POPs to COFs by post-modification: CO chemisorption and dissolution.

Porous organic polymers (POPs) and covalent organic frameworks (COFs) are hierarchical nano materials with variable applications. To our knowledge, this is the first report of a post-modified, non-renewable, DMSO-soluble M-POP/1,8-diazabicyclo[5.4.

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

We report on the reaction of ethylene-terminated heteroatoms (CX; X = N, O, and S) with CS/CO 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, , H/C nuclear magnetic resonance (NMR) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy methods verified the reaction of CS/CO with the ethylene-based substrates and subsequently the formation of cyclic products. The experimental data indicated the formation of the -form of imidazolidin-2-one and oxazolidin-2-one, while the -form was obtained for their thione correspondents.

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.

activation of green sorbents for CO capture upon end group backbiting.

Thermolysis of a urethane end group was observed as a first time phenomenon during activation. This unzipping mechanism revealed a new amine tethering point producing a diamine-terminated oligourea ([10]-OU), acting as a green sorbent for CO capturing. The oligomer backbites its end group to form propylene carbonate (PC), as proved by TGA-MS, which can reflect the polymer performance by maximizing its capturing capacity.

Chemisorption of CO by diamine-tetraamido macrocyclic motifs: a theoretical study.

Although alkanolamines have been systematically utilized for CO2 capture, intensive research efforts are still required to ultimately design more efficient CO2 sorbents with appropriate sorption characteristics. In this article, we have explored a series of diamine-tetraamido macrocyclic molecules with different organic linkers, namely, pyridine, phenylene, pyrrole, furan, and thiophene, for the titled purpose using quantum chemical calculations. The optimized structures of the sequestration reaction revealed the formation of a carbamate anion within the macrocyclic cavity that was stabilized through several intramolecular interactions compared to parent amines.

Morphological and Interaction Characteristics of Surface-Active Ionic Liquids and Palmitic Acid in Mixed Monolayers.

A series of water soluble, surface-active ionic liquids (SAILs), namely, 1-alkyl-3-methyl imidazolium chlorides ([C -mim]Cl) and their mixtures with palmitic acid (PA) are investigated in Langmuir monolayers and Langmuir-Blodgett films. It is inferred from the surface pressure-area isotherms that C -mim-IL mixes non-ideally with PA and stabilizes the binary mixed films. In addition, the residence of mim-IL at the water surface is enhanced as a function of the increasing alkyl side chain length.

CO 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 CO coupling with epoxides under ambient conditions was reported. Spectroscopic measurements indicated that CO 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 CO activation.

The eternal battle to combat global warming: (thio)urea as a CO 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+).

Encapsulation of ionic liquids inside cucurbiturils.

Cucurbit[n]urils (CBn, n = 6-8) serve as molecular receptors for imidazolium-based ionic liquids (ILs) in aqueous solution. The amphiphilic nature of 1-alkyl-3-methylimidazolium guests (Cnmim), with a cationic imidazolium residue and a hydrophobic alkyl chain, enabled their complexation with CBn through a combination of the hydrophobic effect and ion-dipole interactions. 1H NMR experiments revealed that the cavity of CBn can host the hydrophobic chain of the ILs, while one of the carbonyl rims served as a docking site for the imidazolium ring.

CO activation through C-N, C-O and C-C bond formation.

A comparative model for the chemisorption of CO was explored via three representative reaction pathways: carboxylation of cyclohexanone, carbonation of cyclohexanol, and carbamation of cyclohexylamine. The model substrates were activated using 1,8-diazabicyclo[5.4.

Biomaterials for CO Harvesting: From Regulatory Functions to Wet Scrubbing Applications.

A new series of 2-aminoethyl-benzene-based biomaterials, namely, dopamine (DOP), tyramine (TYR), phenylethylamine (PEA), and epinephrine (EPN), dissolved in dimethylsulfoxide (DMSO) have been investigated for CO capture upon activatiing their hydhydrochloride salts  with a NaOH pellet. Spectroscopic measurements, including ex situ ATR-FTIR, 1D and 2D NMR experiments have been applied to verify the formation of the sodium carbamate adducts (RR'N-CO Na). The emergence of new peaks in the IR spectra ranging between 1702 and 1735 cm together with the chemical shift within 157-158 ppm in the C NMR, as well as with cross-peaks obtained by H-N HSQC measurements at ca.

