Solubility of poly(n-alkylmethacrylate)s in hydrocarbons and in alcohols

Poly(methylmethacrylate) (PMMA), poly(butylmethacrylate) (PBMA), and poly(decylmethacrylate) (PDMA) are completely miscible with toluene at normal pressure from room temperature up to the boiling point of the solvent. In alkanes (C₆ to C₁₀) and 1-pentanol the solubility increases with the length of the side chain of the polymer: PMMA always exhibits a solubility gap within the above temperature range, PBMA shows upper critical solution temperatures (except n-hexane, which is a non-solvent), and PDMA mixes completely with all alkanes under consideration. Alcohols (up to C₄) are non-solvents for PMMA but theta solvents for PBMA and PDMA (except ethanol which is a non-solvent for the latter). The low temperature demixing of ethanol/PBMA is shifted towards lower temperatures by pressure.     

Biosynthesis of novel thermoplastic polythioesters by engineered Escherichia coli

The development of non-petrochemical sources for the plastics industry continues to progress as large multinationals focus on renewable resources to replace fossil carbon. Many bacteria are known to accumulate polyoxoesters as water-insoluble granules in the cytoplasm. The thermoplastic and/or elastomeric behaviour of these biodegradable polymers holds promise for the development of various technological applications. Here, we report the synthesis and characterization of microbial polythioesters (PTEs), a novel class of biopolymers of general technological relevance. Biosynthesis of PTE homopolymers was achieved using a recombinant strain of Escherichia coli that expressed a non-natural pathway consisting of a butyrate kinase, a phosphotransbutyrylase, and a PHA synthase. Different homopolymers were produced, consisting of either 3-mercaptopropionate, 3-mercaptobutyrate, or 3-mercaptovalerate repeating units, if the respective mercaptoalkanoic acids were provided as precursor substrates to the fermentative process. The PTEs contributed up to 30% (w/w) of the cellular dry weight and were identified as hydrophobic inclusions in the cytoplasm. The chemical and stereochemical homogeneity of the purified PTEs were identified by different methods, and the estimated physical properties were compared to the oxypolyester equivalents, revealing low crystalline order and, for the poly(3-mercaptopropionate) improved thermal stability. The ability to produce PTEs through a biosynthetic route opens up new avenues in the field of biomaterials.     

4-Nitro-7-piperazino-2,1,3-benzoxadiazole as a reagent for monitoring of airborne isocyanates by liquid chromatography

4-Nitro-7-piperazino-2,1,3-benzoxadiazole (NBDPZ) is presented as a new reagent for the determination of mono- and diisocyanates in air samples. NBDPZ readily reacts with the airborne analytes, thus yielding the corresponding urea derivatives, which are subsequently separated by means of reversed-phase liquid chromatography. On a phenyl-modified stationary phase, excellent baseline separation for numerous mono- and diisocyanate derivatives is obtained. Both diode array and fluorescence detection are performed with limits of detection of 11-35 and 5-9 nmol/L for the individual derivatives, respectively. In contrast to established derivatizing agents for the analysis of isocyanates, NBDPZ provides for increased selectivity due to the favorable detection wavelengths in the visible range (UV/visible, absorption maximums approximately 480 nm; fluorescence, excitation maximums approximately 470 nm, emission maximums approximately 535 nm). In addition, the high molar absorptivities of the reagent and the derivatives provide excellent sensitivity that is superior to most literature-known methods. Finally, air sampling methods comprising both the use of impingers and test tubes are developed and successfully applied to the determination of isocyanates in gaseous samples. Excellent recovery reaching values of >90% is observed for each of the two techniques investigated.     

Anisotropic Crystalline Protein Nanolayers as Multi‐Functional Biointerface for Patterned Co‐Cultures of Adherent and Non‐Adherent Cells in Microfluidic Devices

The spatial arrangement of cells in their microenvironment is known to significantly influence cellular behavior, thus making the control of cellular organization an important parameter of in vitro co‐culture models. However, recent advances in micropatterning co‐culture methods within biochips do not address the simultaneous cultivation of anchorage‐dependent and non‐adherent cells. To address this methodological gap we combine S‐layer technology with microfluidics to pattern co‐cultures to study the cell‐to‐cell and cell‐to‐surface interactions under physiologically relevant conditions. We exploit the unique self‐assembly properties of SbpA and SbsB S‐layers to create an anisotropic protein nanobiointerface on‐chip with spatially‐defined cytophilic (adhesive) and cytophobic (repulsive) properties. While microfluidics control physical parameters such as shear force and flow velocities, our anisotropic protein nanobiointerface regulates the biological aspects of the co‐culture method including biocompatibility, biostability, and affinity to non‐adherent cells. The reliability and reproducibility of our microfluidic co‐culture strategy based on laminar flow patterned protein nanolayers is envisioned to advance in vitro models for biomedical research.     

Untersuchungen zum Kristallabbau bei der Reduktion von Wüstit

Reduktionsversuche an auf Eisen aufoxydiertem Wüstit mit Kohlenmonoxid-Kohlendioxid-Stickstoff- und Wasserstoff-Wasserdampf-Stickstoff-Gasgemischen. Mikroskopische Beobachtung der anreduzierten Wüstitoberfläche. Beeinflussung der Reduktion durch die Oberflächentopographie des Wüstits. Analogie der Wüstitreduktion unter gleichgewichtsnahen Bedingungen zur Kristallverdampfung.