CO Hydrogenation on Cobalt‐Based Catalysts: Tin Poisoning Unravels CO in Hollow Sites as a Main Surface Intermediate

Site poisoning is a powerful method to unravel the nature of active sites or reaction intermediates. The nature of the intermediates involved in the hydrogenation of CO was unraveled by poisoning alumina‐supported cobalt catalysts with various concentrations of tin. The rate of formation of the main reaction products (methane and propylene) was found to be proportional to the concentration of multi‐bonded CO, likely located in hollow sites. The specific rate of decomposition of these species was sufficient to account for the formation of the main products. These hollow‐CO are proposed to be main reaction intermediates in the hydrogenation of CO under the reaction conditions used here, while linear CO are mostly spectators.     

Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction

The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. The orientation of H₂O is well known to affect the dissociation process, but H₂O orientation is hard to control because of its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single-atom sites (IrRu DSACs) to tune the H₂O adsorption configuration and orientation, thus optimizing its dissociation process. The electric field intensity of IrRu DSACs is over 4.00×10¹⁰ N/C. The ab initio molecular dynamics simulations combined with in situ Raman spectroscopy analysis on the adsorption behavior of H₂O show that the M−H bond length (M=active site) is shortened at the interface due to the strong local electric field gradient and the optimized water orientation promotes the dissociation process of interfacial water. This work provides a new way to explore the role of single atomic sites in alkaline hydrogen evolution reaction.     

Magnetic resonance study of a vanadium pentoxide gel

In this work we report results from continuous-wave (CW) and pulsed electron paramagnetic resonance (EPR) and proton nuclear magnetic resonance (NMR) studies of the vanadium pentoxide xerogel V₂O₅:nH₂O (n ≈ 1.6). The low temperature CW-EPR spectrum shows hyperfine structure due to coupling of unpaired V⁴⁺ electron with the vanadium nucleus. The analysis of the spin Hamiltonian parameters suggests that the V⁴⁺ ions are located in tetragonally distorted octahedral sites. The transition temperature from the rigid-lattice low-temperature regime to the high temperature liquid-like regime was determined from the analysis of the temperature dependence of the hyperfine splitting and the V⁴⁺ motional correlation time. The Electron Spin Echo Envelope Modulation (ESEEM) data shows the signals resulting from the interaction of ¹H nuclei with V⁴⁺ ions. The modulation effect was observed only for field values in the center of the EPR absorption spectrum corresponding to the single crystals orientated perpendicular to the magnetic field direction. At least three protons are identified in the xerogel by our magnetic resonance experiments: (I) the OH groups in the equatorial plane, (ii) the bound water molecules in the axial V=O bond and (iii) the free mobile water molecules between the oxide layers. Proton NMR lineshapes and spin-lattice relaxation times were measured in the temperature range between 150 K and 323 K. Our analysis indicates that only a fraction of the xerogel protons contribute to the measured conductivity.     

Phyllostictines A-D, oxazatricycloalkenones produced by Phyllosticta cirsii, a potential mycoherbicide for Cirsium arvense biocontrol

Phyllosticta cirsii, a fungal pathogen isolated from Cirsium arvense and proposed as biocontrol agent of this noxious perennial weed, produces in liquid cultures different phytotoxic metabolites with potential herbicidal activity. Four new oxazatricycloalkenones, named phyllostictines A-D, were isolated and characterized using essentially spectroscopic and chemical methods. Tested by leaf-puncture assay on the fungal host plant phyllostictine A proved to be highly toxic. The phytotoxicity decreases when both the dimension and the conformational freedom of the macrocyclic ring change, as in phyllostictines B and D, and it is totally lost when also the functionalization of the same ring is modified, as in phyllostictine C. Beside its phytotoxic properties, phyllostictine A has no antifungal activity, an interesting antibiotic activity only against Gram+ bacteria, and a noticeable zootoxic activity when tested at high concentrations. The integrity of the oxazatricycloalkenone system appears to be an important feature to preserve these activities.     

