Modification of Polycarbonate and Glycol Modified Poly(ethylene terephthalate) by Addition of Silica‐Nanoparticles Grafted with SAN Copolymer Using “Classical” and ARGET ATRP

This study presents a nanocomposite manufacturing route starting from non‐functionalized nanosilica and SAN surface modification via “grafting from” ATRP up to processing of transparent polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites. Synthesis limitations of low molecular weight graft SAN derived from “classical” ATRP are overcome by employment of the emerging ARGET ATRP. Mechanical investigations of polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites present up to 80% enhancement of creep performance and additionally 70% enhancement against wear abrasion for glycol modified poly(ethylene terephthalate) nanocomposites. Strength and tensile modulus are only moderately influenced by the addition of nanoparticles. Morphological studies confirm that the present modification route is able to create uniform dispersions of single particles and small particle aggregates in polymer matrices.

     

Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd^III (phen)₃ (NCX)₃] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN⁻ by SeCN⁻. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption.     

Mitochondrial Dysfunction in Spinocerebellar Ataxia Type 3 Is Linked to VDAC1 Deubiquitination

Dysfunctional mitochondria are linked to several neurodegenerative diseases. Metabolic defects, a symptom which can result from dysfunctional mitochondria, are also present in spinocerebellar ataxia type 3 (SCA3), also known as Machado–Joseph disease, the most frequent, dominantly inherited neurodegenerative ataxia worldwide. Mitochondrial dysfunction has been reported for several neurodegenerative disorders and ataxin-3 is known to deubiquitinylate parkin, a key protein required for canonical mitophagy. In this study, we analyzed mitochondrial function and mitophagy in a patient-derived SCA3 cell model. Human fibroblast lines isolated from SCA3 patients were immortalized and characterized. SCA3 patient fibroblasts revealed circular, ring-shaped mitochondria and featured reduced OXPHOS complexes, ATP production and cell viability. We show that wildtype ataxin-3 deubiquitinates VDAC1 (voltage-dependent anion channel 1), a member of the mitochondrial permeability transition pore and a parkin substrate. In SCA3 patients, VDAC1 deubiquitination and parkin recruitment to the depolarized mitochondria is inhibited. Increased p62-linked mitophagy, autophagosome formation and autophagy is observed under disease conditions, which is in line with mitochondrial fission. SCA3 fibroblast lines demonstrated a mitochondrial phenotype and dysregulation of parkin-VDAC1-mediated mitophagy, thereby promoting mitochondrial quality control via alternative pathways.     

Classifying and Formally Verifying Integer Constant Folding

Constant folding is a well-known optimization of compilers which evaluates constant expressions already at compile time. Constant folding is valid only if the results computed by the compiler are exactly the same as the results which would be computed at run-time by the target machine arithmetic. We classify different arithmetics by deriving a general condition under which a target-machine arithmetic can be replaced by a compiler arithmetic. Furthermore, we consider integer arithmetics as a special case. They can be described by residue class arithmetics. We show that these arithmetics form a lattice. Using the order relation in this lattice, we establish a necessary and sufficient criterion under which constant folding can be done in a residue class arithmetic that is different from the one of the target machine. Concerning formal verification, we have formalized our proofs in the Isabelle/HOL system. As examples, we discuss the Java and C integer arithmetics and show which compiler arithmetics are valid for constant folding. This discussion reveals also potential sources of incorrect behavior of C compilers.     

Design and Synthesis of Dihydroxamic Acids as HDAC6/8/10 Inhibitors

We report the synthesis and evaluation of a class of selective multitarget agents for the inhibition of HDAC6, HDAC8, and HDAC10. The concept for this study grew out of a structural analysis of the two selective inhibitors Tubastatin A (HDAC6/10) and PCI-34051 (HDAC8), which we recognized share the same N-benzylindole core. Hybridization of the two inhibitor structures resulted in dihydroxamic acids with benzyl-indole and -indazole core motifs. These substances exhibit potent activity against HDAC6, HDAC8, and HDAC10, while retaining selectivity over HDAC1, HDAC2, and HDAC3. The best substance inhibited the viability of the SK-N-BE(2)C neuroblastoma cell line with an IC₅₀ value similar to a combination treatment with Tubastatin A and PCI-34051. This compound class establishes a proof of concept for such hybrid molecules and could serve as a starting point for the further development of enhanced HDAC6/8/10 inhibitors.     

Effect of A-site substitutions on energy storage properties of BaTiO3-BiScO3 weakly coupled relaxor ferroelectrics

Weakly coupled relaxors based on compositions (1-x) BaTiO₃-xBiMeO₃, where Me is a metal ion, have attracted attention as potential candidates for high-temperature high-energy density capacitors. However, the necessary Bi content is typically high with x = 0.3-0.4. In order to reduce problems associated with compatibility for base metal electrodes and due to additional problems due to Bi volatility, it is desirable to lower the Bi content in the overall composition for these materials. Here, we have explored a possible way to reduce BiMeO₃ content through additional A-site substitutions viz. Ca and Sn. The relaxor nature and energy storage properties of Sn-modified (Ba,Ca)(Ti)O₃-BiScO₃ ceramics were determined from their dielectric and ferroelectric behaviors. The material showed attractive properties in terms of a frequency-independent (200 Hz-1 MHz) dielectric response from room temperature to 200°C, extremely low loss and high-energy storage efficiency. The structural phenomena underlying the functional properties of Sn-modified (Ba,Ca)TiO₃-BiScO₃ are characterized from temperature-dependent X-ray diffraction and pair distribution function analysis. In broader terms, the study illustrates the potential for tailoring relaxor behavior in Pb-free ferroelectrics by combining phenomena, such as quantum fluctuations and lone pair stereochemical effect associated with different solid-solution substitutions.