New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph2P(X)NH(C6H3Pri 2-2,6) (X = O,S) and (OPPh2)(O2SMe)N(C6H3Pri 2-2,6)

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ ₂–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph₂P(O)NR] with MeSO₂Cl in a 1:1 molar ratio. The precursor Ph₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O?P(C)₂–N–S(C)(?O)₂ skeleton.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Investigation of the complexation of essential oil components with cyclodextrins

The formation of inclusion complexes of six essential oil (EO) components (β-caryophyllene, cis-ocimene, trans-ocimene, sabinene hydrate (thujanol), γ-terpinene and α-terpineol) with six cyclodextrins (CDs) (α-CD, β-CD, γ-CD, HP-β-CD, RAMEB and CRYSMEB) was investigated by using static headspace-gas chromatography and UV–visible spectroscopy. Retention studies showed that CDs could efficiently reduce the volatility of EO components except for β-caryophyllene with α-CD. In this case, no inclusion complex was detected while for other compounds the formation of 1:1 inclusion complexes was observed. Results revealed that the inclusion stability mainly depends on geometric complementarity between encapsulated molecule and CD's cavity. Molecular modelling was used to investigate the complementarities between host and guest. Thus, CDs could efficiently be regarded as promising encapsulants for EO components leading to improve their application in cosmetic, pharmaceutical and agriculture fields.     

Free-radical selective functionalization of 1,4-naphthoquinones by perfluorodiacyl peroxides

Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity.     

Use of green alternative solvents in dispersive liquid-liquid microextraction: A review

Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the analytical chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low-density solvents, such as alkanols, switchable hydrophobicity solvents, and ionic liquids were the first and most popular replacements for halogenated solvents, which provided similar or better results than these classical dispersive liquid-liquid microextraction solvents. However, despite the good performances obtained with low-density solvents and ionic liquids, researchers have continued investigating in order to obtain even greener solvents for dispersive liquid-liquid microextraction. For that reason, in this review, the evolution over the last five years of the three types of solvents already mentioned and two of the most promising solvent alternatives (i.e., deep eutectic solvents and supramolecular solvents), have been studied in detail with the purpose of discussing which one provides the greenest alternative.     

Attempts for Developing Novel Sugar-Based and Sugar-Free Sea Buckthorn Marmalades

Sea buckthorn (Hippophaė rhamnoides L.) is recognized as a valuable source of vitamin C and antioxidants, frequently used as nutraceuticals and cosmeceuticals. In the present study, attempts are made to produce and characterize a novel type of marmalade using sea buckthorn berries processed at 102 °C into marmalade in two combinations, with whole cane or stevia sugar. Changes in the phytochemical profile, antioxidant activity, color, shelf-life, texture, microbiological, and sensorial characteristics were determined. The total carotenoids content in the marmalades were significantly different, with values of 0.91 ± 0.03 mg/g dry weight (DW) in the sample with whole sugar cane (C_z) and 2.69 ± 0.14 mg/g DW in the sample with Stevia sugar (C_s). Significant values of polyphenols were found, of 59.41 ± 1.13 mg GAE/g DW in C_z and 72.44 ± 2.31 mg GAE/g DW in C_s, leading to an antioxidant activity of 45.12 ± 0.001 μMol Trolox/g DW and 118.07 ± 0.01 μMol Trolox/g DW, respectively. Accelerated storage study showed a decrease in all the phytochemicals, however no significant changes were found in antioxidant activity. Values of <100 CFU/g for yeasts and molds and <5 CFU/g for Enterobacteriaceae after 21 days of storage at the room temperature of the marmalades were determined. The sensorial and color results were more than acceptable. Overall, the results highlighted the potential of using sea buckthorn as a potential rich source of bioactive compounds to be used in the sugar-based products manufacturing.     

The B-factor index for the binding site (BFIbs) to prioritize crystal protein structures for docking

Structural Chemistry - In cheminformatics, protein-ligand docking is a powerful tool applied for virtual screening, pose prediction, and binding affinity estimation. However, docking results depend...     

Wastes from Wood Extraction Used in Composite Materials: Behavior after Accelerated Weathering

New materials were obtained by incorporating in polypropylene (PP) matrix 60% wood wastes resulting after extraction with supercritical carbon dioxide, water, and ethanol. Structural, mechanical, thermal, and rheological characterizations, as well as moisture uptake of the composites, were evaluated before and after accelerated weathering. It was found that the extraction method influenced the composite properties due to the hydrophilic-hydrophobic balance. The addition of extracted fibers results in an increase in hardness and tensile properties and a decrease of impact strength as compared to PP.