Effect Of Counterions Research Articles

The Effect of Counterions on the Detection of Cu2+ Ions in Aqueous Solutions Using Quartz Tuning Fork (QTF) Sensors Modified with L-Cysteine Self-Assembled Monolayers: Experimental and Quantum Chemical DFT Study

In this study, a sensing device employing a gold-coated quartz tuning fork (QTF) modified with a self-assembled monolayer (SAM) of L-cysteine was evaluated for the sensitive detection of Cu2+ ions in aqueous solutions. Three copper (II) salts, CuSO4, CuCl2, and Cu(NO3)2, at four different concentrations (10−12, 10−10, 10−8, and 10−6 M) in small (100 μL) water sample amounts were each used as analytes to investigate the influence of their counterions in the detection of the Cu2+ ions. It was found that, among the counterions, the sulfate anion had the largest effect upon the detection of Cu2+ in water, in the following order: SO42− > Cl− > NO3−. The lower limit of detection of the Cu2+ ions detected was in the 10−12 M range. The frequency shifts measured with the QTFs relative to deionized water were inversely proportional to the concentration/mass of the analytes. Density functional theory calculations were conducted to understand the effect of the counterions on the respective electronic interaction energies for the apparent host–guest binding of the analytes with L-cysteine and with gold surface-bound L-cysteine molecules. Gas phase (both with and uncorrected BSSE) and solution phase interaction energies (ΔIE) calculated at the B3LYP/LANL2DZ and ωB97XD levels of theory showed that the stability for the complexes were in the following order: [L-cysteine]⊃[CuSO4] > [L-cysteine]⊃[CuCl2] > [L-cysteine]⊃[Cu(NO3)2], which supports our experimental findings, as they were in the same order as the experimentally observed order for the copper salts tested: CuSO4 > CuCl2 > Cu(NO3)2.

Catalyst Design: Counter Anion Effect on Ni Nanocatalysts Anchored on Hollow Carbon Spheres.

Herein, the influence of the counter anion on the structural properties of hollow carbon spheres (HCS) support was investigated by varying the nickel metal precursor salts applied. TEM and SEM micrographs revealed the dimensional dependence of the HCS shell on the Ni precursor salt, as evidenced by thick (~42 nm) and thin (~23 nm) shells for the acetate and chloride-based salts, respectively. Importantly, the effect of the precursor salt on the textural properties of the HCS nanosupports (~565 m2/gNi(acet)) and ~607 m2/gNiCl), influenced the growth of the Ni nanoparticles, viz for the acetate-(ca 6.4 nm)- and chloride (ca 12 nm)-based salts, respectively. Further, XRD and PDF analysis showed the dependence of the reduction mechanism relating to nickel and the interaction of the nickel-carbon support on the type of counter anion used. Despite the well-known significance of the counter anion on the size and crystallinity of Ni nanoparticles, little is known about the influence of such counter anions on the physicochemical properties of the carbon support. Through this study, we highlight the importance of the choice of the Ni-salt on the size of Ni in Ni-carbon-based nanocatalysts.

High-Temperature Spin Crossover in FeIII N4O2 Complexes Incorporating an [R-sal2323] Backbone

Of the multitude of [FeIII(R-sal2323)]X complexes reported in the literature, only four have demonstrated spin crossover (SCO). Herein, we report four additional examples of thermal spin crossover in [FeIII(R-sal2323)]X complexes (where R = Br, NEt2, and X = ClO4–, BF4–). Magnetic susceptibility measurements reveal gradual, high-temperature spin transitions in all four compounds with onsets near room temperature. To investigate the emergence of SCO behaviors being observed in these compounds, a range of intramolecular and intermolecular structural parameters were examined. The effect that ligand substituents may have on the electronic environment, as well as the effect of counterions and various intermolecular interactions on the crystal packing, were investigated and compared to the literature of [FeIII(R-sal2323)]X compounds for which magnetic measurements are reported. This comparison found that neither intramolecular subtleties nor intermolecular interactions have a large impact on whether or not these compounds are SCO active. Instead, it is shown and proposed that many compounds in the [FeIII(R-sal2323)]X family may demonstrate SCO activity if measured to higher temperatures (above 300 K). This would provide a wide range of FeIII compounds that are SCO active near or above room temperature to be explored in future work.

