Carboxylate Anions Research Articles

High-Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions.

Organic room-temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade-off issue between luminescence efficiency (Φ) and dissymmetry factor (glum) is still challenging to be solved. Here, chiroptical ionic crystals (R/S-DNP) are constructed through ionization-induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long-range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high-density electrostatic interactions, thus enabling the simultaneous realization of excellent single-molecule RTP emission and efficient chirality transfer. The synchronous enhancement of ΦP and glum is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric-driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications.

Thermal and Luminescent Properties of Multi-Ligand Complexes of Europium(III) with Pyrazine-2-carboxylic Acid

Eu(III) compounds with pyrazine-2-carboxylic acid and nitrogen- and phosphorus-containing neutral ligands were synthesized. Using the methods of chemical elemental and thermal analysis and IR spectroscopy, the composition of the complexes and the method of coordination of carboxylate ions were established. The most thermally stable compounds have been identified. The luminescent characteristics of complex compounds have been studied. It was found that the maximum luminescence intensity is characteristic of europium(III) pyrazinate with triphenylphosphine oxide. The morphological structure and dispersion of the complexes were determined.

The Fischer‐Lactonization‐Driven Mechanism for Ultra‐Efficient Recycling of Spent Lithium‐Ion Batteries

AbstractHydrometallurgy remains a major challenge to simplify its complex separation and precipitation processes for spent lithium‐ion batteries (LIBs). Herein, we propose a Fischer‐lactonization‐driven mechanism for the cascade reaction of leaching and chelation of spent LIBs. Citric acid undergoes a two‐step dissociation of the carboxylic acid (−COOH) and complexes with the leached metal ion, while the residual −COOH is attacked by H protons to form a protonated carboxyl ion (−COO −). Subsequently, the lone pair of electrons in the hydroxyl of the same molecule attack the carbon atom in −COO − to facilitate ester bonding, leading to the formation of a lactonized gel. The leaching rates of Li, Ni, Co and Mn are 99.3, 99.1, 99.5 and 99.2 %, respectively. The regenerated monocrystalline LiNi0.5Co0.2Mn0.3O2 (NCM523) has a uniform particle size distribution and complete lamellar structure, with a capacity retention rate of 70.6 % after 250 cycles at 0.5 C. The mechanism achieves a one‐step chelation reaction, and the energy consumption and carbon emissions are only 26 % and 44 %, respectively, of that of the conventional hydrometallurgical. The strategy achieves a double breakthrough in simplifying the process and improving environmental friendliness, offering a sustainable approach to the re‐utilization of spent LIBs.

The Ordering and Arrangement of Intercalated Carboxylate Ions in Anion‐Exchangeable Layered Yttrium Hydroxides

AbstractThe intercalation chemistry is essential in the application of anion‐exchangeable layered metal hydroxides. However, much of the key information regarding intercalated anions, such as the degree of ordering and arrangement is still not clear or missing to date, due to the difficulty in probing the local environment of anions by routine characterization techniques. Herein, we employed solid‐state NMR (ssNMR) spectroscopy to offer valuable complementary insights into the ordering and arrangement of a series of monocarboxylate anions (RCOO−: R=HO, H, CH3, C2H5, and C3H7) within the interlayer space of two layered yttrium hydroxides (LYH‐Cl and LYH‐Br). The results imply that the two smaller carboxylate anions (R=HO and H) are disordered after intercalation, while the larger carboxylate anions (R=CH3, C2H5, and C3H7) are relatively ordered. We further explored if the intercalated anions are parallel arranged as those in sodium salts or antiparallel arranged as those predicted in the majority of previous reports. We uncovered that the intercalated anions are antiparallel arranged based on the formation energy obtained in density functional theory calculations and ssNMR data. Our results therefore contribute to a deeper and comprehensive understanding of the intercalation chemistry of layered rare earth hydroxides.

Polyanionic Receptors for Carboxylates in Water.

