Chaotropic Anions Research Articles

On the mechanisms of ion adsorption to aqueous interfaces: air-water vs. oil-water

The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN-) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN- adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN-, and the Gibb's free energies of adsorption for these three different interfaces all agree within error. We employed molecular dynamics simulations to develop a molecular-level understanding of the adsorption mechanism and found that the adsorption for SCN- to both water-toluene and water-decane interfaces is driven by an increase in entropy, with very little enthalpic contribution. This is a qualitatively different mechanism than reported for SCN- adsorption to the air-water and graphene-water interfaces, wherein a favorable enthalpy change was the main driving force, against an unfavorable entropy change.

Chaotropic Anion-Based "Water-in-Salt" Electrolytes for Beyond Li-Ion Energy Storage Systems

Electrochemical energy storage systems (EESS) with high energy density, safety, low cost, and low carbon footprint have become indispensable in the modern era of ubiquitous electronics, electric vehicles, and grid storage. Current EESS lack these characteristics due to the utilization of critical materials that are precious, flammable, difficult to recycle, and pose a threat to the environment. Whereas aqueous electrolytes offer higher safety and lower cost. Nevertheless, their biggest bottleneck is the narrow electrochemical stability window (ESW) that is preventing them from attaining higher energy and power densities in most of the aqueous EESS. For instance, multivalent metal-ion-based aqueous rechargeable batteries promise high energy density due to the multivalent redox chemistry of metal ions (Al3+, Zn2+, etc.) but they exhibit much lower energy density in real experiments due to the limited ESW of the aqueous electrolytes. The water-in-salt (WIS) electrolytes can potentially eliminate this barrier by offering a larger ESW. However, an anion’s nature, i.e., kosmotropic (water structure-maker) or chaotropic (water structure breaker) plays an important role in the expansion of the ESW in WiS-electrolytes. In general, the kosmotropic anions have a negative impact on the ESW by disturbing the solvation shell of the counter cations. On the other hand, chaotropic anions increase the ESW by limiting the fraction of free water in the electrolytes by pushing water molecules into the solvation shells of the cations.We demonstrate WIS-electrolytes of metal-perchlorates (metal: Al, Zn, etc.) containing strong chaotropic anion (ClO4 -). As a result, the WiS-electrolytes of Zn- and Al-perchlorates demonstrate expanded ESW of 2.80 V and 4 V, respectively. The electrochemical tests of the electrolytes are performed using carbon-based redox-active electrode materials. We employ the new electrochemical systems in aqueous rechargeable multivalent dual-ion batteries, revealing superior performance to standard aqueous electrolytes. Our findings provide new possibilities for widening the ESW and enhancing the energy and power density in aqueous EESS, especially for grid storage applications. A. Zafar, G. Abbas, K. Knizek, M. Silhavik, P. Kumar, P. Jiricek, J. Houdkova, O. Frank, J. Cervenka, Journal of Materials Chemistry A, 2022, 10, 2064-2074.A. Zafar, G. Abbas, M. Silhavik, K. Knizek, O. Kaman, F. J. Sonia, P. Kumar, P. Jiricek, J. Houdková, O. Frank, J. Cervenka, Electrochimica Acta, 2022 404, 139754.

Anion Selection Criteria for Water-in-Salt Electrolytes

Water-in-salt electrolytes have enabled the development of novel high-voltage aqueous lithium-ion batteries due to their wide electrochemical stability window. Here, we explore why analogous sodium electrolytes have struggled to reach the same level of electrochemical stability and compare solution structure and electrochemical stability for eleven sodium salts, selected among the major classes of salts proposed for highly concentrated electrolytes.[1-3] We relate the water environment established for each anion to its position in the Hofmeister series, finding a strong correlation between the chaotropicity of the anion and the resulting electrochemical stability of the electrolyte. We discuss the importance of the solid-electrolyte interphase for stable battery performance, how it relates to the choice of anion, and further show that the search for suitable sodium salts is complicated by the fact that higher salt concentrations are needed than for their lithium equivalents.[4] Reaching such a high concentration of 25 to 30 mol/kg with one or a combination of multiple sodium salts that have the desired properties remains a major challenge. We conclude that alternative approaches such as mixed water/organic solvent or dual-cation electrolytes should be pursued to enable the development of high-voltage aqueous sodium-ion batteries. We demonstrate the potential of the mixed-solvent approach by showing that the water solubility of NaTFSI can be increased from 8 to 30 mol/kg in the presence of ionic liquids. Such a ternary electrolyte, based on highly chaotropic anions, enables stable cycling of a 2 V-class sodium-ion battery based on the NaTi2(PO4)3/Na2Mn[Fe(CN)6] electrode couple for 300 cycles at 1C with a Coulombic efficiency of >99.5%.[5]

Competitive Ion Pairing and the Role of Anions in the Behavior of Hydrated Electrons in Electrolytes.

