Reinforcement of a Magnesium‐Ammonium‐Phosphate Cement with Calcium Phosphate Whiskers

Self‐setting resorbable phosphate cements are characterized by an excellent biocompatibility and bioactivity. However, poor mechanical properties restrict their application. Most studies which characterize phosphate cements mechanically focus on strength measurements. Examinations of mechanical reliability and facture toughness were hardly performed. In this study, calcium phosphate whisker‐reinforced magnesium‐ammonium‐phosphate (struvite) cements were examined at the whisker–matrix interface and the measured strength, reliability and toughness values were correlated to these observations. Moreover, the toughening mechanisms were evaluated. It was shown that whisker incorporation is not beneficial for material strength. It led to a strength decrease from 29.8 to 21.8 MPa by the incorporation of 15 vol% calcium‐deficient hydroxyapatite (CDHA) whiskers compared to the pure struvite cement. Weibull statistics and microstructural observations revealed that this is caused by the whisker–matrix interface, which acts as a flaw. In contrast with that, the reliability increases upon whisker incorporation. Furthermore, the critical stress intensity factor K_IC as well as the work‐of‐fracture γ_wof increase from 0.52 to 0.60 MPam^1/2 and from 9.5 to 12.9 J/m² by the addition of 15 vol% CDHA whiskers compared to the original struvite cement. It was shown that whisker pull‐out and crack deflection are the main mechanisms responsible for this increase.     

Polymerization Catalysis in Liquid Propylene: High Activities and Molecular Weights in Propylene/CO Copolymerization Reactions

Summary: The dicationic [(dppp)Pd(NCCH₃)₂](BF₄)₂ catalyst (dppp = 1,3‐bis(diphenylphosphino)propane) was applied in a liquid monomer, two phase process for the CO/propene copolymerization reaction. For the first time it was possible to synthesize propene/CO copolymers with an activity up to 7 500 g/(mol · h) and molecular weights of 500 000 g/mol. Activities up to 40 000 g/(mol · h) could be obtained with the use of the unsymmetric catalyst [(CF₃‐dppp)Pd(NCCH₃)](BF₄)₂ (CF₃‐dppp = 1‐diphenylphosphino‐3‐bis[3,5‐di(trifluormethyl)phenyl]phosphinopropane) in homogeneous liquid propene solution.

Granules found after copolymerization.     

Polymerelektrolytmembranen für Hoch‐ und Niedertemperatur‐Brennstoffzellen aus strahlungsinduzierter Pfropfcopolymerisation

Radiation‐induced graft copolymerization of hydroxyethyl methacrylate with hydroxyethyl acrylate, acrylic acid or glycidyl methacrylate on ethylene tetrafluoroethylene (ETFE) films allow for tailor‐made synthesis of membranes for high and low temperature fuel cell applications. According to the operating temperatures proton conductivity may be achieved via doping with phosphoric acid or a two‐step sulfonation of the functional monomers. Fuel cell tests provide power densities and internal resistances, which indicate that the membranes are suitable for high and low temperature fuel cells.     

Erosion behavior of EB-PVD 7YSZ coatings under corrosion/erosion regime: Effect of TBC microstructure and the CMAS chemistry

Aero-engines operating in dust-laden environments often encounter a lot of dust/sand that causes a severe problem to the TBCs by means of erosion. As the turbine entry temperatures are rising, molten sand is also a big concern to the life-time of TBCs.This paper deals with the TBC behavior under the combined influence of erosion and corrosion attack. Variations in TBC morphology, CMAS infiltration time and CMAS composition and their influence on the erosion resistance at room temperature were investigated. Two different EB-PVD 7YSZ morphologies consisting of a different porosity arrangement were tested in the erosion/corrosion regime. The more ‘Feathery’ structure has a better resistance to erosion compared to a more columnar ‘Normal’ structure, which leads to less degradation of the TBC. However, under the influence of CMAS infiltration the effect was found to be reversed. In general, CMAS-infiltrated EB-PVD TBCs exhibit a higher erosion resistance than the non-infiltrated ones.     

