Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.     

Exsolution of Nickel Nanoparticles from Mixed-Valence Metal Oxides: A Quantitative Evaluation by Magnetic Measurements

A fast and accurate experimental method is demonstrated to assess the fraction of exsolved metallic nanoparticles using magnetic measurements. As a benchmark, nanometric metallic nickel exsolved from (La_1−xSr_x)(Cr_1−yNi_y)O_3−δ is used for its high relevance as a solid oxide fuel cell component. The method is based on the difference in the magnetic response of the exsolved metallic nickel (ferromagnetic) and Sr-doped lanthanum chromite ceramic matrix (paramagnetic). The exsolved nickel results in coherent nanoparticles pinned on the surface of the Sr-doped lanthanum chromite ceramic matrix, as evidenced by electron microscopy analyses. The results obtained indicate the procedure as a fast and sensitive method to study the exsolution of ferromagnetic nanoparticles.     

Quantum mechanical modeling of Zn-based spinel oxides: Assessing the structural,vibrational, and electronic properties

The structural, electronic, and vibrational properties of two leading representatives of the Zn-based spinel oxides class, normal ZnX₂O₄ (X = Al, Ga, In) and inverse Zn₂MO₄ (M = Si, Ge, Sn) crystals, were investigated. In particular, density functional theory (DFT) was combined with different exchange-correlation functionals: B3LYP, HSE06, PBE0, and PBESol. Our calculations showed good agreement with the available experimental data, showing a mean percentage error close to 3% for structural parameters. For the electronic structure, the obtained HSE06 band-gap values overcome previous theoretical results, exhibiting a mean percentage error smaller than 10.0%. In particular, the vibrational properties identify the significant differences between normal and inverse spinel configurations, offering compelling evidence of a structure-property relationship for the investigated materials. Therefore, the combined results confirm that the range-separated HSE06 hybrid functional performs the best in spinel oxides. Despite some points that cannot be directly compared to experimental results, we expect that future experimental work can confirm our predictions, thus opening a new avenue for understanding the structural, electronic, and vibrational properties in spinel oxides.     

2-Methyltetrahydrofuran (2-MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP,FRP, and RAFT tandem polymerizations

2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines.     

A Journey from Thermally Tunable Synthesis to Spectroscopy of Phenylmethanimine in Gas Phase and Solution

Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined.     

Understanding the source of signal fluctuations in laser-induced breakdown spectroscopy analytical applications

A recent paper [¹] by the group of Prof. Zhe Wang, Beijing, China reveals the physical mechanism responsible of the signal fluctuations in laser-induced breakdown spectroscopy analysis.     

Synthesis of Ir Catalysts Featuring Amide-functionalized NHC Ligands and Survey of their Activity on Formic Acid Dehydrogenation

2 a and 2 b , [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), have been prepared via transmetallation from NHC−Ag complexes. [Rh(CI)(COD)(NHC)] ( 4 ) was prepared analogously. [Ir({κ-C,N-(NHC-acetamide−1H)}(COD)] ( 3 c ) has been synthesized via transmetallation from the deprotonated NHC−Ag complex. [IrCp*({κ-C,N-(NHC-acetamide−1H)}] ( 5 ) (Cp*=pentamethylcyclopentadienyl), has been obtained analogously. [Ir(CI)(CO)₂(NHC)] ( 6 ) and [Ir({κ-C,N-(NHC-acetamide−1H)}(CO)₂] ( 7 ) have been prepared by carbonylation of 2 b and 3 c , respectively. The catalytic activity of these complexes has been evaluated in the dehydrogenation of formic acid, under solventless conditions, in the presence of water as a cosolvent, and in a 5 : 2 HCOOH/Et₃N mixture, with the best TOF values being obtained in the case of the latter. Stoichiometric experiments suggest COD hydrogenation as the preactivation step.     

Non‐Invasive Salivary Electrochemical Quantification of Paraquat Poisoning Using Boron Doped Diamond Electrode

The present work describes the first electrochemical method for quantifying paraquat herbicide poisoning in human saliva samples. Paraquat shows two couples of well‐defined peaks in aqueous solution using a boron doped diamond (BDD) electrode. By using square wave voltammetry (SWV) technique under optimum experimental conditions, a linear analytical curve was obtained for paraquat concentrations ranging from 0.800 to 167 µmol L^?1, with a detection limit of 70 nmol L^?1. This method was applied to quantify paraquat spikes in human saliva samples and in two different water samples (tap and river). The recovery values obtained ranged from 83.0 to 104 % and 99.1 to 105 %, respectively, which highlight the accuracy of the proposed method.