Exploiting the Catalytic Diversity of Short‐Chain Dehydrogenases/Reductases: Versatile Enzymes from Plants with Extended Imine Substrate Scope

Numerous short‐chain dehydrogenases/reductases (SDRs) have found biocatalytic applications in C=O and C=C (enone) reduction. For NADPH‐dependent C=N reduction, imine reductases (IREDs) have primarily been investigated for extension of the substrate range. Here, we show that SDRs are also suitable for a broad range of imine reductions. The SDR noroxomaritidine reductase (NR) is involved in Amaryllidaceae alkaloid biosynthesis, serving as an enone reductase. We have characterized NR by using a set of typical imine substrates and established that the enzyme is active with all four tested imine compounds (up to 99 % conversion, up to 92 % ee). Remarkably, NR reduced two keto compounds as well, thus highlighting this enzyme family's versatility. Using NR as a template, we have identified an as yet unexplored SDR from the Amaryllidacea Zephyranthes treatiae with imine‐reducing activity (≤95 % ee). Our results encourage the future characterization of SDR family members as a means of discovering new imine‐reducing enzymes.     

Morphology- and ion size-induced actuation of carbon nanotube architectures

ABSTRACT

Future adaptive applications require lightweight and stiff materials with high active strain but low energy consumption. A suitable combination of these properties is offered by carbon nanotube-based actuators. Papers made of carbon nanotubes (CNTs) are charged within an electrolyte, which results in an electrical field forming a double-layer of ions at their surfaces and a deflection of the papers can be detected. Until now, there is no generally accepted theory for the actuation mechanism. This study focuses on the actuation mechanism of CNT papers, which represent architectures of randomly oriented CNTs. The samples are tested electrochemically in an in-plane set-up to detect the free strain. The elastic modulus of the CNT papers is analyzed in a tensile test facility. The influence of various ion sizes of water-based electrolytes is investigated.

During the tests, four parameters that have a significant influence on the mechanical performance of CNT papers were identified: the test conditions, the electrical charging, the microstructure and the ion size. All of these influencing factors point to the mechanically weak inter-tube linking at which the actuation seems to take place. Quadratic voltage-strain correlation suggests a combination of electrostatic and volumetric effects as the possible reason for CNT paper actuation.

Abbreviations: CNT: carbon nanotubes; CV: cyclic voltammetry; CVD: chemical vapor deposition; HiPCO: high pressure carbon monoxide; IL: ionic liquid; MWCNT: multi-walled carbon nanotube; MW: multi-walled; NHE: normal hydrogen electrode; PDMS: polydimethylsiloxane; PMMA: polymethylmethacrylate; PPy: polypyrrole; PVDF: polyvinylidenefluoride; SCE: saturated calomel electrode; SWCNT: single-walled carbon nanotube; SW: single-walled; 1M: one molar concentration     

Introducing a Semi-Coated Model to Investigate Antibacterial Effects of Biocompatible Polymers on Titanium Surfaces

Peri-implant infections from bacterial biofilms on artificial surfaces are a common threat to all medical implants. They are a handicap for the patient and can lead to implant failure or even life-threatening complications. New implant surfaces have to be developed to reduce biofilm formation and to improve the long-term prognosis of medical implants. The aim of this study was (1) to develop a new method to test the antibacterial efficacy of implant surfaces by direct surface contact and (2) to elucidate whether an innovative antimicrobial copolymer coating of 4-vinyl-N-hexylpyridinium bromide and dimethyl(2-methacryloyloxyethyl) phosphonate (VP:DMMEP 30:70) on titanium is able to reduce the attachment of bacteria prevalent in peri-implant infections. With a new in vitro model with semi-coated titanium discs, we were able to show a dramatic reduction in the adhesion of various pathogenic bacteria (Streptococcus sanguinis, Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis), completely independently of effects caused by soluble materials. In contrast, soft tissue cells (human gingival or dermis fibroblasts) were less affected by the same coating, despite a moderate reduction in initial adhesion of gingival fibroblasts. These data confirm the hypothesis that VP:DMMEP 30:70 is a promising antibacterial copolymer that may be of use in several clinical applications.     

