Design,Synthesis, and Evaluation of ω‐(Isothiocyanato)alkylphosphinates and Phosphine Oxides as Antiproliferative Agents

A series of 21 novel, structurally diverse ω‐(isothiocyanato)alkylphosphinates and phosphine oxides (ITCs) were designed and synthesized in moderate to good yields. The synthesized compounds were evaluated for in vitro antiproliferative activity using LoVo and LoVo/DX cancer cell lines. The biological activity of the synthesized compounds was higher than that of natural isothiocyanates such as benzyl isothiocyanate or sulforaphane. The antiproliferative activity of selected ITCs was also tested on selected cancer cell lines: A549, MESSA and MESSA/DX‐5, HL60 and HL60MX2, BALB/3T3, and 4T1. These compounds were assessed for their mechanism of action as inducers of cell‐cycle arrest and apoptosis. Ethyl (6‐isothiocyanatohexyl)(phenyl)phosphinate ( 71 ) was tested in vivo on the 4T1 cell line and demonstrated moderate antitumor activity, similar to that benzyl isothiocyanate and cyclophosphamide.     

Natural Polyphenols Selectively Inhibit β‐Carbonic Anhydrase from the Dandruff‐Producing Fungus Malassezia globosa: Activity and Modeling Studies

Around 50 % of the worldwide population is affected by dandruff, which is triggered by a variety of factors. The yeast Malassezia globosa has been labeled as the most probable causative agent for the onset of dandruff. The β‐carbonic anhydrase (CA) of MgCA was recently validated as an anti‐dandruff target, with its inhibition being responsible for in vivo growth defects in the fungus. As classical CA inhibitors of the sulfonamide type give rise to permeability problems through biological membranes, finding non‐sulfonamide alternatives for MgCA inhibition is of considerable interest in the cosmetic field. We recently screened a large library of human (h) CA inhibitors for MgCA inhibition, including different chemotypes, such as monothiocarbamates, dithiocarbamates, phenols, and benzoxaboroles. Herein, we expanded the research toward new MgCA inhibitors by considering a set of natural polyphenols (including flavones, flavonols, flavanones, flavanols, isoflavones, and depsides) that exhibited MgCA inhibitory activity in the micromolar range, as well as selectivity for the fungal isozyme over off‐target human isoforms. The binding mode of representative derivatives within the MgCA catalytic cleft was investigated by docking studies using a homology‐built model.     

Hot‐melt adhesives based on co‐polyamide and multiwalled carbon nanotubes

Composites of two hot melt adhesives based on co‐polyamides, one high viscosity (coPA_A), the other low viscosity (coPA_B), and multiwalled carbon nanotubes (MWCNTs) were prepared using twin‐screw extrusion via dilution of masterbatches. Examination of these composites across the length scales confirmed that the MWCNTs were uniformly dispersed and distributed in the polymer matrices, although some micron size agglomerations were also observed. A rheological percolation was determined from oscillatory rheology measurements at a mass fraction of MWCNTs below 0.01 for coPA_B and, between 0.01 and 0.02 for coPA_A. Significant increases in complex viscosity and storage modulus confirmed the “pseudo‐solid” like behavior of the composite materials. Electrical percolation, determined from dielectric spectroscopy was, found to be at 0.03 and 0.01 MWCNT mass fraction for coPA_A and coPA_B based composites, respectively. Addition of MWCNTs resulted in heterogeneous nucleation and altered the crystallization kinetics of both copolymers. Indirect evidence from contact angle measurements and surface energy calculations confirmed that MWCNT addition enhanced the adhesive properties of coPA_B to a level similar to coPA_A. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45999.     

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.     

Tetraacylgermanes as highly efficient photoinitiators for visible light cured dimethacrylate resins and dental composites

Tetrabenzoylgermane 1 and various substituted tetrabenzoylgermanes 2 – 7 were investigated as visible light (VL) photoinitiators (PIs) for dental dimethacrylate resins and dimethacrylate‐based composites. The tetrabenzoylgermanes 1 – 7 show a very strong VL absorption between 400 and 450 nm. Substituents on the benzoyl chromophore strongly influence their properties such as melting point, solubility, absorption behavior, or PI reactivity. A good photobleaching behavior and a very high reactivity as VL PI was found in photo‐differential scanning calorimeter experiments for selected tetrabenzoylgermanes. Composite pastes containing only ～0.1 wt % of Ge‐PI exhibited a sufficient photocuring due to the high PI‐reactivity of the tetraacylgermanes. Among the investigated germane PIs, tetrakis(2‐methylbenzoyl)germane 2 shows the best performance as VL PI for restorative composites and enables the composites to be photocured using an LED with an emission maximum of 500 nm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46115.     

Low temperature ferroelectric behavior in morphotropic Pb (Zr1−xTix)O3

We provide an insight into the switching of near‐morphotropic composition of PZT, using molecular dynamics simulations and electrical measurements. The simulations and experiments exhibit qualitatively similar hysteretic behavior of the polarization for different temperatures showing widening of the P‐E loops and the decrease in the coercive field toward high temperatures. Remarkably, we have shown that polarization switching at low temperatures occurs via polarization rotation, that is a fundamentally different mechanism from high‐temperature switching, which is nucleation driven.     

Porosity effect on microstructure,mechanical, and fluid dynamic properties of Ti2AlC by direct foaming and gel‐casting

In this study, Ti₂AlC foams were fabricated by direct foaming and gel‐casting using agarose as gelling agent. Slurry viscosity, determined by the agarose content (at a fixed solids loading), as well as surfactant concentration and foaming time were the key parameters employed for controlling the foaming yield, and hence the foam porosity after sintering process. Fabricated foams having total porosity in the 62.5‐84.4 vol% range were systematically characterized to determine their pore size and morphology. The effect of the foam porosity on the room‐temperature compression strength and elastic modulus was also determined. Depending on the amount of porosity, the compression strength and Young's modulus were found to be in the range of 9‐91 MPa and 7‐52 GPa, respectively. Permeability to air flow at temperatures up to 700°C was investigated. Darcian (k₁) and non‐Darcian (k₂) permeability coefficients displayed values in the range 0.30‐93.44 × 10^?11 m² and 0.39‐345.54 × 10^?7 m, respectively. The amount of porosity is therefore a very useful microstructural parameter for tuning the mechanical and fluid dynamic properties of Ti₂AlC foams.     

Boundary Limit Theory for Functional Local to Unity Regression

This article studies functional local unit root models (FLURs) in which the autoregressive coefficient may vary with time in the vicinity of unity. We extend conventional local to unity (LUR) models by allowing the localizing coefficient to be a function which characterizes departures from unity that may occur within the sample in both stationary and explosive directions. Such models enhance the flexibility of the LUR framework by including break point, trending, and multidirectional departures from unit autoregressive coefficients. We study the behavior of this model as the localizing function diverges, thereby determining the impact on the time series and on inference from the time series as the limits of the domain of definition of the autoregressive coefficient are approached. This boundary limit theory enables us to characterize the asymptotic form of power functions for associated unit root tests against functional alternatives. Both sequential and simultaneous limits (as the sample size and localizing coefficient diverge) are developed. We find that asymptotics for the process, the autoregressive estimate, and its t‐statistic have boundary limit behavior that differs from standard limit theory in both explosive and stationary cases. Some novel features of the boundary limit theory are the presence of a segmented limit process for the time series in the stationary direction and a degenerate process in the explosive direction. These features have material implications for autoregressive estimation and inference which are examined in the article.