Cation Dynamics Research Articles

Collision-Induced Unfolding Is Sensitive to the Polarity of Proteins and Protein Complexes.

Collision-induced unfolding (CIU) uses ion mobility to probe the structures of ions of proteins and noncovalent complexes as a function of the extent of gas-phase activation prior to analysis. CIU can be sensitive to domain structures, isoform identities, and binding partners, which makes it appealing for many applications. Almost all previous applications of CIU have probed cations. Here, we evaluate the application of CIU to anions and compare the results for anions with those for cations. Towards that end, we developed a "similarity score" that we used to quantify the differences between the results of different CIU experiments and evaluate the significance of those differences relative to the variance of the underlying measurements. Many of the differences between anions and cations that were identified can be attributed to the lower absolute charge states of anions. For example, the extents of the increase in collision cross section over the full range of energies depended strongly on absolute charge state. However, over intermediate energies, there are significant difference between anions and cations with the same absolute charge state. Therefore, CIU is sensitive to the polarity of protein ions. Based on these results, we propose that the utility of CIU to differentiate similar proteins or noncovalent complexes may also depend on polarity. More generally, these results indicate thatthe relationship between the structures and dynamics of native-like cations and anions deserve further attention and that future studies may benefit from integrating results from ions of both polarities.

Charge Carriers Are Not Affected by the Relatively Slow-Rotating Methylammonium Cations in Lead Halide Perovskite Thin Films.

Recently, several studies have investigated dielectric properties as a possible origin of the exceptional optoelectronic properties of metal halide perovskites (MHPs). In this study we investigated the temperature-dependent dielectric behavior of different MHP films at different frequencies. In the gigahertz regime, dielectric losses in methylammonium-based samples are dominated by the rotational dynamics of the organic cation. Upon increasing the temperature from 160 to 300 K, the rotational relaxation time, τ, decreases from 400 (200) to 6 (1) ps for MAPb-I3 (-Br3). By contrast, we found negligible temperature-dependent variations in τ for a mixed cation/mixed halide FA0.85MA0.15Pb(I0.85Br0.15)3. From temperature-dependent time-resolved microwave conductance measurements we conclude that the dipolar reorientation of the MA cation does not affect charge carrier mobility and lifetime in MHPs. Therefore, charge carriers do not feel the relatively slow-moving MA cations, despite their great impact on the dielectric constants.

Decoupling of plant and soil metal nutrients as affected by nitrogen addition in a meadow steppe

Determining base cation and trace element dynamics in plant-soil systems is important for sustainable utilization of grasslands affected by global ecosystem nitrogen (N) enrichment. A 4-year field experiment was conducted with urea addition rates of 0, 2.5, 5, 7.5, 10, 15, 20, and 30 g N m−2 yr.−1 to investigate the dynamics of base cations (Ca, Mg, K) and trace elements (Fe, Mn, Cu and Zn) in soil and a dominant species Leymus chinensis in a semi-arid meadow grassland of northeast China. Soil showed a significant decrease in exchangeable Ca and increases in extractable Fe, Mn and Zn concentrations, while plant Ca and Zn remained unchanged and plant Fe decreased with N addition. For both plant and soil compartments, stoichiometric ratios of trace elements were more variable than base cations, mainly driven by plant physiological requirements, plant nutrient uptake intensity, and elemental interactions. Excessive soil Mn mobilization and plant uptake affected concentrations of Fe, Cu and Zn in the plant and even inhibited Fe absorption (antagonistic interactions), resulting in a plant Fe:Mn ratio lower than 1.5 with high N addition rates, indicating Mn phytotoxicity or Fe deficiency. As a result, plant elemental stoichiometry did not remain homeostatic and was even more variable than in soil. Our results provided direct evidence of decoupled plant-soil elemental responses, stricter homeostatic control of macronutrients than trace elements in plants, and altered stoichiometric variability in the plant-soil system, and suggest that N addition enhances metal nutrient imbalances in the meadow steppe grassland.

Emerging Perspectives on Pain Management by Modulation of TRP Channels and ANO1.

