Effect of film thickness on the electro-reduction of molecular oxygen on electropolymerized cobalt tetra-aminophthalocyanine films

We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O₂) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O₂ reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O₂ to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy.     

Sorption of uranium by non-living water hyacinth roots

Summary Many studies have shown that water hyacinth (Eichhornia crassipes) roots can be used to accumulate high concentrations of organic as well as inorganic pollutants. They are currently used to remediate aquatic environments and aqueous solutions. In the present study, sorption of uranium from aqueous solutions by using dried roots of water hyacinth has been investigated. The sorption of uranium was examined as a function of initial concentration, pH, weight of roots and contact time. Five different concentrations 20, 40, 60, 80, and 100 μg ^. ml^-1 were used. Sorption proves to be very rapid and depend on pH, weight of roots and concentration of uranium. Maximum sorption capacity of water hyacinth roots was 64,000 U⁶⁺ μg/g. The sorption of uranium by water hyacinth roots follows a Langmuir isotherm.     

Stabilization of γ‘ phase in Bi<Subscript>4</Subscript>V<Subscript>2-x</Subscript>Fe<Subscript>x</Subscript><Superscript>II</Superscript>O<Subscript>11-1.5x</Subscript> series

Summary This work reports the room-temperature stabilization of the Bi₄V_2-xFe_x^IIO_11-1.5x γ ‘ phase, a promising ionic conductive material that finds application in solid oxide fuel cell and oxygen sensor devices. The Fe(II) cation proved to be a better stabilizer than Fe(III), which was previously used, since a lower substitution degree of V⁵⁺ is needed for the former. Powder X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry were used in these experiments.     

Synthesis of fluorinated imines and carbodiimides from azides via aza-Wittig reaction

The Staudinger reaction of fluoroalkylazides were studied. A series of N-fluoroalkylimines were synthesized via aza-Wittig reaction of N-fluoroalkyliminophosphoranes. The N,N′-difluoroalkylated carbodiimide was also synthesized via the reaction of N-fluoroalkyliminophosphoranes with carbon dioxide or carbon disulfide.     

Trennung,Identifizierung und Bestimmung von Bactericiden auf der Basis von halogenierten Aromaten mittels Gas-Chromatographie

The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection.     

2-Amino-4-bromobutanoic Acid

(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic.     

Lyotropic liquid crystalline poly(aryl ether ketone) copolymer containing phthalazinone moiety and biphenyl mesogen

A novel lyotropic liquid crystalline material poly(aryl ether ketone) copolymer containing phthalazinone moiety and biphenyl mesogen named P-8515 was developed by a mild solution polycondensation method. The molecular weight (M_n) was 53,000 and the value of molecular weight distribution index (MDI) was 2.49 detected by GPC. The critical concentration (C^∗) of P-8515 was 36 wt% and P-8515 exhibited characteristic nematic lyotropic liquid crystalline phases in NMP solution at different concentrations and the phase morphology changed to a typical threaded texture when shear forces were induced from PLM observations. The T_g value was 238 °C and the value for 5% weight loss temperature was 515 °C in nitrogen from DSC and TGA determinations, respectively.     

A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation

General photoactivation of electron donor–acceptor (EDA) complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane with visible light or natural sunlight was discovered. This practical and efficient mode enables the production of aryl radicals under mild conditions, providing an unrealized opportunity for two-step para-selective C–H functionalization of complex arenes. The novel mode for generating aryl radicals via an EDA complex was well supported by UV-vis absorbance measurements, nuclear magnetic resonance titration experiments, and density functional theory (DFT) calculations. The method was applied to the regio- and stereo-selective arylation of various N-heterocycles under mild conditions, yielding an assembly of challengingly linked heteroaryl–(hetero)aryl products. Remarkably, the meaningful couplings of bioactive molecules with structurally complex drugs or agricultural pharmaceuticals were achieved to display favorable in vitro antitumor activities, which will be of great value in academia or industry.

General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation of aryl radicals for C–H functionalization of arenes.     

Enhancing cell membrane phase separation for inhibiting cancer metastasis with a stimuli-responsive DNA nanodevice

Phase separation in cell membranes promotes the assembly of transmembrane receptors to initiate signal transduction in response to environmental cues. Many cellular behaviors are manipulated by promoting membrane phase separation through binding to multivalent extracellular ligands. However, available extracellular molecule tools that enable manipulating the clustering of transmembrane receptors in a controllable manner are rare. In the present study, we report a DNA nanodevice that enhances membrane phase separation through the clustering of dynamic lipid rafts. This DNA nanodevice is anchored in the lipid raft region of the cell membrane and initiated by ATP. In a tumor microenvironment, this device could be activated to form a long DNA duplex on the cell membrane, which not only enhances membrane phase separation, but also blocks the interaction between the transmembrane surface adhesion receptor and extracellular matrix, leading to reduced migration. We demonstrate that the ATP-activated DNA nanodevice could inhibit cancer cell migration both in vitro and in vivo. The concept of using DNA to regulate membrane phase separation provides new possibilities for manipulating versatile cell functions through rational design of functional DNA structures.

A DNA nanodevice is developed to enhance the cell membrane phase separation in a tumor microenvironment to weaken the formation of focal adhesion. As a result, the migration of cancer cells is inhibited both in vitro and in vivo.     

Quantum Information Entropies on Hyperbolic Single Potential Wells

In this work, we study the quantum information entropies for two different types of hyperbolic single potential wells. We first study the behaviors of the moving particle subject to two different hyperbolic potential wells through focusing on their wave functions. The shapes of these hyperbolic potentials are similar, but we notice that their momentum entropy densities change along with the width of each potential and the magnitude of position entropy density decreases when the momentum entropy magnitude increases. On the other hand, we illustrate the behaviors of their position and momentum entropy densities. Finally, we show the variation of position and momentum entropies Sx and Sp with the change of the potential well depth u and verify that their sum still satisfies the BBM inequality relation.