What is behind a gas stream scrubbing liquid? Monoethanolamine/water mixtures as seen by dielectric relaxation spectroscopy.

High-quality dielectric data for monoethanolamine (MEA)/water mixtures covering the entire miscibility range are presented. For MEA concentrations c1 ≥ 1 M the obtained complex permittivity spectra, covering the frequency range from 0.05 to 89 GHz, are best described by a sum of four Debye relaxations. Modes at ∼3 GHz and ∼10 GHz are solute-specific. Whilst the first can be assigned to MEA aggregates, the second is a composite arising from "free" MEA dipoles with dynamically retarded water hydrating them. The relaxations at ∼18 GHz and ∼200 GHz essentially reflect the cooperative H-bond fluctuations of more-or-less unperturbed "bulk" water, albeit with minor solute contributions. Evaluation of the bulk-water amplitude reveals that in water-rich mixtures (c1 ≤ 3.5 M) Zt = 3.5 ± 0.2 H2O molecules hydrate a MEA molecule. Then Zt drops linearly, reaching zero for neat MEA. Supported by the literature, this concentration dependence suggests that only H2O molecules H-bonded to the NH2 and OH groups of MEA contribute to Zt. At concentrations beyond hydration shell overlap (c1 ≥ 3.5 M) these H-bonds are gradually eliminated, while new interactions with neighboring MEA molecules are formed. From the evaluation of the MEA-specific amplitudes we conclude that for c1 ≥ 2 M, including neat MEA, ∼35% of the solute molecules are in aggregates, where breaking the intermolecular NH⋯O hydrogen bond determines the dynamics.

In-depth study of binary ethanol-triacetin mixtures in relation to their excellent solubilization power.

A significant synergistic effect is observed when solubilizing curcumin or tetrahydrocurcumin in binary mixtures of ethanol and triacetin. The present work deals with a detailed investigation of the solvent system by means of COSMO-RS-based calculations, dynamic light scattering, small-and-wide-angle X-ray scattering, and dielectric relaxation spectroscopy. Theoretical calculations lead to the conclusion that the enhanced solubility is not primarily the result of an interaction optimum between individual surface charge densities. Scattering experiments also exclude the formation of mesoscopic structures as the main reason. However, dielectric relaxation spectra suggest that in the concentration range of 0.3 ≤ x(triacetin) ≤ 0.6, ethanol molecules are released from their living polymer ethanol network and can interact with triacetin on a molecular level. The mesoscopic aggregation, thus, decreases. The concentration range of the ethanol-triacetin complexes has a significant overlap with the range of maximum solubility of (tetrahydro)curcumin. Nevertheless, despite detailed investigations, the exact origin of the solubilization power of the solvent remains speculative.

Why Does Ethaline Apparently Behave as an Ideal Binary Mixture?

Phase diagram mixtures of the salt choline chloride (ChCl) with ethylene glycol (EG) surprisingly seem to behave as ideal binary nonelectrolyte mixtures [Agieienko, V.; Buchner, R. Phys. Chem. Chem. Phys.2022, 24, 5265]. To shed some light on this conundrum, results of broad-band dielectric relaxation spectroscopy (DRS) and quantum-chemical calculations are reported for solutions of ChCl, choline iodide (ChI), and chlorocholine chloride (ClChCl), in EG up to saturation at 298.15 K. The data revealed that all three solutes are only weakly solvated in the sense that on average per equivalent of solute only one EG OH-group is dynamically affected. While contact ion pairs are significant for solute concentrations of ≲1 M, free cation concentrations are rather low. Instead, over the entire concentration range a large fraction of the dipolar cations could not be detected by DRS. We argue that the latter are embedded in large solute aggregates, explaining thus the phase diagram of ChCl + EG and the very low ionicity of all systems.

Correction: Is ethaline a deep eutectic solvent?

Correction for 'Is ethaline a deep eutectic solvent?' by Vira Agieienko et al., Phys. Chem. Chem. Phys., 2022, 24, 5265-5268, DOI: https://doi.org/10.1039/D2CP00104G.