Receptor-type ion channels are critical for detection of noxious stimuli in primary sensory neurons. Transient receptor potential (TRP) channels mediate pain sensations and promote a variety of neuronal signals that elicit secondary neural functions (such as calcitonin gene-related peptide [CGRP] secretion), which are important for physiological functions throughout the body. In this review, we focus on the involvement of TRP channels in sensing acute pain, inflammatory pain, headache, migraine, pain due to fungal infections, and osteo-inflammation. Furthermore, action potentials mediated via interactions between TRP channels and the chloride channel, anoctamin 1 (ANO1), can also generate strong pain sensations in primary sensory neurons. Thus, we also discuss mechanisms that enhance neuronal excitation and are dependent on ANO1, and consider modulation of pain sensation from the perspective of both cation and anion dynamics.

Screening Ferroelastic Transitions in Switchable Cyano-Bridged Perovskites: [CH3C(NH2)2]2[KM(CN)6], M = Cr3+, Fe3+, Co3+. Crystal Structure Characterization, Dielectric Properties, 1H NMR, and Quasielastic Neutron Scattering Studies

Here we report the dynamics of organic cations as guest molecules in the novel perovskite host framework. The novel switchable crystals from the coordination family [CH3C(NH2)2]2[KB″(CN)6] were con...

Preparation and Dielectric Characterization of P(VDF–TrFE) Copolymer-Based Composites Containing Metal–Formate Frameworks

We report the synthesis and dielectric characterization of novel polyvinylidene fluoride-trifluoroethylene P(VDF-TrFE) composite films containing [(CH3)2NH2][Mg(HCOO)3] (DMAMg) and [NH4][Zn(HCOO)3] (AmZn) dense metal-organic frameworks (MOFs). The optical camera and Raman microscopies are used to map the distribution of the MOF fillers in the prepared films. The dielectric spectroscopy experiments of the DMAMg/P(VDF-TrFE) composite performed in a broad temperature range demonstrate rich dielectric behavior originating from the dipolar dynamics of the (CH3)2NH2+ molecular cations and glassy behavior of the copolymer matrix. An anomalous behavior of the complex dielectric permittivity is also observed because of the structural phase transition of DMAMg fillers. The dielectric properties of the AmZn/P(VDF-TrFE) composite film are mainly determined by the dipolar glass relaxation of the P(VDF-TrFE) polymer. The frequency-dependent dielectric spectra of both composites allow us to characterize the observed dipolar relaxation processes. The (CH3)2NH2+ cation dynamics follows the Arrhenius law, whereas the glassy behavior of P(VDF-TrFE) is described by the Vogel-Fulcher equation. For both composites, we observe a significant increase of the dielectric permittivity compared with the P(VDF-TrFE) film without MOF fillers.

Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

The hexagonal mixed-anion solid solution Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1H and 23Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na2(CB9H10)(CB11H12) over the temperature range of 80–435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na+ jump process is characterized by the activation energy of 353(11) meV. Although Na+ mobility in Na2(CB9H10)(CB11H12) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na+ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na2(CB9H10)(CB11H12) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, both reorientational processes are found to be faster than the Na+ jump process responsible for the long-range diffusion.

The Relation between Rotational Dynamics of the Organic Cation and Phase Transitions in Hybrid Halide Perovskites.

The rotational dynamics of an organic cation in hybrid halide perovskites is intricately linked to the phase transitions that are known to occur in these materials; however, the exact relation is not clear. We have performed detailed model studies on methylammonium lead iodide and formamidinium lead iodide to unravel the relation between rotational dynamics and phase behavior. We show that the occurrence of the phase transitions is due to a subtle interplay between dipole–dipole interactions between the organic cations, specific (hydrogen bonding) interactions between the organic cation and the lead iodide lattice, and deformation of the lead iodide lattice in reaction to the reduced rotational motion of the organic cations. This combination of factors results in phase transitions at specific temperatures, leading to the formation of large organized domains of dipoles. The latter can have significant effects on the electronic structure of these materials.

A Small Lattice Change Induces Significant Dynamic Changes of CH3NH3+ Caged in Hybrid Perovskite Crystals: Toward Understanding the Interplay between Host Lattices and Guest Molecules.