Receptors for carboxylate anions have many possible biomedical applications, including mimicry of the vancomycin group of antibiotics. However, binding carboxylates in water, the biological solvent, is highly challenging due to the hydrophilicity of these polar anions. Here we report, for the first time, the recognition of simple carboxylates such as acetate and formate in water by synthetic receptors with charge-neutral binding sites. The receptors are solubilised by polyanionic side-chains which, remarkably, do not preclude anion binding. The tricyclic structures feature two identical binding sites linked by polyaromatic bridges, capable of folding into closed, twisted conformations. This folding is hypothesised to preorganise the structures for anion recognition, mimicking the process which generates many protein binding sites. The architecture is suitable for elaboration into enclosed structures with potential for selective recognition of biologically relevant carboxylates.

Polyanionic Receptors for Carboxylates in Water

AbstractReceptors for carboxylate anions have many possible biomedical applications, including mimicry of the vancomycin group of antibiotics. However, binding carboxylates in water, the biological solvent, is highly challenging due to the hydrophilicity of these polar anions. Here we report, for the first time, the recognition of simple carboxylates such as acetate and formate in water by synthetic receptors with charge‐neutral binding sites. The receptors are solubilised by polyanionic side‐chains which, remarkably, do not preclude anion binding. The tricyclic structures feature two identical binding sites linked by polyaromatic bridges, capable of folding into closed, twisted conformations. This folding is hypothesised to preorganise the structures for anion recognition, mimicking the process which generates many protein binding sites. The architecture is suitable for elaboration into enclosed structures with potential for selective recognition of biologically relevant carboxylates.

Electrostatically Dominated Pre-Organization inCyclodextrin Metal-Organic Frameworks.

Electrostatic interactions between oppositely charged entities play a key role in pre-organizing substrates and stabilizing transition states of reactions in enzymes. The use of electrostatic interactions to pre-organize ions in nanoconfined pores, however, has not been investigated to its full potential. Herein, we describe how carboxylate anions can be pre-organized at the behest of their electrostatic interactions with K+ cations in nanoconfined tunnels present in γ-cyclodextrin metal-organic frameworks, i.e., CD-MOFs. Several carboxylate anions, which are all much smaller than the cavities of the tunnels, were visualized by X-ray crystallography when nanoconfined in CD-MOFs, despite the large voids present in the tunnels. These anions were found to be aligned within a planar array defined by four K+ cations, positioned around the periphery of the tunnels. The strong electrostatic interactions between the carboxylate anions and the K+ cations dictate the orientation of the anions and override the influence of other possible noncovalent bonding interactions between them and the tunnels. Consequently, the aligned pairs of γ-cyclodextrin rings constituting the tunnels become distorted, resulting in their lower symmetry and fewer disordered carboxylate anions in the solid-state. Our findings offer a transformative strategy for controlling the packing and orientation of ions in nanoconfined environments.

Anion Effect in Electrochemical CO2 Reduction: From Spectators to Orchestrators.

The electrochemical CO2 reduction reaction (eCO2RR) offers a pathway to produce valuable chemical fuels from CO2. However, its efficiency in aqueous electrolytes is hindered by the concurrent H2 evolution reaction (HER), which takes place at similar potentials. While the influence of cations on this process has been extensively studied, the influence of anions remains largely unexplored. In this work, we study how eCO2RR selectivity and activity on a gold catalyst are affected by a wide range of inorganic and carboxylate anions. We utilize in situ differential electrochemical mass spectrometry (DEMS) for real-time product monitoring coupled with molecular dynamics (MD) simulations. We show that anions significantly impact eCO2RR kinetics and eCO2RR selectivity. MD simulations reveal a new descriptor─free energy of anion physisorption─where weakly adsorbing anions enable favorable CO2 reduction kinetics, despite the negative charge carried by the electrode surface. By leveraging these fundamental insights, we identify propionate as the most promising anion, achieving nearly 100% Faradaic efficiency while showing high CO production rates that are comparable to those in bicarbonate. These insights underscore the vital role of anion selection in achieving a highly efficient eCO2RR in aqueous electrolytes.