One Step Selective Counterion Dependent Formation of Conjugated Chiral N-Sulfinylimines from Aldehydes.

We report a detailed study on the synthesis and aldehyde vinylogation applications of chiral N-sulfinyl imine phosphonate reagents. Two complementary scalable reagent routes, from trialkyl phosphites and methyl phosphonates, respectively, are presented. This reagent class enables significant streamlining in synthesis of conjugated Ellman imines from aldehydes, which can now be accomplished in a single step compared to a more classic 4-step redox-based approach. Aldehyde vinylogation optimizations have revealed significant counterion effects and unexpected competing reaction challenges that needed to be addressed to achieve high yields.

Impact of counteranions on N-heterocyclic carbene gold(i)-catalyzed cyclization of propargylic amide.

N-Heterocyclic carbene (NHC) Au(i)-catalyzed organic synthesis has recently been receiving increasing attention, especially with the activation of alkynes. In contrast, counteranions, being widely problematic in Au(i)-catalyzed transformations, are commonly considered as innocent partners and are not respectably included in a computational model. Herein, we report density functional theory (DFT) investigations of the Au(i)-catalyzed cyclization of propargylic amides to exploit the mechanistic effect of several counteranions to shed some light for further future developments. Among the counteranions used in this study, NTf2 -, ClO4 -, TsO-, TFA-, TfO-, MsO-, and SbF6 -, both the cyclization and protodeauration step favor the 5-exo-dig product over the 6-endo-dig product when the alkyne moiety is terminated with hydrogen. These anions reveal a crucial influence on the energy profile through lowering the barriers of the reaction. Mechanistically, the results obtained from all counteranions show that the protodeauration is slower than the cyclization. By using an energetic span model, the results clearly indicate that the rate-determining state is the protodeauration step for all counteranions, and thus protodeauration is the turnover-limiting step. The turnover frequency (TOF) results for the formation of the 5-exo-dig product show cyclization reactivity in the order of MsO- > TFA- > ClO4 - > NTf2 - > TfO- > TsO- ≫ SbF6 -, whereas an order of TFA- > MsO- > NTf2 - > TfO- ≈ ClO4 - > SbF6 - ⋙ TsO- is calculated for the protodeauration, suggesting that SbF6 - and TsO- are disfavored due to their slow protodeauration. In this regard, and for the 6-endo-dig pathway, our conclusions demonstrate an order of TfO- > TFA- > MsO- > NTf2 - > ClO4 - > TsO- ⋙ SbF6 - for the cyclization and TFA- > TsO- > MsO- > TfO- > NTf2 - > ClO4 - ⋙ SbF6 - for the protodeauration, advocating that the anions SbF6 -, NTf2 - and ClO4 - are unlikely partners for the 6-endo-dig pathway because of their slow protodeauration. Finally, the findings here advise that any engineering of the counteranion to increase the efficiency of catalytic system would be more effective on the protodeauration step rather than the cyclization step.

Fluoride counterions boost gold(i) catalysis: case studies for hydrodefluorination and CO2 hydrosilylation

We reported a prominent counterion effect, where bifluoride synergistically activates hydrosilane to promote the formation of an active gold hydride intermediate, on hydrodefluorination and hydrosilylation of CO2.