A catecholamine neurotransmitter: epinephrine as a CO wet scrubbing agent.

Bio-renewables are emerging as potential materials for CO2 sorption. Epinephrine is employed as a green scrubbing agent for CO2 capturing through the formation of a metal carbamate as proved by 1H, 13C and 1H-15N NMR and ex situ ATR-FTIR spectroscopy, as well as supported by quantum-chemical calculations.

A green sorbent for CO capture: α-cyclodextrin-based carbonate in DMSO solution.

Cyclodextrin (α-CD)/KOH pellet dissolved in DMSO was utilized to capture CO. KOH has a dual function of enhancing the nucleophilicity of the hydroxyl groups on the α-CD rims and acting as a desiccant. C NMR spectroscopy provided evidence for the chemisorption of CO through the formation of organic carbonate (RO-CO ·K).

Inedible saccharides: a platform for CO capturing.

The economic viability of eco-friendly and renewable materials promotes the development of an alternative technology for climate change mitigation. Investigations reported over the past few years have allowed understanding the mechanism of action for a wide spectrum of saccharides toward carbon dioxide (CO), in terms of reactivity, reversibility, stability and uptake. Exploiting bio-renewables, , inedible saccharides, to reduce the anthropogenic carbon footprint upon providing a sustainable and promising technology that is of interest to different groups of scientists, to overcome demerits associated with the current state-of-the-art aqueous amine scrubbing agents, following a "green chemistry guideline", by employing materials with properties relevant to the environment toward sustainable development.

New insights into the chemistry of ionic alkylorganic carbonates: a computational study.

A library of hydrogenated, perfluorinated aliphatic and aromatic (p-substituted) alcohols are selected together with a combination of superbases (SBs) and metal hydrides (MHs) to understand the thermodynamic parameters of the binary mixtures once serving as sorbents for the capture of COvia ionic organic alkyl-carbonate (RCO) formation. Data are obtained using density functional theory (DFT) calculations with the B3LYP/6-31+G* level of theory and compared with the experimental results acquired from the literature using different spectroscopic techniques. It is found that the capturing process has a favourable enthalpic contribution and an unfavourable entropic penalty regardless the identity of the base, where the enthalpy values of alcohol/MH binary mixtures are almost two-fold higher compared to their SB-based mixtures.

An investigation of carbon dioxide capture by chitin acetate/DMSO binary system.

Chitin is considered to be the second most abundant naturally-occurring polysaccharide. Also, dimethyl sulfoxide (DMSO) is the second highest dielectric constant polar solvent after water. Despite the low solubility of chitin in common organic solvents, and due to its high nitrogen content, it may serve as a potential scrubbing agent "wet scrubbing" for carbon dioxide (CO2) capturing as an alternative to monoethanolamine "renewables for renewables approach".

[n]-Oligourea-Based Green Sorbents with Enhanced CO2 Sorption Capacity.

A new series of [n]-oligoureas ([n]-OUs, n=4, 7, 10, and 12) green solid sorbents was prepared following a base-catalyzed, microwave-assisted oligomerization reaction. The materials were characterized by NMR and IR spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and XRD. Decomposition temperatures at 50 % weight loss (Td50 ) were ca.

New palladium(II) complexes bearing pyrazole-based Schiff base ligands: synthesis, characterization and cytotoxicity.

Reactions of 5-hydrazino-1,3-dimethyl-4-nitro-1H-pyrazole (1) with substituted benzaldehydes (2-5) in methanol gave the new substituted benzaldehyde (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)hydrazone Schiff base ligands (6-9) benzaldehyde (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)hydrazone (H-BDH, 6), 2,3-dimethoxybenzaldehyde (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)hydrazone (MeO-BDH, 7), 4-chlorobenzaldehyde (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)hydrazone (Cl-BDH, 8), and 4-hydroxybenzaldehyde (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)hydrazone (OH-BDH, 9) in moderate to excellent yields. Reactions of these pyrazole-based Schiff bases with [PdCl(2)(NCPh)(2)] in acetone at room temperature gave the trans-palladium(II) complexes trans-[PdCl(2)(L)(2)] (10-13) (L=6-9). The isolated compounds were characterized by their physical properties, elemental analysis, IR-, MS (EI)- and NMR-spectroscopy.