Adsorption, Aggregation, and Application Properties of Green Pluronic Aliphatic Alcohol Ether Carboxylic Acids and Nonionic/Amphoteric Surfactants in Water.

In the realm of colloid and interface science, new types of green surfactants, including anionic Pluronic alcohol ether carboxylate (AEC), branched alkyl glucoside (IG), and zwitterionic coconut oil amide propyl betaine (CAB), have been identified and merit further exploration. AEC, characterized by its inclusion of 5 EO and 3.5 PO units, was synthesized, and its behavior in aqueous solutions with IG and CAB was meticulously examined. Their performance in applications such as foam generation, wetting, and the dispersion and stabilization of graphene was also evaluated. At αAE5P3C = 0.5, AE5P3C/CAB exhibited superior surface and interfacial properties compared to AE5P3C/IG. In these hybrid systems, the self-assembly of micelles is predominantly influenced by hydrogen bonding, electrostatic interactions, and hydrophobic forces. Kinetic analysis further confirmed that the driving force for micelle formation in these hybrid systems is enthalpy, with the adsorption process involving a mixed diffusion-kinetic adsorption mechanism. AE5P3C/CAB demonstrated enhanced foaming ability, foam stability, and wetting properties compared to AE5P3C/IG. Intriguingly, the optimal dispersion and stabilization of graphene were achieved with AE5P3C/IG at αAE5P3C = 0.2, providing a foundational basis for its potential application in graphene-based systems. A thorough examination of the synergistic mechanisms and application potential of these three distinct surfactants in aqueous solutions was presented, taking into account various charged ions and the specific hydrophilic and hydrophobic groups of EO and PO. This study not only provides fundamental insights into their intrinsic properties but also offers a fresh perspective for the ongoing exploration of green surfactants.

The Fischer-Lactonization-Driven Mechanism for Ultra-Efficient Recycling of Spent Lithium-Ion Batteries.

Hydrometallurgy remains a major challenge to simplify its complex separation and precipitation processes for spent lithium-ion batteries (LIBs). Herein, we propose a Fischer-lactonization-driven mechanism for the cascade reaction of leaching and chelation of spent LIBs. Citric acid undergoes a two-step dissociation of the carboxylic acid (-COOH) and complexes with the leached metal ion, while the residual -COOH is attacked by H protons to form a protonated carboxyl ion (-COO -). Subsequently, the lone pair of electrons in the hydroxyl of the same molecule attack the carbon atom in -COO - to facilitate ester bonding, leading to the formation of a lactonized gel. The leaching rates of Li, Ni, Co and Mn are 99.3, 99.1, 99.5 and 99.2 %, respectively. The regenerated monocrystalline LiNi0.5Co0.2Mn0.3O2 (NCM523) has a uniform particle size distribution and complete lamellar structure, with a capacity retention rate of 70.6 % after 250 cycles at 0.5 C. The mechanism achieves a one-step chelation reaction, and the energy consumption and carbon emissions are only 26 % and 44 %, respectively, of that of the conventional hydrometallurgical. The strategy achieves a double breakthrough in simplifying the process and improving environmental friendliness, offering a sustainable approach to the re-utilization of spent LIBs.

