Ion-pair Research Articles

Effect of Methyl Red on the surface properties of DTAB in CH3OH–H2O

The purpose of this study is to investigate the effect of Methyl Red (MR) on the micellization and surface properties of a cationic surfactant, dodecyl trimethylammonium bromide (DTAB), in CH3OH–H2O mixed solvent systems at varying CH3OH parts by volumes (0.1, 0.2, 0.3, and 0.4) and temperatures (298.15 K, 308.15 K and 318.15 K). Surface tension and conductivity measurements were conducted to obtain the critical micelle concentration (CMC) and various surface properties such as premicellar slope (dγdlogC), maximum surface concentration (Γmax), minimum surface area occupied (πCMC), free energy of adsorption (ΔGadso), adsorption efficiency (pC20), packing parameter (P), and aggregation number (Nagg). The results indicate that the presence of MR significantly influences the behavior of DTAB in the mixed solvent system. In the absence of MR, the CMC increased with higher CH3OH content, while MR reduced the CMC, promoting micelle formation through dye-surfactant-ion-pair (DSIP) formation. Surface properties were enhanced in the presence of MR leading to higher surface pressure. Additionally, the free energy of adsorption (ΔGadso) became more negative with MR, indicating a more favorable adsorption process. Correlations of (dγdlogC), Γmax,γ0/γcmc, pC20, Nagg, CMC/C20 with the parts by volume of CH3OH at 298.15 K, 308.15 K, and 318.15 K are discussed with and without MR. The obtained results were used to examine the effect of MR on the surface properties of DTAB in the CH3OH–H2O medium. The change in properties can be explained in terms of the change in polarity of the medium and dye-surfactant ion pair (DSIP) formation.

Synergistic effect of ceramic filler in polymer salt complex for improved ion dissociation and migration mechanism

Abstract Use of Ceramic filler is one of the most common approaches to improve the conductivity and stability properties of a solid polymer electrolyte (SPE) cum separator. Among them, active fillers like Garnet have been extensively used to enhance the stability and conductivity of SPE. However, SPE suffers from limited ion migration at room temperature acting as a bottleneck for their application in all solid-state batteries. An extensive study on these fillers' role in ion dissociation and migration can be a stepping stone for advanced SPE. In the present work, an FTIR analysis has primarily been used to identify and evaluate cation coordinate site-cation, and ion pair interactions in a Li6.5La3Zr1.75Te0.25O12 loaded polyethylene oxide-LiCF3SO3 matrix with varying ceramic concentrations. Further, the Trukhan model has been used to calculate diffusion coefficient, mobility, and charge carrier density to interpret relaxation parameters, conductivity, and FTIR results in the SPE samples. Finally, an ion migration model has been proposed based on the results obtained in experimental studies.

Charging of DNA Complexes in Positive-Mode Native Electrospray Ionization Mass Spectrometry.

Native mass spectrometry (nMS) provides insights into the structures and dynamics of biomacromolecules in their native-like states by preserving noncovalent interactions through "soft" electrospray ionization (ESI). For native proteins, the number of charges that are acquired scales with the surface area and mass. Here, we explore the effect of highly negatively charged DNA on the ESI charge of protein complexes and find a reduction of the mass-to-charge ratio as well as a greater variation. The charge state distributions of pure DNA assemblies show a lower mass-to-charge ratio than proteins due to their greater density in the gas phase, whereas the charge of protein-DNA complexes can additionally be influenced by the distribution of the ESI charges, ion pairing events, and collapse of the DNA components. Our findings suggest that structural features of protein-DNA complexes can result in lower charge states than expected for proteins.