Is ethaline a deep eutectic solvent?

With the present contribution we clarify the phase behaviour of choline chloride (ChCl) + ethylene glycol (EG) mixtures for ChCl mole fractions (xChCl) less than 0.333 and temperatures below 323 K by providing melting points obtained by differential scanning calorimetry for samples containing <300 ppm of water. We show that ethaline, the ChCl : EG mixture of molar ratio 1 : 2 that is usually believed to be the composition of the eutectic point, actually lies in the ChCl-saturated region of the {ChCl + EG} phase diagram. The real eutectic point was found to be at the 1 : 4.85 molar ratio of ChCl : EG (xChCl = 0.171) which is characterized by a melting point of 244 K. This temperature is only 16 K below the melting point of neat EG. Thus, neither from its particular composition nor from the observed melting-point depression of {ChCl + EG} mixtures can ethaline be considered a "deep eutectic solvent". Surprisingly, despite ChCl being an electrolyte dissolved in EG, the phase diagram is that of an ideal binary mixture.

Dipolar Interactions and Protein Hydration in Highly Concentrated Antibody Formulations.

Molecular interaction mechanisms in high-concentrated protein systems are of fundamental importance for the rational development of biopharmaceuticals such as monoclonal antibody (mAb) formulations. In such high-concentrated protein systems, the intermolecular distances between mAb molecules are reduced to the size of the protein diameter (approx. 10 nm). Thus, protein-protein interactions are more pronounced at high concentrations; so a direct extrapolation of physicochemical properties obtained from measurements at a low protein concentration of the corresponding properties at a high protein concentration is highly questionable. Besides the charge-charge interaction, the effects of molecular crowding, dipolar interaction, changes in protein hydration, and self-assembling tendency become more relevant. Here, protein hydration, protein dipole moment, and protein-protein interactions were studied in protein concentrations up to 200 mg/mL (= 1.3 mM) in different formulations for selected mAbs using dielectric relaxation spectroscopy (DRS). These data are correlated with the second virial coefficient, A2, the diffusion interaction parameter, kD, the elastic shear modulus, G', and the dynamic viscosity, η. When large contributions of dipolar protein-protein interactions were observed, the tendency of self-assembling and an increase in solution viscosity were detected. These effects were examined using specific buffer conditions. Furthermore, different types of protein-water interactions were identified via DRS, whereby the effect of high protein concentration on protein hydration was investigated for different high-concentrated liquid formulations (HCLFs).

Ionic effects on supramolecular hosts: solvation and counter-ion binding in polar media.

For the progress of synthetic supramolecular chemistry in aqueous solution the design of host molecules soluble in this medium is essential. A possible route is the introduction of ionic residues, with the additional advantage that also electrostatic interactions can be used to form supramolecular architectures. In this work we study the effect of different ionic substituents on a resorcin[4]arene host on solvation and counterion binding in water and dimethyl sulfoxide (DMSO). To do so, we combine dielectric relaxation spectroscopy (DRS) at 298.15 K and dilute-solution conductivity measurements covering 278.15-308.15 K. The results indicate that studied substituents lead to a comparable increase in solubility in both water and the dipolar-aprotic DMSO. However, solvation and counterion binding not only depend on the nature of the ionic substituent but also on the solvent. Although intrinsically hydrophobic in nature, resorcin[4]arenes with ionic substituents also show strong hydrophilic hydration in water, with the extent depending on the nature of the ionic group. In contrast to that, solvophobicity apparently dominates the interactions of DMSO with the solute. Counterion binding was found for both solvents and is essentially determined by solvent polarity. It appears that, compared to neat DMSO, the solubility of the cationic resorcin[4]arene with dimethylamine substituents is strongly increased in water-DMSO mixtures due to the formation of hydrogen bonds between two DMSO molecules and one water molecule.

Hydration and counterion binding of aqueous acetylcholine chloride and carbamoylcholine chloride.

