SkaSim – Skalierbare HPC‐Software für molekulare Simulationen in der chemischen Industrie

This article outlines advances in molecular modeling and simulation using massively parallel high‐performance computers (HPC). In the SkaSim project, partners from the HPC community collaborated with users from science and industry. The aim was to optimize the prediction of thermodynamic property data in terms of efficiency, quality and reliability using HPC methods. In this context, various topics were dealt with: atomistic simulation of homogeneous gas bubble formation, surface tension of classical fluids and ionic liquids, multicriteria optimization of molecular models, the development of the molecular simulation codes ls1 mardyn and ms2, atomistic simulation of gas separation processes, molecular membrane structure generators, transport resistors and the evaluation of predictive property data models based on specific mixture types.     

Chemical hydrodynamics of a downward microbubble flow for intensification of gas‐fed bioreactors

Bioreactors are of interest for value‐upgrading of stranded or waste industrial gases. Reactor intensification requires development of low cost bioreactors with fast gas–liquid mass transfer rate. Here we assess published reactor technology in comparison with a novel downward bubble flow created by a micro‐jet array. Compared to known technology, the advanced design achieves higher volumetric gas transfer efficiency (k_La per power density) and can operate at higher k_La. We measure the effect of four reactor heights (height‐to‐diameter ratios of 12, 9, 6, and 3) on the gas transfer coefficient k_L, total interfacial area a, liquid residence time distribution, energy consumption, and turbulent hydrodynamics. Leading models for predicting k_L and a are appraised with experimental data. The results show k_L is governed by “entrance effects” due to Higbie penetration dominate at short distances below the micro‐jet array, while turbulence dominates at intermediate distances, and finally terminal rise velocity dominates at large distances. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1399–1411, 2018     

Enhanced gas migration through permeable bubble networks within consolidated soft sediments

Many consolidated sediments experience in situ gas generation from methanogenesis, corrosion, or radiolysis reactions and can retain bubbles for long periods. Particular interest is motivated by the retention and acute release of flammable hydrogen from nuclear legacy waste sludge. X‐ray computed tomography was employed to observe 0.07–10 mm bubble populations within 30–1112 Pa yield strength Mg(OH)₂ sediments. High rates of partial coalescence were observed among sub‐millimeter microvoids, forming extensive bubble networks which spanned the 32 mm field of view. Lattice Boltzmann and Monte Carlo modeling demonstrated these networks to be highly pervious to gas, with effective diffusivities for hydrogen of 3.7–12.5 × 10^?5 m² s^?1. Continuous vessel‐spanning bubble networks, dynamic connectivity between ganglia of coalesced bubbles, Haines jumps, and composite diffusion through the gas and aqueous phase can account for enhanced gas migration over length‐scales of several meters, thus enabling chronic gas release from low‐intermediate strength sediments ( kPa) too strong for buoyant bubble ebullition and too weak for vertical channel formation. © 2018 The Authors. AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers. AIChE J, 64: 4131–4147, 2018     

The fate of iron during the alkali‐activation of synthetic (CaO‐)FeOx‐SiO2 slags: An Fe K‐edge XANES study

Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali‐activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeO_x–SiO₂ system, representing typical compositions of Fe‐rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali silicate solutions have been studied by means of X‐ray absorption near‐edge structure (XANES) spectroscopy at the Fe K‐edge. The iron in the slags was largely Fe²⁺, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali‐activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe‐rich slags studied here are not Fe‐analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.     

Microton irradiation induced tuning of dielectric properties of nano ZnO–natural rubber disks

The effect of electron beam irradiation of dielectric and conductivity properties of nano ZnO–natural rubber (NR) disks was investigated here. It is revealed that electric properties such as AC conductivity, dielectric constant, and loss tangent of the irradiated samples were improved significantly as compared to the non-irradiated samples, which have been associated with defects in the composites. The total number of dipoles was generated inside the polymer matrix upon irradiation depends on the dislocations formed inside the matrix. From the experiments, we observe that in the amorphous region electron beam irradiation fetches crosslinking and breakdown at the same time. The enhancement of the dielectric and conductivity properties demonstrates that nano ZnO–NR disks will be a promising candidate for the optoelectronic industry. Finally, we also examined the influences of temperature on the electrical conductivity of irradiated samples.     

A Systematic Approach to Achieving High Performance Hybrid Lighting Phosphors with Excellent Thermal‐ and Photostability

The authors have designed and synthesized a family of high‐performance inorganic–organic hybrid phosphor materials composed of extended and robust networks of one, two, and three dimensions. Following a bottom‐up solution‐based synthetic approach, these structures are constructed by connecting highly emissive Cu₄I₄ cubic clusters via carefully selected ligands that form strong Cu? N bonds. They emit intensive yellow‐orange light with high luminescence quantum efficiency, coupled with large Stokes shift, which greatly reduces self‐absorption. They also demonstrate exceptionally high framework‐ and photostability, comparable to those of commercial phosphors. The high stabilities are the result of significantly enhanced Cu? N bonds, as confirmed by the density functional theory (DFT) binding energy and electron density calculations. Possible emission mechanisms are analyzed based on the results of theoretical calculations and optical experiments. Two‐component white phosphors obtained by blending blue and yellow emitters reach an internal quantum yield as high as 82% and correlated color temperature as low as 2534 K. The performance level of this subfamily exceeds all other types of Cu–I based hybrid systems. The combined advantages make them excellent candidates as alternative rare‐earth element‐free phosphors for possible use in energy‐efficient lighting devices.     