Two perovskite-type compounds, (MA)2[B'Co(CN)6] (MA = methylammonium, B' = K(I) and Na(I)), have very similar structures, but exhibit marked differences in the phase and dielectric transitions. Solid state 2H NMR studies reveal the detailed dynamic changes of the caged methylammonium (MA) cations before and after the phase transitions, which are correlated with the different dielectric states of the compounds. Using solid state 59Co NMR, the dynamic changes of the host lattices before and after the transitions, which accompany the changes in the dynamics of the caged MA cations, are unveiled, demonstrating the intriguing interplay between the MA cations and the host lattices. On the basis of these observations, the molecular origins of the dielectric transitions are discussed in detail.

Base cation dynamics in rainfall, throughfall, litterflow and soil solution under Oriental beech (Fagus orientalis Lipsky) trees in northern Iran

Fluxes of base cations were studied in an Oriental beech forest and an adjacent forest gap. The fluxes of base cations in throughfall, litterflow, topsoil and subsoil solution were higher in a mixed Oriental beech forest compared to the fluxes in rainfall and topsoil and subsoil solution in the forest gap. A large proportion of cations were adsorbed or biologically immobilised by passing through the litter layer in the forest. In the mineral topsoil, a new equilibrium between the solid phase and soil solution was established where desorption/leaching surpassed adsorption/immobilisation for Ca 2+ and Mg 2+ while the opposite was true for K + . The contribution of throughfall is considerable in biogeochemical cycling. Although it is important to measure nutrient fluxes to establish forest soil chemical fertility, little data is available for Oriental beech forests, one of the most important commercial hardwood forests in Iran. The quantification of nutrient fluxes above and below ground is essential because nutrients in the soil solution are most easily available for tree uptake. A thorough understanding of biogeochemical nutrient cycling requires an investigation of nutrient fluxes between different compartments. We evaluated the effect of Oriental beech forests on biogeochemical cycling of Ca2+, Mg2+, K+ and Na+ by analysing their fluxes in rainfall, throughfall, litterflow and soil solution. Throughfall, litterflow and soil solution were sampled during one whole year under five Oriental beech trees in a mixed Hyrcanian beech forest. The amounts of Ca2+, Mg2+, K+ and Na+ in these fluxes were calculated based on their concentrations and the sampled volumes and subsequently compared with the respective fluxes in the rainfall and soil solution of an adjacent forest gap. We found significantly higher fluxes in all the measured base cations in throughfall compared to rainfall. Entering the litter layer in the forest, nearly 50% of the dissolved base cations adsorb to the solid phase or are biologically immobilised prohibiting their leaching to deeper soil horizons. In the mineral soil, the interactions between the solid phase and soil solution were comparable between the forest and the forest gap. This study highlights the role of interactions of rainwater with tree crowns and the litter layer in biogeochemical cycling and emphasises its importance for the maintenance of soil chemical fertility in Oriental beech forests.

Coherent Vibrational and Dissociation Dynamics of Polyatomic Radical Cations.

The ultrafast dynamics of polyatomic radical cations contribute to important processes including energy transfer in photovoltaics, electron transfer in photocatalysis, radiation-induced DNA damage, and chemical reactions in the upper atmosphere and space. Probing these dynamics in the gas phase is challenging due to the rapid dissociation of polyatomic radical cations following electron removal, which arises from excess electronic excitation of the molecule during the ionization process. This Concept article introduces the reader to how the pump-probe technique of femtosecond time-resolved mass spectrometry (FTRMS) can overcome this challenge to capture coherent vibrational dynamics on the femtosecond timescale in polyatomic radical cations and enable the analysis of their dissociation pathways. Examples of FTRMS applied to three families of polyatomic radical cations are discussed.

Ionic conduction in Li3Na(NH2)4: Study of the material design for the enhancement of ion conductivity in double-cation complex hydrides