Experiments have shown that in the presence of electrolytes, the hydrated electron's absorption spectrum experiences a blue shift whose magnitude depends on both the salt concentration and chemical identity. Previous computer simulations have suggested that the spectral blue shift results from the formation of (cation, electron) contact pairs and that the concentration dependence arises because the number of cations simultaneously paired with the electron increases with increasing concentration. In this work, we perform new simulations to build an atomistic picture that explains the effect of salt identity on the observed hydrated electron spectral shifts. We simulate hydrated electrons in the presence of both monovalent (Na+) and divalent (Ca2+) cations paired with both Cl- and a spherical species representing ClO4- anions. Our simulations reproduce the experimental observations that divalent ions produce larger blue shifts of the hydrated electron's spectrum than monovalent ions with the same anion and that perchlorate salts show enhanced blue shifts compared to chloride salts with the same cation. We find that these observations can be explained by competitive ion pairing. With small kosmotropic cations such as Na+ and Ca2+, aqueous chloride salts tend to form (cation, anion) contact pairs, whereas there is little ion pairing between these cations and chaotropic perchlorate anions. Hydrated electrons also strongly interact with these cations, but if the cations are also paired with anions, this affects the free energy of the electron-cation interaction. With chloride salts, hydrated electrons end up in complexes containing multiple cations plus a few anions as well as the electron. Repulsive interactions between the electron and the nearby Cl- anions reduce the cation-induced spectral blue shift of the hydrated electron. With perchlorate salts, hydrated electrons pair with multiple cations without any associated anions, leading to the largest possible cation-induced spectral blue shift. We also see that the reason multivalent cations produce larger spectral blue shifts than monovalent cations is because hydrated electrons are able to simultaneously pair with a larger number of multivalent cations due to a larger free energy of interaction. Overall, the interaction of hydrated electrons with electrolytes fits well with the Hofmeister series, where the electron behaves as an anion that is slightly more able to break water's H-bond structure than chloride.

Highly Efficient and Selective Recognition of Dicyanoaurate(I) by a Bambusuril Macrocycle in Water.

Dicyanoaurate(I) anion, [Au(CN)2 ]- , plays a central role in the current industrial production of gold, as its extraction from crude ore samples represents the most money-consuming step. Herein, we present the strongest host-guest recognition of dicyanoaurate anion using the bambusuril receptor in water, a highly competitive solvent. The micromolar stability of such a complex facilitated the up to date most efficient supramolecular stripping of dicyanoaurate from activated carbon at ambient temperature. Thermodynamic characteristics of bambusuril binding with [Au(CN)2 ]- differing from binding of other inorganic chaotropic anions are rationalized, as well as the bambusuril selectivity for [Au(CN)2 ]- over [Ag(CN)2 ]- .

Highly Efficient and Selective Recognition of Dicyanoaurate(I) by a Bambusuril Macrocycle in Water

AbstractDicyanoaurate(I) anion, [Au(CN)2]−, plays a central role in the current industrial production of gold, as its extraction from crude ore samples represents the most money‐consuming step. Herein, we present the strongest host–guest recognition of dicyanoaurate anion using the bambusuril receptor in water, a highly competitive solvent. The micromolar stability of such a complex facilitated the up to date most efficient supramolecular stripping of dicyanoaurate from activated carbon at ambient temperature. Thermodynamic characteristics of bambusuril binding with [Au(CN)2]− differing from binding of other inorganic chaotropic anions are rationalized, as well as the bambusuril selectivity for [Au(CN)2]− over [Ag(CN)2]−.