Electrostatic fence induced assembly of low-concentration colloidal nanospheres to form liquid photonic crystals

Liquid photonic crystals (LPCs) have great application potential in sensors, anti-counterfeiting materials and detection due to their sensitive dynamic responsiveness. Currently, the preparation of LPCs mainly relies on the supersaturation of colloidal nanospheres. However, the supersaturation method usually fails to obtain LPCs based on low-concentration colloidal nanospheres. In turn, the use of high-concentration colloidal nanospheres results in poor mobility of LPCs, which makes them inappropriate for subsequent utilization in responsive systems. In this study, self-assembly of LPCs with vibrant structural colors is achieved through the electrostatic fence effect by introducing an anionic carboxylate-containing polymer as an inducer into the system of low-concentration negatively charged colloidal nanospheres (≥1.25 wt%). It is shown that the anionic carboxylate groups on the inducer molecules and the appropriate molecular chain length are the decisive factors for the inducing effect. The obtained LPCs exhibit a typical non-close-packed structure with a face-centered cubic arrangement of nanospheres. The nearest inter-nanosphere surface distance is 12.10 nm, and the farthest one is as long as 40.30 nm. The LPCs possess good dynamic recovery performance and sensitive optical response characteristics, which are conducive to application in responsive optical sensors directly or after filling.

Probing the Closed Association of Oligoquinoline Foldamers by Time-Resolved Fluorescence Anisotropy.

The metal-mediated dimerization of oligoquinoline foldamers terminated at one end with an oligo(phenylenevinylene) and at the other with a carboxylic acid (OPV-QnA, where n = 4, 8, 17, and 33), and the complexation of OPV-Q8A and Q16A was promoted in chloroform by the addition of a concentrated 16 M aqueous sodium hydroxide solution. UV-vis absorption and time-resolved fluorescence anisotropy (TRFA) experiments were conducted to determine, respectively, the concentration and the average rotational time ⟨ϕ⟩ of the mixture of unassociated and associated foldamers across a range of foldamer concentrations spanning 5 orders of magnitude. Plots of ⟨ϕ⟩ as a function of acid group concentration revealed that ⟨ϕ⟩ increased with increasing foldamer concentration only when the foldamer solution in chloroform was vigorously mixed with the 16 M sodium hydroxide aqueous solution. Furthermore, all plots showed that ⟨ϕ⟩ reached a plateau at high foldamer concentration. The increase in ⟨ϕ⟩ reflected the association of foldamers into larger objects through metal ion coordination with the carboxylate anions generated by deprotonation of the carboxylic acid of OPV-QnA with NaOH, while the plateau obtained at high foldamer concentration indicated that these interactions led to the dimerization of the foldamers via a closed association mechanism. Analysis of the ⟨ϕ⟩ trends yielded the equilibrium constants (K) describing the foldamer dimerization, whose value equaled 1.0 (±0.2) × 106 M-1 for the three longer OPV-QnA foldamers, but was about 10 times smaller for the shortest one (n = 4). Association of OPV-Q8A and Q16A yielded a complex with a ⟨ϕ⟩ matching that of OPV-Q24A, and K for this complexation was similar to that for dimerization. These experiments illustrate the robust nature of TRFA as an experimental method to probe the size of rigid, self-assembled foldamers in solution.

Dependence of Carboxylate Anions on Physicochemical Properties of Tributyloctylphosphonium-Based Ionic Liquids

A new group of tributyloctylphosphonium-based ionic liquids containing several carboxylate anions was designed, prepared and physicochemically characterized. All phosphonium carboxylates obtained in this study became viscous liquids at room temperature. The formate-based ionic liquid exhibited the highest density and number density due to the smallest anion size. All ionic liquids exhibited typical ionic conduction behavior, since the viscosity decreased and the conductivity increased with increasing temperature. It was also found that the viscosity tended to decrease with increasing the carbon numbers of the alkyl chains of lower carboxylate anions. Compared to the propionate-based ionic liquids, lactate-based ionic liquids exhibited higher viscosity. The phosphonium ionic liquids based on carboxylate anions showed higher thermal stability than nitrogen-based counterpart ionic liquids.