Complex hydrides have collected recent attention as a new class of solid electrolytes with potential applications in all-solid-state batteries. To improve ionic conduction in the complex hydrides, multi-cation crystal structure can be attractive. It will allow tuning the cation dynamics via structure modification depending on types and number of additional cations. However, multi-cation crystal structure struggles with the inter-cation scattering among different cations. To address this issue, understanding the conduction mechanisms in the multi-cationic crystals is indispensable. Here, we study cationic conduction in a double-cation (Li and Na) complex hydride Li3Na(NH2)4, which is formed by replacing Li (with Na) from specific lattice site of LiNH2 without altering the crystal symmetry. The nuclear magnetic resonance (NMR) measurements found that Li3Na(NH2)4 is a Li-ion conductor with negligibly small Na-ion conduction. This finding is critically important to elucidate Li-ion conduction mechanism in Li3Na(NH2)4. Enhanced Li-ion conduction in Li3Na(NH2)4 is achieved by (a) suppressing diffusion of Na cation trapped at the strategically located 2c lattice sites under deep potential well; and (b) by increasing the Li defect concentration influenced by the larger volume of the Li metastable sites due to Na substitution into LiNH2. Our study will provide the design principle for multi-cation complex hydrides, and accelerate development of superior solid electrolytes for all-solid-state batteries.

Dynamics of sulfate and basic cations in soil solution as affected by gypsum fertilization in an Ultisol of Southern Brazil

ABSTRACTThe objective of this study was to evaluate the short-term dynamics of chemical species of sulfate and the main basic cations in the soil solution affected by the application of different sulfur (S) rates using agricultural gypsum. The experiment was carried out in an Ultisol with 14% clay, managed under no-tillage for 14 yrs in Southern Brazil. Four rates of S (0, 5, 10 and 20 kg of S ha−1) were evaluated using agricultural gypsum (CaSO4) as S-source. The soil solution was collected using porous capsule lysimeters before and at 9, 17, 37, 60, 76 and 109 d after the gypsum application, at depths of 20 and 60 cm. Surface application of gypsum rapidly increases the sulfate concentration in the soil solution at 20 cm depth. However, in less than 30 d, the effect of the S rates on the soil solution at 20 cm was minimal, with an increase in sulfate concentration in the soil solution at 60 cm depth after 17 d. Sulfated fertilization via agricultural gypsum at rates greater than 10 kg ha−1 in sandy soil with low cation exchange capacity increased the mobility of Ca and Mg in the soil profile.

Effects of fertilizer of calcium silicon magnesium potassium on the dynamics of soil acidity and exchangeable base cation in paddy field of southern China

Soil acidification of large areas of paddy fields in southern China has become an important problem in rice production. Therefore, how to ameliorate or remedy the acidifying paddy soil and to exposit its mechanism has important theoretical and practical significance for rebuilding healthy soils and guaranteeing national food security. Although lime has already been extensively used to remedy acidified soils, long-term application of a large amount of lime would not only cause the soil to harden, but also disturb the balance between calcium, potassium and magnesium in the soil. Given the advantages of lower solubility and comprehensive nutrient supply, fertilizer of calcium silicon magnesium potassium (CSMP) may be used as an alternative. The aim of this study was to clarify the functions of CSMP and its effects on soil acidification in paddy fields. A four-year field experiment was conducted to investigate the dynamics of soil pH, exchangeable acidi-ty, exchangeable base cation and available silicon, as well as 0~30 cm pH buffer capacity (pHBC), net base production under CSMP fertilization in the paddy soil. There were five treatments, i.e. CK (traditional fertilization practice of the local farmers), treatment I (CK plus 750 kg·hm-2 CSMP); treatment II (CK plus 1125 kg·hm-2 CSMP), treatment III (CK plus 1500 kg·hm-2 CSMP), and treatment IV (CK plus 1875 kg·hm-2 CSMP). The results showed that the traditional fertilization practice of the local farmers resulted in a decline of soil pH, soil exchangeable base cation and base saturation year by year, but soil exchangeable acid was increased with year. Conversely, CSPM fertlization significantly raised soil pH, with the magnitude of increases positively depending on the number of application times or application rate. Continuous and repeated application of CSMP effectively promoted the accumulation of exchangeable base cation and the consumption of soil exchangeable acid in paddy soil, especially for the accumulation of soil exchangeable Ca2+, Mg2+ and the consumption of soil exchangeable Al3+. Furthermore, the more amount of CSPM application resulted in the more accumulation or consumption, but with relatively slower rate. The exchangeable base cation and alkali released by CSMP contributed 108.8% to the total reduction of soil exchangeable acid, suggesting that it was the main path to reduce soil exchangeable acid. Meanwhile, CSMP application improved soil acidity in paddy field, with the content of available silicon increased year by year and the increase amplitude became larger with the more amount of CSMP application. The traditional fertilization of local farmers resulted in soil acidification, with a acidification rate was 2.86 kmol H+·hm-2·a-1. CSMP application could effectively control soil acidification, producing a lot of alkalinity with net alkalinity production of 9.93-13.82 kmol OH-·hm-2·a-1. CSPM could release Ca2+, Mg2+ and alkali, which would mitigate soil acidification in paddy fields.