Chlorine counterion effect into the supramolecular arrangement of phenylephrine solid state

Phenylephrine is widely used as a nasal and mydriatic decongestant in various nasal and ophthalmic formulations. Phenylephrine is traditionally commercialized in its saline form as phenylephrine hydrochloride. Due to changes in crystalline packing, counterion inclusion affects the chemical, physical, biological properties, and reactivity. Structural, topological, and energy analyses are essential to compare and understand those changes in physicochemical properties and their impacts on drug production. This study evaluates the conformational changes, crystalline packaging, and interactions of phenylephrine and phenylephrine hydrochloride. Theoretical calculations were used to assess the stability and supramolecular arrangement. The energetic gap ΔELUMO-HOMO shows that the Cl– counterion provides greater stability for phenylephrine. Phenylephrine exhibits a more significant number of interactions O···O and O···H that increase hygroscopicity and chemical reactivity of a compound. The presence of the counterion alters the conformational and structural properties of phenylephrine, causing changes in its properties and influencing its use.

モンモリロナイトの膨潤挙動に及ぼす層間対イオンの影響：

モンモリロナイトの膨潤挙動に及ぼす層間対イオンの影響：

Designing Nanofluidic Diode from a Hybrid-Bilayer Covalent Organic Framework: Molecular Simulation Investigation.

Nanofluidic diodes are potentially useful in many important applications such as sensing, electronics, and energy conversion. However, the manufacturing of controllable nanopores for nanofluidic diodes is technically challenging. Herein, a nanofluidic diode is designed from a highly programmatic covalent organic framework (COF). Through molecular simulation, remarkable diode behavior is observed in a hybrid-bilayer COF but not in its constituent single-layer COFs. The rectification effect of ion current in the hybrid-bilayer COF is attributed to an asymmetric electrostatic potential across the COF nanopore. Furthermore, a synergistic effect of counterion is unraveled in the hybrid-bilayer COF, and the presence of counterion is found to reduce the entry barrier and facilitate ion transport. The performance of the hybrid-bilayer COF as a nanofluidic diode is comprehensively investigated by varying salt concentration, layer number, interlayer spacing, and slipping. This proof-of-concept simulation study demonstrates the feasibility of the hybrid-bilayer COF as a nanofluidic diode and the finding may stimulate the development of new nanofluidic platforms.

Effect of Counterions on the Physicomechanical Properties of Copper-Nitrogen-Coordinated Metallosupramolecular Elastomers.

Metallosupramolecular elastomers have attracted much attention due to their excellent mechanical properties, flexible tailoring of performance, and responsiveness to photo and thermal stimuli. The physicomechanical properties of metallosupramolecular elastomers are highly dependent on metal salts and ligand units; however, the role of counterions lacks practical exploration. To this end, we synthesized a simple acrylate copolymer model and introduced copper salts with different counterions to construct dynamic copper-nitrogen coordination cross-linked networks. This approach generated a series of elastomers with a tensile strength of over 10 MPa and a laser self-healing efficiency of over 90% within 2 min. In particular, we studied the effects of counterions on the thermodynamic, viscoelastic, mechanical, photothermal, and self-healing properties of the materials. Therefore, this work can provide instruction for the preparation and performance tailoring of metallosupramolecular elastomers.

Probing Pharmaceutical Strategies to Promote the Skin Delivery of Asiatic Acid from Hydrogels: Enhancement Effects of Organic Amine Counterions, Chemical Enhancers, and Microneedle Pretreatment.

Asiatic acid (AA) is a pentacyclic triterpene isolated from Centella asiatica, holding great promise for treating a variety of skin disorders. However, the dermal application of AA is limited by its poor solubility and permeability. This study aimed to identify a hydrogel formulation for AA and improve its skin penetration by various penetration enhancement methods. Four kinds of hydrogel bases were selected to prepare the AA hydrogel, in which different organic amines and chemical enhancers were incorporated in combination with microneedle pretreatment. The results showed that AA had good release profiles in the presence of hyaluronic acid as the hydrogel base and organic amines as the counter-ions. Diethylamine and Span 80 could promote drug penetration into the skin, and pretreatment with microneedles could further increase the drug permeability. In conclusion, the optimized hyaluronic acid hydrogel has great potential for use in the topical delivery of AA, and its penetration via the skin can be further improved by different pharmaceutical approaches.

