Chromatographische Untersuchungen zur Polydispersität von Hydroxyethylstärke

Chromatographic Studies on the Polydispersity of Hydroxyethyl Starch. A representative sample of clinically used hydroxyethyl starch was separated by semipreparative HPSEC into narrow fractions in the range of approx. 3.000 to 800.000 D. The original sample and selected fractions were characterised by gaschromatographic methylation analysis according to their substitution degrees MS and DS, which were differentiated by the substitution positions at C2, C3 and C6 of the anhydroglucoses and their kind of glycosidic bonding α-1, α-1,4 or α-1,4,6, respectively. Furthermore, polydispersity in relations to the degree of branching was determined. Mark-Houwink and molecular weight distribution parameters determined by multi-detection HPSEC are reported. The presented data demonstrate a extensive homogeneity of the original sample. The clinical relevance is discussed.     

The Fifth WS/DGAT Enzyme of the Bacterium Marinobacter aquaeolei VT8

Wax esters (WE) belong to the class of neutral lipids. They are formed by an esterification of a fatty alcohol and an activated fatty acid. Dependent on the chain length and desaturation degree of the fatty acid and the fatty alcohol moiety, WE can have diverse physicochemical properties. WE derived from monounsaturated long-chain acyl moieties are of industrial interest due to their very good lubrication properties. Whereas WE were obtained in the past from spermaceti organs of the sperm whale, industrial WE are nowadays mostly produced chemically from fossil fuels. In order to produce WE more sustainably, attempts to produce industrial WE in transgenic plants are steadily increasing. To achieve this, different combinations of WE producing enzymes are expressed in developing Arabidopsis thaliana or Camelina sativa seeds. Here we report the identification and characterization of a fifth wax synthase from the organism Marinobacter aquaeolei VT8, MaWSD5. It belongs to the class of bifunctional wax synthase/acyl-CoA:diacylglycerol O-acyltransferases (WSD). The protein was purified to homogeneity. In vivo and in vitro substrate analyses revealed that MaWSD5 is able to synthesize WE but no triacylglycerols. The protein produces WE from saturated and monounsaturated mid- and long-chain substrates. Arabidopsis thaliana seeds expressing a fatty acid reductase from Marinobacter aquaeolei VT8 and MaWSD5 produce WE. Main WE synthesized are 20:1/18:1 and 20:1/20:1. This makes MaWSD5 a suitable candidate for industrial WE production in planta.     

Phytochemical composition and antioxidant capacity of various botanical parts of the fruits of Prunus × domestica L. from the Lorraine region of Europe

Mirabelle plums represent a famous fruit from the Lorraine region, however little is known about their phytochemical composition. The oil of the fruit contained predominantly oleic acid (59%) and linoleic acid (29%). The total content of phenolic antioxidants in the whole fruits was 5.338 g/kg with 456 mg/kg (9%), 701 mg/kg (13%) and 4159 mg/kg (78%) detected in the peels, flesh and pits respectively. The peels contained solely 3,4-dihydroxybenzoic acid (270 mg/kg) and rutin (186 mg/kg), the flesh exclusively echinoids (723 mg/kg), whereas the pits contained a rich variety of phenolic compounds (4.2 g/kg) dominated by amygdalin (3.8 g/kg), but with significant contributions from vanillin (102 mg/kg), guajacyl-glycerin-coniferyl aldehyde isomers (87 mg/kg), dehydro-diconiferyl aldehyde (52 mg/kg), and vanillin diglucoside (48 mg/kg). Of the major phenolic compounds tested across a range of in vitro assays, rutin was the superior antioxidant.     

Konduktometrische und spektroskopische Untersuchungen der Wechselwirkung von Lewis-Säuren mit Halogenkomplexen

Conductometric and Spectroscopic Investigations of the Interaction of Lewis Acids with Halide Complexes The interaction of counter ions with Lewis acids has been investigated using mode systems of the type (C₆H₅)₃C^⊕ MX_n+1^⊖ (M = Sb, As, B, Fe; X = Cl, F) by means of conductometrical and UV-spectroscopic methods. The changes of conductivity were strongly dependent on the nature and concentration of the Lewis acid. The results point to 1:1-complexes between Lewis acids and counter ions. The behaviour was found to be complicated by dissoziation resp. assoziation processes. Ligand exchange reactions between Lewis acid and counter ion have also been found.     

Spinning Beta Silks Requires Both pH Activation and Extensional Stress

Synthetic silk production has undergone significant technological and commercial advances over the past 5 years, with fibers from most labs and companies now regularly matching the properties of natural silk by one metric or another. Yet the fundamental links between silk protein processing and performance remain largely unresolved and fiber optimization is commonly achieved through non-natural methods. In an effort to address this challenge, data that closes this loop of processing and performance is presented by spinning a native silk feedstock ex vivo into a near-native fiber using just two naturally occurring parameters; pH activation and extensional flow (i.e., spinning rate). This allows us to link previous experimental and modelling hypothesis surrounding silk's pH responsiveness directly to multiscale hierarchical structure development during spinning. Finally, fibers that match, and then exceed, natural silk's mechanical properties are spun and understood by rate of work input. This approach not only provides energetic insights into natural silk spinning and controlled protein denaturation, but is believed will help interpret and improve synthetic silk processing. Ultimately, it is hoped that these results will contribute towards novel bioinspired energy-efficient processing strategies that are driven by work input optimization and where excellent mechanical properties are self-emergent.     

Mutations in the nucleotide-binding domain of putative sterol importers Aus1 and Pdr11 selectively affect utilization of exogenous sterol species in yeast

Sterol uptake in the yeast Saccharomyces cerevisiae is mediated by two plasma membrane ATP-binding cassette transporters, Aus1 and Pdr11. Their expression is regulated by oxygen and is triggered by anaerobic growth conditions. Under these conditions, internal ergosterol synthesis is arrested and utilization of exogenous sterol is vital for yeast cells. Here, we demonstrate that Aus1 is the major importer of non–yeast sterols, mammalian cholesterol, and plant sterols under anaerobic conditions. In contrast, uptake of yeast native sterol, ergosterol, is relatively low. This uptake could not be enhanced by overexpression of either of the transporters. Interestingly, overexpression of the minor importer Pdr11 resulted in a substantial import of non–yeast sterols. We show that mutation of the conserved residue in one of the ABC characteristic motifs—the H-loop in Aus1 and Pdr11—lowered their ATPase activity. The residual activity was sufficient to import exogenous sterols and to preserve cell viability. Importantly, the reduction of sterol import was dramatic for mammalian cholesterol and plant sterols, whereas import of yeast ergosterol was decreased only slightly indicating substrate selectivity of the sterol utilization process.     

Carbonylation of chloromethylated polystyrene resins with NaCo(CO)4 in phase-transfer catalysis

Summary The carbonylation of Chloromethylated and partial quaternizated Chloromethylated polystyrene resins with cobalt tetracarbonyl anion in phase-transfer conditions is described. Dedicated to Prof. C. I. Simionescu on his 65th birthday     

A user-friendly interface to Kendrick's DUAL code

For the well-known stochastic quadratic linear programming problem, the coding of Kendrick is embedded into a user-friendly sequence of interactively used input-generator-optimization-output-generator programs. All three codes are in FORTRAN 77 and implemented on a small mainframe UNIVAC 1180 computer. Some illustrations are given for the ease of use.