A CaAl 2 Si 2 -Type Magnetic Semiconductor (Sr, Na)(Zn, Mn)2Sb2 Isostructural to 122-Type Iron-Based Superconductors

A new diluted magnetic semiconductor (Sr, Na)(Zn, Mn)2Sb2 has been successfully synthesized by doping Na and Mn into the parent compound SrZn 2 Sb 2 , which has a CaAl 2 Si 2 -type crystal structure (space group P 3 ¯ m 1 , No. 164, h P 5 ) isostructural to the 122-type iron-based superconductor CaFe 2 As 2 . No magnetic ordering has been observed when only spins are doped by (Zn, Mn) substitution. Only with carriers codoped by (Sr, Na) substitution, a ferromagnetic ordering occurs below the maximum Curie temperature T C ∼9.5 K. Comparing with other CaAl 2 Si 2 -type diluted magnetic semiconductors, we will show that negative chemical pressure suppresses the Curie temperature.

The First Dimeric Derivatives of the Glycopeptide Antibiotic Teicoplanin

Various dimeric derivatives of the glycopeptide antibiotic teicoplanin were prepared with the aim of increasing the activity of the parent compound against glycopeptide-resistant bacteria, primarily vancomycin-resistant enterococci. Starting from teicoplanin, four covalent dimers were prepared in two orientations, using an α,ω-bis-isothiocyanate linker. Formation of a dimeric cobalt coordination complex of an N-terminal L-histidyl derivative of teicoplanin pseudoaglycone has been detected and its antibacterial activity evaluated. The Co(III)-induced dimerization of the histidyl derivative was demonstrated by DOSY experiments. Both the covalent and the complex dimeric derivatives showed high activity against VanA teicoplanin-resistant enterococci, but their activity against other tested bacterial strains did not exceed that of the monomeric compounds.

Computational Estimation of the Acidities of Pyrimidines and Related Compounds

Pyrimidines are key components in the genetic code of living organisms and the pyrimidine scaffold is also found in many bioactive and medicinal compounds. The acidities of these compounds, as represented by their pKas, are of special interest since they determine the species that will prevail under different pH conditions. Here, a quantum chemical quantitative structure–activity relationship (QSAR) approach was employed to estimate these acidities. Density-functional theory calculations at the B3LYP/6-31+G(d,p) level and the SM8 aqueous solvent model were employed, and the energy difference ∆EH2O between the parent compound and its dissociation product was used as a variation parameter. Excellent estimates for both the cation → neutral (pKa1, R2 = 0.965) and neutral → anion (pKa2, R2 = 0.962) dissociations were obtained. A commercial package from Advanced Chemical Design also yielded excellent results for these acidities.

Attaining Low Lattice Thermal Conductivity in Half-Heusler Sublattice Solid Solutions: Which Substitution Site Is Most Effective?

Low thermal conductivity is an important materials property for thermoelectricity. The lattice thermal conductivity (LTC) can be reduced by introducing sublattice disorder through partial isovalent substitution. Yet, large-scale screening of materials has seldom taken this opportunity into account. The present study aims to investigate the effect of partial sublattice substitution on the LTC. The study relies on the temperature-dependent effective potential method based on forces obtained from density functional theory. Solid solutions are simulated within a virtual crystal approximation, and the effect of grain-boundary scattering is also included. This is done to systematically probe the effect of sublattice substitution on the LTC of 122 half-Heusler compounds. It is found that substitution on the three different crystallographic sites leads to a reduction of the LTC that varies significantly both between the sites and between the different compounds. Nevertheless, some common criteria are identified as most efficient for reduction of the LTC: The mass contrast should be large within the parent compound, and substitution should be performed on the heaviest atoms. It is also found that the combined effect of sublattice substitution and grain-boundary scattering can lead to a drastic reduction of the LTC. The lowest LTC of the current set of half-Heusler compounds is around 2 W/Km at 300 K for two of the parent compounds. Four additional compounds can reach similarly low LTC with the combined effect of sublattice disorder and grain boundaries. Two of these four compounds have an intrinsic LTC above ∼15 W/Km, underlining that materials with high intrinsic LTC could still be viable for thermoelectric applications.

Doping dependent electronic and magnetic ordering in mixed-valent La1−xSrxMnO3 thin films

We have investigated the collective electronic and magnetic orderings of a series of La1−xSrxMnO3 thin films grown epitaxially strained to (001) oriented strontium titanate substrates as a function of doping, x, for 0 ≤ x ≤ 0.4. We find that the ground states of these crystalline thin films are, in general, consistent with that observed in bulk crystals and thin film samples synthesized under a multitude of techniques. Our systematic study, however, reveal subtle features in the temperature dependent electronic transport and magnetization measurements, which presumably arise due to Jahn-Teller type distortions in the lattice for particular doping levels. For the parent compound LaMnO3 (x = 0), we report evidence of a strain-induced ferromagnetic ordering in contrast to the antiferromagnetic ground state found in bulk crystals.

Universal spin-glass behaviour in bulk LaNiO2, PrNiO2 and NdNiO2

Motivated by the recent discovery of superconductivity in infinite-layer nickelate thin films, we report on a synthesis and magnetization study on bulk samples of the parent compounds RNiO2 (R=La, Pr, Nd). The frequency-dependent peaks of the AC magnetic susceptibility, along with remarkable memory effects, characterize spin-glass states. Furthermore, various phenomenological parameters via different spin glass models show strong similarity within these three compounds as well as with other rare-earth metal nickelates. The universal spin-glass behaviour distinguishes the nickelates from the parent compound CaCuO2 of cuprate superconductors, which has the same crystal structure and d9 electronic configuration but undergoes a long-range antiferromagnetic order. Our investigations may indicate a distinctly different nature of magnetism and superconductivity in the bulk nickelates than in the cuprates.