Sputtered Titanium Carbide Thick Film for High Areal Energy on Chip Carbon‐Based Micro‐Supercapacitors

The areal energy density of on‐chip micro‐supercapacitors should be improved in order to obtain autonomous smart miniaturized sensors. To reach this goal, high surface capacitance electrode (>100 mF cm^?2) has to be produced while keeping low the footprint area. For carbide‐derived carbon (CDC) micro‐supercapacitors, the properties of the metal carbide precursor have to be fine‐tuned to fabricate thick electrodes. The ad‐atoms diffusion process and atomic peening effect occurring during the titanium carbide sputtering process are shown to be the key parameters to produce low stress, highly conductive, and thick TiC films. The sputtered TiC at 10^?3 mbar exhibits a high stress level, limiting the thickness of the TiC‐CDC electrode to 1.5 µm with an areal capacitance that is less than 55 mF cm^?2 in aqueous electrolyte. The pressure increase up to 10^?2 mbar induces a clear reduction of the stress level while the layer thickness increases without any degradation of the TiC electronic conductivity. The volumetric capacitance of the TiC‐CDC electrodes is equal to 350 F cm^?3 regardless of the level of pressure. High values of areal capacitance (>100 mF cm^?2) are achieved, whereas the TiC layer is relatively thick, which paves the way toward high‐performance micro‐supercapacitors.     

[4]Helicene–Squalene Fluorescent Nanoassemblies for Specific Targeting of Mitochondria in Live‐Cell Imaging

Ester, amide, and directly linked composites of squalene and cationic diaza [4]helicenes 1 are readily prepared. These lipid‐dye constructs 2 , 3 , and 4 give in aqueous media monodispersed spherical nanoassemblies around 100–130 nm in diameter with excellent stability for several months. Racemic and enantiopure nanoassemblies of compound 2 are fully characterized, including by transmission electron microscope and cryogenic transmission electron microscope imaging that did not reveal higher order supramolecular structures. Investigations of their (chir)optical properties show red absorption maxima ≈600 nm and red fluorescence spanning up to the near‐infrared region, with average Stokes shifts of 1350–1550 cm^?1. Live‐cell imaging by confocal microscopy reveals rapid internalization on the minute time scale and organelle‐specific accumulation. Colocalization with MitoTracker in several cancer cell lines demonstrates a specific staining of mitochondria by the [4]helicene–squalene nanoassemblies. To our knowledge, it is the first report of a subcellular targeting by squalene‐based nanoassemblies.     

Structural Insights into the Recognition of N2‐Aryl‐ and C8‐Aryl DNA Lesions by the Repair Protein XPA/Rad14

Aromatic amines are strongly carcinogenic. They are activated in the liver to give reactive nitrenium ions that react with nucleobases within the DNA duplex. The reaction occurs predominantly at the C8 position of the dG base, thereby giving C8‐acetyl‐aryl‐ or C8‐aryl‐dG adducts in an electrophilic aromatic substitution reaction. Alternatively, reaction with the exocyclic 2‐NH₂ group is observed. Although the C8 adducts retain base‐pairing properties, base pairing is strongly compromised in the case of the N² adducts. Here we show crystal structures of two DNA lesions, N²‐acetylnaphthyl‐dG and C8‐fluorenyl‐dG, within a DNA duplex recognized by the repair protein Rad14. The structures confirm that two molecules of the repair protein recognize the lesion and induce a 72 or 78° kink at the site of the damage. Importantly, the same overall kinked structure is induced by binding of the repair proteins, although the structurally different lesions result in distinct stacking interactions of the lesions within the duplex. The results suggest that the repair protein XPA/Rad14 is a sensor that recognizes flexibility. The protein converts the information that structurally different lesions are present in the duplex into a unifying sharply kinked recognition motif.     

"It Gets You Away From Everyday Life": Local Woodlands and Community Use—What Makes a Difference?

This paper explores who uses woodlands near their homes, why they visit, what benefits they believe they obtain and what makes the difference between them choosing to visit or not. In the research, supported by the Forestry Commission, a multi-method, user-led approach was used, based on focus groups, questionnaire surveys and on-site observation in relation to five different communities in the central belt of Scotland. The conclusions demonstrate the overriding importance of childhood woodland visits as predictors of adult patterns of use. Proximity of woodlands is important for regular woodland users and freedom from rubbish is the physical quality people care most about. The physical qualities that make a difference as to whether people visit woodlands or not include directional signs, good information boards, variety of trees and tidiness of appearance. Perceptions of woodlands differ according to age and sex but are predominantly positive across all groups sampled: most people feel at peace in a woodland.