Sustainable corrosion inhibitor for steel embedded in concrete by Guar Gum: Electrochemical and theoretical analyses

Guar gum is recently being extensively used in a broad range of applications because of its distinctive physico-chemical properties. Guar gums have been used to prepare different concrete specimens. After the guar gum concrete has been scrutinized, the binding characteristics of the concrete are determined. Experimental studies using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDS), scanning electron microscopy (SEM), and quantum chemical calculations revealed that guar gum effectively protects structural steel from corrosion. The experimental analyses showed that 1.4% of guar gum exhibited maximum protection exhibited from maximum surface orientation values as 0.7874 and the same is fixed as optimum dose to examine the cooperative effect of counter ions on the corrosion progression. Furthermore, Monte Carlo (MC) simulations were used to investigate the surface interactions between the inhibitors and the metal surface. Finally, the results indicated that the ingredients of Guar Gum such as Mannose, Galactose, and Galactomannan have strong interactions with the surface of Fe (110) and thus have processed modelling inhibition strength against metal corrosion.

Condensation of capillary water and decreased surface energy cause increased soil water repellency in sandy soil

AbstractPredicting soil water availability to crops in water‐repellent sandy soil is complicated as soil water repellency (SWR) responds non‐linearly to soil water content. Others have hypothesised that the development of a monolayer of water molecules results in SWR increasing before SWR declines with a further increase in soil water content. In a previous study, we found that SWR increases when above 0.28–0.86% threshold soil water content. Thus, our objective was to determine the underlying mechanisms responsible for why SWR increases when above a certain threshold soil water content in a sandy soil. A water adsorption isotherm was constructed by exposing a water‐repellent sandy soil to increasing relative humidity (dynamic vapour sorption technique) to evaluate if the development of a monolayer of water molecules was responsible for the increased SWR response. The increased SWR when above 0.66% threshold soil water content was found to coincide with the capillary condensation of water in the soil. The inverse gas chromatography technique was used for the first time in soil particles' surface energy analysis to investigate why SWR increases when above the threshold soil water content by determining the total, dispersive (non‐polar), and specific surface (polar) energy of the soil at two relative humidities (0% and 90%). Wettable sandy soil (98% soil organic carbon removed) was included as a control to further assess if soil organic carbon in the water‐repellent soil influences the surface energy of the soil. The mean of total, dispersive, and specific surface energy decreased for both wettable and water‐repellent sandy soils when exposed to 90% relative humidity, suggesting that there was limited effect of soil carbon on the increased SWR when above the threshold soil water content since most organic carbon was removed from the wettable soil. We also investigated if there is any difference in the surface energy heterogeneity when exposed to 90% relative humidity to gain insight into surface chemistry heterogeneity of the soil particles' surfaces. Exposing soils to 90% relative humidity decreased the heterogeneity of the total and dispersive surface energy of both wettable and water‐repellent sandy soil indicating a more uniform surface chemistry than when exposed to 0% relative humidity.Highlights Examined why soil water repellency (SWR) in a sandy soil increases at low soil water content. Explored underlying mechanisms via water adsorption isotherm and surface energy of a sandy soil. Increased SWR coincided with capillary water condensation and is likely due to counterion effects. Quantitative data presented new mechanisms on why SWR increases with increasing soil water content.

Impact of Methylaluminoxane Oxidation on Ethylene Polymerization Using Ni Catalysts

The effect of oxidation of methylaluminoxane (MAO) on ethylene polymerization was investigated to see the effect of aging and the possibility of using monomer gas that is not purified enough. In the polymerization using phenoxyimine-ligated titanium catalyst, almost no changes in polymerization behavior were observed until 35% of O2 was added to MAO at enough Al/Ti ratio. However, Brookhart-type nickel-diimine catalysts activated with oxidized MAO gave polyethylenes with improved molecular weight and linearity. NMR, UV–vis, and electron paramagnetic resonance studies combined with theoretical prediction revealed that the electronic property on nickel was consistent, regardless of MAO modification. The effect on the polymerization behavior can thus be explained by the change of steric effect of counteranions derived from MAO via modification with oxygen.

