Alkene epoxidation with mesoporous materials assembled from TS-1 seeds – Is there a hierarchical pore system?

Hexagonal mesoporous solids were synthesized from solutions containing TS-1 seeds. The products were characterized by XRD, nitrogen and argon physisorption, TEM, TG/DTA of template decomposition (also after extraction of the mesopore template), UV–Vis and IR spectroscopy, and XANES at the TiK edge. Their catalytic activities were assessed for cyclohexene epoxidation in hydrophilic and hydrophobic environment (CH₃OH/water, with H₂O₂ oxidant, and decane, with tert-butyl hydro-peroxide oxidant, respectively) and for n-hexene epoxidation in hydrophilic environment. The mesopore system was clearly documented by XRD, physisorption measurements, and TEM, whereas evidence for micropores by physisorption proved elusive. However, the micropore template was detected in the solids by TG/DTA even after extraction of the mesopore template, and among the Ti sites, which were confirmed to be tetrahedrally coordinated by UV–Vis and XANES, a clear majority was able to coordinate two water molecules. It was concluded that the pore walls had been built up from nanoparticulate TS-1 precursors resulting in walls of ca. 1.5 nm thickness, which resemble rather the exterior layers of a TS-1 crystallite than its (hydrophobic) interior. In cyclohexene epoxidation, the micro-mesophases were by 1–2 orders of magnitude more active than TS-1 and outperformed also Ti-MCM-41, at similar selectivity in hydrophobic medium. With 1-hexene in hydrophilic medium, however, the micro-mesophases failed completely whereas TS-1 exhibited high activity.     

Natural products as leads for anticancer drug discovery: discovery of new chemotypes of microtubule stabilizers through reengineering of the epothilone scaffold

Epothilones are bacterial macrolides with potent microtubule-stabilizing and antiproliferative activity, which have served as successful lead structures for the discovery of several clinical candidates for cancer treatment. Overall, seven epothilone-type agents have been advanced to clinical evaluation in humans so far and one of these has been approved by the FDA in 2007 for clinical use in breast cancer patients. Notwithstanding these impressive numbers, however, the structural diversity represented by the collection of epothilone analogs that have been (or still are) investigated clinically is rather limited and their individual structures show little divergence from the original natural product leads. In contrast, we have elaborated a series of epothilone-derived macro-lactones, whose overall structural features significantly deviate from those of the natural epothilone scaffold and thus define new structural families of microtubule-stabilizing agents. Key elements of our hypermodification strategy are the change of the natural epoxide geometry from cis to trans, the incorporation of conformationally constrained side chains, the removal of the C(3)-hydroxyl group, and the replacement of C(12) with nitrogen. The latter modification leads to aza-macrolides that may be described as 'non-natural natural products'.     

Network formation by aza‐Michael addition of primary amines to vinyl end groups of enzymatically synthesized poly(glycerol adipate)

A highly efficient approach for the synthesis of polyester‐based networks via aza‐Michael addition of primary amines to α,β‐unsaturated (vinyl) end groups of poly(glycerol adipate) (PGA) was achieved. By acylation of PGA with 6‐(Fmoc‐amino)hexanoic acid side chains via Steglich esterification, protected amine‐functionalized PGA was obtained. This was followed by the removal of fluorenylmethyloxycarbonyl (Fmoc) protecting groups and the synthesis of PGA‐based networks under catalyst‐free conditions. The successful conjugate addition of primary amines to vinyl end groups and network formation were confirmed using ¹³C magic angle spinning NMR and Fourier transform infrared spectroscopy. Network heterogeneity and defects were quantitatively investigated using ¹H double‐quantum NMR spectroscopy. Finally, a hydrogel was prepared with potential biomedical applications.     

A high-reliability alumina-platinum multilayer system for implantable medical devices

A new Pt-Al₂O₃ multilayer composite system has been developed and validated with an Accelerated Life Test (ALT) to confirm its potential for long-term use in implantable medical devices (IMD). Panels containing over 100 Pt vias were subjected to highly accelerated immersion testing in deionized water at temperatures ranging from 90 to 175°C. Deionized water was employed as it best represents the IMD use environment. Degradation of individual Pt vias was evaluated using fluorescent dye infiltration into the subsurface of the panels. ALT guided refinement of materials and processing to produce a Pt-Al₂O₃ multilayer composite system with promising performance for possible use in implantable devices.     

Structure of an antioxidant from fermented soybeans (tempeh)

In an exhaustive investigation of the antioxidative properties of tempeh constituents, the substance at R _f 0.58 (cyclohexane/ethyl ether, 9:1) was isolated and purified. Until now, only the ultraviolet and fluorescence data of the substance were known, and the presence of an OH group was indicated. In the present paper, the structure of the substance at R _f 0.58 was elucidated by the application of spectroscopic methods and found to be 5-(δ-tocopheroxy)-δ-tocopherol. That previous researchers did not confirm antioxidant activity in tempeh oil has been related to the way the tempeh oil was prepared. Previous suggestions regarding the substance at R _f 0.58 as being one of the main tempeh antioxidants could not be proved. The antioxidative effect of tempeh oil seems to be the result of a synergistic effect of tocopherols (present in the soybeans) and amino acids (liberated during the fermentation process with Rhizopus oligosporus).     