Specific anion effects on the interfacial properties and aggregation of alkylphenol ethoxylate surfactants

The effect of Hofmeister anions on aggregation of nonionic surfactants and the formation of microemulsion systems was evaluated. Added salt effects on the interfacial properties and aggregation of ethylene oxide condensates of nonylphenol were characterized by cloud point measurements, surface tension, fluorescence spectroscopy, light scattering, and formulation scans. The specific effects of anions on the cloud point followed the trend predicted by the Hofmeister series: H2PO4− < Cl− < Br− < NO3− < I− < SCN−, with the H2PO4− being the most kosmotropic anion and generating the most significant cloud point reduction. The specific effects of anions on the critical micelle concentration (CMC) also followed the Hofmeister series, with kosmotropic anions causing a decrease and chaotropic anions generating an increase in the CMC. Chaotropic anions decreased the size of the aggregates, while kosmotropic anions increased it, as evaluated by dynamic light scattering. The effect of Hofmeister anions on microemulsion formation in nonionic surfactant-oil–water (SOW) systems was assessed by formulation scans. Although the kosmotropicity of the anion did not influence the optimum formulation value, it did affect the phase behavior around the optimum formulation, pointing to the possibility of tuning microemulsion formulations via the choice of added electrolyte.

Room-Temperature Annealing-Free Gold Printing via Anion-Assisted Photochemical Deposition.

Metal patterning via additive manufacturing has been phasing-in to broad applications in many medical, electronics, aerospace, and automotive industries. While previous efforts have produced various promising metal-patterning strategies, their complexity and high cost have limited their practical application in rapid production and prototyping. Herein, a one-step gold printing technique based on anion-assisted photochemical deposition (APD), which can directly print highly conductive gold patterns (1.08 × 107 S m-1 ) under ambient conditions without post-annealing treatment, is introduced. Uniquely, the APD uses specific ion effects with projection lithography to pattern Au nanoparticles and simultaneously sinter them into tunable porous gold structures. The significant influence of kosmotropic or chaotropic anions in the precursor ink on tuning the morphologies and conductivities of the printed patterns by employing a series of different ions, including Cl- ions, in the printing process is presented. Additionally, the resistance stabilities and the electrochemical properties of the APD-printed gold patterns are carefully investigated. The high conductivity and excellent conformability of the printed Au electrodes are demonstrated with reliable performance in electrophysiological signal delivery and acquisition for biomedical applications. This work exploits the potential of photochemical-deposition-based metal patterning in flexible electronic manufacturing.

Hofmeister effect in gelatin-based hydrogels with shape memory properties

The soaking strategy with the Hofmeister effect has been proposed to fabricate gelatin- based hydrogels with excellent properties. However, the modulation mechanism of hydrogels lacks in-depth study. In this work, we studied in detail the effects of Hofmeister ions on the structural, thermal, viscoelastic and mechanical properties of gelatin hydrogels. The results showed that kosmotropic anions (Cit3−, SO42−, H2PO4− and S2O32−) enhanced hydrogen bonds and hydrophobic interactions between gelatin molecules, resulting in increases in the length and content of triple helices and thus improving the properties of gelatin hydrogels. In contrast, chaotropic anions (I− and SCN−) weakened the interactions between gelatin molecules, and thus attenuated the properties. Based on the Hofmeister effect, we successfully fabricated gelatin poly N-methylolacrylamide (PNMA) double network hydrogels with shape memory properties. The Hofmeister effect provides an excellent route for the rational design and fabrication of functional gelatin-based hydrogels.

Non-Globular Organic Ionic Plastic Crystal Containing a Crown-Ether Moiety - Tuning Its Behaviour Using Sodium Salts.

Organic ionic plastic crystals (OIPCs) are a class of soft materials showing positional order while still allowing orientational freedom. Due to their motional freedom in the solid state, they possess plasticity, non‐flammability and high ionic conductivity. OIPC behavior is typically exhibited by ‘simple’ globular molecules allowing molecular rotation, whereas the interactions that govern the formation of OIPC phases in complex non‐globular molecules are less understood. To better understand these interactions, a new family of non‐globular OIPCs containing a 15‐crown‐5 ether moiety was synthetized and characterized. The 15C5BA molecule prepared does not exhibit the sought‐after behavior because of its non‐globular nature and strong intermolecular H‐bonds that restrict orientational motion. However, the OIPC behavior was successfully obtained through complexation of the crown‐ether moiety with sodium salts containing chaotropic anions. Those anions weaken the interactions between the molecules, allowing rotational freedom and tuning of the thermal and morphological properties of the OIPC.

