The effect of structural changes on the self-assembly of novel green pyridinium-carboxylate gemini surfactants in Langmuir and Langmuir-Blodgett films.

Engineered molecules with tailored molecular structures have the potential to advance various disciplines by enhancing the properties of biological membranes. In this study, we investigated the fundamental interfacial behavior of newly synthesized, water insoluble, cationic pyridinium-carboxylate based gemini surfactants (GSs) using picolinic acid (PA), nicotinic acid (NA), and isonicotinic acid (INA) and their interactions with dipalmitoylphosphatidylcholine (DPPC) in Langmuir and Langmuir-Blodgett (LB) films. Two synthetic methodologies were employed: (a) connecting two alkyl pyridinecarboxylates through the nitrogen atoms with a xylenyl spacer, namely, PAGS, NAGS1, and INAGS; and (b) dimerizing two nicotinic acid molecules through ester linkages with 1,4-benzenedimethanol, and then quaternizing the pyridine nitrogens with hexadecyl chains to yield NAGS2. A combination of Brewster angle microscopy (BAM) and atomic force microscopy (AFM) imaging techniques yielded valuable insights into the morphology of the GS films and their mixtures with DPPC. Density functional theory (DFT) calculations were used to gain further information on the GSs structures and understand their assembly. The results indicate that the film of INAGS is the most hydrophobic film, and its monolayer is the least compressible. When the nitrogen atom and a carboxylate group of the headgroup are positioned closer to each other, the GS molecules tend to form aggregates instead of a continuous film which is observed for the INAGS surfactant. This observation is consistent with the DFT energy values of pair interactions, indicating that both PAGS and NAGS1 have closely packed conformations with high stabilization energy.

POPs to COFs by post-modification: CO2 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[5.4.0]undec-7-ene (DBU) upon atmospheric H2O/CO2 trapping after 48 h, forming a DBUH+·HCO3- adduct, as verified by solution carbon-13 nuclear magnetic resonance (13C NMR) spectroscopy. The success of the post-modification resulting from aldehyde enriched POPs was proven spectroscopically. The accessible functional group was reacted with excess monoethanolamine (MEA) resulting in the formation of M-POP. Away from CO2 physisorption, only few examples have been reported on the chemisorption process. One such example is the ethylene diamine-functionalized E-COF, capable of capturing CO2via carbamation. This was evidenced by several qualitative measurements including colorimetry and conductivity, which showed an unprecedented water solubility for a 2D COF material. The crystallinity of COFs as a result of post-modification was proven by powder X-ray diffraction (PXRD).

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.

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.

In situ activation of green sorbents for CO2 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 CO2 capturing. The oligomer backbites its end group to form propylene carbonate (PC), as proved by in situ TGA-MS, which can reflect the polymer performance by maximizing its capturing capacity. Cross polarization magic angle spinning (CP-MAS) NMR spectroscopy verified the formation of the proven ionic carbamate (1:2 mechanism) with a chemical shift at 161.7 ppm due to activation desorption at higher temperatures, viz., 100 °C (in vacuo) accompanied with bicarbonate ions (1:1 mechanism) with a peak centered at 164.9 ppm. Fortunately, the amines formed from in situ thermolysis explain the abnormal behavior (carbamates versus bicarbonates) of the prepared sample. Finally, ex situ ATR-FTIR proved the decomposition of urethanes, which can be confirmed by the disappearance of the pre-assigned peak centered at 1691 cm-1. DFT calculations supported the thermolysis of the urethane end group at elevated temperatures, and provided structural insights into the formed products.

Chemisorption of CO2 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. The reaction thermodynamics indicated that the macrocyclic compounds with pyridine, pyrrole and furan can effectively capture CO2. The results highlight the potential application of macrocyclic structures as efficient CO2 capturing agents.