The hydration and Cl- ion binding of the neurot†ransmitter acetylcholine (ACh+) and its synthetic analogue, carbamoylcholine (CCh+), were studied by combining dilute-solution conductivity measurements with dielectric relaxation spectroscopy and statistical mechanics calculations at 1D-RISM and 3D-RISM level. Chloride ion binding was found to be weak but not negligible. From the ∼30 water molecules coordinating ACh and CCh+ only ∼1/3 is affected in its rotational dynamics by the cation, with the majority - situated close to the hydrophobic moieties - only retarded by a factor of ∼2.5. At vanishing solute concentration cations and the ∼3-4 H2O molecules hydrogen bonding to the CO group of the solute exhibit similar rotational dynamics but increasing concentration and temperature markedly dehydrates ACh+ and CCh+.

Hydration and dynamics of L-glutamate ion in aqueous solution.

Aqueous solutions of sodium l-glutamate (NaGlu) in the concentration range 0 < c/M ≤ 1.90 at 25 °C were investigated by dielectric relaxation spectroscopy (DRS) and statistical mechanics (1D-RISM and 3D-RISM calculations) to study the hydration and dynamics of the l-glutamate (Glu-) anion. Although at c → 0 water molecules beyond the first hydration shell are dynamically affected, Glu- hydration is rather fragile and for c ⪆ 0.3 M apparently restricted to H2O molecules hydrogen bonding to the carboxylate groups. These hydrating dipoles are roughly parallel to the anion moment, leading to a significantly enhanced effective dipole moment of Glu-. However, l-glutamate dynamics is determined by the rotational diffusion of individual anions under hydrodynamic slip boundary conditions. Thus, the lifetime of the hydrate complexes, as well as of possibly formed [Na+Glu-]0 ionpairs and l-glutamate aggregates, cannot exceed the characteristic timescale for Glu- rotation.

Effect of Brønsted Acidity on Ion Conduction in Fluorinated Acetic Acid and N-Methylimidazole Equimolar Mixtures as Pseudo-protic Ionic Liquids.

To clarify proton conduction mechanism in protic ionic liquids (PILs) and pseudo-PILs (pPILs), equimolar mixtures of N-methylimidazole (C1Im) with fluorinated acetic acids were investigated by Raman spectroscopy, X-ray scattering, and dielectric relaxation spectroscopy (DRS). Only the ionic species exist in the equimolar mixture of C1Im and HTFA (HTFA: trifluoroacetic acid). On the other hand, the equimolar mixture of C1Im and HDFA (HDFA: difluoroacetic acid) consists of both ionic and electrically neutral species. In particular, not only the electrostatic but also van der Waals interactions with the F atoms were observed in the liquid structures of both [C1hIm+][TFA-] and [C1hIm+][DFA-]. The concept for proton conduction mechanism that we have proposed in previous study was revisited; the proton conduction mechanism could be classified with two linear free energy relationship lines for proton exchange reaction and translation/rotation of proton carriers. Our results exhibit that the proton conduction mechanism changes from proton hopping to vehicle mechanism with increasing acidity of an acid HA in PILs.

Equilibria and Dynamics of Sodium Citrate Aqueous Solutions: The Hydration of Citrate and Formation of the Na3Cit0 Ion Aggregate.

Sodium citrate (Na3Cit) has a crucial role in many biological and industrial processes. Yet, quantitative information on its hydration and the ion association between Na+ and Cit3- ions in a broad range of salt concentrations is still lacking. In this work, we study both ion association equilibria and relaxation dynamics of sodium citrate solutions by combining potentiometry, spectrophotometry, and dielectric spectroscopy. From photometric and potentiometric measurements, we detect the formation of the NaCit2- ion-pair and the neutral Na3Cit0 ion aggregate in a wide range of ionic strengths (0.5-4 M). Due to its remarkable stability, the latter becomes the prevailing species at higher salt concentrations. In the dielectric spectra, we observe the dipolar relaxation of Cit3- and NaCit2- and two solvent-related processes, associated with the collective rearrangement of the H-bond network (cooperative water mode) and the H-bond flip of water molecules (fast water mode). Unlike numerous other salt solutions, the relaxation time of the cooperative mode scales with the viscosity indicating that the strongly hydrated anion fits well into the water network. That is, the stabilizing effect of anion-solvent interactions on the H-bond network outweighs the destructive impact of the cations as the latter are only present at low concentration, due to strong ion association. In conclusion, the affinity of citrate toward Na+ binding not only governs solution equilibria but also has a strong impact on water dynamics.

