Interfacial Behavior of Modified Nicotinic Acid as Conventional/Gemini Surfactants.

We report the synthesis and monolayer properties of conventional and gemini surfactants composed of nicotinic acid-based head groups with an emphasis on assessing how chemical structures affect the behavior of monolayers. A combination of Brewster angle microscopy and atomic force microscopy showed that pure hexadecyl nicotinate formed rippled strands in monolayers, and the gemini correspondents with either flexible or rigid organic linkers resulted in lobed-compact domains, which provides a simple method for patterning air-water and solid-air interfaces. The structural differences between conventional and gemini nicotinic acid-based surfactants could be explained by the interplay between line tension (that favors the formation of circular domains), balanced by dipole-dipole repulsion interaction between headgroups, which promotes extended domains. Miscibility and morphology studies of the modified nicotinic acid surfactants with palmitic acid demonstrated that the properties of mixed films can be controlled by the structure of the former. Excess Gibbs free energies of mixing indicated that the mixed films were less stable than the pure monolayers, and the positive deviations from ideality were the largest in the case of gemini surfactants.

The eternal battle to combat global warming: (thio)urea as a CO2 wet scrubbing agent.

(Thio)Urea scaffolds are best known for their importance as intermediates in organic synthesis. In this work, a mechanistic study of the reaction between urea (U), (2-hydroxyethyl)urea (U-EtOH) and thiourea (tU)/NaH in DMSO with CO2 was carried out. While both U/tU reacted with CO2via a 1 : 2 mechanism through the formation of the keto (thio)carbamide-carboxylate adducts (k-U/tU-CO2- Na+), U-EtOH gave mixed CO2-adducts composed of organic carbonate and carbamide-carboxylate moieties (Na+-CO2-U-Et-OCO2- Na+). Moreover, we recorded for the first time, a new type of bond, namely sodium carbamimidothiocarbonate (e-tU-SCO2- Na+), upon bubbling CO2 in the DMSO solution of tU due to the persistence of the enol form (e-tU) and the better nucleophilicity of sulfur over nitrogen focal points. The reaction mechanisms were proven by 1D and 2D nuclear magnetic resonance (NMR) and ex situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopies. The stability of these bonds was studied following the changes in 1H-NMR as a function of temperature, which indicated the reversibility of these reactions. Furthermore, the proposed mechanisms were explored theoretically via density functional theory (DFT) calculations by analyzing the energetics of the anticipated products.

Pyridinethiol-Assisted Dissolution of Elemental Gold in Organic Solutions.

Dissolution of elemental gold in organic solutions is a contemporary approach to lower the environmental burden associated with gold recycling. Herein, we describe fundamental studies on a highly efficient method for the dissolution of elemental Au that is based on DMF solutions containing pyridine-4-thiol (4-PSH) as a reactive ligand and hydrogen peroxide as an oxidant. Dissolution of Au proceeds through several elementary steps: isomerization of 4-PSH to pyridine-4-thione (4-PS), coordination with Au0 , and then oxidation of the Au0 thione species to AuI simultaneously with oxidation of free pyridine thione to elemental sulfur and further to sulfuric acid. The final dissolution product is a AuI complex bearing two 4-PS ligands and SO4 2- as a counterion. The ligand is crucial as it assists the oxidation process and stabilizes and solubilizes the formed Au cations.

CS2/CO2 Utilization Using Mukaiyama Reagent as a (Thio)carbonylating Promoter: A Proof-of-Concept Study.

We report on the reaction of ethylene-terminated heteroatoms (C2X; X = N, O, and S) with CS2/CO2 using Mukaiyama reagent (2-chloro-1-methylpyridinium iodide, CMPI) as a promoter for the preparation of imidazolidin-2-one, oxazolidin-2-one, 1,3-dioxolan-2-one, 1,3-dithiolan-2-one, and their thione counterparts at ambient temperature and pressure. Spectroscopic measurements, viz., 1H/13C nuclear magnetic resonance (NMR) and ex situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy methods verified the reaction of CS2/CO2 with the ethylene-based substrates and subsequently the formation of cyclic products. The experimental data indicated the formation of the enol-form of imidazolidin-2-one and oxazolidin-2-one, while the keto-form was obtained for their thione correspondents. Furthermore, density functional theory calculations revealed the stability of the keto- over the enol-form for all reactions and pointed out the solvent effect in stabilizing the latter.

CO2 coupling with epoxides catalysed by using one-pot synthesised, in situ activated zinc ascorbate under ambient conditions.

An in situ generated zinc ascorbate pre-catalyst for cyclic carbonate (CC) synthesis via CO2 coupling with epoxides under ambient conditions was reported. Spectroscopic measurements indicated that CO2 was inserted into the zinc ascorbate complex through the formation of an activated zinc carbonate catalyst upon abstracting the enediol protons with sodium hydride. The aliphatic diols were not activated under the applied conditions and did not interfere with either the process of cycloaddition or CO2 activation. The catalyst was active against different terminal epoxides, with a conversion of 75 and 85%, when propylene oxide and styrene oxide were used at 20 and 50 °C, respectively under 1 atm CO2 for 17 h, which was considered a good advancement for heterogeneous based catalysis. Moreover, green chemistry principles were applied to ultimately end up with more ecofriendly approaches for the synthesis of CC following a simple balloon technique. Herein, we used zinc as a sustainable metal, together with ascorbic acid as a bio-renewable material in addition to CO2 as a renewable feed-stock. Furthermore, waste prevention was achieved using the reaction side product, viz., NaBr as a co-catalyst.