Processing of the Multifunctional Polymer Poly(phenylene methylene) into Fibers,Films, Foams,and Microspheres

Poly(phenylene methylene) (PPM) has recently emerged as a promising multifunctional polymer, requiring straightforward one‐step synthesis to achieve high molar mass and featuring a range of attractive properties. Its processability, however, has not been explored in detail to date. Therefore, this study presents a comprehensive investigation of the processability of PPM into a wide range of forms by employing various polymer processing techniques. Thin fibers (diameter ≈100 µm) over 1 km in length and shorter thick fibers (diameter ≈1 mm) are produced by melt spinning. Although no crystallinity is observed, the fibers surprisingly exhibit pronounced birefringence. The capability for waveguiding red light within the fibers is also demonstrated. Furthermore, films with a broad thickness range, spanning nanometer to millimeter length scales, are fabricated using different approaches such as spin‐coating, hot pressing, and die casting. All films feature a very smooth and crack‐free surface topography. Additionally, freestanding foams of PPM are obtained by foaming highly concentrated solutions, and quasi‐monodisperse microspheres are prepared by a microfluidic high‐throughput emulsification. The material properties of these different specimen forms are investigated and discussed for implementation as products ranging from plastic optical fibers and light emitting diodes, to protective coatings and packaging, as well as insulators and separation membranes.     

Micromechanics of ITZ‐Aggregate Interaction in Concrete Part II: Strength Upscaling

Cracking in concrete typically starts in the immediate vicinity around the aggregates, i.e., in the region of the so‐called interfacial transition zones (ITZs), but the process is still not fully understood. Notably, crushing of concrete in compression results in fragments with interesting aggregate surface textures. Part of the aggregate surfaces is cleanly separated from the ITZ, while another part of the aggregate surfaces remains covered with a thin layer of cement paste. This suggests two different types of failure: ITZ‐aggregate separation and ITZ failure; which we here study based on the continuum micromechanics approach of the companion paper (part I). It provides access to both traction vectors acting on aggregate surfaces and three‐dimensional stress states within representative ITZ volumes for loading states below the elastic limit of concrete. When inserting these microtractions and microstresses into Rankine‐type strength criteria for the aggregate‐ITZ interface and for the ITZ, respectively, the micromechanics model allows for upscaling this microscopic failure behavior to concrete‐level criteria for crack onset. Comparing the latter to corresponding experimental results, reveals that under tension‐dominated loading both ITZ failure and ITZ‐aggregate separation appear to be realistic, while under compression‐dominated loading ITZ failure appears as the more likely mechanism. Also, comparing model and experiments shows that the ITZ‐aggregate separation strength amounts to at least half of the internal ITZ cohesion strength, but may be much larger than the latter.     

Modellierung und Simulation von Strömungen und biologischen Reaktionen innerhalb eines Belebtschlammbeckens

With the aim to increase the efficiency of the aeration tanks of municipal wastewater treatment plants, the implementation of a biological model system (ASM1) into the CFD code ANSYS CFX® is presented for modeling a full‐scale aeration tank and verified with experimental data. Taking into account the biological processes, hydrodynamics and gas‐liquid mass transfer, simulations were performed and compared to experimental concentration profiles for ammonium and nitrate. The assumptions made are explained in detail. While the simulated ammonium concentration profile is in good agreement with the measured values, deviations occur for the nitrate profile. However, the CFD simulations exceed the prediction accuracy of conventional 0D simulation software.     

Optimization models for planning shale gas well refracture treatments

Refracturing is a promising option for addressing the characteristically steep decline curves of shale gas wells. In this work we propose two optimization models to address the refracturing planning problem. First, we present a continuous‐time nonlinear programming model based on a novel forecast function that predicts pre‐ and post‐treatment productivity declines. Next, we propose a discrete‐time, multi‐period mixed‐integer linear programming (MILP) model that explicitly accounts for the possibility of multiple refracture treatments over the lifespan of a well. In an attempt to reduce solution times to a minimum, we compare three alternative formulations against each other (big‐M formulation, disjunctive formulation using Standard and Compact Hull‐Reformulations) and find that the disjunctive models yield the best computational performance. Finally, we apply the proposed MILP model to two case studies to demonstrate how refracturing can increase the expected recovery of a well and improve its profitability by several hundred thousand USD. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4297–4307, 2016     

Structural Impact of Single Ribonucleotide Residues in DNA

Single ribonucleotide intrusions represent the most common nonstandard nucleotide type found incorporated in genomic DNA, yet little is known of their structural impact. This lesion incurs genomic instability in addition to affecting the physical properties of the DNA. To probe for structural and dynamic effects of single ribonucleotides in various sequence contexts—AxC, CxG, and GxC, where x=rG or dG—we report the structures of three single‐ribonucleotide‐containing DNA duplexes and the corresponding DNA controls. The lesion subtly and locally perturbs the structure asymmetrically on the 3′ side of the lesion in both the riboguanosine‐containing and the complementary strand of the duplex. The perturbations are mainly restricted to the sugar and phosphodiester backbone. The ribose and 3′‐downstream deoxyribose units are predominately in N‐type conformation; backbone torsion angles ? and/or ζ of the ribonucleotide or upstream deoxyribonucleotide are affected. Depending on the flanking sequences, the C2′?OH group forms hydrogen bonds with the backbone, 3′‐neighboring base, and/or sugar. Interestingly, even in similar purine‐rG‐pyrimidine environments (A‐rG‐C and G‐rG‐C), a riboguanosine unit affects DNA in a distinct manner and manifests different hydrogen bonds, which makes generalizations difficult.