Dielectric relaxation of deep eutectic solvent + water mixtures: structural implications and application to microwave heating.

We studied the dielectric response of deep eutectic solvents (DESs) composed of choline chloride (ChCl) and such hydrogen bond donors (HBDs) as glycerol (glyceline) and urea (reline) mixed with water at T = 298.15 K and frequencies varying from 0.05 to 89 GHz. The dielectric loss data were used to calculate normalized heating rates for these systems upon electromagnetic irradiation at operating frequencies of domestic (ν = 2.45 GHz) and industrial (ν = 900 MHz) microwave ovens. We show that due to slow dynamics and substantial Ohmic-loss contributions DES/water mixtures constitute promising solvents for microwave synthesis. Their dielectric spectra can be best fit by a superposition of relaxation processes assigned to the reorientation of dipolar DES components and water molecules. Static permittivities were found to smoothly decrease from the value of neat water (78.4) to 22.8 for glyceline and 41.2 for reline. The analysis of the obtained relaxation amplitudes suggests that the studied systems can be viewed as mixtures of individual choline, HBD and water dipoles without pronounced dipole-dipole correlations and negligible ChCl ion pairs. However, rotational motions of the dipoles are partly synchronized, leading to the slow-down of 22 water molecules for glyceline and 9.2 for reline at infinite dilution. At vanishing DES concentration ChCl-HBD interactions appear to be negligible. Relaxation times as a function of viscosity show a break point at the ChCl : HBD : H2O ratio equal to 1 : 2 : 4. This supports the suggestion of a structural transition from homogeneous electrolyte solution to a micro-heterogeneous mixture already discussed in the literature.

Interplay between aggregation number, micelle charge and hydration of catanionic surfactants.

Catanionic mixtures are commonly used in applications due to synergetic properties of both cationic and anionic surfactants. To better understand the mechanism of the micellization process of salt-free catanionic surfactants, alkyltrimethylammonium alkanecarboxylates, [CxMe3N]+[Cy]-, with medium to long alkyl chains on both cation and anion (x,y = 6-10), were investigated in aqueous solution by density and zeta potential measurements, isothermal titration calorimetry (ITC), and dielectric relaxation spectroscopy (DRS). The obtained ITC data was analysed with the help of a two-step model equation, yielding the thermodynamic parameters, micelle charge and aggregation numbers. Comparison with the "parent" decyltrimethylammonium chloride and sodium decanoate reveals that combined dehydration of both alkyl chains increases entropy upon micellization. In the first step neutral smaller micelles with partly dehydrated alkyl chains are formed, while in the second step larger charged micelles with fully dehydrated alkyl chains are equally favourable. At low temperature both formations are thermodynamically equivalent, while with increasing temperature neutral micelles become more entropically favourable and charged micelles more enthalpically favourable. The resulting average micelle charge and average aggregation number are decreasing with temperature. From the DRS spectra, effective hydration numbers of the free monomers and micelles were deduced and are comparable to the "parent" cationic surfactant micelles.

Systematic Variations of Ion Hydration in Aqueous Alkali Metal Fluoride Solutions.

