Origin of the X‐ray magnetic circular dichroism at the L‐edges of the rare‐earths in RxR1−x′Al2 systems

An X‐ray magnetic circular dichroism (XMCD) study performed at the rare‐earth L_2,3‐edges in the R_xR_1?x′Al₂ compounds is presented. It is shown that both R and R′ atoms contribute to the XMCD recorded at the L‐edges of the selected rare‐earth, either R or R′. The amplitude of the XMCD signal is not directly correlated to the magnetization or to the value of the individual (R, R′) magnetic moments, but it is related to the molecular field acting on the rare‐earth tuned in the photoabsorption process. This result closes a longstanding study of the origin of the XMCD at the L‐edge of the rare‐earths in multi‐component systems, allowing a full understanding of the exact nature of these signals.     

On the mechanism of decomposition of the benzyl radical

The C₇H₇ potential energy surface was studied from first principles to determine the benzyl radical decomposition mechanism. The investigated high temperature reaction pathway involves 15 accessible energy wells connected by 25 transition states. The analysis of the potential energy surface, performed determining kinetic constants of each elementary reaction using conventional transition state theory, evidenced that the reaction mechanism has as rate determining step the isomerization of the 1,3-cyclopentadiene, 5-vinyl radical to the 2-cyclopentene,5-ethenylidene radical and that the fastest reaction channel is dissociation to fulvenallene and hydrogen. This is in agreement with the literature evidences reporting that benzyl decomposes to hydrogen and a C₇H₆ species. The benzyl high-pressure decomposition rate constant estimated assuming equilibrium between the rate determining step transition state and benzyl is k₁(T) = 1.44 × 10¹³T^0.453exp(−38400/T) s⁻¹, in good agreement with the literature data. As fulvenallene reactivity is mostly unknown, we investigated its reaction with hydrogen, which has been proposed in the literature as a possible decomposition route. The reaction proceeds fast both backward to form again benzyl and, if hydrogen adds to allene, forward toward the decomposition into the cyclopentadienyl radical and acetylene with high-pressure kinetic constants k₂(T) = 8.82 × 10⁸T^1.20exp(1016/T) and k₃(T) = 1.06 × 10⁸T^1.35exp(1716/T) cm³/mol/s, respectively. The computed rate constants were then inserted in a detailed kinetic mechanism and used to simulate shock tube literature experiments.     

Fisher zeros in the Kallen–Lehmann approach to 3D Ising model

The distribution of the Fisher zeros in the Kallen–Lehmann approach to three-dimensional Ising model is studied. It is argued that the presence of a non-trivial angle (a cusp) in the distribution of zeros in the complex temperatures plane near the physical singularity is realized through a strong breaking of the 2D Ising self-duality. Remarkably, the realization of the cusp in the Fisher distribution ultimately leads to an improvement of the results of the Kallen–Lehmann ansatz. In fact, excellent agreement with Monte Carlo predictions both at high and at low temperatures is observed. Besides, agreement between both approaches is found for the predictions of the critical exponent α   and of the universal amplitude ratio Δ=A₊/A₋$\Delta =A_{+}/A_{-}$, within the 3.5% and 7% of the Monte Carlo predictions, respectively.     

Coherent Superpositions of Photon Creation Operations and Their Application to Multimode States of Light

We present a concise review of recent experimental results concerning the conditional implementation of coherent superpositions of single-photon additions onto distinct field modes. Such a basic operation is seen to give rise to a wealth of interesting and useful effects, from the generation of a tunable degree of entanglement to the birth of peculiar correlations in the photon numbers and the quadratures of multimode, multiphoton, states of light. The experimental investigation of these properties will have an impact both on fundamental studies concerning, for example, the quantumness and entanglement of macroscopic states, and for possible applications in the realm of quantum-enhanced technologies.     

Kinetic and Stoichiometric Parameters in the Production of Carotenoids by <Emphasis Type="Italic">Sporidiobolus salmonicolor</Emphasis> (CBS 2636) in Synthetic and Agroindustrial Media

With the objective of determining the kinetic behavior (growth, substrate, pH, and carotenoid production) and obtain the stoichiometric parameters of the fermentative process by Sporidiobolus salmonicolor in synthetic and agroindustrial media, fermentations were carried out in shaken flasks at 25°C, 180 rpm, and initial pH of 4.0 for 120 h in the dark, sampling every 6 h. The maximum concentrations of total carotenoids in synthetic (913 μg/L) and agroindustrial (502 μg/L) media were attained approximately 100 h after the start of the fermentative process. Carotenoid bioproduction is associated with cell growth and the ratio between carotenoid production and cell growth (Y _P/X) is 176 and 163 μg/g in the synthetic and agroindustrial media, respectively. The pH of the agroindustrial fermentation medium varied from 4.2 to 8.5 during the fermentation. The specific growth rate (μ _X) for S. salmonicolor in synthetic and agroindustrial media was 0.07 and 0.04 h⁻¹, respectively. The synthetic medium allowed for greater productivity, obtaining maximum cell productivity (P _x) of 0.08 g L⁻¹ h⁻¹ and maximum total carotenoid productivity (P _car) of 14.2 μg L⁻¹ h⁻¹. Knowledge of the kinetics of a fermentative process is of extreme importance when transposing a laboratory experiment to an industrial scale, as well as making a quantitative comparison between different culture conditions.     

Microwave-assisted organocatalytic multicomponent Knoevenagel/hetero Diels-Alder reaction for the synthesis of 2,3-dihydropyran[2,3-c]pyrazoles

A rapid protocol for the multicomponent microwave-assisted organocatalytic domino Knoevenagel/hetero Diels-Alder reaction (DKHDA) has been developed for the synthesis of 2,3-dihydropyran[2,3-c]pyrazoles. The reported procedure could be used for the fast generation of novel substituted 2,3-dihydropyran[2,3-c]pyrazoles with potential anti-tuberculosis activity.     

Environmental biodegradation of synthetic polymers I. Test methodologies and procedures

Biodegradation of synthetic polymers is an important property that is used in many applications. Evaluation of the extent of biodegradation has used different methods in recent years. For each environmental compartment, different approaches have to be made in order to obtain valuable data on biodegradability.This review describes validated and accepted methods based on standardized biodegradation tests, analytical tests, enzymatic tests or tests of physical properties to evaluate the biodegradability of synthetic polymers for different types of environmental compartments (e.g., soil, compost or aqueous media).Part II of this review will subsequently report on the environmental biodegradation of different groups of synthetic polymers.     

Regioselectivity Control in the Metal‐Catalyzed Functionalization of γ‐Allenols,Part 2: Theoretical Study

Calculating cyclization : Theoretical work directed towards the elucidation of the mechanisms of the gold‐, palladium‐, and lanthanum‐catalyzed oxycyclizations (5‐exo versus 6‐endo versus 7‐endo) of γ‐allenols has been pursued in close relationship with the experimental study (Part 1, accompanying paper) and has corroborated the bench results to provide a complete study of the reactivity of γ‐allenols under different metal‐catalyzed conditions.

     

A Simple and Versatile Re‐Catalyzed Meyer–Schuster Rearrangement of Propargylic Alcohols to α,β‐Unsaturated Carbonyl Compounds

Rhenium does the job! A readily available rhenium complex efficiently catalyzed the direct Meyer–Schuster‐like rearrangement of different alkyl‐ and aryl‐substituted propargylic secondary and tertiary alcohols to the corresponding α,β‐unsaturated compounds, which were produced with virtually complete E stereoselectivity. The reaction proceeded under neutral conditions and no racemization of potentially enolizable stereocenters was observed.