Nanocluster Transformation Induced by SbF6- Anions toward Boosting Photochemical Activities.

The interactions between SbF6- and metal nanoclusters are of significance for customizing clusters from both structure and property aspects; however, the whole-segment monitoring of this customization remains challenging. In this work, by controlling the amount of introduced SbF6- anions, the step-by-step nanocluster evolutions from [Pt1Ag28(S-Adm)18(PPh3)4]Cl2 (Pt1Ag28-Cl) to [Pt1Ag28(S-Adm)18(PPh3)4](SbF6)2 (Pt1Ag28-SbF6) and then to [Pt1Ag30Cl1(S-Adm)18(PPh3)3](SbF6)3 (Pt1Ag30-SbF6) have been mapped out with X-ray crystallography, with which atomic-level SbF6- counterion effects in reconstructing and rearranging nanoclusters are determined. The structure-dependent optical properties, including optical absorption, photoluminescence, and electrochemiluminescence (ECL), of these nanoclusters are then explored. Notably, the Pt1Ag30-SbF6 nanocluster was ultrabright with a high phosphorescence quantum yield of 85% in N2-purged solutions, while Pt1Ag28 nanoclusters were fluorescent with weaker emission intensities. Furthermore, Pt1Ag30-SbF6 displayed superior ECL efficiency over Pt1Ag28-SbF6, which was rationalized by its increased effectively exposed reactive facets. Both Pt1Ag30-SbF6 and Pt1Ag28-SbF6 demonstrated unprecedented high absolute ECL quantum efficiencies at sub-micromolar concentrations. This work is of great significance for revealing the SbF6- counterion effects on the control of both structures and luminescent properties.

Counter Anion Effects on PEDOT Properties and Implications on Photosystem I Incorporation

As energy consumption increases in tandem with the global warming crisis, the need for cleaner, renewable energy is at an all-time high. Inspired by nature’s billion-year-old process for energy production, biohybrid solar approaches have been shown to hold much promise in many aspects that are required in renewable energy. By leveraging Photosystem I (PSI), a key protein of the electron transport chain in photosynthesis, it is possible to hijack the electrons to perform an array of light-driven processes. In many areas of PSI research, conductive polymers are employed to wire the protein so that electrons can be directed to and from the reaction centers along favorable paths. Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) is commonly used in these applications as it is water soluble and thus compatible with PSI. Electro-polymerization allows for direct contact of the PEDOT with an electrode surface; however, electropolymerized PEDOT:PSS is mechanically unstable. Limited research has been conducted to demonstrate the effects of other counter anions on PEDOT properties and their implications on the incorporation of PSI into a hybrid device. In this work, we describe the methodologies employed to synthesize and characterize PEDOT thin films with varying counter anions. Our findings indicate that the counter anion during the electropolymerization process affects morphology, charge transfer kinetics, and optical properties of the resulting film. Coupling these observations to the photoactivity of PEDOT-PSI hybrid films, we provide explanations for the varied performance based upon fundamental understandings of chemical and electrochemical phenomena.

Theoretical analysis of the effects of counterions on the supramolecular arrangement of sulfamethoxazole.

Active pharmaceutical ingredients are formulated as the salt form, aiming to modulate their physicochemical properties. In this regard, the optimization and choice of the salt former have a strong influence on toxicity, therapeutic efficiency, and bioavailability. Sulfamethoxazole (SMZ) salts with Na+, Cl-, and Br- counterions influence in the supramolecular arrangement as well as in their thermodynamic and kinetic parameters. Herein, we analyzed the interactions of the Na+, Cl-, and Br- counterions on the supramolecular arrangement of the sulfamethoxazole salts by Hirshfeld surfaces, fingerprint plots, and theoretical methods-quantum theory of atoms in molecules and natural bond orbitals. Moreover, we evaluated their electronic structure by density functional theory using calculation of the frontier molecular orbitals. Molecular electrostatic potential maps were also obtained to predict the interactions of the counterions along crystalline arrangements. We observed that the structures of [SMZ]+ and [SMZ]- ions differ slightly from the SMZ. The chemical reactivity indices show that the SMZ is kinetically more stable than its respective ions, while its anion is more polarizable, and its cation has a higher global electrophilicity index. The molecular electrostatic potential maps show high charge density in the sulfonyl group (nucleophilic region) and the heterocyclic amino group (electrophilic region). Although the molecular skeleton is identical among the three SMZ species and the presence of different counterions in the formation of the crystalline structure of the salts results in supramolecular arrangements with different patterns of intermolecular interactions, despite being very similar in terms of intensities.

