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The glass formation and the dipolar reorientational motions in deep eutectic solvents (DESs) are frequently overlooked, despite their crucial role in defining the room-temperature physiochemical properties. To understand the effects of these dynamics on the ionic conductivity and their relation to the mechanical properties of the DES, we conducted broadband dielectric and rheological spectroscopy over a wide temperature range on three well-established carboxylic acid-based natural DESs. These are the eutectic mixtures of choline chloride with oxalic acid (oxaline), malonic acid (maline), and phenylacetic acid (phenylaceline). In all three DESs, we observe signs of a glass transition in the temperature dependence of their dipolar reorientational and structural dynamics, as well as varying degrees of motional decoupling between the different observed dynamics. Maline and oxaline display a breaking of the Walden rule near the glass-transition temperature, while the relation between the dc conductivity and dipolar relaxation time in both maline and phenylaceline is best described by a power law. The glass-forming properties of the investigated systems not only govern the orientational dipolar motions and rheological properties, which are of interest from a fundamental point of view, but they also affect the dc conductivity, even at room temperature, which is of high technical relevance. [ABSTRACT FROM AUTHOR]

Oscillatory shear rheology has been employed to access the structural rearrangements of deeply supercooled sulfuric acid tetrahydrate (SA4H) and phosphoric acid monohydrate, the latter in protonated (PA1H) and deuterated (PA1D) forms. Their viscoelastic responses are analyzed in relation to their previously investigated electric conductivity. The comparison of the also presently reported dielectric response of deuterated sulfuric acid tetrahydrate (SA4D) and that of its protonated analog SA4H reveals an absence of isotope effects for the charge transport in this hydrate. This finding clearly contrasts with the situation known for PA1H and PA1D. Our analyses also demonstrate that the conductivity relaxation profiles of acid hydrides closely resemble those exhibited by classical ionic electrolytes, even though the charge transport in phosphoric acid hydrates is dominated by proton transfer processes. At variance with this dielectric simplicity, the viscoelastic responses of these materials depend on their structural compositions. While SA4H displays a "simple liquid"-like viscoelastic behavior, the mechanical responses of PA1H and PA1D are more complex, revealing relaxation modes, which are faster than their ubiquitous structural rearrangements. Interestingly, the characteristic rates of these fast mechanical relaxations agree well with the characteristic frequencies of the charge rearrangements probed in the dielectric investigations, suggesting appearance of a proton transfer in mechanical relaxation of phosphoric acid hydrates. These findings open the exciting perspective of exploiting shear rheology to access not only the dynamics of the matrix but also that of the charge carriers in highly viscous decoupled conductors. [ABSTRACT FROM AUTHOR]

The self-diffusion coefficient of viscous liquids is estimated on the basis of a simple analysis of their rheological shear spectra. To this end, the Almond–West approach, previously employed to access single-particle diffusivities in ionic conductors, is generalized for application to molecular dynamics in supercooled liquids. Rheology based estimates, presented for indomethacin, ortho-terphenyl, and trinaphthylbenzene, reveal relatively small, yet systematic differences when compared with diffusivity data directly measured for these highly viscous liquids. These deviations are discussed in terms of mechanical Haven ratios, introduced to quantify the magnitude of collective translational effects that have an impact on the viscous flow. [ABSTRACT FROM AUTHOR]

Combining results from impedance spectroscopy and oscillatory shear rheology, the present work focuses on the relation between the mass and charge flows and on how these are affected by the H-bonding in viscous ionic liquids (ILs). In particular, we compare the relaxational behaviors of the paradigmatic IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and its OH-functionalized counterpart 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (OHEMIM-TFSI). Our results and their analysis demonstrate that the presence of cationic OH-groups bears a strong impact on the overall dynamics of OHEMIM-TFSI, although no signatures of suprastructural relaxation modes could be identified in their dielectric and mechanical responses. To check whether at the origin of this strong variation is the H-bonding or merely the difference between the corresponding cation sizes (controlling both the hydrodynamic volume and the inter-charge distance), the present study includes 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PMIM-TFSI), mixtures of EMIM-TFSI and PMIM-TFSI with lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and mixtures of OHEMIM-TFSI with PMIM-TFSI. Their investigation clearly reveals that the dynamical changes induced by H-bonding are significantly larger than those that can be attributed to the change in the ion size. Moreover, in the mixtures of OHEMIM-TFSI with PMIM-TFSI, a dilution of the OH-groups leads to strong deviations from ideal mixing behavior, thus highlighting the common phenomenological ground of hydroxy-functionalized ILs and other H-bonded liquids. [ABSTRACT FROM AUTHOR]

Many glassformers display electrorheological effects and a pronounced maximum in their frequency dependent nonlinear dielectric response. The latter so-called "hump" feature was often linked to correlated-particle motions and, so far, was not explored in the large-perturbation mechanical response of viscous liquids. To first clarify the electro-viscoelastic coupling in the linear domain, using the modified Gemant, DiMarzio, and Bishop model, it is demonstrated how the small-amplitude shear mechanical response of S -methoxy-PC, a derivative of propylene carbonate, can be related to its complex dielectric permittivity. Then, in the nonlinear regime, a "hump" feature is identified in the rheological third-order shear modulus of S -methoxy-PC and of another polar glassformer, propylene glycol. Thus, the observation of a "hump" in the cubic response of viscous liquids does not necessarily rely on the application of electrical fields.