RAFT-derived polymer-drug conjugates: poly(hydroxypropyl methacrylamide) (HPMA)-7-ethyl-10-hydroxycamptothecin (SN-38) conjugates

A series of well‐defined polymer–drug conjugates were prepared in order to modify the physical properties of a known cytotoxic drug, 7‐ethyl‐10‐hydroxycamptothecin (SN‐38), the active metabolite of irinotecan (CPT‐11). Reversible addition–fragmentation chain transfer (RAFT) polymerisation was used to covalently and site‐specifically append a defined N‐(2‐hydroxypropyl)methacrylamide (HPMA) polymer to SN‐38 using a graft‐from process. These poly‐HPMA–SN‐38 conjugates displayed excellent aqueous solubility and stability, whilst retaining the cytotoxic activity of the parent SN‐38. In vitro co‐culture assays containing both cancer and noncancer cell lines demonstrated the specificity of RAFT‐derived poly‐HPMA–SN‐38 conjugates for cancerous cells. The concept of post‐optimisation modification of small‐molecule drugs through a graft‐from polymer conjugation method is introduced.     

Protein Engineering of the Progesterone Hydroxylating P450‐Monooxygenase CYP17A1 Alters Its Regioselectivity

The CYP171 enzyme is known to catalyse a key step in the steroidogenesis of mammals. The substrates progesterone and pregnenolone are first hydroxylated at the C17 position, and this is followed by cleavage of the C17?C20 bond to yield important precursors for glucosteroids and androgens. In this study, we focused on the reaction of the bovine CYP17A1 enzyme with progesterone as a substrate. On the basis of a created homology model, active‐site residues were identified and systematically mutated to alanine. In whole‐cell biotransformations, the importance of the N202, R239, G297 and E305 residues for substrate conversion was confirmed. Additionally, mutation of the L206, V366 and V483 residues enhanced the formation of the 16α‐hydroxyprogesterone side product up to 40 % of the total product formation. Furthermore, residue L105 was found not to be involved in this side activity, which contradicts a previous study with the human enzyme.     

Abwasserreinigung mit Schilf in einer mobilen Wurzelraumkläranlage

A mobile root‐zone wastewater treatment system with a reaction zone consisting solely of reed roots as the growth surface for microorganisms was tested for temporary applications in the treatment of municipal wastewater. Pretreated municipal wastewater from a large‐scale wastewater treatment plant was fed to this system during the 2016 vegetation period. The outlet limit values for chemical oxygen demand and biochemical oxygen demand were adhered to reliably at an inlet volumetric flow rate of 1200 L d^?1. Short‐term loading peaks of up to 1800 L d^?1 did not lead to overloading of the system.     

An investigation into the synthesis of polycarbazole squaraine derivatives

The polycondensation of squaric acid with 1,2-(9-Ethylcarbazol-3-yl)ethene and N-ethyliminostilbene in polyphosphoric acid yielded insoluble polymers which included substituted phosphate groups on the phenyl rings. The presence of phosphorus in these polymers was identified using solid-state ³¹P NMR and EDAX techniques. Furthermore the phosphate groups were not ionic, hence no charge-balancing anions were present. Both polymers did not electrically conduct but exhibited dielectric breakdown values of 0.1 and 0.06 MV cm⁻¹ respectively. Received: 16 December 1996/Revised: 10 March 1997/Accepted: 10 March 1997     

A Peroxygenase from Chaetomium globosum Catalyzes the Selective Oxygenation of Testosterone

Unspecific peroxygenases (UPO, EC 1.11.2.1) secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less‐activated hydrocarbons, by transferring peroxide‐borne oxygen. We investigated a cell‐free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg^?1. Although the well‐known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5‐epoxide of testosterone in β‐configuration and 16α‐hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules.