Sensitivity Increase in Headspace Analysis of Hydrocarbons in Water by Using Online Selective Elimination of Gas Extractant

In this study, a novel approach in headspace gas chromatographic analysis using the selective absorption of the gas extractant during concentration of the analytes was developed. The carbon dioxide used as the gas extractant was removed from the sample flow by passing it through a column packed with microdispersed sodium hydroxide granules. The analytical capabilities of the suggested method were illustrated by the determination of aliphatic and aromatic hydrocarbons in water. We established that this method allows the preconcentration of analytes in the gas phase to be increased proportionally to the volume ratios of the gas extractant before and after absorption, while the analyte limits of detection decrease 30-fold. For example, benzene can be detected in water at a concentration of 0.5 μg/L.

Chemical profile of manually extracted andiroba oil (Carapa guianensis Aubl., Meliaceae) from Mamangal community, located in Igarapé-Miri, Pará, Brazil

Carapa guianensis species belongs to the Meliaceae family and, in the Brazilian Amazon, it has great importance in folk medicine, mainly because the oil extracted from its seeds presents varied biological activities. Thus, the present work aimed to analyze, by gas phase chromatography coupled to mass spectrometry (GC/MS), the chemical composition of manually extracted andiroba oil, from Mamangal community, located in Igarapé-Miri, Pará, Brazil. As results, 99.63% of the constituents of the oil sample were identified and quantified from which the main components were oleic, palmitic, stearic, and linoleic acids. The manual oil extraction from andiroba seeds in the Mamangal community is sustainable and economically viable. Due to the high content of saturated and unsaturated fatty acids C. guianensis oil can be considered interesting useful for pharmaceutical and cosmetic industries. Indeed, the unsaturated fatty acids represented 57.5% of the oil constituents, among which the essential ones stand out, as they have great applicability in healing drugs formulation.

Chalcogen···Chalcogen Bonding in Molybdenum Disulfide, Molybdenum Diselenide and Molybdenum Ditelluride Dimers as Prototypes for a Basic Understanding of the Local Interfacial Chemical Bonding Environment in 2D Layered Transition Metal Dichalcogenides

An attempt was made, using computational methods, to understand whether the intermolecular interactions in the dimers of molybdenum dichalcogenides MoCh2 (Ch = chalcogen, element of group 16, especially S, Se and Te) and similar mixed-chalcogenide derivatives resemble the room temperature experimentally observed interactions in the interfacial regions of molybdenites and their other mixed-chalcogen derivatives. To this end, MP2(Full)/def2-TVZPPD level electronic structure calculations on nine dimer systems, including (MoCh2)2 and (MoChCh′2)2 (Ch, Ch′ = S, Se and Te), were carried out not only to demonstrate the energetic stability of these systems in the gas phase, but also to reproduce the intermolecular geometrical properties that resemble the interfacial geometries of 2D layered MoCh2 systems reported in the crystalline phase. Among the six DFT functionals (single and double hybrids) benchmarked against MP2(full), it was found that the double hybrid functional B2PLYPD3 has some ability to reproduce the intermolecular geometries and binding energies. The intermolecular geometries and binding energies of all nine dimers are discussed, together with the charge density topological aspects of the chemical bonding interactions that emerge from the application of the quantum theory of atoms in molecules (QTAIM), the isosurface topology of the reduced density gradient noncovalent index, interaction region indicator and independent gradient model (IGM) approaches. While the electrostatic surface potential model fails to explain the origin of the S···S interaction in the (MoS2)2 dimer, we show that the intermolecular bonding interactions in all nine dimers examined are a result of hyperconjugative charge transfer delocalizations between the lone-pair on (Ch/Ch′) and/or the π-orbitals of a Mo–Ch/Ch′ bond of one monomer and the dπ* anti-bonding orbitals of the same Mo–Ch/Ch′ bond in the second monomer during dimer formation, and vice versa. The HOMO–LUMO gaps calculated with the MN12-L functional were 0.9, 1.0, and 1.1 eV for MoTe2, MoSe2 and MoS2, respectively, which match very well with the solid-state theoretical (SCAN-rVV10)/experimental band gaps of 0.75/0.88, 0.90/1.09 and 0.93/1.23 eV of the corresponding systems, respectively. We observed that the gas phase dimers examined are perhaps prototypical for a basic understanding of the interfacial/inter-layer interactions in molybdenum-based dichalcogenides and their derivatives.