Anion Identity Research Articles

SERIAL CHANGES IN METABOLIC ACID-BASE STATUS IN THREE SPECIES OF ANESTHETIZED CAPTIVE LARGE FELID.

Determination of acid-base status contributes important information about patient health, including for patients under anesthesia. There is a paucity of information about the determinants of acid-base status of large felids managed under anesthesia, and advancement of such knowledge may contribute to patient safety. This study serially monitored the individual metabolic acid-base status of 11 large felids, including lions (Panthera leo), tigers (Panthera tigris), and cheetahs (Acinonyx jubatus), under general anesthesia. We analyzed the contributions of measured strong ions (sodium, chloride, potassium, lactate), weak acids and buffers (albumin, phosphate and bicarbonate), and unmeasured anions to standardized extracellular base excess (SBE). A general linear model assessed for species differences in these parameters, with time since immobilization, SBE, and mean arterial pressure as covariates. By employing a Stewart-based analytical approach, it was possible to separate chloremic and unmeasured anion contributions to metabolic acid base status. This provided a basis for identifying mixed metabolic processes, generating differentials for underlying causes. Using normal acid base parameters for domestic felids, metabolic acidosis was found to be prevalent. Frequent evidence of unmeasured anion accumulation was also found, with unmeasured anions occasionally exceeding 5mmol/L. These findings warrant further inquiry into the drivers and clinical significance of metabolic acidosis and unmeasured anion accumulations in anesthetized large felids, encouraging further anion identity studies to elucidate possible causes. Reference ranges need to be established for acid-base parameters in large felids as a foundation for interpreting more controlled, prospective research into determinants of metabolic acid-base status in these animals under anesthesia.

Anion Architecture Controls Structure and Electroresponsivity of Anhalogenous Ionic Liquids in a Sustainable Fluid.

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]-), bis(oxalato)borate ([BOB]-), and bis(salicylato)borate ([BScB]-). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

Reducing Ice Adhesion to Polyelectrolyte Surfaces by Counterion-Mediated Nonfrozen Hydration Water.

Hydrophilic anti-icing coatings can be energy-effective passive solutions for combating ice accretion and reducing ice adhesion. However, their underlying mechanisms of action remain inferential and are ill-defined from a molecular perspective. Here, we systematically investigate the influence of the counterion identity on the shear ice adhesion strength to cationic polymer coatings having quaternary alkyl ammonium moieties as chargeable groups. Temperature-dependent molecular information on the hydrated polymer films is obtained using total internal reflection (TIR) Raman spectroscopy, complemented with differential scanning calorimetry (DSC) and ellipsometry. Ice adhesion measurements show a pronounced counterion-specific behavior with a sharp increase in adhesion at temperatures that depend on the anion identity, following the order Cl- < F- < SCN- < Br- < I-. Linked to the freezing of hydration water, the specific ordering results from differences in ion pairing and the amount of water present within the polymer film. Moreover, similar effects can be promoted by varying the cross-linking density in the coating while keeping the anion identity fixed. These findings shed new light on low ice adhesion mechanisms and may inspire novel approaches for improved anti-icing coatings.

Tracking the surface structure and the influence of cations and anions on the double-layer region of a Au(111) electrode.

We examined the electric double-layer (EDL) of a Au(111) electrode in a dilute perchloric acid solution using a combination of capacitance measurements and in situ scanning tunnelling microscopy under electrochemical conditions (ECSTM). The "camel-shaped" capacitance curve of the EDL is studied with different cations and anions, including their impact on the potential of zero charge (PZC). We show that the ECSTM images of thermally reconstructed and of the potential-induced surface reconstruction of Au(111) in perchloric acid electrolyte resemble previous work in sulphuric acid, displaying a herringbone pattern for a thermally reconstructed surface. Once the reconstruction is lifted, the Au(111) forms islands with an average of 1 atomic step height. When the potential is lowered below that of the PZC, the potential-induced surface reconstruction results in a more disoriented pattern than the thermally reconstructed surface. ECSTM images at different potentials are correlated with the voltammogram to understand the time and potential dependence of the surface. This correlation has led to the development of a potential window technique that can be used to reveal the surface structure of Au(111) based on observing the changes in PZC in the voltammogram. This method provides an indirect approach to understanding the surface structure without always relying on ECSTM. From the voltammogram, we also observed that anions (SO42-, CH3SO3-, ClO4-, F-) interact more strongly with the Au(111) surface than the alkali cations. The cation capacitance peak shape does not depend strongly on the identity of the alkali metal cation (Li+, Na+, K+). However, the anion capacitance peak depends strongly on the anion identity. It suggests that some level of specific adsorption cannot be excluded, even for anions that are traditionally not considered to adsorb specifically (perchlorate, fluoride).

