Environmental application of pulsed laser-induced incandescence

A portable instrument based on two-color laser-induced incandescence (LII) technique has been designed and developed for the detection of carbonaceous particles for environmental applications. The instrument has been calibrated by performing LII measurements at the exhaust of a home-made soot generator. The incandescence signal from particles sampled into the instrument has been compared with in situ, calibrated, LII measurements to correlate the incandescence signal by the instrument with particles concentration. Measurements of particulate with the LII instrument were then conducted in different environmental conditions, covering a wide range of concentration (from ambient air to cars’ exhaust). The detection limit of the LII instrument has been estimated to be in the range of 200 ng/m³. These measurements have been also compared with results obtained with a commercial aethalometer. The results show a linear relationship between the two sets of measurements, also in the case where significant variation of the carbon particles concentration has been observed over time. These observations allow us to infer that the two instruments are responding in the same way to different carbon particles load, size and nature.     

21α‐Fluoro‐7‐norvouacapane‐17β,21α‐lactone

The crystal structure of 21α‐fluoro‐7‐norvouacapane‐17β,21α‐lactone, C₂₀H₂₅FO₃, a new synthetic derivative of the diterpenoid 6α,7β‐di­hydroxy­vouacapan‐17β‐oic acid isolated from Pterodon polygalaeflorus Benth fruits, is described.     

Front Cover: Critical Assessment of pH-Dependent Lipophilicity Profiles of Small Molecules: Which One Should We Use and In Which Cases? (ChemPhysChem 24/2023)

Lipophilicity is a physicochemical property with wide relevance in drug design, computational biology, food, environmental and medicinal chemistry. Lipophilicity is commonly expressed as the partition coefficient for neutral molecules, whereas for molecules with ionizable groups, the distribution coefficient (D) at a given pH is used. The logD_pH is usually predicted using a pH correction over the logP_N using the pK_a of ionizable molecules, while often ignoring the apparent ion pair partitioning . In this work, we studied the impact of on the prediction of both the experimental lipophilicity of small molecules and experimental lipophilicity-based applications and metrics such as lipophilic efficiency (LipE), distribution of spiked drugs in milk products, and pH-dependent partition of water contaminants in synthetic passive samples such as silicones. Our findings show that better predictions are obtained by considering the apparent ion pair partitioning. In this context, we developed machine learning algorithms to determine the cases that should be considered. The results indicate that small, rigid, and unsaturated molecules with logP_N close to zero, which present a significant proportion of ionic species in the aqueous phase, were better modeled using the apparent ion pair partitioning . Finally, our findings can serve as guidance to the scientific community working in early-stage drug design, food, and environmental chemistry.     

ChemInform Abstract: Identification of Novel Cu,Ag, and Au Ternary Oxides from Global Structural Prediction.

Ab initio global structural prediction and specifically, the minima hopping method combined with high‐throughput calculations are used to explore the periodic table in search of novel oxide phases.     

Rechargeable sodium-ion battery based on a cathode of copper hexacyanoferrate

Journal of Solid State Electrochemistry - In this work, the performance of copper (II) hexacyanoferrate(III) (CuHCF) as a cathode material for sodium-ion batteries was studied. The compound was...     

Cation Co-intercalation in Potassium Copper(II) Hexacyanoferrates

The cation-insertion solid state electrochemistry of a potassium copper(II) hexacyanoferrate in contact with LiClO₄/DMSO, NaPF₆/DMSO, and KPF₆/DMSO electrolytes has been theoretically and experimentally studied using the voltammetry of immobilized particles methodology. Voltammetric data, combined with SEM/EDS analysis permit to determine a K_0.876Cu^II_1.328Fe^III_0.049[Fe^III_0.318Fe^II_0.682(CN)₆] stoichiometry for the synthesized solid. Separation of electronic and ionic contributions to Gibbs energy changes can be made based on cyclic voltammetric and open circuit potential measurements. These parameters can be combined to measure values of the Gibbs energy of cation-independent electron transfer of 7.2±0.4 (K⁺), 7.1±0.5 (Na⁺) kJ mol⁻¹, in close agreement with the expected independence of this parameter on the electrolyte cation. The reduction Fe(III) centers bound to cyano groups exhibit a cation-dependent, essentially Nernstian character which can be described in terms of Na⁺ and K⁺ insertion/deinsertion while in the case of Li⁺ electrolytes there is significant co-cation diffusion. Chronoamperometric data provide estimates of the diffusion coefficients of Na⁺, and K⁺ ions through the solid around 10⁻⁹ cm² s⁻¹.     

Ring-opening polymerization of lactones by mono(cyclopentadienyl)titanium complexes

Mono(cyclopentadienyl)titanium complexes of the general formula Ti(η⁵-C₅R₅)X₂OR' were designed as structurally well-defined mononuclear initiators for the ring-opening polymerization of four-, six-, and seven-membered lactones. Living pseudo-anionic mechanism with acyl-oxygen cleavage is suggested by various NMR spectroscopic studies as well as the isolation of the mono(insertion) products. The nature of the ancillary ligands lead to significant changes in the polymerization activity and is discussed in terms of electronic and steric effects.