Electronic structure and magnetism in transition metals doped 8-hydroxy-quinoline aluminum

We report the room-temperature ferromagnetism in transition metals (Co, Ni)-doped 8-hydroxy-quinoline aluminum (Alq3) by thermal coevaporation of high purity metal and Alq3 powders. For 5% Co-doped Alq3, a maximum magnetization of approximately 0.33 microB/Co at 10 K was obtained and ferromagnetic behavior was observed up to 300 K. The Co atoms interact chemically with O atoms and provide electrons to Alq3, forming new states acting as electron trap sites. From this, it is suggested that ferromagnetism may be associated with the strong chemical interaction of Co atoms and Alq3 molecules.     

Dependence of the closed-shell repulsive interaction on the overlap of the electron densities

The relationship between the closed-shell repulsive interactions and overlap of the electron densities is investigated. It is found that the repulsive interactions vary in almost direct proportion to the absolute size of the density overlaps.     

Preparation of Antimicrobial Ultrafine Cellulose Acetate Fibers with Silver Nanoparticles

Summary: A feasible method for the preparation of antimicrobial ultrafine fibers with silver nanoparticles was developed by direct electrospinning of a cellulose acetate (CA) solution with small amounts of silver nitrate followed by photoreduction. Silver nanoparticles in ultrafine CA fibers were stabilized by interactions with carbonyl oxygen atoms in CA. Ultrafine CA fibers with silver nanoparticles showed very strong antimicrobial activity.

TEM image of an ultrafine CA fiber electrospun from 10 wt.‐% CA solution with 0.5 wt.‐% AgNO₃.     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

Inhibition of phospholipase D2 induces autophagy in colorectal cancer cells

Autophagy is a conserved lysosomal self-digestion process used for the breakdown of long-lived proteins and damaged organelles, and it is associated with a number of pathological processes, including cancer. Phospholipase D (PLD) isozymes are dysregulated in various cancers. Recently, we reported that PLD1 is a new regulator of autophagy and is a potential target for cancer therapy. Here, we investigated whether PLD2 is involved in the regulation of autophagy. A PLD2-specific inhibitor and siRNA directed against PLD2 were used to treat HT29 and HCT116 colorectal cancer cells, and both inhibition and genetic knockdown of PLD2 in these cells significantly induced autophagy, as demonstrated by the visualization of light chain 3 (LC3) puncta and autophagic vacuoles as well as by determining the LC3-II protein level. Furthermore, PLD2 inhibition promoted autophagic flux via the canonical Atg5-, Atg7- and AMPK-Ulk1-mediated pathways. Taken together, these results suggest that PLD2 might have a role in autophagy and that its inhibition might provide a new therapeutic basis for targeting autophagy.     

Der geschwindigkeitsbestimmende Schritt bei der Decarboxy-lierung von 2,4-Dihydroxybenzoesäure in mässig konzentrierter wässeriger Salzsäure

The decarboxylation kinetics of 2,4-dihydroxybenzoic acid have been studied in 0.1–8 N aqueous HCl at 50°. At low HCl concentrations, the observed first order rate constant, k, increases with increasing acidity of the solution. In solutions with 3.5–6 N HCl, k remains constant. The D₂O solvent isotope effect decreases from ^kH₂O/^kD₂O = 2.0 in 1N HCl to 1.3 in 5 N HCl, and it remains unchanged at 1.3 if the HCl concentration is increased further to 8 N. It is concluded that an increase of the acidity of the solution causes a change of the rate determining step from slow proton transfer to rate limiting C? C bond cleavage.     

Spectroscopic and Computational Insight into the Intermolecular Interactions between Zwitter‐Type Ionic Liquids and Water Molecules

Geometric and conformational changes of zwitter‐type ionic liquids (ZILs) due to hydrogen‐bonding interactions with water molecules are investigated by density functional theory (DFT), two‐dimensional IR correlation spectroscopy (2D IR COS), and pulsed‐gradient spin‐echo NMR (PGSE NMR). Simulation results indicate that molecular structures in the optimized states are strongly influenced by hydrogen bonding of water molecules with the sulfonate group or imidazolium and pyrrolidinium rings of 3‐(1‐methyl‐3‐imidazolio)propanesulfonate ( 1 ) and 3‐(1‐methyl‐1‐pyrrolidinio)propanesulfonate ( 2 ), respectively. Concentration‐dependent 2D IR COS reveals kinetic conformational changes of the two ZIL–H₂O systems attributable to intermolecular interactions, as well as the interactions of sulfonate groups and imidazolium or pyrrolidinium rings with water molecules. The dramatic changes in the ¹H self‐diffusion coefficients elucidate the formation of proton‐conduction pathways consisting of ZIL networks. In ZIL domains, protons are transferred by a Grotthuss‐type mechanism through formation, breaking, and restructuring of bonds between ZILs and H₂O, leading to an energetically favorable state. The simulation and experimental investigations delineated herein provide a perspective to understanding the interactions with water from an academic point of view as well as to designing ILs with desired properties from the viewpoint of applications.