Specific anion effect on properties of HRV 3C protease

Specific salts effect is intensively studied from the prospective of modification of different physico-chemical properties of biomacromolecules. Limited knowledge of the specific salts effect on enzymes led us to address the influence of five sodium anions: sulfate, phosphate, chloride, bromide, and perchlorate, on catalytic and conformational properties of human rhinovirus-14 (HRV) 3C protease. The enzyme conformation was monitored by circular dichroism spectrum (CD) and by tyrosines fluorescence. Stability and flexibility of the enzyme have been analyzed by CD in the far-UV region, differential scanning calorimetry and molecular dynamics simulations, respectively. We showed significant influence of the anions on the enzyme properties in accordance with the Hofmeister effect. The HRV 3C protease in the presence of kosmotropic anions, in contrast with chaotropic anions, exhibits increased stability, rigidity. Correlations of stabilization effect of anions on the enzyme with their charge density and the rate constant of the enzyme with the viscosity B-coefficients of anions suggest direct interaction of the anions with HRV 3C protease. The role of stabilization and decreased fluctuation of the polypeptide chain of HRV 3C protease on its activation in the presence of kosmotropic anions is discussed within the frame of the macromolecular rate theory.

Influence of Hofmeister anions on structural and thermal properties of a starch-protein-lipid nanoparticle

A self-assembled soluble nanoparticle, composed of common food biopolymers (carbohydrate, protein) and lipid, was previously reported by our laboratory. Although carrying capacity of valuable small molecules was demonstrated, physical functional properties are also important. Given the stabilization or destabilization characteristics of Hofmeister anion on macromolecular structures, mainly on proteins, here, we investigated the effects of different sodium salts composed of different Hofmeister anions on the structural and thermal properties of these self-assembled nanoparticles for improved functionalities. The salts were added into the mixture that was prepared in a diluted system during nanoparticle formation. Increased concentration of kosmotropic anions, in contrast to the chaotropic anion tested, resulted in nanoparticles with higher molar mass, hydrodynamic radius, and molecular density with more compact arrangement. The nanoparticles produced in presence of kosmotropic anions dissociated at higher temperatures and required higher enthalpies compared to the control sample. Spherical nanoparticles were formed for the kosmotropes with shear thinning behavior, contrary to rod-like nanoparticles for the chaotrope with near-Newtonian behavior. These findings help to gain an understanding of the effect of altering environmental conditions on the nanoparticles with an aim of producing desired structures for applications.

Switchable DNA-Based Peroxidases Controlled by a Chaotropic Ion.

Here we demonstrate a switchable DNA electron‐transfer catalyst, enabled by selective destabilization of secondary structure by the denaturant, perchlorate. The system is comprised of two strands, one of which can be selectively switched between a G‐quadruplex and duplex or single‐stranded conformations. In the G‐quadruplex state, it binds hemin, enabling peroxidase activity. This switching ability arises from our finding that perchlorate, a chaotropic Hofmeister ion, selectively destabilizes duplex over G‐quadruplex DNA. By varying perchlorate concentration, we show that the DNA structure can be switched between states that do and do not catalyze electron‐transfer catalysis. State switching can be achieved in three ways: thermally, by dilution, or by concentration.

Anionic Species Regulate Chemical Storage in Nanometer Vesicles and Amperometrically Detected Exocytotic Dynamics.

Hofmeister effects have often been ignored in living organisms, although they affect the activity and functions of biological molecules. Herein, amperometry has been applied to show that the vesicular content, dynamics of exocytosis and vesicles opening, depend on the anionic species treatment. Compared to 100 μM Cl– treated chromaffin cells, a similar number of catecholamine molecules is released after chaotropic anions (ClO4– and SCN–) treatment, even though the vesicular catecholamine content significantly increases, suggesting a lower release fraction. In addition, there are opposite effects on the dynamics of vesicles release (shorter duration) and vesicle opening (longer duration) for chaotropic anions treated cells. Our results show anion-dependent vesicle release, vesicle opening, and vesicular content, providing understanding of the pharmacological and pathological processes induced by inorganic ions.

Simultaneous Counting of Molecules in the Halo and Dense‐Core of Nanovesicles by Regulating Dynamics of Vesicle Opening

AbstractWe report the discovery that in the presence of chaotropic anions (SCN−) the opening of nanometer biological vesicles at an electrified interface often becomes a two‐step process (around 30 % doublet peaks). We have then used this to independently count molecules in each subvesicular compartment, the halo and protein dense‐core, and the fraction of catecholamine binding to the dense‐core is 68 %. Moreover, we differentiated two distinct populations of large dense‐core vesicles (LDCVs) and quantified their content, which might correspond to immature (43 %) and mature (30 %) LDCVs, to reveal differences in their biogenesis. We speculate this is caused by an increase in the electrostatic attraction between protonated catecholamine and the negatively charged dense‐core following adsorption of SCN−.

Simultaneous Counting of Molecules in the Halo and Dense-Core of Nanovesicles by Regulating Dynamics of Vesicle Opening.

