contamination with salts (NaCl or K2SO4), methanol or fatty acids. At high cell density fermentation these pollutants could possibly accumulate to inhibiting concentrations. The bacteria used were Paracoccus denitrificans and Cupriavidus necator JMP 134, which accumulate PHB from pure glycerol to a content of 70 % of cell dry mass. When using crude glycerol containing 5.5 % NaCl, a reduced PHB content of 48 % was observed at a bacterial dry mass of 50 g/L. Furthermore the PHB yield coefficient was reduced, obviously due to osmoregulation. The effect of glycerol contaminated with K2SO4 was less pronounced. The molecular weight of PHB produced with P. denitrificans or C. necator from crude glycerol varies between 620000 and 750000 g/mol which allows the processing by common techniques of the polymer industry.
The synthesized title compound 8 crystallizes in three different modifications, which were investigated by electron crystallography, high resolution electron microscopy and X-ray structural analysis. The formation of molecular pairs was studied by an ab initio quantum-chemical approach. The calculated "dimers" were compared to the mutual orientations of nearest neighboring molecules in the crystal structures and to covalently bonded dimers obtained by a topochemical photodimerization.
Dedicated to Prof. Andre M. Braun on the occasion of his 60th birthday [18]-and [24]Annulenes condensed with three pyrene or phenanthrene ring systems show, in solution, especially in apolar solvents, a strong aggregation evidenced, for example, by concentration-dependent 1 H-NMR spectra. However, the fluorescence bands and the fluorescence lifetimes of these compounds depend only to a minor extent on the concentration and correspond essentially to the measurements obtained for the monomer. Among several models discussed, one is favored in which aggregates can be excited, but the emission is due to an almost undisturbed monomer. Even for the pyrene system, an excimer fluorescence cannot be detected. Nevertheless, short-lived excimers are responsible for the regio-and stereoselective photodimerization to belt cyclophanes.
24]Annulenes condensed with three phenanthrene units (11a−d) or with three chrysene ring systems (22) were prepared by multi-step syntheses. The cyclic condensation reaction in the final step led to highly symmetrical compounds. Long flexible alkoxy groups attached to the periphery en-
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