An Alternative Method for the Synthesis of N-Pentafluorophenyl Triazolium Salts.

A route for the synthesis of 1,2,4-triazolium salts via oxidation of a thione precursor is demonstrated. N-Pentafluorophenyl-substituted salts are produced in 20-63% overall yields. Isolation and purification of the azolium salts are simplified compared to the traditional synthetic route. Late-stage selection of the counterion allows the synthesis of a variety of salts from a parent thione. The salts have been compared in Stetter and cross-benzoin reactions with an appreciable counterion effect in both reactions.

Synthesis and characterization of NiFe2O4 nanoparticles as reusable magnetic nanocatalyst for organic dyes catalytic reduction: Study of the counter anion effect

This work concerns the preparation of NiFe2O4 with different counter ions using co-precipitation method to control their crystallite size, the materials were used as catalysts for the photocatalytic reduction of Methylene blue and Orange G dyes. Different characterization methods such as XRD, XPS, FTIR, SEM/EDS, VSM, and Zeta potential were employed for more information on our materials. The obtained results show clearly that the nature of the counter ions influences significantly the phase purity and crystallite size of NiFe2O4 nanoparticles. To study the individual contribution of crystallite size and lattice strain Scherrer formula, Williamson-Hall, and size strain plot calculation methods were employed. The results showed also that the material containing the purest phase and finer size was the best catalyst for the reduction of both dyes; the “NFCP” catalyst allowed a complete conversion of MB and OG dyes in a reaction time of 8 min and 4 min respectively. A study of the reusability was carried out and the obtained results showed that the catalyst can be reused more and more without losing its efficiency even after 5 cycles thus, confirming its stability. The phase purity, crystallite size, the counter ions difference, and the synergy between metals and the surface charge were the key parameters affecting the catalytic property.

PH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [Au2L2]{Re6Q8} Colloids (L = PNNP Ligand; Q = S2- or Se2-).

The present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [Au2L2]2+ complex (Au2, L = 1,5-bis(p-tolyl)−3,7-bis(pyridine-2-yl)−1,5-diaza-3,7-diphosphacyclooctane (PNNP) ligand) and the pH-sensitive red-emitting [{Re6Q8}(OH)6]4− (Re6-Q, Q = S2− or Se2−) cluster units. The protonation/deprotonation of the Re6-Q unit is a prerequisite for the pH-triggered assembly of Au2 and Re6-Q into Au2Re6-Q colloids, exhibiting disassembly in acidic (pH = 4.5) conditions modeling a lysosomal environment. The counter-ion effect of polyethylenimine causes the release of Re6-Q units from the colloids, while the binding with lysozyme restricts their protonation in acidified conditions. The enhanced luminescence response of Re6-S on the disassembly of Au2Re6-S colloids in the lysosomal environment allows us to determine their high lysosomal localization extent through the colocalization assay, while the low luminescence of Re6-Se units in the same conditions allows us to reveal the rapture of the lysosomal membrane through the use of the Acridine Orange assay. The lysosomal pathway of the colloids, followed by their endo/lysosomal escape, correlates with their cytotoxicity being on the same level as that of Au2 complexes, but the contribution of the apoptotic pathway differentiates the cytotoxic effect of the colloids from that of the Au2 complex arisen from the necrotic processes.