We report the discovery that in the presence of chaotropic anions (SCN−) the opening of nanometer biological vesicles at an electrified interface often becomes a two‐step process (around 30 % doublet peaks). We have then used this to independently count molecules in each subvesicular compartment, the halo and protein dense‐core, and the fraction of catecholamine binding to the dense‐core is 68 %. Moreover, we differentiated two distinct populations of large dense‐core vesicles (LDCVs) and quantified their content, which might correspond to immature (43 %) and mature (30 %) LDCVs, to reveal differences in their biogenesis. We speculate this is caused by an increase in the electrostatic attraction between protonated catecholamine and the negatively charged dense‐core following adsorption of SCN−.

Physicochemical characterization of green sodium oleate-based formulations. Part 2. Effect of anions

HypothesisIn Part 1 of this work we reported the behavior of a moderately concentrated dispersion of sodium oleate (NaOL) in water that produces elongated wormlike micelles (WLMs). Prompted by the striking effect induced by adding potassium chloride to the original NaOL dispersion, here we investigate the effect of different anions (with fixed cation) on NaOL or KOL-based hydrogels upon addition of different strong electrolytes. The interest in these investigations relies on the fact that they are among the best candidates for the production of eco-friendly stimulus-responsive materials. ExperimentalThe thermal and rheological properties of a 0.43 M dispersion of NaOL or KOL in water were investigated by steady-state and oscillatory rheology, and DSC experiments in the presence of different potassium or sodium salts at the same concentration (0.54 m), respectively. FindingsThis paper highlights the occurrence of a Hofmeister phenomenon in the case of oleate-based WLMs and illustrates the remarkable effect induced by kosmotropic and chaotropic anions in terms of rheology and hydration of the rod-like nanoassemblies, that reflect the different ion adsorption at the WLM interface. We also discuss the different ion condensation of sodium and potassium ions at the interface that can lead to a significant change in the curvature of the elongated rods.

Effect of dipole potential on the orientation of Voltage-gated Alamethicin peptides regulated by chaotropic anions

• A new tBLMs model was proposed to accommodate the voltage-gated Alm peptides. • Chaotropic anions induce dipole potential decrease by disrupting the water structure. • A lower dipole potential facilitates the peptide to adopt a more upright orientation. Understanding the gating mechanism of ion channel proteins is the basis for regulating cell activity and designing new drug molecules, but it still remains a great challenge. Herein, a new tethered bilayer lipid membranes (tBLMs) model was proposed to accommodate the voltage-gated ion channel model-Alamethicin (Alm) peptides. Using surface-enhanced infrared absorption (SEIRA) spectroelectrochemistry combined with fluorescence spectroscopy, it was found that the orientation of the peptides inserted into the membranes was affected by membrane dipole potential regulated by chaotropic anions. A lower dipole potential could reduce the energy barrier of the insertion of peptides into the membranes, which facilitates the peptides to adopt a more upright orientation in the membranes. This research is of great significance for understanding the mechanism of ion channel-related diseases.

Fine-tuning of the pharmacological potential of novel thiazolium ionic liquids by anion alteration.

A novel series of thiazolium ionic liquids (TILs) bound to chloride (2a–c), tetrafluoroborate (BF4) (3a–c), and bis-(trifluoromethanesulfonimide) (Tf2N) anions (4a–c) was synthesized and their physicochemical characteristics were investigated using various microanalytical techniques. The pharmacological potential of the new TILs was assessed as chemotherapeutic agents for bacterial infections and ovarian cancer (SKOV-3). Notably, ILs with the same cations become more bactericidal upon their binding with the strongest chaotropic anion (TN2f). The in vitro toxicity of the TILs toward ovarian carcinoma cell lines (SKOV-3) and normal human skin fibroblast cells (HSF) revealed that all tested TILs have the capacity to induce a dose- and time-dependent decline in SKOV-3 cell viability, with Tf2N-linked TILs (4a–c) having a preferable efficacy. In addition, the new compounds showed excellent selectivity for cancer cells (SKOV-3) over healthy cells (HSF). [iPBzTh][Tf2N] (4b) is the most cytotoxic and specific one and may act as a promising anti-ovarian cancer agent.

Chaotropic anion based “water-in-salt” electrolyte realizes a high voltage Zn–graphite dual-ion battery

We report a high voltage Zn–graphite dual-ion battery based on Zn(ClO4)2 water-in-salt (WiS) electrolyte with a wide electrochemical window of 2.80 V and high oxidative stability of 2.60 V vs. Zn/Zn2+.