Large-amplitude thermal excursions imposed on deeply supercooled liquids modulate the nonlinear time evolution of their structural rearrangements. The consequent aftereffects are treated within a Wiener-Volterra expansion in laboratory time that allows one to calculate the associated physical-aging and thermal response functions. These responses and the corresponding higher-harmonic susceptibilities are illustrated using calculations based on the Tool-Narayanaswamy-Moynihan (TNM) model. The conversion from laboratory to material time is thoroughly discussed. Similarities and differences to field-induced higher-harmonic susceptibilities are illustrated using Lissajous and Cole-Cole plots and discussed in terms of aging nonlinearity parameters. For the Lissajous plots, banana-type shapes emerge, while the Cole-Cole plots display cardioidic and other visually appealing patterns. For application beyond the regime in which conventional single-parameter aging concepts work, the Wiener-Volterra material-time-series is introduced as the central tool. Calculations and analyses within this general framework in conjunction with suitable choices of higher-order memory kernels and employing correspondingly extended TNM models yield at least qualitative agreement with recent large-perturbation physical aging experiments. Implications for differential scanning calorimetry and related methods are discussed. The introduced concepts and analyses provide a solid foundation for a generalized description of nonlinear thermal out-of-equilibrium dynamics of glass forming materials, differing from the nonlinear responses known from rheology and dielectric spectroscopy., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The present work focuses on the dynamics of the ionic constituents of 1-propyl-3-methyl-imidazolium-bis-(trifluormethylsulfonyl)-imide (PT), a paradigmatic ionic liquid, as an additive in poly(vinylpyrrolidone) (PVP). Hence, the resulting product can be regarded as a polymer electrolyte as well as an amorphous dispersion. Leveraging dielectric spectroscopy and oscillatory shear rheology, complemented by differential scanning calorimetry, the spectral shapes and the relaxation maps of the supercooled PVP-PT mixtures are accessed in their full compositional range. The study also presents dielectric and shear responses of neat PVP with a molecular weight of 2500 g mol -1 . We discuss the plasticizing role of the PT additive and the decoupling between ionic dynamics and segmental relaxation in these mixtures. The extracted relaxation times, steady-state viscosities, and conductivities are employed to estimate the translational diffusivities of the ionic penetrants by means of the Stokes-Einstein, Nernst-Einstein, and Almond-West relations. While some of the estimated diffusivities agree with each other, some do not, pointing to the importance of the chosen hydrodynamic approximations and the type of response considered for the analysis. The present extensive dielectric, rheological, and calorimetric study enables a deeper understanding of relaxation and transport of ionic ingredients in polymers, particularly in the slow-dynamics regime which is difficult to access experimentally by direct-diffusivity probes.

Glutaronitrile (GN) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) at concentrations below and above the room-temperature conductivity optimum near 1M of Li salt is investigated using dielectric spectroscopy and shear rheology. The experiments are carried out from ambient down to the glass transition temperature Tg, which increases considerably as LiTFSI is admixed to GN. As the temperature is lowered, the conductivity optimum shifts to lower salt concentrations, while the power-law exponents connecting resistivity and molecular reorientation time remain smallest for the 1M composition. By contrast, the rheologically detected time constants, as well as those obtained using dielectric spectroscopy, increase monotonically with increasing Li salt concentration for all temperatures. It is demonstrated that the shear mechanical measurements are, nevertheless, sensitive to the 1M conductivity optimum, thus elucidating the interplay of the dinitrile matrix with the mobile species. The data for the Li doped GN and other nitrile solvents all follow about the same Walden line, in harmony with their highly conductive character. The composition dependent relation between the ionic and the reorientational dynamics is also elucidated., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