Fabrication of Scalable Covalent Organic Framework Membrane‐based Electrolytes for Solid‐State Lithium Metal Batteries

AbstractThe conventional covalent organic framework (COF)‐based electrolytes with tailored ionic conducting behaviors are typically fabricated in the powder morphology, requiring further compaction procedures to operate as solid electrolyte tablets, which hinders the large‐scale manufacturing of COF materials. In this study, we present a feasible electrospinning strategy to prepare scalable, self‐supporting COF membranes (COMs) that feature a rigid COF skeleton bonded with flexible, lithiophilic polyethylene glycol (PEG) chains, forming an ion conduction network for Li+ transport. The resulting PEG‐COM electrolytes exhibit enhanced dendrite inhibition and high ionic conductivity of 0.153 mS cm−1 at 30 °C. The improved Li+ conduction in PEG‐COM electrolytes stems from the loose ion pairing in the structure and the production of higher free Li+ content, as confirmed by solid‐state 7Li NMR experiments. These changes in the local microenvironment of Li+ facilitate its directional movement within the COM pores. Consequently, solid‐state symmetrical Li|Li, Li|LFP, and pouch cells demonstrate excellent electrochemical performance at 60 °C. This strategy offers a universal approach for constructing scalable COM‐based electrolytes, thereby broadening the practical applications of COFs in solid‐state lithium metal batteries.

Fabrication of Scalable Covalent Organic Framework Membrane-based Electrolytes for Solid-State Lithium Metal Batteries.

The conventional covalent organic framework (COF)-based electrolytes with tailored ionic conducting behaviors are typically fabricated in the powder morphology, requiring further compaction procedures to operate as solid electrolyte tablets, which hinders the large-scale manufacturing of COF materials. In this study, we present a feasible electrospinning strategy to prepare scalable, self-supporting COF membranes (COMs) that feature a rigid COF skeleton bonded with flexible, lithiophilic polyethylene glycol (PEG) chains, forming an ion conduction network for Li+ transport. The resulting PEG-COM electrolytes exhibit enhanced dendrite inhibition and high ionic conductivity of 0.153 mS cm-1 at 30 °C. The improved Li+ conduction in PEG-COM electrolytes stems from the loose ion pairing in the structure and the production of higher free Li+ content, as confirmed by solid-state 7Li NMR experiments. These changes in the local microenvironment of Li+ facilitate its directional movement within the COM pores. Consequently, solid-state symmetrical Li|Li, Li|LFP, and pouch cells demonstrate excellent electrochemical performance at 60 °C. This strategy offers a universal approach for constructing scalable COM-based electrolytes, thereby broadening the practical applications of COFs in solid-state lithium metal batteries.

Versatile chiroptical induction/manipulation through specific solvation of ion pairs by alcohols

Versatile chiroptical induction/manipulation through specific solvation of ion pairs by alcohols

Mechanisms of the Formation and Function of Dinitrosyl Iron Complexes as a “Working Form” of Nitric Oxide in Living Organisms

It has been proposed that only the introduction of endogenous nitric oxide (NO) into dinitrosyl iron complexes (DNIC) or S-nitrosothiols (RS-NO) can ensure stabilization of NO that is critical for operating in an auto/paracrine manner as a regulator of biological processes in living organisms. Without this introduction, the majority of endogenous NO disappears due to aggressive intra/intercellular environment thereby eliminating it from metabolic processes. Administration of exogenous NO in human and animal organisms (the only possible route of administration is via inhalation when it is in the gaseous state) does not lead to formation of DNIC or RS-NO in blood or other tissues. Hence, the majority of exogenous NO during its inhalation is converted into nitrosonium cations (NO+), the emergence of which is evidenced by their conversion into RS-NO when various thiol-containing compounds are administered to animal blood concomitantly. In turn, RS-NO formation in those animals was manifested by hypotensive effect on them. NO molecule transformation into nitrosonium cations may also occur during DNIC formation induced by a disproportionation reaction of endogenous NO molecules binding with Fe2+ ions in pairs. Subsequent binding of Fe(NO)2 groups to thiol-containing ligands that occur during this reaction promotes formation of rather stable DNICs that act as donors of both neutral molecules of NO and nitrosonium cations (NO+) in living organisms. The transfer of NO and NO+ to targets for nitrosation reactions occurs by the interaction of low molecular DNICs with heme groups of heme-containing proteins (for example, guanylate cyclase) or thiol groups in low molecular or protein thiol-containing compounds. This paper presents different results of NO and NO+ transfer in living organisms disussing both positive, regulatory and negative, toxic effects of it.