Aqueous solutions of three alkali metal fluorides-NaF, KF, and CsF-have been studied by dielectric relaxation spectroscopy (DRS) over the frequency range 0.2 ≲ ν/GHz ≤ 89 at 25 °C and at concentrations 0.05 ≲ c/mol L-1 ≲ 1. The combination of these measurements with analogous literature data for RbF(aq) and M'Cl(aq) (M' = Li, Na, K, and Cs) made possible a systematic analysis of the hydration of F- and the alkali metal cations. Unlike the other halide ions, F- was found to have a well-defined hydration shell which contains ∼7 water molecules, consistent with the appearance of a "slow"-water mode at ∼10 GHz in the spectra. Limiting total effective hydration numbers (Zt0) for M'F(aq), obtained from the solvent-related modes, did not follow a simple sequence, varying in the order CsF < NaF < RbF < KF. However, it is shown that this anomalous sequence results from subtle variations in the strength of the M'+-OH2 bonding. Thus, it was established that Zib0(M'+) values, corresponding to the numbers of strongly ("irrotationally") bound (ib) water molecules around the cations, do vary with charge density in the order Li+ ≫ Na+ > K+ > Rb+ > Cs+. It was also found that Zs0(M'+), the number of moderately bound ("slow") water molecules, varied in the same order: K+ > Rb+ > Cs+. However, the presence of ib water molecules in the hydration shells of Li+ and Na+ attenuates their further interaction with surrounding water molecules such that Zs0(M'+) ≈ 0 for both ions.

Structure, molecular dynamics, and interactions in aqueous xylitol solutions.

The cooperative dynamics and hydration of aqueous xylitol solutions were investigated at 25 °C by broad-band dielectric spectroscopy for solute concentrations c≤ 3.251 M. The spectra could be consistently interpreted by assuming a superposition of five modes. From the combined amplitudes of the bulk-water contributions at ∼18 GHz and ∼600 GHz the effective xylitol hydration number of 5.66 ± 0.08 was derived. These hydrating H2O molecules are retarded by a factor of ∼2.6 compared to the bulk and cause ∼85% of the relaxation resolved at ∼5-10 GHz. The remaining amplitude could be attributed to the three central -OH groups of xylitol, which exhibit slower dynamics than the more exposed distal hydroxyl groups peaking at ∼50 GHz but all having the same effective dipole moment, µ = 3.43 D. A further xylitol-specific relaxation at ∼1.5 GHz probably arises from weak xylitol aggregation.

Possible Proton Conduction Mechanism in Pseudo-Protic Ionic Liquids: A Concept of Specific Proton Conduction.

In a previous work, we have found that the pseudo-protic ionic liquid N-methylimidazolium acetate, [C1HIm][OAc] or [Hmim][OAc], mainly consists of the electrically neutral molecular species N-methylimidazole, C1Im, and acetic acid, AcOH, even though the mixture has significant ionic conductivity. This system was revisited by employing isotopic substitution Raman spectroscopy (ISRS) and pulsed field gradient (PFG) NMR self-diffusion measurements. The ISRS and PFG-NMR results obtained fully confirm our earlier findings. In particular, the self-diffusion coefficient of the hydroxyl hydrogen atom in AcOH is identical to that of the methyl hydrogen atoms within the experimental uncertainty, consistent with very little ionization. Therefore, a proton conduction mechanism similar to the Grotthuss mechanism for aqueous acid solutions is postulated to be responsible for the observed electrical conductivity. Laity resistance coefficients (rij) are calculated from the transport properties, and the negative values obtained for the like-ion interactions are consistent with the pseudo-ionic liquid description, that is, the mixture is indeed a very weak electrolyte. The structure and rotational dynamics of the mixture were also investigated using high-energy X-ray total scattering experiments, molecular dynamics simulations, and dielectric relaxation spectroscopy. Based on a comparison of activation energies and the well-known linear free energy relationship between the kinetics and thermodynamics of autoprotolysis, we propose for [C1HIm][OAc] a Grotthus-type proton conduction mechanism involving fast AcOH/AcO- rotation as a decisive step.

Hydration and ion association of aqueous choline chloride and chlorocholine chloride.