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 ([Cn -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 C16 -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. Generally, the compressional moduli values decrease upon increasing the content of the mim-ILs over a wide range of compositions. Furthermore, film relaxation measurements indicate that the IL component is selectively excluded from the mixed films upon achieving a certain target pressure. Brewster angle microscope images demonstrate minimal changes on the PA domains in the presence of either C4 - and C8 -mim-ILs, whereas presence of the hexadecyl counterpart results in the formation of condensed sheets. Atomic force microscopy imaging of deposited films show the formation of propeller-like aggregates when C8 - or C16 -mim-IL is present in the mixed films.

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.

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.

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. The structure of the complexes was further analyzed by molecular dynamics (MD) simulations, which indicated that the cavity of CB6 can accommodate up to 5 carbon atoms, while the larger cavity of CB7 and CB8 can encapsulate longer alkyl chains in folded conformations. Isothermal titration calorimetry (ITC) experiments provided up to micromolar affinity of ILs to CBn in aqueous solution, which was independently quantified by indicator displacement titrations.

CO2 activation through C-N, C-O and C-C bond formation.

A comparative model for the chemisorption of CO2 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[5.4.0]undec-7-ene (DBU, an amidine superbase). For each of these reactions, the formation of the corresponding CO2 adducts was confirmed by 13C nuclear magnetic resonance and Fourier-transform infrared spectroscopy measurements. It was demonstrated that CO2 fixation occurred through either an enol-CO2 adduct (i.e. carboxylation), proton shuttling process (i.e. carbonation), or self-activation mechanism (i.e. carbamation). Volumetric adsorption measurements indicated that cyclohexanol was superior in its uptake capacity (11.7 mmol CO2 g-1 sorbent) in comparison to cyclohexylamine (9.3 mmol CO2 g-1 sorbent) or cyclohexanone (8.5 mmol CO2 g-1 sorbent). As supported by density functional theory calculations, this trend was expected given the fact that the carbonation reaction proceeded through a more thermodynamically favorable reaction process.

Biomaterials for CO2 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 CO2 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-CO2 - Na+). The emergence of new peaks in the IR spectra ranging between 1702 and 1735 cm-1 together with the chemical shift within 157-158 ppm in the 13C NMR, as well as with cross-peaks obtained by 1H-15N HSQC measurements at ca. 84 and 6.6 ppm verified the formation of RR'N-CO2 - Na+ products upon the chemical fixation of CO2. The CO2 sorption capacity of the examined biomaterials was evaluated volumetrically, with a maximum value of 8.18 mmol CO2·g-1 sorbent (36.0 (w/w)%, including both chemisorption and physisorption), for 5 (w/v)% solutions measured at 5 bar CO2 and 25 °C, for TYR and PEA. DFT calculations indicated that the intramolecular hydrogen bonding within the structural motif of EPN-N-CO2 - Na+ adduct provides an exceptional stability compared to monoethanolamine and other structurally related model compounds.

A catecholamine neurotransmitter: epinephrine as a CO2 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.

Inedible saccharides: a platform for CO2 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 (CO2), in terms of reactivity, reversibility, stability and uptake. Exploiting bio-renewables, viz., 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. The interdisciplinary nature of research in this area provides a large body of literature that would meet the interest of the broad readership of different multidisciplinary fields. Although many reports emphasize the use of biomass in various industrial products ranging from pharmaceutics, medical preparations, soaps, textiles, cosmetics, household cleaners, and so on, to our knowledge there is no focused article that addresses the application of saccharides for CO2 sequestration. In this review, we highlight the recent advances on the use of oligo-, poly- and cyclic saccharides to achieve a reversible binding of CO2. The future research directions are discussed to provide insight toward achieving sustainable development through implementing bio-renewables.

A green sorbent for CO2 capture: α-cyclodextrin-based carbonate in DMSO solution.