The Trifluorooxygenate Anion [OF3]-: Spectroscopic Evidence for a Binary, Hypervalent Oxygen Species.

Experimental evidence for hypervalent compounds of second-row elements is still scarce in literature. Here, we present the first report of the long-sought binary hypervalent trifluorooxygenate anion [OF3]-. It was isolated in solid Ne matrices under cryogenic conditions after reacting oxygen difluoride with free fluoride ions from laser ablation of alkali metal fluorides MF (M = Li-Cs). As predicted by VSEPR theory and calculations at the CCSD(T) level, and confirmed by FTIR spectroscopy as well as isotopic labeling, [OF3]- exhibits a C2v-symmetric T-shaped structure with one short and two long O-F bond distances. Analysis of the natural local molecular orbitals shows the presence of 2c-2e bond and one 3c-4e bond. Natural resonance theory indicates the importance of the stability of [OF2]•- for the stability of [OF3]-. Although free [OF2]•- was not detected, the species MOF2 (M = Na-Cs) could be observed in the same experiments, which are best described as contact ion pairs of M+[OF2]•-.

FORMULATION OF SELF-NANO EMULSIFYING SYSTEM (SNES) CONTAINING SNAKEHEAD FISH EXTRACT PROTEIN INCORPORATED INTO CORN OIL BY HYDROPHOBIC ION PAIRING METHOD

Objective: The purpose of this study was to determine whether the protein complexation of snakehead fish extract using the hydrophobic ion pairing method with Sodium Dodecyl Sulfate (SDS) as a complexing ligand could be loaded into the corn oil component of the SNES and to explore the ratio of oil, surfactant, and cosurfactant in the Self-Nanoemulsifying System (SNES) formula that can produce good SNES characteristics. Methods: Snakehead fish proteins were extracted using pressurized hot water and then complexed with SDS at acidic pH. The SDS-protein complex was loaded into the oil component of the SNES and then combined with the surfactant component (Tween 80) and cosurfactant (propylene glycol) in a ratio of 1:9:1, which, based on the preliminary miscibility screening, has the best miscibility among other screening results. Results: The results of the study were as follows. The binding efficiency of the SDS-protein-complex was 31.74% and the loading efficiency into SNES was 83.17%. The nanoemulsion formed had visible light transmittance of 100.4%, particle size 72.7 nm, zeta potential-53.03 mV, and emulsification time 71.67 seconds. The nanoemulsion was stable at storage and 100 and 1000 times dilution challenges using aqueous media, Simulated Gastric Fluid (SGF), and Simulated Intestinal Fluid (SIF). Conclusion: The hydrophobic ion-pair complexation of snakehead fish protein extract with SDS as the complexing ligand was able to load the protein into the oil component of SNES and the ratio of oil, surfactant, and cosurfactant in the SNES formula that produce good SNES characteristics was corn oil, Tween 80, and propylene glycol at a ratio of 1:9:1

Anion Selectivities in Zwitterion Grafted Nanopores: Effect of Zwitterion Architecture.

The separation of ions of similar charge is a crucial challenge in many applications, from water treatment to precious metal recovery. Membranes with cross-linked zwitterionic amphiphilic copolymer (ZAC-X) selective layers, which feature self-assembled, zwitterion-lined nanodomains for permeation, offer unique permselectivity between monovalent anions (e.g., Cl-/F-). This has motivated studies on the mechanisms of transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the ZI ligands on anion diffusivities, partitioning, and permeabilities. Our model compares systems with contrasting ZI organization: surface-cation-anion (S-ZI+-ZI-, Motif A) and surface-anion-cation (S-ZI--ZI+, Motif B). Our results reveal that Motif A exhibits less pronounced ion pairing due to a spatial separation in the radial profiles of cations and anions. Motif B demonstrates prominent ion pairing for smaller anions owing to their overlap with cation distributions. Further, our potential of mean force profiles reveals that anion partitioning increases with anion size in both ligand motifs, whereas Motif B exhibits significantly higher partitioning selectivity toward larger anions compared to Motif A. Our results for ion diffusivities show that the self-diffusivities of both anions and cations are lower for Motif B compared to Motif A. Such trends in anion partitioning and diffusivities can be explained by differences in the interactions and steric hindrance experienced by the anionic species in Motifs A and B. Finally, our results for anion permselectivity, obtained by combining partitioning and diffusivity, indicate that partitioning trends dominate over diffusivity trends. Consequently, anion permeability increases with anion size, and ligand Motif B yields much higher permselectivity toward larger anions compared to ligand Motif A.

