A ferrocene-based heteroditopic ligand for electrochemical sensing of cations and anions

A ferrocene-based heteroditopic receptor containing urea and crown ether units shows electrochemical responses to dihydrogenphosphate and fluoride anions. K+ cations can only be detected in the presence of dihydrogenphosphate.     

General correlation model for some physical properties of saturated pure fluids

In this work, we use a general expression to accurately correlate the liquid density, the vaporization enthalpy, the surface tension, and the isobaric heat capacity of a saturated liquid versus temperature along the whole coexistence curve. The general expression used is the same for the four thermodynamic properties, and uses both critical and triple point values as reference. As representative examples of the use of the model, results are given for a set of 22 pure substances. We find that this general expression correlates the data with smaller or similar overall deviations when compared with other published models whose number of coefficients are the same or greater.     

Oscillator strengths and photoionisation cross sections for Rydberg transitions in acetaldehyde

Oscillator strengths for electronic transitions involving Rydberg states of acetaldehyde, as well as cross sections for all the dipole allowed photoionisation channels, all ending in the ground state of the molecular cation, are reported. The molecular quantum defect orbital method, which has proved to be reliable in previous applications to molecular Rydberg states, has been used. Despite its relevance for atmospheric chemistry and astrophysics, only a few data seem to be available in the literature. The continuity of the calculated differential oscillator strength across the ionisation threshold has been adopted as a quality criterion. To our knowledge, predictions of oscillator strengths for transitions to high-lying Rydberg states, as well as of photoionisation profiles on acetaldehyde are made here for the first time and we are not aware of any reported experimental data. We, thus, hope the present results may be useful in the interpretation of the spectrum of acetaldehyde and might be of help in future experimental measurements.     

Identification of archaeal proteins that affect the exosome function in vitro

Background  

The archaeal exosome is formed by a hexameric RNase PH ring and three RNA binding subunits and has been shown to bind and degrade RNA in vitro. Despite extensive studies on the eukaryotic exosome and on the proteins interacting with this complex, little information is yet available on the identification and function of archaeal exosome regulatory factors.     

Temporal reduction of the external gamma dose rate due to 137Cs mobility in sandy beaches

In the present paper the contribution to the external gamma dose rate due to ¹³⁷Cs in soil as a function of time is presented. Sampling sites were selected along the Calabria and Basilicata Regions coastal beaches (southern part of Italy) to assess the external gamma dose rate in air, 1 m above the ground level. A convection-dispersion model, with constant parameters was used to approximate the radiocesium soil vertical migration. The model was calibrated using the initial ¹³⁷Cs activity deposition in this region (Chernobyl fallout) and ¹³⁷Cs activity concentration down the soil profile, measured 10 years later. The dispersion coefficient and the advection velocity values, were respectively: 2.17 cm² y⁻¹ and 0.32 cm y⁻¹. The Radionuclide Software Package (RSP), which uses a Monte Carlo simulation code, was used to determine the primary ¹³⁷Cs gamma dose contribution in air 1 m above the ground surface. The resulting ¹³⁷Cs external dose rate ranged from 0.42 nGy h⁻¹ in 1986, to 0.05 nGy h⁻¹ in 2007.     

Exploring the Reactivity of α‐Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]‐Wittig Rearrangement and the Mechanistic Proposal Revisited

By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α‐lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]‐Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α‐lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron‐poor aryl groups that favor the anionic pathway.     

On the mechanism of electroluminescence emission by porous silicon layers

The analytical treatment of a model considering the electrooxidation of p-porous silicon layers under galvanostatic conditions is able to give account of experimental facts such as the shape and location of the electroluminescence peak as well as of the spectral shift of the electroluminescence peak produced by oxidation. The proposed model considers electroluminescence to be the result of electron injection into the conduction band by an adsorbed intermediate produced by electrooxidation of the surface coverage with hydrogen or siloxene of the silicon nanocrystallites. The access of holes to the surface is made possible by low accumulation layer conditions and is the rate determining step in the electroluminescence mechanism. In this way it is possible to give a satisfactory explanation to the shift towards the blue experimented by the electroluminiscence emission maximum as a consequence of electrooxidation.     

Understanding the Effect of Solvent Environment on the Interaction of Hydronium Ion with Biomass Derived Species: A Molecular Dynamics and Metadynamics Investigation

The addition of aprotic solvents results in higher reactivities and selectivities in many key aqueous phase biomass reactions, including the acid-catalyzed conversion of fructose to 5-hydroxyl methyl furfural (HMF). The addition of certain co-solvents inhibits the formation of humins via preferential solvation of key functional groups and can alter reaction kinetics. An important factor in this context is the relative stability of the hydronium ion (the catalyst) in the vicinity of the biomass moiety as compared to that in bulk, as it could determine its efficacy in the protonation step. Hence, in the present work, molecular dynamics (MD) simulations of HMF (the model product) and fructose (the model reactant) in acidic water and water-DMSO mixtures are performed to analyze their interaction with the hydronium ions. We show that the presence of DMSO favors the interaction of the hydronium ion with fructose, whereas it has a detrimental effect on the interaction of hydronium ion with HMF. Well-tempered metadynamics (WT-MTD) simulations are performed to determine the relative stability of the hydronium ion in the immediate vicinity of fructose and HMF, as compared to that in the bulk solvent phase, as a function of solvent composition. We find that DMSO improves the stabilization of the hydronium ions in the first solvation shell of fructose compared to that in the bulk solvent. On the other hand, hydronium ions become less stable in the immediate vicinity of HMF, as the concentration of DMSO increases.     

Electrochemical synthesis of 3,5-diphenyl-2(3H)-furanone

From electrochemical reduction of phenacyl bromide, 3,5-diphenyl-2(3H)-furanone was obtained as a side-product and its structure was determined by chemical and spectral techniques.