Incorporation of reactive silver‐tricalcium phosphate nanoparticles into polyamide 6 allows preparation of self‐disinfecting fibers

Polymer fibers are used for a wide range of materials in contact with the human body. Since bacterial contamination may cause diseases, it is desirable to provide fibers with antimicrobial properties. This work investigates the ability of silver‐tricalcium phosphate nanoparticles (Ag/TCP) to build a reactive system when incorporated in polyamide fibers. In the presence of bacteria, the TCP carrier particles are biodegraded and trigger the release of silver. For this work, Ag/TCP nanoparticles (1.3 wt% silver) were produced by flame spray synthesis and subsequently processed with polyamide 6 to fibers (125‐μm thick, containing 260 ppm silver) with the aid of extrusion and melt‐spinning for subsequent antibacterial testing. The fibers were contaminated with the clinically relevant strains Escherichia coli or Streptococcus sanguinis, respectively. The reactive fibers demonstrated significantly reduced plate count within 24 h (the number of colony forming units was reduced by 99.999% with E. coli and 99.6% with S. sanguinis compared with pure PA6 reference fibers). These reactive properties of easily integrated antibacterial silver suggest an implementation of intelligent fibers to a wide range of applications. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Monitoring of photopolymerization kinetics and network formation by combined real-time near-infrared spectroscopy and ultrasonic reflectometry

For in situ monitoring of fast changes of shear modulus and chemical conversion during UV radiation curing an ultrasonic (US) reflection method was combined with real-time near infrared (NIR) spectroscopy. The combined setup has been applied to study photopolymerization of different resins as acrylates, epoxy acrylates, acrylated polyurethanes and cationic epoxy resins in order to achieve a deeper understanding of the interdependence of reaction kinetics and changes of mechanical/rheological properties. The simultaneously recorded conversion–time and modulus–time curves allow differentiating between mass and diffusion controlled polymerization regime. Light curing and dark curing phases are indicated by two distinct regions in the conversion–time curves. By rescaling the curing time by chemical conversion modulus–conversion curves were constructed, which are described by combining a viscoelastic relaxation model with the conversion dependence of relaxation times. The NIR-US setup was used to study the influence of chemical composition and curing conditions on the polymer network formation.     

Antimicrobial Brushes on Titanium via “Grafting to” Using Phosphonic Acid/Pyridinium Containing Block Copolymers

Coating medical implants with antibacterial polymers may prevent postoperative infections which are a common issue for conventional titanium implants and can even lead to implant failure. Easily applicable diblock copolymers are presented that form polymer brushes via “grafting to” mechanism on titanium and equip the modified material with antibacterial properties. The polymers carry quaternized pyridinium units to combat bacteria and phosphonic acid groups which allow the linear chains to be anchored to metal surfaces in a convenient coating process. The polymers are synthesized via reversible-addition-fragmentation-chain-transfer (RAFT) polymerization and postmodifications and are characterized using NMR spectroscopy and SEC. Low grafting densities are a major drawback of the “grafting to” approach compared to “grafting from”. Thus, the number of phosphonic acid groups in the anchor block are varied to investigate and optimize the surface binding. Modified titanium surfaces are examined regarding their composition, wetting behavior, streaming potential, and coating stability. Evaluation of the antimicrobial properties revealed reduced bacterial adhesion and biofilm formation for certain polymers, albeit the cell biocompatibility against human gingival fibroblasts is also impaired. The presented findings show the potential of easy-to-apply polymer coatings and aid in designing next-generation implant surface modifications.     

Multiscale fluid transport theory for swelling biopolymers

Fluid flow through a (bio) polymeric matrix has multiscale characteristics and is affected by the relaxation of surrounding polymers. Models developed in the past were either single scale (Polymer (1982) 23 (4) 529; Chemical Engineering Science (1992) 47 (12) 3037) or were limited to systems with a short memory (Achanta, 1995; Moisture transport in shrinking gels during drying, Ph.D. thesis, Purdue University, West Lafayette, IN). To address these limitations, we use the generalized Darcy's law equations of Singh (Effect of viscoelastic relaxation on fluid and species transport in biopolymeric materials, Ph.D. thesis) and the mass balance equations of Bennethum and Cushman (International Journal of Engineering Science (1996) 34 (2) 125) to develop a multiscale fluid transport model. The effect of viscoelastic relaxation of solid polymers on the flow of vicinal (adsorbed) fluid is considered at the mesoscale. At the macroscale two bulk fluids are incorporated, one of which is identical to the vicinal fluid. The mass balance equations for the vicinal fluid and its bulk counterpart are coupled via source/sink terms. The resulting fluid transport equation includes a novel integral term related to viscoelastic properties of the biopolymeric matrix. This term incorporates viscoelastic effects with both short and long memory. The model can describe both Darcian (Fickian) and non-Darcian (non-Fickian) modes of fluid transport. The model suggests fluid transport is Darcian in the rubbery and glassy states when the biopolymers are sufficiently far from the glass transition region. In the proximity of glass transition the flow of fluids is anomalous or non-Darcian. These predictions are in agreement with the experimental observations of Kim et al. (Chemical Engineering Science (1996) 51 (21) 4827). In spite of its multiscale characteristics, the resulting transport equation is simple and can be easily solved. The experimental parameters needed to solve the equation are the effective diffusivity, a sorption or drying curve and viscoelastic properties of the material.     

Rückgewinnung und Enantiomerentrennung chiraler Anästhetika mittels modifizierter poröser Gläser

Porous glass can be widely applied due to favorable chemical and physical properties and the possibility to modify the surface. This work describes the synthesis and optimization of porous glass beads for recovering chiral anesthetics and the separation of the enantiomers. Besides a characterization by nitrogen adsorption and mercury intrusion, the retention behavior of desflurane is investigated in chromatographic experiments with the native support and after immobilization of a chiral selector.     