Effect of Ionic Strength and Anion Identity on Rare‐Earth Element Chelation by Poly(acrylic acid)

AbstractRare‐earth elements (REEs) are critical components of many modern technologies, but their efficient separation and purification continue to pose significant challenges. Metal‐binding polymers may enable the development of promising alternative approaches to conventional separation techniques (e.g., solvent extraction), and insights into the interactions between the metal ions and polymers in solution are crucial to such development. In this work, the effect of ionic strength on the chelation of REEs by poly(acrylic acid) is investigated using isothermal titration calorimetry (ITC) to measure the metal‐binding thermodynamics. ITC experiments revealed that when ionic strength increases from increasing the sodium acetate buffer strength, polymer‐REE binding becomes increasingly disfavored. However, when ionic strength is increased by the addition of sodium chloride, binding again becomes increasingly disfavored, but to a lesser extent than when ionic strength increases from increasing the buffer strength. Additionally, the reduction in binding affinity is enthalpically driven when ionic strength is raised with sodium chloride, while it is entropically driven when raised with sodium acetate buffer, suggesting competive binding by the acetate ions. These results highlight the importance of ionic strength in polymer‐metal binding thermodynamics and will guide the development of new processes for the purification of critical metals.

Energetics and Kinetics of Hydrogen Electrosorption on a Graphene-Covered Pt(111) Electrode.

The Angstrom-scale space between graphene and its substrate provides an attractive playground for scientific exploration and can lead to breakthrough applications. Here, we report the energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode using electrochemical experiments, in situ spectroscopy, and density functional theory calculations. The graphene overlayer influences the hydrogen adsorption on Pt(111) by shielding the ions from the interface and weakening the Pt-H bond energy. Analysis of the proton permeation resistance with controlled graphene defect density proves that the domain boundary defects and point defects are the pathways for proton permeation in the graphene layer, in agreement with density functional theory (DFT) calculations of the lowest energy proton permeation pathways. Although graphene blocks the interaction of anions with the Pt(111) surfaces, anions do adsorb near the defects: the rate constant for hydrogen permeation is sensitively dependent on anion identity and concentration.

Oil palm leaf-derived hierarchical porous carbon for "water-in-salt" based supercapacitors: the effect of anions (Cl- and TFSI-) in superconcentrated conditions.

This study investigates the use of a hierarchical porous carbon electrode derived from oil palm leaves in a "water-in-salt" supercapacitor. The impact of anion identity on the electrical performance of the carbon electrode was also explored. The results show that the prepared carbon had a hierarchical porous structure with a high surface area of up to 1840 m2 g-1. When a 20 m LiTFSI electrolyte was used, the carbon electrode had a specific capacitance of 176 F g-1 with a wider potential window of about 2.6 V, whereas the use of a cheaper 20 m LiCl electrolyte showed a higher specific capacitance of 331 F g-1 due to the smaller size of the Cl- anion, which enabled inner capacitance. Therefore, the anion identity has an effect on the electrochemical performance of porous carbon, and this research contributes to the understanding of using "water-in-salt" electrolytes in carbon-based supercapacitors. The study's findings provide insights into developing low-cost, high-performance supercapacitors that can operate in a wider voltage range.

