Photocatalytic Water Oxidation by a Mixed‐Valent MnIII3MnIVO3 Manganese Oxo Core that Mimics the Natural Oxygen‐Evolving Center

The functional core of oxygenic photosynthesis is in charge of catalytic water oxidation by a multi‐redox Mn^III/Mn^IV manifold that evolves through five electronic states (S_i , where i=0–4). The synthetic model system of this catalytic cycle and of its S₀→S₄ intermediates is the expected turning point for artificial photosynthesis. The tetramanganese‐substituted tungstosilicate [Mn^III₃Mn^IVO₃(CH₃COO)₃(A‐α‐SiW₉O₃₄)]^6? (Mn₄POM) offers an unprecedented mimicry of the natural system in its reduced S₀ state; it features a hybrid organic–inorganic coordination sphere and is anchored on a polyoxotungstate. Evidence for its photosynthetic properties when combined with [Ru(bpy)₃]²⁺ and S₂O₈^2? is obtained by nanosecond laser flash photolysis; its S₀→S₁ transition within milliseconds and multiple‐hole‐accumulating properties were studied. Photocatalytic oxygen evolution is achieved in a buffered medium (pH 5) with a quantum efficiency of 1.7 %.     

Lifetime Shortening and Fast Energy‐Tansfer Processes upon Dimerization of a A‐π‐D‐π‐A Molecule

Time‐resolved fluorescence and transient absorption experiments uncover a distinct change in the relaxation dynamics of the homo‐dimer formed by two 2,5‐bis[1‐(4‐N‐methylpyridinium)ethen‐2‐yl)]‐N‐methylpyrrole ditriflate ( M ) units linked by a short alkyl chain when compared to that of the monomer M . Fluorescence decay traces reveal characteristic decay times of 1.1 ns and 210 ps for M and the dimer, respectively. Transient absorption spectra in the spectral range of 425–1050 nm display similar spectral features for both systems, but strongly differ in the characteristic relaxation times gathered from a global fit of the experimental data. To rationalize the data we propose that after excitation of the dimer the energy localizes on one M branch and then decays to a dark state, peculiar only of the dimer. This dark state relaxes to the ground state within 210 ps through non‐radiative relaxation. The nature of the dark state is discussed in relation to different possible photophysical processes such as excimer formation and charge transfer between the two M units. Anisotropy decay traces of the probe‐beam differential transmittance of M and the dimer fall on complete different time scales as well. The anisotropy decay for M is satisfactorily ascribed to rotational diffusion in DMSO, whereas for the dimer it occurs on a faster time scale and is likely caused by energy‐transfer processes between the two monomer M units.     

A Conductive polylactic acid/polyaniline porous scaffold via freeze extraction for potential biomedical applications

This paper reports for the first time a simple yet effective method for fabricating a conductive and highly porous scaffold material made up of polylactic acid (PLA) and conducting polyaniline (PANI). The electrical percolation state was successfully obtained at 3 wt% of PANI inclusions and reached a conductivity level of useable tissue engineering applications at 4 wt%. In addition, preliminary bioactivity test results indicated that the protonating agent could form a chelate at the scaffold surface leading to good in-vitro apatite forming ability during biomimetic immersion. This new conductive scaffold has potential as a suitable biomedical material that requires electrical conductivity.     

Increasing flexibility and productivity in Industry 4.0 production networks with autonomous mobile robots and smart intralogistics

Manufacturing flexibility improves a firm’s ability to react in timely manner to customer demands and to increase production system productivity without incurring excessive costs and expending an excessive amount of resources. The emerging technologies in the Industry 4.0 era, such as cloud operations or industrial Artificial Intelligence, allow for new flexible production systems. We develop and test an analytical model for a throughput analysis and use it to reveal the conditions under which the autonomous mobile robots (AMR)-based flexible production networks are more advantageous as compared to the traditional production lines. Using a circular loop among workstations and inter-operational buffers, our model allows congestion to be avoided by utilizing multiple crosses and analyzing both the flow and the load/unload phases. The sensitivity analysis shows that the cost of the AMRs and the number of shifts are the key factors in improving flexibility and productivity. The outcomes of this research promote a deeper understanding of the role of AMRs in Industry 4.0-based production networks and can be utilized by production planners to determine optimal configurations and the associated performance impact of the AMR-based production networks in as compared to the traditionally balanced lines. This study supports the decision-makers in how the AMR in production systems in process industry can improve manufacturing performance in terms of productivity, flexibility, and costs. 

     

Low temperature X-ray diffraction study of CdI2 crystals

Solid state structural transformations in polytypic crystals of cadmium iodide have been investigated at low temperatures using X-ray diffraction techniques. The crystals were cooled to liquid nitrogen and liquid helium temperatures employing three different methods. The results obtained are discussed on the basis of bond dissociation energies of interlayer and intralayer bonds and the possible mode of layer displacements in MX₂-type polytypic crystals.     

A Comparative Study of Existing Polytype Notations with Reference to the CdI2 Polytypes

Existing polytype notations have been critically examined to select a single notation which can describe the CdI₂ structures completely and most conveniently. A comparative study shows that the Zhdanov notation fulfils both the conditions. However, the ambiguities in the similar looking symbols is removed by employing some simple criteria proposed by Jain and Trigunayat for deciding the equivalent structures. Further, being numerical in nature this is the easiest notation to handle.     

Self-assembling of chain molecules in low dimensions: A Monte Carlo study

We studied the self-assembling of linear chain molecules in insoluble monolayers due to attractive interactions. We used lattice Monte Carlo simulations in a two-dimensional system. The molecules consist of segments occupying adjacent lattice sites. The head segments are confined to move along a line whereas the chain segments can arrange in a plane above the heads. Only one interaction parameter is applied. At high densities and small interaction energy the system shows percolation behavior. At moderate and small densities it can be characterized by a monotonous cluster size distribution. Self-assembling occurs at small densities for strong attractive interactions. The corresponding cluster size distributions indicate preferred cluster sizes which depend upon density and interaction strength. With increasing density the clusters grow. The internal cluster structure depends on the cluster size and the interaction parameter. The clusters tend to minimize their total energy. Molecules at cluster margins contribute less to the cluster energy and are mainly disordered. They cause that the cluster properties strongly depend on the cluster size. Large clusters only have minimum energy if the molecules in the cluster are in stretched-out conformation. With decreasing interaction strength the clusters get disordered thereby producing less energy-minimized domain boundaries.