Non-Covalent Forces in Naphthazarin—Cooperativity or Competition in the Light of Theoretical Approaches

Non-covalent interactions responsible for molecular features and self-assembly in Naphthazarin C polymorph were investigated on the basis of diverse theoretical approaches: Density Functional Theory (DFT), Diffusion Quantum Monte Carlo (DQMC), Symmetry-Adapted Perturbation Theory (SAPT) and Car-Parrinello Molecular Dynamics (CPMD). The proton reaction paths in the intramolecular hydrogen bridges were studied. Two potential energy minima were found indicating that the proton transfer phenomena occur in the electronic ground state. Diffusion Quantum Monte Carlo (DQMC) and other levels of theory including Coupled Cluster (CC) employment enabled an accurate inspection of Potential Energy Surface (PES) and revealed the energy barrier for the proton transfer. The structure and reactivity evolution associated with the proton transfer were investigated using Harmonic Oscillator Model of Aromaticity - HOMA index, Fukui functions and Atoms In Molecules (AIM) theory. The energy partitioning in the studied dimers was carried out based on Symmetry-Adapted Perturbation Theory (SAPT) indicating that dispersive forces are dominant in the structure stabilization. The CPMD simulations were performed at 60 K and 300 K in vacuo and in the crystalline phase. The temperature influence on the bridged protons dynamics was studied and showed that the proton transfer phenomena were not observed at 60 K, but the frequent events were noticed at 300 K in both studied phases. The spectroscopic signatures derived from the CPMD were computed using Fourier transformation of autocorrelation function of atomic velocity for the whole molecule and bridged protons. The computed gas-phase IR spectra showed two regions with OH absorption that covers frequencies from 2500 cm−1 to 2800 cm−1 at 60 K and from 2350 cm−1 to 3250 cm−1 at 300 K for both bridged protons. In comparison, the solid state computed IR spectra revealed the environmental influence on the vibrational features. For each of them absorption regions were found between 2700–3100 cm−1 and 2400–2850 cm−1 at 60 K and 2300–3300 cm−1 and 2300–3200 cm−1 at 300 K respectively. Therefore, the CPMD study results indicated that there is a cooperation of intramolecular hydrogen bonds in Naphthazarin molecule.     

Metals in ALS TDP-43 Pathology

Amyotrophic lateral sclerosis (ALS), Alzheimer’s disease, Parkinson’s disease and similar neurodegenerative disorders take their toll on patients, caregivers and society. A common denominator for these disorders is the accumulation of aggregated proteins in nerve cells, yet the triggers for these aggregation processes are currently unknown. In ALS, protein aggregation has been described for the SOD1, C9orf72, FUS and TDP-43 proteins. The latter is a nuclear protein normally binding to both DNA and RNA, contributing to gene expression and mRNA life cycle regulation. TDP-43 seems to have a specific role in ALS pathogenesis, and ubiquitinated and hyperphosphorylated cytoplasmic inclusions of aggregated TDP-43 are present in nerve cells in almost all sporadic ALS cases. ALS pathology appears to include metal imbalances, and environmental metal exposure is a known risk factor in ALS. However, studies on metal-to-TDP-43 interactions are scarce, even though this protein seems to have the capacity to bind to metals. This review discusses the possible role of metals in TDP-43 aggregation, with respect to ALS pathology.     

Influence of vacuum on the porosity and mechanical properties in rotational molding

Rotational molding allows the production of seamless, hollow parts with a high degree of design flexibility. Nevertheless, the process has limitations such as long cycle times as long holding times are necessary to produce components free of air inclusions. Within the scope of this article, an experimental setup was developed to evaluate the possibility and resulting effects of using vacuum in the rotational molding process. For this purpose, trials with different vacuum pressure levels and holding times were carried out and the resulting porosity and surface quality as well as the mechanical properties of the specimens were determined. The investigations showed that the use of vacuum allows a significant reduction in porosity even at low holding times, which can considerably reduce the cycle time of the process. However, the extent of possible time saving is limited by the requirement of a good surface quality, on which the vacuum application shows no effect. Furthermore, the mechanical properties of the parts could be slightly improved by using vacuum. POLYM. ENG. SCI., 59:1544–1551 2019. © 2019 Society of Plastics Engineers     

Thermochemische Depolymerisation von Lignin zur Gewinnung von Aromaten

In order to develop a valorization strategy for lignin, commercially available Kraft lignin was converted with sub‐ and supercritical water in a high‐pressure vessel. The effects of reaction temperature and phase state on product formation were investigated by GC‐MS analysis. The basic information of these experiments serves to develop processes for the production of aromatic‐based chemicals from biomass.     

Recycling von marinen Sekundärrohstoffen

As a waste product, oyster shells pose a major environmental pollution problem and the reuse of the material is becoming increasingly important. Since the comminution process in the recycling of secondary raw materials defines the properties of the material, oyster shells were grinded using a planetary ball mill and an impact mill and the fractions obtained were analyzed in terms of size and shape and compared with each other. A comminuted material from the impact mill was used for a series of wetting experiments, which helped to demonstrate the surface free energy of the material.     

Carborane-Containing Matrix Metalloprotease (MMP) Ligands as Candidates for Boron Neutron-Capture Therapy (BNCT)

Based on the previously reported potent and selective sulfone hydroxamate inhibitors SC-76276, SC-78080 (SD-2590), and SC-77964, potent MMP inhibitors have been designed and synthesized to append a boron-rich carborane cluster by employing click chemistry to target tumor cells that are known to upregulate gelatinases. Docking against MMP-2 suggests binding involving the hydroxamate zinc-binding group, key H-bonds by the sulfone moiety with the peptide backbone residues Leu82 and Leu83, and a hydrophobic interaction with the deep P1’ pocket. The more potent of the two triazole regioisomers exhibits an IC₅₀ of 3.7 nM versus MMP-2 and IC₅₀ of 46 nM versus MMP-9.     

A comparative study of the electrical and mechanical properties of epoxy nanocomposites reinforced by CVD- and arc-grown multi-wall carbon nanotubes

In this study, three different types of multi-wall carbon nanotubes (MWCNTs) were compared as nanostructured reinforcements in epoxy polymers: commercially available CVD-MWCNTs, synthesised in an industrial process, aligned-CVD-MWCNTs and arc-grown MWCNTs, both obtained from a lab-scale processes. The nanocomposite properties were characterised by means of electron microscopy, rheological, electrical and mechanical methods. Industrial CVD-MWCNTs are favourable for the implication of an electrical conductivity in the epoxy due to their high tendency to form conducting networks. The less entangled structure of aligned-CVD-MWCNTs turns out to be favourable for an easy dispersion and low viscosity in epoxy at similar conductivities compared to the CVD-MWCNTs. Additionally, they provide the highest increase in fracture toughness (∼17%). Arc-grown MWCNTs do not offer any electrical conductivity in epoxy without sufficient purification methods. Their high level of impurities and short length further complicate the transfer of their good electrical and mechanical properties into the nanocomposite.