Formation of Temporary Negative Ions and Their Subsequent Fragmentation upon Electron Attachment to CoQ0 and CoQ0H2

Ubiquinone molecules have a high biological relevance due to their action as electron carriers in the mitochondrial electron transport chain. Here, we studied the dissociative interaction of free electrons with CoQ₀, the smallest ubiquinone derivative with no isoprenyl units, and its fully reduced form, 2,3-dimethoxy-5-methylhydroquinone (CoQ₀H₂), an ubiquinol derivative. The anionic products produced upon dissociative electron attachment (DEA) were detected by quadrupole mass spectrometry and studied theoretically through quantum chemical and electron scattering calculations. Despite the structural similarity of the two studied molecules, remarkably only a few DEA reactions are present for both compounds, such as abstraction of a neutral hydrogen atom or the release of a negatively charged methyl group. While the loss of a neutral methyl group represents the most abundant reaction observed in DEA to CoQ₀, this pathway is not observed for CoQ₀H₂. Instead, the loss of a neutral OH radical from the CoQ₀H₂ temporary negative ion is observed as the most abundant reaction channel. Overall, this study gives insights into electron attachment properties of simple derivatives of more complex molecules found in biochemical pathways.     

Regulatory impact of environmental standards on the eco-efficiency of firms

In this paper, we propose an approach to implement environmental standards into Data Envelopment Analysis (DEA) and in this way to measure their regulatory impact on eco-efficiency of firms. One standard feature of basic DEA models lies in the exogeneity of inputs, desirable and undesirable outputs. Taking into account the environmental constraints, we therefore apply the bounded variable DEA model. The regulatory impact is assessed as difference in eco-efficiency scores before and after fictive introduction of an environmental standard. Furthermore, we distinguish between weak and strong disposability of undesirable outputs and develop corresponding models. Assessing the regulatory impact of environmental standards in advance provides support for environmental policymakers in choosing appropriate instruments and in adjusting the intensity of regulation.     

Thermally‐activated post‐growth dewetting of fullerene C60 on mica

Understanding and controlling the growth and stability of molecular thin films on solid surfaces is necessary to develop nanomaterials with well‐defined physical properties. As a prominent model system in organic electronics, we investigate the post‐growth dewetting kinetics of the fullerene C₆₀ on mica with real‐time and in situ X‐ray scattering. After layer‐by‐layer growth of C₆₀, we find a thermally‐activated post‐growth dewetting, where the smooth C₆₀‐layer breaks up into islands. This clearly shows that growth is kinetically limited before the system moves over an activation barrier into an energetically favored configuration. From the temperature‐dependent dewetting kinetics we find an effective activation barrier of 0.33 eV, which describes both the temperature‐dependent macroscopic changes in the surface morphology and the microscopic processes of inter‐ and intralayer diffusion during dewetting.

     

Optical and electronic properties of air-stable organoboron compounds with strongly electron-accepting bis(fluoromesityl)boryl groups

Three compounds with phenyl (1), 4-tert-butylphenyl (2) and 4-N,N-diphenylaminophenyl (3) groups attached to bis(fluoromesityl)boryl ((FMes)₂B) through B–C bonds have been prepared. The restricted rotation about the B–C bonds of boron-bonded aryl rings in solution has been studied by variable-temperature ¹⁹F NMR spectroscopy, and through-space F–F coupling has been observed for 3 at low temperature. Steric congestion inhibits binding of 1 by Lewis bases DABCO and tBu₃P and the activation of H₂ in their presence. Photophysical and electrochemical studies have been carried out on 2, 3, and an analogue of 3 containing a bis(mesityl)boryl ((Mes)₂B) group, namely 4. Both 2 and 3 show bright emission in nonpolar solvents and in the solid-state, very strong electron-accepting ability as measured by cyclic voltammetry, and good air-stability. In addition, 2 displayed unusually long-lived emission (τ = 2.47 s) in 2-MeTHF at 77 K. The much stronger acceptor strength of (FMes)₂B than (Mes)₂B leads to significantly red-shifted emission in solution and the solid state, stronger emission solvatochromism, and significantly lower reduction potentials. Theoretical calculations confirm that 2 and 3 tend to form highly twisted excited states with good conjugation between one FMes group and the boron atom, which correlate well with their blue-shifted solid-state emissions and low k _r values in solution.     

The deterministic product location problem under a pick-by-order policy

This paper treats the product location problem in warehouses, i.e., stock keeping units (SKUs) are to be assigned to storage positions in order to minimize the resulting picking effort when retrieving SKUs in a pick-by-order environment. We restrict our view on warehouses having a single cross aisle and show that already very simple layouts consisting of only a single rack lead to NP-hard optimization problems. In addition to a complexity analysis for different layouts, elementary solution procedures are introduced and tested. Finally, we investigate the robustness of our deterministic problem when facing erroneous input data.     

Fibrillation of β-lactoglobulin at low pH in the presence of a complexing anionic polysaccharide

The influence of electrostatic complexation with κ-carrageenan was tested on the fibrillation process of β-lactoglobulin at pH 2.0. Morphology and structural development were monitored through cross correlation dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Scattering indicated that noncomplexed β-lactoglobulin monomers aggregated to form fibrils after 15-90 min of heating at 90 °C. However, electrostatic protein-carrageenan complexes found in the unheated system were unchanged by the thermal process. Images and scattering results showed that carrageenan complexes slowed fibrillation kinetics, possibly through reduction in available monomer concentration. Complexes adhered to fibrils at ends and junctions in TEM images, indicating interactive affinity with the fibers, presumably as heterogeneous nucleation sites.     

Synthesis and characterization of nanostructured sulfated zirconias

Thermally stable sulfated zirconia catalysts were synthesized via a new templating procedure and compared with standard zirconia materials prepared by precipitation without templates. Two preparation routes with various amphiphilic systems were employed as structure directing agents: (1) synthesis with hexadecyltrimethylammonium bromide, and (2) combined use of surfactant Brij-56^® and triblock-copolymer Pluronic P123^®. The formation of materials was characterized by TEM, SEM, X-ray diffraction as well as nitrogen adsorption and mercury intrusion techniques. Different self-assembling properties of the structure directing compounds led to sulfated zirconia materials exhibiting improved morphological and structural properties in terms of thermal stability, specific surface areas, pore diameters and porosity factors. Notably, hierarchical pore structures were obtained for the synthesis route via a combined use of Brij-56^® and P123^®. Moreover, the morphological features of these materials were evidenced by a significantly improved isomerization activity of n-butane.     

The biological targets of acivicin inspired 3-chloro- and 3-bromodihydroisoxazole scaffolds

Target analysis of acivicin derived 3-halodihydroisoxazoles scaffolds in living non-pathogenic and pathogenic bacteria.