From Hofmeister to hydrotrope: Effect of anion hydrocarbon chain length on a polymer brush

HypothesisSpecific ion effects govern myriad biological phenomena, including protein–ligand interactions and enzyme activity. Despite recent advances, detailed understanding of the role of ion hydrophobicity in specific ion effects, and the intersection with hydrotropic effects, remains elusive. Short chain fatty acid sodium salts are simple amphiphiles which play an integral role in our gastrointestinal health. We hypothesise that increasing a fatty acid’s hydrophobicity will manifest stronger salting-out behaviour. ExperimentsHere we study the effect of these amphiphiles on an exemplar thermoresponsive polymer brush system, conserving the carboxylate anion identity while varying anion hydrophobicity via the carbon chain length. Ellipsometry and quartz crystal microbalance with dissipation monitoring were used to characterise the thermoresponse and viscoelasticity of the brush, respectively, whilst neutron reflectometry was used to reveal the internal structure of the brush. Diffusion-ordered nuclear magnetic resonance spectroscopy and computational investigations provide insight into polymer-ion interactions. FindingsSurface sensitive techniques unveiled a non-monotonic trend in salting-out ability with increasing anion hydrophobicity, revealing the bundle-like morphology of the ion-collapsed system. An intersection between ion-specific and hydrotropic effects was observed both experimentally and computationally; trending from good anti-hydrotrope towards hydrotropic behaviour with increasing anion hydrophobicity, accompanying a change in hydrophobic hydration.

Anion Effects on the Supramolecular Self-Assembly of Cationic Phenylalanine Derivatives.

Supramolecular hydrogels have emerged as a class of promising biomaterials for applications such as drug delivery and tissue engineering. Self-assembling peptides have been well studied for such applications, but low molecular weight (LMW) amino acid-derived gelators have attracted interest as low-cost alternatives with similar emergent properties. Fluorenylmethyloxycarbonyl-phenylalanine (Fmoc-Phe) is one such privileged motif often chosen due to its inherent self-assembly potential. Previously, we developed cationic Fmoc-Phe-DAP gelators that assemble into hydrogel networks in aqueous NaCl solutions of sufficient ionic strength. The chloride anions in these solutions screen the cationic charge of the gelators to enable self-assembly to occur. Herein, we report the effects of varying the anions of sodium salts on the gelation potential, nanoscale morphology, and hydrogel viscoelastic properties of Fmoc-Phe-DAP and two of its fluorinated derivatives, Fmoc-3F-Phe-DAP and Fmoc-F5-Phe-DAP. It was observed that both the anion identity and gelator structure had a significant impact on the self-assembly and gelation properties of these derivatives. Changing the anion identity resulted in significant polymorphism of the nanoscale morphology of the assembled states that was dependent on the chemical structure of the gelator. The emergent viscoelastic character of the hydrogel networks was also found to be reliant on the anion identity and gelator structure. These results demonstrate the complex interplay between the gelator and environment that have a profound and often unpredictable impact on both self-assembly properties and emergent viscoelasticity in supramolecular hydrogels formed by LMW compounds. This work also illustrates the current lack of understanding that limits the rational design of potential biomaterials that will be in contact with complex biological fluids and provides motivation for additional research to correlate the chemical structure of LMW gelators with the structure and emergent properties of the resulting supramolecular assemblies as a function of environment.

Electrochemical Investigation of Kinetics and Mechanisms of Charge Transfer in Nonaqueous Zinc and Magnesium Electrolytes

Nonaqueous multivalent systems are competitive as future lithium-ion battery (LIB) replacements to address growing energy storage needs. High volumetric specific capacity, low cost, long lifetime, are some driving advantages of these systems. Their development has been slowed by a plethora of fundamental unknowns. Mechanisms of multivalent charge transfer are complicated and not well understood in detail. Strategic electrochemical investigation into fundamental redox mechanisms and kinetics of multi-charge transfer of Magnesium and Zinc nonaqueous electrolytes will be presented here. Influence of solvent system, concentration, anion identity, and solvent structure are investigated as each has an integral role.

Bis(fluorosulfonyl)imide-based electrolyte for rechargeable lithium batteries: A perspective

The inherent properties of non-aqueous electrolytes are highly associated with the identity of salt anions. To build highly conductive and chemically/electrochemically robust electrolytes for lithium-ion batteries (LIBs) and rechargeable lithium metal batteries (RLMBs), various kinds of weakly coordinating anions have been proposed as counterparts of lithium salts and ionic liquids. Among them, bis(fluorosulfonyl)imide anion ([N(SO2F)2]−, FSI−) has aroused special attention in battery field due to the unique physical, chemical, and electrochemical properties of the FSI-based electrolytes. Herein, an overview on the synthetic methodologies of the FSI-based salts (e.g., alkali metal salts, ionic liquids) is provided, and their applications in LIBs and RLMBs are also updated. Future directions on developing FSI-based and/or FSI-derived electrolytes are presented. The present work is anticipated to inspire the design and screening of new anions for battery use, particularly, those stemming from sulfonimide anions.

