Similarities and differences : Far‐infrared spectra of protic ionic liquids could be assigned to intermolecular bending and stretching modes of hydrogen bonds. The characteristics of the low‐frequency spectra resemble those of water. Both liquids form three‐dimensional network structures, but only water is capable of building tetrahedral configurations. EAN: ethylammonium nitrate, PAN: propylammonium nitrate, DMAN: dimethylammonium nitrate.
[AAE]X composed of amino acid ester cations is a sort of typically “bio-based” protic ionic liquids (PILs). They possess potential Brønsted acidity due to the active hydrogens on their cations. The Brønsted acidity of [AAE]X PILs in green solvents (water and ethanol) at room temperature was systematically studied. Various frameworks of amino acid ester cations and four anions were investigated in this work from the viewpoint of structure–property relationship. Four different ways were used to study the acidity. Acid dissociation constants (pKa) of [AAE]X determined by the OIM (overlapping indicator method) were from 7.10 to 7.73 in water and from 8.54 to 9.05 in ethanol. The pKa values determined by the PTM (potential titration method) were from 7.12 to 7.82 in water. Their Hammett acidity function (H0) values (0.05 mol·L−1) were about 4.6 in water. In addition, the pKa values obtained by the DFT (proton-transfer reactions) were from 7.11 to 7.83 in water and from 8.54 to 9.34 in ethanol, respectively. The data revealed that the cationic structures of [AAE]X had little effect and the anions had no effect on the acidity of [AAE]X. At the same time, the OIM, PTM, Hammett method and DFT method were reliable for determining the acidic strength of [AAE]X in this study. 相似文献
Electrical conductivity (σ), viscosity (η), and self‐diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium‐based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1‐butyl‐3‐methylimidazolium tetrafluoroborate, [bmIm][BF4], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the 1H NMR chemical shifts of the ionic liquids. The self‐diffusion coefficients D of the cation and anion of [HmIm][CH3COO] in D2O and in [D6]DMSO are determined by using 1H nuclei with pulsed field gradient spin‐echo NMR spectroscopy. 相似文献
The function and structural changes of an AMP molecular aptamer beacon and its molecular recognition capacity for its target, adenosine monophosphate (AMP), was systematically explored in solution with a protic ionic liquid, ethylammonium nitrate (EAN). It could be proven that up to 2 M of EAN in TBS buffer, the AMP molecular aptamer beacon was still capable of recognizing AMP while also maintaining its specificity. The specificity was proven by using the guanosine monophosphate (GMP) as target; GMP is structurally similar to AMP but was not recognized by the aptamer. We also found that in highly concentrated EAN solutions the overall amount of double stranded DNA formed, as well as its respective thermal stability, diminished gradually, but surprisingly the hybridization rate (kh) of single stranded DNA was significantly accelerated in the presence of EAN. The latter may have important implications in DNA technology for the design of biosensing and DNA‐based nanodevices in nonconventional solvents, such as ionic liquids. 相似文献
A hundred years ago, Paul Walden studied ethyl ammonium nitrate (EAN), which became the first widely known ionic liquid. Although EAN has been investigated extensively, some important issues still have not been addressed; they are now tackled in this communication. By combining experimental thermogravimetric analysis with time of flight mass spectrometry (TGA‐ToF‐MS) and transpiration method with theoretical methods, we clarify the volatilisation of EAN from ambient to elevated temperatures. It was observed that up to 419 K, EAN evaporates as contact‐ion pairs leading to very low vapour pressures of a few Pascal. Starting from 419 K, the decomposition to nitric acid and ethylamine becomes more thermodynamically favourable than proton transfer. This finding was supported by DFT calculations, which provide the free energies of all possible gas‐phase species, and show that neutral molecules dominate over ion pairs above 500 K, an observation that is in nearly prefect agreement with the experimental boiling point of 513 K. This result is crucial for the ongoing practical applications of protic ionic liquids such as electrolytes for batteries and fuel cells because, in contrast to high‐boiling conventional solvents, EAN exhibits no significant vapour pressure below 419 K and this property fulfils the requirements for the thermal behaviour of safe electrolytes. Overall, EAN shows the same barely measurable vapour pressures as typical aprotic ionic liquids at temperatures only 70 K lower. 相似文献
Protic ionic liquids (PILs) in solution especially in water have attracted more and more attention due to their unique properties. The solvation of PILs in water is important to their properties and applications. To explore the solvation of bio-based PILs in water, acidity of 49 [AA]X amino acid ionic liquids (AAILs) consisting of 7 different cations and 7 different anions was studied as a favorable probe. The pKa values for [AA]X PILs containing same cations were obtained and discussed. The acidity strength of the [AA]X PILs varies with both cation and anion which does not follow the conventional assumption that the acidity for PILs is independent of anions. The acidic discrepancy of [AA]X PILs aqueous solution is probably mediated by the formation of ion pairs according to a revised solvation model of PILs. Quantum-chemistry calculation was employed to unpuzzle anion's different effects on the acid balance of cations where cation-anion hydrogen bonds play an important role. Such difference in acidity allows us to understand the formation of solvated ion pairs. This work provides an insight into the fundamental solvation of PILs from acid perspective and their influence on acidity properties for the first time. 相似文献
Ionic liquids (ILs) are promising electrolytes, although their often high viscosity remains a serious drawback. The latter can be addressed by the introduction of multiple ether functionalization. Based on the highly atom efficient synthesis of tris(2-ethoxyethyl) phosphine, several new phosphonium ionic liquids were prepared, which allows studying the influence of the ether side chains. Their most important physicochemical properties have been determined and will be interpreted using established approaches like ionicity, hole theory, and the Walden plot. There is striking evidence that the properties of phosphonium ionic liquids with the methanesulfonate anion are dominated by aggregation, whereas the two triple ether functionalized ILs with the highest fluidity show almost ideal behavior with other factors being dominant. It is furthermore found that the deviation from ideality is not significantly changed upon introduction of the ether side chains, although a very beneficial impact on the fluidity of ILs is observed. Multiple ether functionalization therefore proves as a powerful tool to overcome the disadvantages of phosphonium ionic liquids with large cations. 相似文献