UV-cross-linked poly(ethylene oxide carbonate) as free standing solid polymer electrolyte for lithium batteries

Aliphatic polycarbonates have emerged as promising polymer electrolytes due to their combination of moderate ionic conductivity and high lithium transference numbers. However, the mechanical properties of the aliphatic polycarbonates polymer electrolytes are usually weak due to the low molecular weight achieved and plasticization effect of the added lithium salt. In this article, we present a copolymer having poly(ethylene oxide) segments linked by carbonate groups with cross-linkable methacrylic pendant groups. Once the polymer and the lithium salt were mixed, the poly(ethylene oxide carbonate) was cross-linked by UV light producing a free standing solid polymer electrolyte (SPE). Different SPE formulations were designed by varying the LiTFSI concentration within the polymer matrix showing the highest ionic conductivity of 1.3·10−3 S cm−1 and a lithium transference number of 0.59 at 70 °C. 7Li solid-state NMR experiments were used to correlate the lithium cation environment and dynamics with ionic conductivity. At the same temperature the electrochemical stability window was analyzed, and a reasonable value of 4.9 V was achieved. The study was complemented by mechanical and thermal stability measurements. Finally, the optimized UV-cross-linked poly(ethylene oxide carbonate) was tested as electrolyte in lithium metal symmetric cell at 70 °C, showing low over-potential values and a stable solid electrolyte interphase layer.

Photoelectron imaging spectroscopy and photodynamics of m-xylene cations

The delayed photofragmentation and photoelectron spectroscopy coupled with DFT calculations were employed for the investigation of the relaxation dynamics of m-xylene cations. The multiphoton ionization induced by the pump pulse was used for the preparation of the m-xylene cations, and the population was characterized by the technique of photoelectron imaging. A time-delayed probe pulse was used to excite the prepared m-xylene cations to energetically higher electronic states, which undergo fragmentation. The relaxation dynamics of the m-xylene cations was tracked by monitoring the depletion of excited parent-ion and the formation of the fragment-ion. Two relaxation time constants are determined by monitoring the depletion of the excited parent-ion and the formation of the fragment-ion with the delay time. The first component of τ1 = 764 (±25) fs is attributed to an intramolecular vibrational redistribution process within the D0 state and the slow one of τ2 > 440 ns is ascribed to the long lifetime of the cations.

Role of Water on the Rotational Dynamics of the Organic Methylammonium Cation: A First Principles Analysis

Understanding the degradation mechanisms of lead-halide perovskites (CH3NH3PbI3) under exposure to liquid/aerosol water is an essential problem within the photovoltaic community. Herein we investigate both the static and the dynamic properties of the methylammonuim cation (MA) as it coordinates with invading water molecules (MA.(H2O)n, n = 1, 2, 3, 4) using both stationary state quantum mechanics and first principle molecular dynamics simulations. Various solvation structures of MA were characterized by their stabilization energies, dipoles, and Maximally-Localized Wannier Function (MLWF) centers. Calculation – and analysis – of vibrational shifts in the IR spectral region were performed for hydrated complexes; the locations of {bf{N}}{{bf{H}}}_{{bf{3}}}^{{boldsymbol{+}}} stretching vibrations allude to significant hydrogen bonding between MA and the water molecules. Through Fourier analysis of the rotational dynamics on several MA · (H2O)n complexes, we conclude that the water molecules dampen the rotational motion of the MA as the intermolecular bonds formed between the water molecules and the MA act to hinder the rotation of the cation; these findings give explanatory support to earlier computational observations of humidity effects on perovskites (i.e., CH3NH3PbI3) materials. This work is a step toward understanding the water-MA cation interaction in bulk perovskites, thus providing greater understanding of in situ instability/degradation of perovskite bulk materials.