Hofmeister effects of anions on self-assembled thermogels

Thermogels are temperature-responsive soft biomaterials with numerous biomedical applications. They possess high water content and can spontaneously gelate by forming non-covalent physical crosslinks between their constituent amphiphilic polymers when warmed. However, despite the ubiquity of salts in biological fluids and buffer media, the influence of salts on thermogelling polymers and the overall physical properties of the resulting hydrogels are poorly understood. Herein, we elucidate the effects of common inorganic salts on the gelation and micellization properties of a thermogelling polymer containing poly(ethylene glycol), poly(propylene glycol), and poly(caprolactone) components. The identity of the salts' anions and their concentrations was found to exhibit significant effects on the thermogel properties, in some cases being able to decrease the sol-to-gel phase transition by up to 10 °C. We demonstrate that these notable influences are likely brought about by the changes in solvation of both the polymer's hydrophobic and hydrophilic segments, as well as by direct interactions of poorly hydrated anions with the hydrophobic polymer segments. Our findings show that the effects of salts on amphiphilic thermogelling polymers are non-negligible and hence need to be taken into account for engineering and optimization of thermogel properties for different biomedical applications.

Partitioning of Ambient Organic Gases to Inorganic Salt Solutions: Influence of Salt Identity, Ionic Strength, and pH

AbstractInorganic salts present in the atmosphere may affect the composition and abundance of secondary organic aerosol. Here, we quantify the effects of salt identity, salt concentration (ionic strength), and solution pH on the partitioning of ambient water‐soluble organic gases (WSOCg) at a site in the eastern United States. The experimental pH (pH = 1–6) and ionic strengths (10−3–101 mol kg−1) span a wide range of conditions found in atmospheric particles, clouds, and fog droplets. Chloride salts (NaCl, NH4Cl, and KCl) exhibit a strong salting‐out effect at all ionic strengths &gt;0.005 mol kg−1 and pH = 1.8–6. In contrast, sulfate salts (Na2SO4, (NH4)2SO4, and K2SO4) induce both salting‐in and salting‐out behaviors, depending on ionic strength and pH. These results suggest that monovalent cations have minimal effect, while ionic strength, pH, and anion identity exert strong effects on the partitioning of ambient organic gases in the atmosphere.

Effects of electrolyte concentration and anion identity on photoelectrochemical degradation of phenol: Focusing on the change at the photoanode/solution interface

The effects of electrolytes on phenol degradation by typical photoelectrochemical cell (PEC) composed of TiO2-nanotube array (TNTA) and Pt were studied in terms of interfacial parameters; quantum efficiency, h+ generation rate, relative interfacial electron transfer rate, and equivalent resistances. Three different anions, Cl−, ClO4−, and SO42−, and 10−5 to 10−1 M of electrolyte concentrations have been covered. For all concentrations of interest, pseudo-1st-order kinetic constants for phenol degradation were 4.775 × 10−4–1.175 × 10−3, 3.974 × 10−4–8.893 × 10−3, and 3.902 × 10−4–8.810 × 10−4 min−1 for SO42−, Cl−, and ClO4−, respectively. The results of h+-generation rate, and relative electron transfer rate confirms that the rate of reactions at electrode/solution interface is in the order of SO42−, ClO4−, and Cl−; 0.038–3.552%, 0.023–2.900%, and 0.021–2.814% were obtained for the quantum efficiency of SO42−, ClO4−, and Cl−, respectively. The inconsistent trend between phenol degradation kinetic and quantum efficiency in terms of anion species shows that the phenol is mainly decomposed by the oxidant produced through the interfacial reactions, not by direct reaction between TiO2 and phenol. The difference in terms of anions would be attributed to the product of anions since the radicals other than hydroxyl radical would provide the retardation pathways to prolong the lifetime of radicals.