Structure and properties of the cellulose fibres spun from imidazolium-based carboxylate functionalized zwitterionic liquid

Dissolution of cellulose without further derivatization has been an active area of research in recent years. There are still challenges in developing a commercially viable solvent system for the dissolution and regeneration of cellulose as films and fibres. We report here a process for making cellulose fibres through the dry-jet wet spinning method by utilizing aqueous zwitterionic liquid (ZIL), viz., (6-(1-(2-methoxyethyl) imidazol-3-io)-hexanoate), in which oxyethylene substituted imidazolium-based cation and a carboxylate anion is covalently tethered. Our results suggest that 11 % ZIL dope could be successfully prepared and spun under industrially viable process conditions. The resultant fibres have properties comparable to that of commercial-grade Lyocell fibres. Particularly, the cellulose fibres spun from a cellulose ZIL solution exhibited a denier of 1.2–1.6, a tenacity of 3.5–4.0 g per denier (gpd), and an elongation at break of 8–10 %, which is comparable to cellulose fibres produced using ionic liquid and N-methyl-morpholine-N-oxide (NMMO) solvent. Cellulose fibres obtained from zwitterionic liquid have a crystallinity of 60 %, which is comparable to Lyocell fibres. To the best of our knowledge, this is the first report to demonstrate the successful spinning of regenerated cellulose fibres using zwitterionic liquids with mechanical properties comparable to commercial Lyocell fibres.

Tribological properties of the P and S-free protic ionic liquids as water-based lubricants

Three kinds of P and S-free 1,8-Diazabicyclo[5.4.0] undec-7-ene water-soluble protic ionic liquids (PILs) were successfully synthesized and applied as additives in water-1,2-Propylene glycol (PG). The physicochemical properties of PILs and the anti-friction, anti-wear and anti-corrosion properties were investigated. Research results demonstrated that the addition PILs lubricant additive could greatly improve the tribological properties of water-1,2-PG. The addition of 5 wt% PILs with long alkyl chain will result in the reduction of friction coefficient and wear volume by about 45 % and 95 %, respectively. Meanwhile, the PILs with long-chain show more effect lubrication behavior than the short one. In addition, the obtained PILs also possess excellent anti-corrosion properties as water-based lubrication additives. The elemental analysis of the contact area showed that the PILs would generate a chemical reaction film during the friction process, and the carboxylate anion could form a chemical and physical adsorption film on the surface of contact area, which would provide better anti-friction and anti-wear properties.

Desulfonation-associated direct amide bond formation between N-sulfonyl-1,2,3-triazoles with carboxylic acids

We have developed a highly N2-regioselective method for direct construction of amide bond from N-sulfonyl-1,2,3-triazoles and carboxylic acids in the presence of bases at 60 °C in air. The developed reaction provides the corresponding products with high yields (up to 90 %) and a broad substrate compatibility including aryl acids, heterocyclic acids, and alkyl acids. Mechanistic studies show that the reaction proceeds through a direct nucleophilic attack of N-sulfonyl-1,2,3-triazoles to carboxylate anions via a base- and water-involved synergistic desulfonation process. This work presents an unusual water-involved example for direct synthesis of amides utilizing readily available starting materials under mild conditions.

Effect of PCE anionic charge density on fly ash cementitious system-PCE compatibility

In this study, the compatibility of polycarboxylate-based water-reducing admixtures (PCEs) with cementitious systems containing fly ash (FA) was investigated. For this purpose, PCEs with carboxylate, phosphate, and sulfonate anionic groups having different anionic charge densities were synthesized. The effects of PCEs on fresh properties and compressive strength of cementitious systems containing FA were investigated. The PCE with 9% phosphate substitution and high anionic charge density was found to be the most effective, requiring the least amount for the target flow. Similarly, in terms of the PCE requirement for the minimum Marsh funnel flow time and rheological parameters, the best performance was obtained with 5% sulfonate substituted PCE having high anionic charge density. While FA had a positive effect on the PCE requirement and consistency retention of the mixtures; it had a negative effect on Marsh funnel flow time, rheological properties, and compressive strength. However, the rheological properties of the mortar mixtures were not adversely affected by the FA substitution as much as that of the paste mixtures. Regarding the 28-day compressive strength of mortar mixtures, the optimum FA substitution ratio was 15%. Fly ash substitution above this level reduced the compressive strength at all ages including 28-day strength. Anionic charge density variation of PCE had no significant influence on the compressive strength of the mortars.