Li- and Mg-codoped bismuth niobate pyrochlores: Synthesis, structure, electrical properties

The structure and conductivity of the new Li- and Mg-codoped bismuth niobates Bi1.5Mg1−xLixNb1.5O7−δ (0 ≤ x ≤ 0.50) with the pyrochlore structure have been investigated. The samples were synthesized by the method of organic-inorganic precursors combustion. A structural characterization was performed using 7Li nuclear magnetic resonance (NMR) spectroscopy in combination with the fitting of X-ray diffraction patterns. The Li+ cations dynamics were studied by temperature-dependent 7Li NMR lineshape analysis. The measurements have shown that the Li+ cations are distributed in one of two possible sublattices in the structure and are not mobile up to 120 °C. According to the results of structural analysis of the Bi1.5Mg1−xLixNb1.5O7−δ (x = 0.25; 0.50) pyrochlores the lithium atoms are distributed in the bismuth sites. The electrical properties were investigated by impedance spectroscopy method in the air, oxygen and “wet” atmospheres in the 25–750 °C temperature range. The activation energy value of dc conductivity is about 1.2–1.3 eV for the all samples and corresponds to the ionic (oxygen) conductivity at T > 400 °C. Electronic (p-type) conductivity was determined at T < 360 °C. 1H MAS NMR data and the results of the comparison of the conductivity of Li- and Mg-codoped bismuth niobates in dry and “wet” atmospheres point to the proton conductivity up to 500 °C. The dielectric permittivity ε′ values increase with lithium content from 86 (x = 0) to 143 (x = 0.5) at the same dielectric loss tanδ = 0.002 (1 MHz, 25 °C), TCC values vary from −590 to −530 ppm/°C in the 25–280 °C temperature range.

Lithium Imide (Li2NH) as a Solid-State Electrolyte for Electrochemical Energy Storage Applications

We here report the prospect of lithium imide, Li2NH, as a solid-state electrolyte for the rechargeable Li-ion battery. Our study reveals that the ionic conductivity in Li2NH is greatly improved by the cation and anion ordering, which is a gradual process that is initiated by Li-filling in the LiNH2 lattice (forming nonstoichiometric Li1+xNH2−x) and sequentially forms the orthorhombic α-Li2NH (lower structural ordering) followed by the cubic β-Li2NH (higher structural ordering). The process, thus, enables synchronization between the cation and anion dynamics in β-Li2NH making this Li2NH phase as one of the fastest Li-ion conducting lightweight ionic alkaline hydrides. Our study also indicates high electrochemical stability for the Li/Li2NH interface in β-Li2NH contradicting the existing perception. The study may aid the existing research in developing a cost-effective commercial Li superionic conductor with high electrochemical and thermal stabilities and high energy density at room- to moderate-temperature.

NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid

With the aim to analyze the microstructure of the polar nanoregions of mixtures of ionic liquids and inorganic salts and the single particle dynamics of metal cations in these densely ionic environments, solutions of inorganic nitrate salts (lithium, magnesium, calcium and aluminium nitrates) in the protic ionic liquid ethylammonium nitrate have been characterized by means of nuclear magnetic resonance. The measured spectra reveal that, despite being dried under vacuum, all the studied mixtures contained variable amounts of water, but, while in those with the salt cations of lower ionic potentials (Li+, Ca2+) only bulk free water that can be almost completely removed from the mixture is found, mixtures with the cations of higher ionic potentials (Mg2+, Al3+) contain only hydration water structurally anchored in the primary solvation shells of the metal cations forming coordination complexes inside the polar nanoregions of the densely ionic solvent and, thus, non-removable under vacuum. This hydration water is not properly detected by common Karl Fisher methods and these solutions are sometimes mistakenly considered anhydrous. Moreover, our NMR measurements confirm the nanostructured solvation paradigm, since they show that the influence of the addition of salt on the chemical shifts of the signals associated to hydrogen atoms in the apolar regions of the protic ionic liquid is negligible. Single-particle dynamics of cations of low and high ionic potentials was also studied, and our observations for the diffusion coefficients of lithium and aluminium cations support the conclusion that Li+ diffusion takes place inside anhydrous [Li(NO3)4]3− complexes, while kinetic complexes with Al3+ gather around [Al(H2O)6]3+) aqua ions.