Quantitative analysis of protein adsorption via atomic force microscopy and surface plasmon resonance

Surface properties have a significant influence on the performance of biomedical devices. The influence of surface chemistry on the amount and distribution of adsorbed proteins has been evaluated by a combination of atomic force microscopy (AFM) and surface plasmon resonance (SPR). Adsorption of albumin, fibrinogen, and fibronectin was analyzed under static and dynamic conditions, employing self-assembled monolayers (SAMs) as model surfaces. AFM was performed in tapping mode with antibody-modified tips. Phase-contrast images showed protein distribution on SAMs and phase-shift entity provided information on protein conformation. SPR analysis revealed substrate-specific dynamics in each system investigated. When multi-protein solutions and diluted human plasma interacted with SAMs, SPR data suggested that surface chemistry governs the equilibrium composition of the protein layer.     

The formation of nanotubes and nanocoils of molybdenum disulphide

This work reports the successful realization of MoS₂ nanotubes by a novel intercalation chemistry and hydrothermal treatment. An inorganic-organic precursor of hexadecylamine (HDA) and molybdenum disulphide (MoS₂) were used in synthesizing the nanocomposite comprising laminar MoS₂ with HDA intercalated in the interlaminar spacing. The formation of MoS₂ nanotubes occurred during hydrothermal treatment (HT) by a self-organized rolling mechanism. The nanotubes were observed to have dimensions 2-12 m in length and inner diameters typically in the range of 25-100 nm. We also report the formation of amorphous nanocoils of MoS₂ obtained during similar procedures.     

Butadiene–isoprene copolymerization with V(acac)3‐MAO. Crystalline and amorphous trans‐1,4 copolymers

Butadiene‐isoprene copolymerization with the system V(acac)₃‐MAO was examined. Crystalline or amorphous copolymers were obtained depending on isoprene content. Both butadiene and isoprene units exhibit a trans‐1,4 structure and are statistically distributed along the polymer chain. Polymer microstructure, comonomer composition, and distribution along the polymer chain were determined by ¹³C and ¹H NMR analysis. The thermal and X‐ray behaviors of the copolymers were also investigated and compared with results from solid‐state ¹³C NMR experiments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4635–4646, 2007     

Highly fluorescent semiconductor core–shell CdTe–CdS nanocrystals for monitoring living yeast cells activity

Fluorescent semiconductor nanocrystals in quantum confinement regime (quantum dots) present several well-known features which make them very useful tools for biological labeling purposes. Low photobleaching rates, high chemical stability and active surface allowing conjugation to living cells explain the success of this labeling procedure over the commonly used fluorescent dyes. In this paper we report the results obtained with highly fluorescent core–shell CdTe–CdS (diameter=3–7 nm) colloidal nanocrystals synthesized in aqueous medium and conjugated to glucose molecules. The conjugated nanocrystals were incubated with living yeast cells, in order to investigate their glucose up-take activity in real time, by confocal microscopy analysis. PACS 87.83.+a; 61.46.Hk; 81.07.Ta     

Evaluation of Mechanical Properties and Water Vapor Permeability in Chitosan Biofilms Using Sorbitol and Glycerol

Summary: Chitosan biofilms were prepared with and without plasticizer (glycerol and sorbitol). The physical and mechanical properties of chitosan biofilms with and without plasticizer were evaluated. Chitosan was obtained from shrimp wastes and characterized. The film forming solution (FFS) was obtained through chitosan dissolution and drying. The solution had its pH adjusted to 6.0 and oven dried (40 °C, 24 h) with forced air circulation. Chitosan biofilms without plasticizer showed a tensile strength about 36% higher than biofilms produced with plasticizer. On the other hand, biofilms with plasticizer presented superior values of elongation. The permeability of the water vapor and color presented significant difference (p < 0.05) between all biofilms. Chitosan/plasticizer biofilms showed higher values of water vapor permeability in relation to chitosan biofilms without plasticizer.     

The Bar-Radical of a Class of Almost Alternative Baric Algebras

In this article we prove that, if (U, ω) is a finite dimensional baric algebra of (γ, δ) type over a field F of characteristic ≠ 2,3,5 such that γ² ? δ² + δ = 1 and δ ≠ 0,1, then rad(U) = R(U) ∩ (bar(U))², where R(U) is the nilradical (maximal nil ideal) of U.