A high-resolution, temperature oscillation-based probe of physical aging in complex systems is introduced. The Fourier analysis of the measured responses allows one to extract high-order, aging-related nonlinearities that are not accessible via traditional temperature-jump and temperature-ramp procedures. To demonstrate the potential of this oscillatory approach, we analyze the periodic time evolution of glycerol's structural relaxation using shear rheology as a vehicle. Thereby, we access up to the sixth harmonic and detect aging fingerprints within a resolution range of three orders of magnitude for temperature amplitudes of up to 4 K. The even harmonics are present since aging is not symmetrical with respect to the direction of temperature change. The high-order aging coefficients obtained for glycerol are described reasonably well within the Tool-Narayanaswamy-Moynihan formalism., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Solvated in propylene carbonate, viscous phenol is studied using dielectric spectroscopy and shear rheology. In addition, several oxygen-17 and deuteron nuclear magnetic resonance (NMR) techniques are applied to specifically isotope labeled equimolar mixtures. Quantum chemical calculations are used to check the electrical field gradient at phenol's oxygen site. The chosen combination of NMR methods facilitates the selective examination of potentially hydrogen-bond related contributions as well as those dominated by the structural relaxation. Taken together the present results for phenol in equimolar mixtures with the van der Waals liquid propylene carbonate provide evidence for the existence of a very weak Debye-like process that originates from ringlike supramolecular associates.

Currently, there is a debate whether the structural relaxation of polar liquids is more faithfully reflected (i) by the generically shaped response detected by dynamic light scattering or rather (ii) by the slower, more stretched, system-dependent susceptibility response recorded by dielectric spectroscopy. In this work, nonlinearly induced transients probing structural relaxation reveal that near the glass transition, alternative (ii) is appropriate for propylene glycol. Results from shear rheology and from calorimetry corroborate this finding, underscoring the previously advanced notion (Moch et al., Phys. Rev. Lett. 128, 228001, 2022) that the reorientationally probed structural susceptibility of viscous liquids displays a nongeneric spectral shape.

Acetaminophen, nicotine, and lidocaine hydrochloride were investigated in their deeply supercooled liquid states using oscillatory shear rheology. The mechanical spectra of these drugs are presented in modulus, compliance, as well as fluidity formats. Their frequency profiles can be described via models adapted from the field of charge transport. Inspired by the success of this approach, the Barton-Nakajima-Namikawa relation, best known from the same field, was also tested. When adapted to rheology, this approach interrelates static and dynamic characteristics of viscous flow and was found to work excellently. The temperature dependence of the characteristic shear frequencies was checked against the shoving model, which relates them to the temperature-dependent instantaneous shear modulus and acceptable agreement was found. Combined with shear mechanical literature data on ibuprofen and indomethacin, a modified version of the phenomenological model by Gemant, DiMarzio, and Bishop (GDB) was employed to successfully predict the shape and amplitude of the dielectric spectra for all studied liquids, except for lidocaine hydrochloride. For the latter, the modified GDB model is suggested to aid in mapping out the reorientational part of the dielectric response, while the experimental results are strongly superimposed by ionic conduction phenomena. The reverse transformation, the calculation of rheological spectra based on dielectric ones, is also successfully demonstrated. For the example of acetyl salicylic acid, it is shown how dielectric spectra can be used to even predict rheological ones. The limits of the central parameter governing these mutual transformations, the electroviscoelastic material constant, and indications for its correlation with the dielectric relaxation strength are discussed. For pharmaceuticals characterized by a strong dynamical decoupling of the electrical from the mechanical degrees of freedom, the modified GDB model is not expected to be applicable.

Nonlinear rheological properties of viscous indomethacin are studied in the frequency range of its structural relaxation, that is, in a range so far inaccessible to standard techniques involving medium-amplitude oscillatory shear amplitudes. The first- and third-order nonlinearity parameters thus recorded using a sequence of small and large shear excitations in a time efficient manner are compared with predictions from rheological models. By properly phase cycling the shear amplitudes, build-up and decay transients are recorded. Analogous to electrical-field experiments, these transients yield direct access to the structural relaxation times under linear and nonlinear shearing conditions. To demonstrate the broader applicability of the present approach, transient analyses are also carried out for the glass formers glycerol, ortho-terphenyl, and acetaminophen.

The annotated sequence of chromosome 2 of Plasmodium falciparum was examined for genes encoding proteins that may be of interest for vaccine development. We describe here the characterization of a protein with an altered thrombospondin Type I repeat domain (PfSPATR) that is expressed in the sporozoite, asexual, and sexual erythrocytic stages of the parasite life cycle. Immunoelectron microscopy indicated that this protein was expressed on the surface of the sporozoites and around the rhoptries in the asexual erythrocytic stage. An Escherichia coli-produced recombinant form of the protein bound to HepG2 cells in a dose-dependent manner and antibodies raised against this protein blocked the invasion of sporozoites into a transformed hepatoma cell line. Sera from Ghanaian adults and from a volunteer who had been immunized with radiation-attenuated P. falciparum sporozoites specifically recognized the expression of this protein on transfected COS-7 cells. These data support the evaluation of this protein as a vaccine candidate.