We focus on a series of protic ionic liquids (PILs) with imidazolium and alkylimidazolium (1R3HIm, R=methyl, ethyl, propyl, and butyl) cations. Using the literature data and our experimental results on the thermal and transport properties, we analyze the effects of the anion nature and the alkyl radical length in the cation structure on the above properties. DFT calculations in gas and solvent phase provide further microscopic insights into the structure and cation-anion binding in these PILs. We show that the higher thermodynamic stability of an ion pair raises the PIL decomposition temperature. The melting points of the salts with the same cation decrease as the hydrocarbon radical in the cation becomes longer, which correlates with the weaker ion-ion interaction inthe ion pairs. A comparative analysis of the protic ILs and corresponding ILs (1R3MeIm) with the same radical (R) in the cation structure and the same anion has been performed. The lower melting points of the ILs with 1R3MeIm cations are assumed to result from the weakening of both the ion-ion interaction and the hydrogen bond. 相似文献
There has been an ongoing need to develop polymer materials with increased performance as proton exchange membranes (PEMs) for middle- and high-temperature fuel cells. Poly(vinyl alcohol) (PVA) is a highly hydrophilic and chemically stable polymer bearing hydroxyl groups, which can be further altered. Protic ionic liquids (proticILs) have been found to be an effective modifying polymer agent used as a proton carrier providing PEMs’ desirable proton conductivity at high temperatures and under anhydrous conditions. In this study, the novel synthesis route of PVA grafted with fluorinated protic ionic liquids bearing sulfo groups (–SO3H) was elaborated. The polymer functionalization with fluorinated proticILs was achieved by the following approaches: (i) the PVA acylation and subsequent reaction with fluorinated sultones and (ii) free-radical polymerization reaction of vinyl acetate derivatives modified with 1-methylimidazole and sultones. These modifications resulted in the PVA being chemically modified with ionic liquids of protic character. The successfully grafted PVA has been characterized using 1H, 19F, and 13C-NMR and FTIR-ATR. The presented synthesis route is a novel approach to PVA functionalization with imidazole-based fluorinated ionic liquids with sulfo groups. 相似文献
Ionic liquids, which are extensively known as low-melting-point salts, have received significant attention as the promising solvent for CO2 capture. This work presents the synthesis, thermophysical properties and the CO2 absorption of a series of ammonium cations coupled with carboxylate anions producing ammonium-based protic ionic liquids (PILs), namely 2-ethylhexylammonium pentanoate ([EHA][C5]), 2-ethylhexylammonium hexanoate ([EHA][C6]), 2-ethylhexylammonium heptanoate ([EHA][C7]), bis-(2-ethylhexyl)ammonium pentanoate ([BEHA][C5]), bis-(2-ethylhexyl)ammonium hexanoate ([BEHA][C6]) and bis-(2-ethylhexyl)ammonium heptanoate ([BEHA][C7]). The chemical structures of the PILs were confirmed by using Nuclear Magnetic Resonance (NMR) spectroscopy while the density (ρ) and the dynamic viscosity (η) of the PILs were determined and analyzed in a range from 293.15K up to 363.15K. The refractive index (nD) was also measured at T = (293.15 to 333.15) K. Thermal analyses conducted via a thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) indicated that all PILs have the thermal decomposition temperature, Td of greater than 416K and the presence of glass transition, Tg was detected in each PIL. The CO2 absorption of the PILs was studied up to 29 bar at 298.15 K and the experimental results showed that [BEHA][C7] had the highest CO2 absorption with 0.78 mol at 29 bar. The CO2 absorption values increase in the order of [C5] < [C6] < [C7] anion regardless of the nature of the cation. 相似文献
In the past decade, innovative protein therapies and bio-similar industries have grown rapidly. Additionally, ionic liquids (ILs) have been an area of great interest and rapid development in industrial processes over a similar timeline. Therefore, there is a pressing need to understand the structure and function of proteins in novel environments with ILs. Understanding the short-term and long-term stability of protein molecules in IL formulations will be key to using ILs for protein technologies. Similarly, ILs have been investigated as part of therapeutic delivery systems and implicated in numerous studies in which ILs impact the activity and/or stability of protein molecules. Notably, many of the proteins used in industrial applications are involved in redox chemistry, and thus often contain metal ions or metal-associated cofactors. In this review article, we focus on the current understanding of protein structure-function relationship in the presence of ILs, specifically focusing on the effect of ILs on metal containing proteins. 相似文献
The local solvation environment of uracil dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute (ionic liquid:uracil) ratios of 3:1 and 2:1, little perturbation of the ion–ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia‐Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109–4120 ). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favourable uracil–uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution. 相似文献
Modelling, predicting, and understanding the factors influencing the viscosities of ionic liquids and related mixtures are sequentially checked in this work. The molecular maps of atom-level properties (MOLMAP codification system) is adapted for a straightforward inclusion of ionic liquids and mixtures containing ionic liquids. Random Forest models have been tested in this context and an optimal model was selected. The interpretability of the selected Random Forest model is highlighted with selected structural features that might contribute to identify low viscosities. The constructed model is able to recognize the influence of different structural variables, temperature, and pressure for a correct classification of the different systems. The codification and interpretation systems are highlighted in this work. 相似文献