Microenvironment Effects on Electrocatalytic Oxygen Reduction: The Role of Acid Electrolyte Anions

The surface-electrolyte microenvironment plays an important role in the performance of electrochemical systems. Better understanding the role that electrolyte ions play at or near the surface is an avenue to optimizing the local electrocatalyst reaction microenvironment in renewable electrochemical energy technologies such as fuel cells, electrolyzers, and batteries. Focusing on the oxygen reduction reaction (ORR), as one of the key half reactions often involved in these electrochemical technologies, better understanding acid electrolyte anion effects may help facilitate the design of non-Pt catalyst material alternatives for proton exchange membrane fuel cells (PEMFCs) and/or engineer better electrolyte-electrode interfaces with tuned local microenvironments. Previous work has focused on studying anion effects in acidic media using Pt electrocatalysts, and changes in performance as a function of anion species have been generally attributed to competitive adsorption. In addition to acid electrolyte anion effects not being widely studied outside of on Pt materials, possible anion effects outside competitive adsorption on the ORR have, in general, not been investigated in detail. Therefore, to better understand acid electrolyte anion effects on the ORR activity and selectivity of both strong and weak oxygen-binding materials, smooth Pd and Ag thin films specifically, we employed cyclic voltammetry with a rotating (ring) disk electrode to investigate the ORR performance response of these metals in various electrolytes (HClO4, HNO3, H2SO4, H3PO4, HCl, and HBr) at pH 1. Moreover, we employ extensive physical characterization methods to measure exposed electrocatalyst surface area (atomic force microscopy, AFM), composition & electronic structure (x-ray photoelectron spectroscopy, XPS), and mass/thickness (inductively coupled plasma optical emission spectrometry, ICP-OES) of the thin films before and after ORR testing in each electrolyte. In this work, we demonstrate anion identity plays a significant role in modifying ORR activity and selectivity on both smooth thin film Ag and Pd polycrystalline electrocatalysts; notably including decreased hydrogen peroxide selectivity in nitric acid compared to in the other investigated electrolytes. Moreover, we combine physics-based modeling and data science to gain insight into the fundamental nature of anion interactions in the electrochemical double layer microenvironment that result in the observed performance changes as a function of anion species. These insights provide guidance on opportunities to improve performance for ORR catalysts in PEMFCs and related applications.

Probing the Effects of Acid Electrolyte Anions on Electrocatalyst Activity and Selectivity for the Oxygen Reduction Reaction

AbstractThe local microenvironment at the electrode‐electrolyte interface plays an important role in electrocatalytic performance. Herein, we investigate the effect of acid electrolyte anion identity on the oxygen reduction reaction (ORR) activity and selectivity of smooth Ag and Pd catalyst thin films. Cyclic voltammetry in perchloric, nitric, sulfuric, phosphoric, hydrochloric, and hydrobromic acid, at pH 1, reveals that Ag ORR activity trends as follows: HClO4&gt;HNO3&gt;H2SO4&gt;H3PO4&gt;HCl≫HBr, while Pd ORR activity trends as: HClO4&gt;H2SO4&gt;HNO3&gt;H3PO4&gt;HCl≫HBr. Moreover, rotating‐ring‐disk‐electrode selectivity measurements demonstrate enhanced 4e− selectivity on both Ag and Pd, by up to 35 %H2O2 and 10 %H2O2 respectively, in HNO3 compared to in HClO4. Relating physics‐based modeling and experimental results, we postulate that ORR performance depends greatly on anion‐related phenomena in the double layer, for instance competitive adsorption and non‐covalent interactions.

Effect of anion identity on ion association and dynamics of sodium ions in non-aqueous glyme based electrolytes-OTf vs TFSI.

Sodium-based rechargeable battery technologies are being pursued as an alternative to lithium, in part due to the relative abundance of sodium compared to lithium. Despite their low dielectric constant, glyme-based electrolytes are particularly attractive for these sodium-based batteries due to their ability to chelate with the sodium ion and their high electrochemical stability. While the glyme chain length is a parameter that can be tuned to modify solvation properties, charge transport behavior, reactivity, and ultimately battery performance, anion identity provides another tunable variable. Trifluoromethanesulfonate (triflate/OTf) and bis(trifluoromethane)sulfonamide (TFSI) are chemically similar anions, which are often used in battery electrolytes for lithium-based batteries. In this paper, molecular simulations are used to examine the differences in ion association and charge transport between sodium salts of these two anions at different salt concentrations in glymes with the increasing chain length. The use of the modified force field developed for NaOTf in glymes for the NaTFSI electrolytes was validated by comparing the TFSI-sodium ion radial distribution functions to the results from ab initio molecular dynamics simulations on 1.5M NaTFSI in diglyme. While the ion association behavior as a function of salt concentration showed similar trends for both NaOTf and NaTFSI in tetraglyme and triglyme electrolytes, the dominant solvation structures for the two sets of electrolytes are distinctly different in the monoglyme and diglyme cases. The conductivity is impacted by both the ion association behavior in these electrolytes and the non-vehicular or hopping transport of the anions in these systems.