Asymmetric Reduction of (R)-Carvone through a Thermostable and Organic-Solvent-Tolerant Ene-Reductase

Ene-reductases allow regio- and stereoselective reduction of activated C=C double bonds at the expense of nicotinamide adenine dinucleotide cofactors [NAD(P)H]. Biological NAD(P)H can be replaced by synthetic mimics to facilitate enzyme screening and process optimization. The ene-reductase FOYE-1, originating from an acidophilic iron oxidizer, has been described as a promising candidate and is now being explored for applied biocatalysis. Biological and synthetic nicotinamide cofactors were evaluated to fuel FOYE-1 to produce valuable compounds. A maximum activity of (319.7±3.2) U mg⁻¹ with NADPH or of (206.7±3.4) U mg⁻¹ with 1-benzyl-1,4-dihydronicotinamide (BNAH) for the reduction of N-methylmaleimide was observed at 30 °C. Notably, BNAH was found to be a promising reductant but exhibits poor solubility in water. Different organic solvents were therefore assayed: FOYE-1 showed excellent performance in most systems with up to 20 vol% solvent and at temperatures up to 40 °C. Purification and application strategies were evaluated on a small scale to optimize the process. Finally, a 200 mL biotransformation of 750 mg (R)-carvone afforded 495 mg of (2R,5R)-dihydrocarvone (>95 % ee), demonstrating the simplicity of handling and application of FOYE-1.     

Reprogramming the Biosynthesis of Cyclodepsipeptide Synthetases to Obtain New Enniatins and Beauvericins

Non‐ribosomal peptide synthetases are complex multimodular biosynthetic machines that assemble various important and medically relevant peptide antibiotics. An interesting subgroup comprises the cyclodepsipeptide synthetases from fungi synthesizing cyclohexa‐ and cyclo‐octadepsipeptides with antibacterial, anthelmintic, insecticidal, and anticancer properties; some are marketed drugs. We exploit the modularity of these highly homologous synthetases by fusing the hydroxy‐acid‐activating module of PF1022 synthetase with the amino‐acid‐activating modules of enniatin and beauvericin synthetase, thus yielding novel hybrid synthetases. The artificial synthetases expressed in Escherichia coli and the fungus Aspergillus niger yielded new cyclodepsipeptides, thus paving the way for the exploration of these derivatives for their bioactivity.     

Perpendicular and In‐Plane Conductivity of Poly(methyl methacrylate) Composite Films Filled with Carbon‐Based Fillers Prepared from Solution Casting Process

In this study, poly(methyl methacrylate) (PMMA)/carbon black (CB), PMMA/carbon fiber (CF), and PMMA/carbon nanotube (CNT) conductive composite films with different filler concentrations are prepared using the solution casting technique. Both perpendicular and in‐plane direction conductivity of all the binary composite films are investigated, percolation thresholds (?_c) of both directions of PMMA/CB, PMMA/CF, and PMMA/CNT composite films are investigated and the experimental data are fitted using McLachlan’s equation. For all the three investigated films, the perpendicular ?_c,⊥ and in‐plane ?_c,∥ with different fillers show totally different behaviors. Pristine CB, CF, and CNT as well as PMMA/CB, PMMA/CF, and PMMA/CNT composite films are discussed. The gravity effect of the fillers is found to be most significant in the PMMA/CB system. A schematic diagram of PMMA composite films with CB, CF, and CNT as filler prepared from solution casting process is presented to explain the distribution gradient of the fillers in the perpendicular direction of the film after solution casting. A power law behavior is revealed for different filler types (CB, CF, CNT) correlating the exponent t for McLachlan’s equation and corresponding ?_c for in‐plane and perpendicular directions.     

Improving Biocatalytic Properties of an Azoreductase via the N-Terminal Fusion of Formate Dehydrogenase

Azoreductases require NAD(P)H to reduce azo dyes but the high cost of NAD(P)H limits its application. Formate dehydrogenase (FDH) allows NAD(P)⁺ recycling and therefore, the fusion of these two biocatalysts seems promising. This study investigated the changes to the fusion protein involving azoreductase (AzoRo) of Rhodococcus opacus 1CP and FDH (FDH_C23S and FDH_{C23SD195QY196H}) of Candida boidinii in different positions with His-tag as the linker. The position affected enzyme activities as AzoRo activity decreased by 20-fold when it is in the N-terminus of the fusion protein. FDH_C23S+AzoRo was the most active construct and was further characterized. Enzymatic activities of FDH_C23S+AzoRo decreased compared to parental enzymes but showed improved substrate scope – accepting bulkier dyes. Moreover, pH has an influence on the stability and activity of the fusion protein because at pH 6 (pH that is suboptimal for FDH), the dye reduction decreased to more than 50 % and this could be attributed to the impaired NADH supply for the AzoRo part.     

Genetic Survey of Psilocybe Natural Products

Psilocybe magic mushrooms are best known for their main natural product, psilocybin, and its dephosphorylated congener, the psychedelic metabolite psilocin. Beyond tryptamines, the secondary metabolome of these fungi is poorly understood. The genomes of five species (P. azurescens, P. cubensis, P. cyanescens, P. mexicana, and P. serbica) were browsed to understand more profoundly common and species-specific metabolic capacities. The genomic analyses revealed a much greater and yet unexplored metabolic diversity than evident from parallel chemical analyses. P. cyanescens and P. mexicana were identified as aeruginascin producers. Lumichrome and verpacamide A were also detected as Psilocybe metabolites. The observations concerning the potential secondary metabolome of this fungal genus support pharmacological and toxicological efforts to find a rational basis for yet elusive phenomena, such as paralytic effects, attributed to consumption of some magic mushrooms.