Identification of a Thyroid Hormone Derivative as a Pleiotropic Agent for the Treatment of Alzheimer’s Disease

The identification of effective pharmacological tools for Alzheimer’s disease (AD) represents one of the main challenges for therapeutic discovery. Due to the variety of pathological processes associated with AD, a promising route for pharmacological intervention involves the development of new chemical entities that can restore cellular homeostasis. To investigate this strategy, we designed and synthetized SG2, a compound related to the thyroid hormone thyroxine, that shares a pleiotropic activity with its endogenous parent compound, including autophagic flux promotion, neuroprotection, and metabolic reprogramming. We demonstrate herein that SG2 acts in a pleiotropic manner to induce recovery in a C. elegans model of AD based on the overexpression of Aβ42 and improves learning abilities in the 5XFAD mouse model of AD. Further, in vitro ADME-Tox profiling and toxicological studies in zebrafish confirmed the low toxicity of this compound, which represents a chemical starting point for AD drug development.

Improved Anticancer Activities of a New Pentafluorothio-Substituted Vorinostat-Type Histone Deacetylase Inhibitor

The development of new anticancer drugs is necessary in order deal with the disease and with the drawbacks of currently applied drugs. Epigenetic dysregulations are a central hallmark of cancerogenesis and histone deacetylases (HDACs) emerged as promising anticancer targets. HDAC inhibitors are promising epigenetic anticancer drugs and new HDAC inhibitors are sought for in order to obtain potent drug candidates. The new HDAC inhibitor SF5-SAHA was synthesized and analyzed for its anticancer properties. The new compound SF5-SAHA showed strong inhibition of tumor cell growth with IC50 values similar to or lower than that of the clinically applied reference compound vorinostat/SAHA (suberoylanilide hydroxamic acid). Target specific HDAC inhibition was demonstrated by Western blot analyses. Unspecific cytotoxic effects were not observed in LDH-release measurements. Pro-apoptotic formation of reactive oxygen species (ROS) and caspase-3 activity induction in prostate carcinoma and hepatocellular carcinoma cell lines DU145 and Hep-G2 seem to be further aspects of the mode of action. Antiangiogenic activity of SF5-SAHA was observed on chorioallantoic membranes of fertilized chicken eggs (CAM assay). The presence of the pentafluorothio-substituent of SF5-SAHA increased the antiproliferative effects in both solid tumor and leukemia/lymphoma cell models when compared with its parent compound vorinostat. Based on this preliminary study, SF5-SAHA has the prerequisites to be further developed as a new HDAC inhibitory anticancer drug candidate.

In Silico Taste – Toxicological Study of Chlorfenvinphos, Dichlofluanid, Fonofos, or Methacrifos Partial Degradation Products

Toxicity is important factor to human and environment and can be tested in lab and by computerized models. ProTox-II is in Silico method to assess safety of chemicals to minimize risk health threating to human and other living organisms in nature. Taste of material is another character can be calculated in Silico model like virtualtaste. Here, first attempt of using two computerized methods and hypothetical partial degradation products of four toxics materials used to control agricultural productivity was carried out to predicate taste and toxicity characters. LD50, Toxicity Class, organ and end point toxicities, Tox21-Nuclear receptor signaling and stress response pathways of Chlorfenvinphos, Dichlofluanid, Fonofos, and Methacrifos with their hypothetical degradation products were calculated. Hypothetical degradation products were a results of (C-C, C-O, C-N, C-S, C-P, P-O, P-S, or N-S) bond breakage. The hypothesized degradation chemicals showed that most of them were with sour taste and their toxicity were less class compared to the parent compound but not to non-toxic material (Class 6, LD50 more than 5000 mg/kg). Also, they were structurally toxics and could be interact with molecular cellular target resulting than parent compound if they presented in required concentration.

Distribution, Function, and Evolution of a Gene Essential for Trichothecene Toxin Biosynthesis in Trichoderma

Trichothecenes are terpenoid toxins produced by species in 10 fungal genera, including species of Trichoderma. The trichothecene biosynthetic gene (tri) cluster typically includes the tri5 gene, which encodes a terpene synthase that catalyzes formation of trichodiene, the parent compound of all trichothecenes. The two Trichoderma species, Trichoderma arundinaceum and T. brevicompactum, that have been examined are unique in that tri5 is located outside the tri cluster in a genomic region that does not include other known tri genes. In the current study, analysis of 35 species representing a wide range of the phylogenetic diversity of Trichoderma revealed that 22 species had tri5, but only 13 species had both tri5 and the tri cluster. tri5 was not located in the cluster in any species. Using complementation analysis of a T. arundinaceum tri5 deletion mutant, we demonstrated that some tri5 homologs from species that lack a tri cluster are functional, but others are not. Phylogenetic analyses suggest that Trichoderma tri5 was under positive selection following its divergence from homologs in other fungi but before Trichoderma species began diverging from one another. We propose two models to explain these diverse observations. One model proposes that the location of tri5 outside the tri cluster resulted from loss of tri5 from the cluster in an ancestral species followed by reacquisition via horizontal transfer. The other model proposes that in species that have a functional tri5 but lack the tri cluster, trichodiene production provides a competitive advantage.