Towards a metallic quasi‐d9 system without copper: AgO at high pressure

AgO is a prototypical mixed‐valence compound, with markedly different coordination environment of dumbbell Ag(1+) and low‐spin square‐planar Ag(3+) which render it a narrow band gap semiconductor. The hybrid HSE06 functional reproduces fairly well the band gap of its P 2₁/c form at ambient conditions (ΔE_exp = 1.0–1.1 eV, ΔE_theor = 0.94 eV) and suggest progressive band gap decrease with external pressure with metallization at 50 GPa via band overlap. Dynamic (phonon) instability appears at the onset of metallization leading to a structural phase transition to a more stable but still metallic $$P\stackrel{?}{1}$$ form. The density of electronic states at the Fermi level of the $$P\stackrel{?}{1}$$ polymorph is small and a pseudo‐gap at the Fermi level is preserved.

Illustration of the predicted P2₁/c → $$P\stackrel{?}{1}$$ transformation.     

Fractional plasticity for over-consolidated soft soil

The stress–strain response of over-consolidated soft soil, e.g., clay, is dependent on its pre-consolidation history and material state. In this study, a state-dependent constitutive model for over-consolidated soft soils is proposed by extending the fractional plasticity originally developed for granular soil. The state-dependent stress-dilatancy and peak failure behaviour of over-consolidated soft soil are analytically captured through stress-fractional gradient of the current yielding surface. In addition, a reference yielding surface describing the pre-consolidation history of soft soil is proposed. A combined hardening rule expressed as a function of both the incremental plastic volumetric and shear strains is suggested. To validate the proposed model, a series of drained and undrained test results of different soft soils with a wide range of over-consolidation ratios are simulated and compared. It is found that without using additional plastic potentials and state parameters, the developed fractional model can capture the state-dependent hardening and softening responses of soft soils subjected to different over-consolidation states.

     

Catalysis of water oxidation in acetonitrile by iridium oxide nanoparticles

Water oxidation catalysed by iridium oxide nanoparticles (IrO₂ NPs) in water–acetonitrile mixtures using [Ru^III(bpy)₃]³⁺ as oxidant was studied as a function of the water content, the acidity of the reaction media and the catalyst concentration. It was observed that under acidic conditions (HClO₄) and at high water contents (80% (v/v)) the reaction is slow, but its rate increases as the water content decreases, reaching a maximum at approximately equimolar proportions (≈25% H₂O (v/v)). The results can be rationalized based on the structure of water in water–acetonitrile mixtures. At high water fractions, water is present in highly hydrogen-bonded arrangements and is less reactive. As the water content decreases, water clustering gives rise to the formation of water-rich micro-domains, and the number of bonded water molecules decreases monotonically. The results presented herein indicate that non-bonded water present in the water micro-domains is considerably more reactive towards oxygen production. Finally, long term electrolysis of water–acetonitrile mixtures containing [Ru^II(bpy)₃]²⁺ and IrO₂ NPs in solution show that the amount of oxygen produced is constant with time demonstrating that the redox mediator is stable under these experimental conditions.     

Chlorine substitution promotes phenyl radical loss from C8‐phenoxy‐2′‐deoxyguanosine adducts: implications for biomarker identification from chlorophenol exposure

Chlorophenols are persistent organic pollutants, which undergo peroxidase‐mediated oxidation to afford phenolic radical intermediates that react at the C8‐site of 2′‐deoxyguanosine (dG) to generate oxygen‐linked C8‐dG adducts. Such adducts are expected to contribute to chlorophenol toxicity and serve as effective dose biomarkers for chlorophenol exposure. Electrospray ionization mass spectrometry (ESI‐MS) was employed to study collision induced dissociation (CID) for a family of such phenolic O‐linked C8‐dG adducts. Fragmentation of the deprotonated nucleosides demonstrates that an unexpected homolytic cleavage of the ether linkage to release phenyl radicals and a nucleoside distonic ion with m/z 281 competes effectively with commonly observed breakage of the glycosidic bond to release the deprotonated nucleobase. Increased chlorination of the phenyl ring enhances phenyl radical loss. Density functional theory calculations demonstrate that Cl‐substitution decreases phenyl radical stability but promotes homolytic breakage of the C8–phenyl bond in the C8‐dG adduct. The calculations suggest that phenyl radical loss is driven by destabilizing steric (electrostatic repulsion) interactions between the ether oxygen atom and ortho‐chlorines on the phenyl ring. The distonic ion at m/z 281 represents a unique dissociation product for deprotonated O‐linked C8‐dG adducts and may prove useful for selective detection of relevant biomarkers for chlorophenol exposure by tandem mass spectrometry using selective reaction monitoring. Copyright © 2015 John Wiley & Sons, Ltd.     

A Functional Role for Aβ in Metal Homeostasis? N‐Truncation and High‐Affinity Copper Binding

Accumulation of the β‐amyloid (Aβ) peptide in extracellular senile plaques rich in copper and zinc is a defining pathological feature of Alzheimer′s disease (AD). The Aβ1–x (x=16/28/40/42) peptides have been the primary focus of Cu^II binding studies for more than 15 years; however, the N‐truncated Aβ4–42 peptide is a major Aβ isoform detected in both healthy and diseased brains, and it contains a novel N‐terminal FRH sequence. Proteins with His at the third position are known to bind Cu^II avidly, with conditional log K values at pH 7.4 in the range of 11.0–14.6, which is much higher than that determined for Aβ1–x peptides. By using Aβ4–16 as a model, it was demonstrated that its FRH sequence stoichiometrically binds Cu^II with a conditional K_d value of 3×10^?14 M at pH 7.4, and that both Aβ4–16 and Aβ4–42 possess negligible redox activity. Combined with the predominance of Aβ4–42 in the brain, our results suggest a physiological role for this isoform in metal homeostasis within the central nervous system.     

GC-MS Study of the Products Cleaved from RP-18 Chemically Bonded Phases for TLC During Thermal Modification

JPC – Journal of Planar Chromatography – Modern TLC -     

Periodic solutions to impulsive differential inclusions with constraints

The existence of a periodic solution to an impulsive differential inclusion being invariant with respect to a non-convex set of state constraints is established by the use a Lefschetz type fixed-point theorem for set-valued maps.     

Classical solvability of 1‐D Cahn–Hilliard equation coupled with elasticity

In this paper, we prove the classical solvability of a nonlinear 1‐D system of hyperbolic–parabolic type arising as a model of phase separation in deformable binary alloys. The system is governed by the nonstationary elasticity equation coupled with the Cahn–Hilliard equation. The existence proof is based on the application of the Leray–Schauder fixed point theorem and standard energy methods. Copyright © 2006 John Wiley & Sons, Ltd.     

Approximative compactness and continuity of metric projector in Banach spaces and applications

First we prove that the approximative compactness of a nonempty set C in a normed linear space can be reformulated equivalently in another way.It is known that if C is a semi-Chebyshev closed and approximately compact set in a Banach space X,then the metric projectorπC from X onto C is continuous.Under the assumption that X is midpoint locally uniformly rotund,we prove that the approximative compactness of C is also necessary for the continuity of the projectorπC by the method of geometry of Banach spaces.Using this general result we find some necessary and sufficient conditions for T to have a continuous Moore-Penrose metric generalized inverse T~ ,where T is a bounded linear operator from an approximative compact and a rotund Banach space X into a midpoint locally uniformly rotund Banach space Y.