The choline ion (Ch+) is ubiquitous in nature and also its synthetic homologue, chlorocholine (ClCh+), is widely used. Nevertheless, surprisingly little information on the hydration and counter-ion binding of these cations can be found in the literature. In this contribution we report effective hydration numbers, determined by dielectric relaxation spectroscopy, and ion-pair association constants with Cl-, determined by dilute-solution conductivity measurements. In combination with RISM calculations the obtained data suggest that for Ch+ water is bound to the hydroxy group via hydrogen bonds whereas for ClCh+ a rather stiff clathrate-like shell around the chlorine atom seems to be formed. With Cl- both cations form contact ion pairs with association constants of only ∼2 to 3 M-1.

Hydration and Counterion Binding of an Aminomethylated Resorcin[4]arene.

Supramolecular chemistry based on host-guest complexes is a rapidly evolving research field with numerous potential applications. However, up to date investigations mainly focused on molecular recognition and self-assembly in nonpolar media where hydrogen-bond formation could be used for selective host-guest binding. Obviously, in aqueous solutions hydration will compete, hampering supramolecular chemistry to go green. As practically no information on host hydration is available yet, we study in this contribution the competition of hydration and counterion binding for the aminomethylated resorcin[4]arene hydrochloride, TAM·(HCl)4, using dielectric spectroscopy. We find that TAM·(HCl)4 is strongly hydrated but binds Cl- ions only weakly in a noncooperative manner.

Insight into the Hydration of Cationic Surfactants: A Thermodynamic and Dielectric Study of Functionalized Quaternary Ammonium Chlorides.

Hydrophobic interactions are one of the main thermodynamic driving forces in self-assembly, folding, and association processes. To understand the dehydration-driven solvent exposure of hydrophobic surfaces, the micellization of functionalized decyldimethylammonium chlorides, XC10Me2N+Cl-, with a polar functional group, X = C2OH, C2OMe, C2OC2OMe, C2OOEt, together with the "reference" compound decyltrimethylammonium chloride, C10Me3N+Cl-, was investigated in aqueous solution by density measurements, isothermal titration calorimetry (ITC), and dielectric relaxation spectroscopy (DRS). From the density data, the apparent molar volumes of monomers and micelles were estimated, whereas the ITC data were analyzed with the help of a model equation, yielding the thermodynamic parameters and aggregation number. From the DRS spectra, effective hydration numbers of the free monomers and micelles were deduced. The comprehensive analysis of the obtained results shows that the thermodynamics of micellization are strongly affected by the nature of the functional group. Surprisingly, the hydration of micelles formed by surfactant cations with a single alkyl chain on quaternary ammonium is approximately the same, regardless of the alkyl chain length or functionalization of the headgroup. However, notable differences were found for the free monomers where increasing polarity lowers the effective hydration number.

Cation Hydration and Ion Pairing in Aqueous Solutions of MgCl2 and CaCl2.

Broadband dielectric relaxation spectroscopy (DRS) has been used to investigate aqueous solutions of MgCl2 and CaCl2 up to concentrations of about 1.8 mol L-1 at 25 °C over the frequency range 0.07 ≤ ν/GHz ≤ 89. Detailed analysis of the dominant solvent mode centered at ∼20 GHz showed that both Mg2+ and Ca2+ are strongly solvated, each immobilizing ∼20 water molecules on the DRS timescale. This is consistent with the formation of two well-defined hydration layers around both cations. The hydration shell of Ca2+(aq) was found to be slightly more labile compared with Mg2+(aq). Two or three low-intensity solute-related modes were observed at frequencies ≲10 GHz for MgCl2(aq) and CaCl2, respectively. Two of these modes were attributed to the formation of double-solvent-separated and solvent-shared 1:1 ion pairs. The third mode (observed at very low frequencies and only for some CaCl2 solutions) was thought to be due to an ion-cloud relaxation. No evidence was found for "slow" water or, consistent with the strong cation hydration, for contact ion pairs. The overall association constants for MgCl+(aq) and CaCl+(aq) calculated from the ion-pairing constants were very small but in good agreement with literature values obtained from other techniques.