Cyclodextrin (α-CD)/KOH pellet dissolved in DMSO was utilized to capture CO2. KOH has a dual function of enhancing the nucleophilicity of the hydroxyl groups on the α-CD rims and acting as a desiccant. 13C NMR spectroscopy provided evidence for the chemisorption of CO2 through the formation of organic carbonate (RO-CO2 -·K+). This was supported by the spectral changes obtained using ex situ ATR-FTIR spectroscopy upon bubbling CO2. Activation of α-CD with NaH or bubbling with 13CO2 verified that chemisorption occurred solely via RO-CO2 -·K+ rather than inorganic bicarbonate. Volumetric gas uptake demonstrated a sorption capacity of 21.3 wt% (4.84 mmol g-1). To the best of our knowledge, this is the highest chemisorption value reported to date for CD-based sorbents. DFT calculations of the Gibbs free energies indicated that the formation of RO-CO2 -·K+ was more favoured at the primary carbinol rather than its secondary counterpart.

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 CO2via ionic organic alkyl-carbonate (RCO3-) 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. The utilisation of perfluorinated aliphatic alcohols instead of hydrogenated alcohols shows a negative impact on the formation of carbonate adducts, due to the less reactive alkoxide anion along the carbon skeleton, which is attributed to the low charge density of the nucleophilic oxygen atom. While perfluorinated phenol shows a higher reactivity than the parent phenol. The calculations indicate that the reactivity of phenolic compounds is highly affected by the electronic nature of the substituting groups, in which p-substituted phenols are more reactive towards CO2 capturing when electron releasing groups are utilised. A pronounced solvent effect is observed, in which the alkylcarbonate salts (RCO3- SBH+) are stabilized in solvents with high dielectric constant (e.g., DMSO and MeCN). Simulated NMR and IR spectra of RCO3- are consistent with those reported for the affiliated systems, which fortifies the results obtained for the unexplored substrate/MH mixtures, filling a gap in the literature of CO2 sequestration using CO2 binding organic liquids (CO2BOLs) and enabling a fair/quick prediction of potential substrates to be used as CO2 sorbents.

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". Briefly, a detailed investigation for the utilization of low molecular weight, chitin-acetate (CA) in DMSO for the capturing of CO2 is reported. As carbonation process takes place, the formation of ionic alkylcarbonate was confirmed throughout spectroscopic and computational studies. Supramolecular chemisorption was proven throughout (1)H Nuclear Magnetic Resonance ((1)H NMR) together with the absence of sorption of CO2 by the monomeric repeating unit, glucosamine hydrochloride. Further, Density Functional Theory (DFT) calculations supported the formation of the CA/CO2 adduct through a newly formed supramolecular ionic interaction and hydrogen bonding along the oligosaccharide backbone between the neighboring ammonium ion and hydroxyl functional groups. The sorption capacity was measured volumetrically within an in situ Attenuated Total Reflectance-Fourier Transform Infrared coupled (in situ ATR-FTIR) autoclave at 25.0°C, and 4.0bar CO2, with a maximum sorption capacity of 3.63 [Formula: see text] /gsorbent at 10.0% (w/v).

[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. 350 °C for all oligomers. Urea and urethane functional groups indicated by IR spectroscopy confirmed the formation of the sorbent. The CO2 capturing capacities were determined at 35 °C and 1.0 bar (gravimetric method). Accordingly, [10]-OU had the highest CO2 sorption capacity among the others (18.90 and 22.70 mg CO 2 gsorbent (-1) ) at two different activation temperatures (60 or 100 °C, respectively). Chemisorption was the principal mechanism for CO2 capture. Cyclic CO2 sorption/desorption measurements were carried out to test the recyclability of [10]-OU. Activating the sample at 60 °C, three stable CO2 sorption cycles were achieved after running the first cycle.

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. The cytotoxic effect of these complexes against the fast growing head and neck squamous carcinoma cells SQ20B and SCC-25 has been studied. The influence was dose dependent and varies by cell type. The complexes 11, 12, and 13 had higher clonogenic cytotoxic effect than cisplatin when tested on SQ20B cell line.