Mitigating heat dissipation in Raman lasers using coherent anti-stokes Raman scattering

We present a novel technique that intrinsically mitigates the quantum-defect heating in Raman lasers. The basic principle of this so-called "coherent anti-Stokes Raman scattering (CARS)-based heat mitigation" is to suppress the phonon creation in the Raman medium by increasing the number of out-coupled anti-Stokes photons with respect to the number of out-coupled Stokes photons. We demonstrate with the aid of numerical simulations that for a hydrogen and a silicon Raman laser, CARS-based heat mitigation efficiencies of at least 30% and 35%, respectively, can be obtained.     

Ab initio method for calculating electron-phonon scattering times in semiconductors: application to GaAs and GaP

We propose a fully ab initio approach to calculate electron-phonon scattering times for excited electrons interacting with short-wavelength (intervalley) phonons in semiconductors. Our approach is based on density functional perturbation theory and on the direct integration of electronic scattering probabilities over all possible final states with no ad hoc assumptions. We apply it to the deexcitation of hot electrons in GaAs, and calculate the lifetime of the direct exciton in GaP, both in excellent agreement with experiments. Matrix elements of the electron-phonon coupling, and their dependence on the wave vector of the final state and on the phonon modes, are shown to be crucial ingredients of the evaluation of electron-phonon scattering times.     

Chemical Behaviour of a Prototype Boryl(phosphino)carbene

We recently disclosed the synthesis of a novel “push–pull” boryl(phosphino)carbene. To determine the influence of this substitution pattern on the chemical behaviour, a study into the reactivity of the prototype ( 1 ) of this new family of B(sp²)‐substituted phosphinocarbenes was undertaken. Carbene 1 exhibits one of the most common intramolecular rearrangements of singlet carbenes, involving a 1,2‐mesityl shift, and typical [2+1] cycloaddition reactions with electron‐poor acrylonitrile. A pronounced α,β‐ambiphilic character was also shown by the reaction of 1 with benzaldehyde, leading to phosphorylalkene 4 . Due to its specific electronic properties, carbene 1 also exhibits unprecedented reactivity with chloroacrylonitrile, enabling the formation of bicyclo[1.1.0]phosphetanium salt 6 and borylcyclopropene 9 , which have been fully characterised by NMR spectroscopy and X‐ray crystallography.     

1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction

The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (U^VI, Np^V,VI, Am^III, Cm^III, and Pu^IV) from an acidic solution (3 M HNO₃). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture.     

Catalytic Asymmetric Torgov Cyclization: A Concise Total Synthesis of (+)‐Estrone

An asymmetric Torgov cyclization, catalyzed by a novel, highly Brønsted acidic dinitro‐substituted disulfonimide, is described. The reaction delivers the Torgov diene and various analogues with excellent yields and enantioselectivity. This method was applied in a very short synthesis of (+)‐estrone.     

Kinetics and efficiency displayed by supported and suspended TiO2 catalysts applied to the disinfection of Escherichia coli

TiO₂-mediated photocatalysis is widely used in a variety of applications and products in the environmental and energy fields, including photoelectrochemical conversion, self-cleaning surfaces, and especially water purification systems. The dimensionality of the structure of a TiO₂ material can affect its properties, functions, and more specifically, its photocatalytic performance. In this work, the photocatalytic inactivation of Gram-negative Escherichia coli using three photocatalysts, differing in their structure and other characteristics, was studied in a batch reactor under UVA light. The aim was to establish the disinfection efficiency of solid TiO₂ compared with that of suspended catalysts, widely considered as reference cases for photocatalytic water disinfection. The bacterial inactivation profiles obtained showed that: (1) the photoinactivation was exclusively related to the quantity of photons retained per unit of treated volume, irrespective of the characteristics of the photocatalyst and the emitted light flux densities; (2) across the whole UV light range studied, each of the photocatalytic solids was able to achieve more than 2 log bacterial inactivation with less than 2 h UV irradiation; (3) none of the used catalysts achieved a total bacterial disinfection during the treatment time. For each of the catalysts the quantum yield has been assessed in terms of disinfection efficiency, the 2D material showed almost the same performance as those of suspended catalysts. This catalyst is promising for supported photocatalysis applications.     

NMR studies of interactions of new CB2 cannabinoid receptor ligands with cyclodextrins hosts. Correlation with micellar electrokinetic chromatography and reversed phase high performance liquid chromatography

Three selective CB₂ cannabinoid receptor ligands have recently been discovered to be promising anti-inflammatory agents but their low water solubility hinder their per os administration. The popularity of the cyclodextrins, from a pharmaceutical standpoint lies on their ability to interact with poorly water-soluble drugs and improve their solubility. Herein, three experimental approaches for calculating the stability constant of complexes between the selective CB₂ ligands and either the β-CD or the HP-β-CD, were tested: nuclear magnetic resonance, micellar electrokinetic chromatography and high performance liquid chromatography in reversed phase. In NMR studies the calculated K values were relatively high and were between 1486 and 3571 M^?1 with β-CD. With HP-β-CD they were between 1203 and 2650 M^?1. Concerning the two others techniques the K values were found lower. In MECK studies with β-CD they were between 308 and 792 M^?1 and with HP-β-CD between 124 and 764 M^?1. Finally in RP-HPLC studies with β-CD, they were between 539 and 1144 M^?1 and with HP-β-CD between 196 and 396 M^?1. These calculated constants suggest that a complexation phenomenon occurs. A model for inclusion of one of the CB₂ ligands in the β-CD was then proposed from molecular modeling studies.     

Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.     

Gold(III) π-Allyl Complexes

Gold(III) π-complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of Pd^II π-allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π-allyl complexes, which have remained elusive so far. The (P,C)Au^III(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air-stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi-symmetric η³-coordination of the allyl moiety. The π-allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β-diketo enolates.