Superparamagnetic composites of lignin regenerated from ionic liquid solutions for the efficient and selective removal of cationic dyes

Magnetic lignin nanoparticles (MLNs) were prepared by inducing their self-assembly through lignin regeneration in the [N-methyl-2-pyrrolidone][C1–C4 carboxylic acid] ionic liquids ([NMP]ILs), which are low-cost protic ionic liquid. [NMP]ILs are self-assembling solvent that can enhance the adsorption capacity of MLNs to a greater degree than tetrahydrofuran or H2O. Additionally, the anion types of [NMP]IL greatly influence the physiochemical properties of MLNs. The MLNs prepared through self-assembly with [NMP][formate] (MLN/[NMP][For]) exhibited a higher maximum adsorption capacity (134.53 mg/g) than the [NMP]ILs of C2–C4 carboxylate anions. MLN/[NMP][For] demonstrated stable adsorption within a pH range of 6–10 or at high salt concentrations (0.01–0.5 mol/L), retaining over 80 % of its regeneration efficiency after 5 cycles. In addition, MLN/[NMP][For] selectively removed cationic dyes in mixed binary anionic–cationic dye solutions. This work demonstrated the feasibility of preparing magnetic biosorbents with good selectivity and stability though regeneration and by adjusting the anions of ionic liquids.

Effect of the alkyl chain length of α,ω-dichloroalkane on the Gibbs energy of transfer for functional groups.

Ion-transfer reactions of alkyl and perfluoroalkyl carboxylate ions (CH3(CH2)n-2COO- with n = 8-12 and CF3(CF2)n-2COO- with n = 3-9) were investigated at the polarized Cl-(CH2)m-Cl with m = 2, 4, 6, and 8 (O) | water (W) interface to evaluate the effects of n and m on the solvation energy of the ions, as well as on their methylene and terminal groups. These ions exhibited reversible or quasi-reversible voltammetric waves due to their transfer across the O | W interfaces, enabling the determination of formal potentials and formal Gibbs transfer energies from O to W, . The values for CH3(CH2)n-2COO- and CF3(CF2)n-2COO- increased linearly with n, allowing the estimation of for methylene and difluoromethylene groups, (CH2) and (CF2), and for their terminal groups, (COO- + CH3) and (COO- + CF3). Whereas the (CH2) and (CF2) hardly changed with the variation in m, the (COO- + CH3) and (COO- + CF3) decreased noticeably. These results suggest that the solvation energy for ions in Cl-(CH2)m-Cl increases with m, regardless of hydrophilic or lipophilic nature of the ions. Based on these findings, the advantage of using Cl-(CH2)m-Cl with a large m as a non-aqueous solvent for ion-transfer voltammetry was discussed.

Structural effect on physicochemical properties of ethanolamine carboxylate ionic liquids by experimental and theoretical study

The hydroxylammonium ionic liquids (ILs) falling within the category of protic ionic liquids (PILs) have garnered attention from researchers, owing to their outstanding solubility properties. A one-step method was employed to synthesize a series of ethanolamine ILs. The thermodynamic properties of the ILs, including surface tension, density, and electrical conductivity, were measured across varying temperatures. Essential parameters such as thermal expansion coefficient, molecular volume, surface entropy, and surface energy were estimated using empirical equations. In order to elucidate the intermolecular interactions within the ethanolamine carboxylate ILs, the sigma profiles of ILs were determined using COSMO-RS. It was observed that the ethanolamine cation has a strong potential as a H-bond donor, while the carboxylate anion demonstrates significant capability as a hydrogen bond acceptor. By DFT calculations, it was observed that the NH in the ethanolamine cation can form H-bonds with the oxygen atom in the carboxylate anion.