Structural Analysis of the cl-Par-4 Tumor Suppressor as a Function of Ionic Environment

Prostate apoptosis response-4 (Par-4) is a proapoptotic tumor suppressor protein that has been linked to a large number of cancers. This 38 kilodalton (kDa) protein has been shown to be predominantly intrinsically disordered in vitro. In vivo, Par-4 is cleaved by caspase-3 at Asp-131 to generate the 25 kDa functionally active cleaved Par-4 protein (cl-Par-4) that inhibits NF-κB-mediated cell survival pathways and causes selective apoptosis in tumor cells. Here, we have employed circular dichroism (CD) spectroscopy and dynamic light scattering (DLS) to assess the effects of various monovalent and divalent salts upon the conformation of cl-Par-4 in vitro. We have previously shown that high levels of sodium can induce the cl-Par-4 fragment to form highly compact, highly helical tetramers in vitro. Spectral characteristics suggest that most or at least much of the helical content in these tetramers are non-coiled coils. Here, we have shown that potassium produces a similar effect as was previously reported for sodium and that magnesium salts also produce a similar conformation effect, but at an approximately five times lower ionic concentration. We have also shown that anion identity has far less influence than does cation identity. The degree of helicity induced by each of these salts suggests that the “Selective for Apoptosis in Cancer cells” (SAC) domain—the region of Par-4 that is most indispensable for its apoptotic function—is likely to be helical in cl-Par-4 under the studied high salt conditions. Furthermore, we have shown that under medium-strength ionic conditions, a combination of high molecular weight aggregates and smaller particles form and that the smaller particles are also highly helical, resembling at least in secondary structure, the tetramers found at high salt.

Understanding Degradation at the Lithium-Ion Battery Cathode/Electrolyte Interface: Connecting Transition-Metal Dissolution Mechanisms to Electrolyte Composition.

Lithium transition-metal oxides (LiMn2O4 and LiMO2 where M = Ni, Mn, Co, etc.) are widely applied as cathode materials in lithium-ion batteries due to their considerable capacity and energy density. However, multiple processes occurring at the cathode/electrolyte interface lead to overall performance degradation. One key failure mechanism is the dissolution of transition metals from the cathode. This work presents results combining scanning electrochemical microscopy with inductively coupled plasma (ICP) and electron paramagnetic resonance (EPR) spectroscopies to examine cathode degradation products. Our effort employs a LiMn2O4 (LMO) thin film as a model cathode to monitor the Mn dissolution process without the potential complications of conductive additive and polymer binders. We characterize the electrochemical behavior of LMO degradation products in various electrolytes, paired with ICP and EPR, to better understand the properties of Mn complexes formed following metal dissolution. We find that the identity of the lithium salt anions in our electrolyte systems [ClO4-, PF6-, and (CF3SO2)2N-] appears to affect the Mn dissolution process significantly as well as the electrochemical behavior of the generated Mn complexes. This implies that the mechanism for Mn dissolution is at least partially dependent on the lithium salt anion.

Not‐So‐Innocent Anions Determine the Mechanism of Cationic Alkylators

Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods. Thioimidazolium cations transfer alkyl substituents to nucleophiles, however the reaction rate was highly dependent on anion identity, demonstrating that the anion is not innocent in the mechanism. Detailed analysis of the computationally‐derived potential energy surfaces associated with possible mechanisms indicated that this dependence arises from a combination of anion induced electronic, steric and coordinating effects, with highly nucleophilic anions catalyzing a 2‐step process while highly non‐nucleophilic, delocalized anions favor a 1‐step reaction. This work also confirms the presence of ion‐pairs and aggregates in solution thus supporting anion‐induced control over the reaction rate and mechanism. These findings provide new insight into an old reaction allowing for better design of cationic alkylators in synthesis, gene expression, polymer science, and protein chemistry applications.