Method for Characterization of Solvents for Physical Absorption Processes

A method for solvent screening and searching for additives in the field of physical absorption processes is presented. A model based on the concept of virtual components and on the concept of a simplified abstract flow sheet is created. An estimation procedure for thermodynamically consistent property sets for the virtual component is developed. The model is implemented into MATLAB®. Its application is demonstrated in two studies including a study for a solvent additive. Potential candidates can be characterized and ranges for properties of the solvent or additive are found by means of the model. Conclusions obtained from the model support the screening process by a reduction of the number of further investigated components.     

Escherichia coli Biofilm Characteristics on Polymeric Heat Exchanger Surfaces

Time‐dependent effects on the apparent roughness and surface free energy of different polymeric surfaces and stainless steel were studied during the biofouling process for Escherichia coli K12. The surface roughness increases during primary adhesion of E. coli on the surfaces and is later reduced as the surface between scattered bacteria is completely covered, forming a uniform biofilm. During the fouling process, the polar fraction of the surface free energy significantly increased, whereas the dispersive fraction decreased for all substrates. The attachment of E. coli and subsequent bacterial production of extracellular polymeric substances increased the polarity of the initially nonpolar polymeric surfaces to increase wettability.     

Immobilization of α‐amylase in polyelectrolyte complexes

Herein, we report the formation of α‐amylase containing polyelectrolyte complexes (PECs). The method for the encapsulation of α‐amylase is based on interactions between two oppositely charged polyelectrolytes, poly(acrylic acid) (PAA) and polyethylenimine (PEI). We could show that electrostatic interactions ensure the incorporation of the enzyme into the formed polyelectrolyte complexes. The encapsulation has no negative effect on enzyme activity and protects against denaturation of the enzyme initiated by low pH values. The resulting PECs are 150–250 nm in size with narrow size distribution, appear in a spherical shape and are colloidally stable. The complexation of both polyelectrolytes and the immobilization of α‐amylase are investigated using fractionating techniques mainly the analytical ultracentrifugation and asymmetrical‐flow field‐flow fractionation. The formation of PECs represents a simple method for the encapsulation of α‐amylase without the use of organic solvents and requires no additional purifications steps. This one‐step approach, yielding high encapsulation efficiencies, shows the potential as a drug delivery system for sensitive hydrophilic actives in future. α‐amylase is immobilized in polyelectrolyte complexes made of polyethylenimine and poly(acrylic acid). Optimized encapsulation conditions and the resulting polyelectrolyte complexes are investigated via determination of IEP, α‐amylase activity assays, nanoDSC measurements, zeta potential values, dynamic light scattering, microscopy, and fractionating techniques. The encapsulated enzyme is protected against denaturation initiated by low pH values. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45036.     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Oxidative Folding of Peptides with Cystine‐Knot Architectures: Kinetic Studies and Optimization of Folding Conditions

Bioactive peptides often contain several disulfide bonds that provide the main contribution to conformational rigidity and structural, thermal, or biological stability. Among them, cystine‐knot peptides—commonly named “knottins”—make up a subclass with several thousand natural members. Hence, they are considered promising frameworks for peptide‐based pharmaceuticals. Although cystine‐knot peptides are available through chemical and recombinant synthetic routes, oxidative folding to afford the bioactive isomers still remains a crucial step. We therefore investigated the oxidative folding of ten protease‐inhibiting peptides from two knottin families, as well as that of an HIV entry inhibitor and of aprotinin, under two conventional sets of folding conditions and by a newly developed procedure. Kinetic studies identified folding conditions that resulted in correctly folded miniproteins with high rates of conversion even for highly hydrophobic and aggregation‐prone peptides in concentrated solutions.     

Partikelcharakterisierung in hochkonzentrierten Dispersionen – Grundlegende Untersuchungen zu einer neuen Ultraschallmethode

A new method for inline characterization of particles in high concentrated dispersions by ultrasonic backscattering is described, that is sensitive against particle size and concentration. Analyzing the backscattering signal yields the sound attenuation as well as a scattering intensity equivalent. The measurement can be performed without sampling and minimally invasive directly in the process.     

Abreicherung von Flüssiggas aus Erdgas mittels Zeolithmembranen

The depletion of higher alkanes from methane is a key aspect during the conditioning of natural gases or accompanying gases. Membrane technologies could be used as alternative to energy and cost intensive purifications. Against this background the influence of membrane geometry, composition of the gas mixture as well as temperature and pressure was investigated in separation experiments for methane/n‐butane mixtures using MFI membranes.