Ultra-Tough, yet Rigid and Healable Supramolecular Polymers with Variable Stiffness for Multimodal Actuators.

Variable stiffness materials have shown considerable application in soft robotics. However, previously reported materials often struggle to reconcile high stiffness, stretchability, toughness, and self-healing ability, because of the inherently conflicting requisite of these properties in molecular design. Herein, we propose a novel strategy that involves incorporating acid-base ionic pairs capable of from strong crosslinking sites into a dense and robust hydrogen-bonding network to construct rigid self-healing polymers with tunable stiffness and excellent toughness. To demonstrate these distinct features, the polymer was employed to serve as the strain-regulation layers within a fiber-reinforced pneumatic actuator (FPA). The exceptional synergy between the configuration versatility of FPA and the dynamic molecular behavior of the supramolecular polymers equips the actuator with simultaneous improvement in motion dexterity, multimodality, loading capacity, robustness, and durability. Additionally, the concept of integrating high dexterity at both macro- and micro-scale is prospective to inspire the design of intelligent yet robust devices across various domains.

Charge‐Sign‐Independent Separation of Mono‐ and Divalent Ions With Nanofiltration Membranes

AbstractAchieving precise selective separation of monovalent and divalent cations, as well as anions, is vital yet challenging in practical applications involving complex component treatments. Current membranes are typically effective for separating either cation pairs or anion pairs. To address this issue, a straightforward strategy for fabricating a nanofiltration (NF) membrane is developed that selectively permeates monovalent ions. This study focused on neutralizing the surface charge and tuning the pore size distribution of the polyamide membranes through a secondary interfacial polymerization using a zwitterionic copolymer consisting of 2‐methacryloyloxyethyl phosphorylcholine and 2‐aminoethyl methacrylate hydrochloride. The optimized NF membrane prepared in this study, with a near‐neutrally charged membrane surface and appropriate pore size distribution, demonstrates favorable performance in precisely separating monovalent and divalent ions, irrespective of the ion charge sign. The optimum NF membrane features high selectivity for both Cl−/SO42− (93) and Li+/Mg2+ (67) ion pairs, along with high water permeance of 8.5 L m−2 h−1 bar−1, making it competitive with many reported membranes. This study offers new insights into the ion‐selective mechanisms of polyamide membranes for monovalent/divalent ions and may guide the development of advanced membranes with single‐solute selectivity.

On the potential of the Cluster Ion Counter (CIC) to observe local new particle formation, condensation sink and growth rate of newly formed particles

Abstract. The Cluster Ion Counter (CIC) is a simple three-channel instrument designed to observe ions in the electrical mobility equivalent diameter range from 1.0 to 5 nm. With the three channels, we can observe concentrations of both ion clusters (sub-2 nm ions) and intermediate ions. Furthermore, as derived here, we can estimate condensation sink (CS), intensity of local new particle formation, growth rate of newly formed particles from 2 to 3 nm and formation rate of 2 nm ions. We compared CIC measurements with those of a multichannel ion spectrometer, the Neutral cluster and Air Ion Spectrometer (NAIS), and found that the concentrations agreed well between the two instruments, with correlation coefficients of 0.89 and 0.86 for sub-2 nm and 2.0–2.3 nm ions, respectively. According to the observations made in Hyytiälä, Finland, and Beijing, China, the ion source rate was estimated to be about two to four ion pairs cm−3 s−1. The new CIC is a simple and cheap instrument that can be used in different environments to obtain information about small ion dynamics, local intermediate ion formation and CS in a robust way when combined with the theoretical framework presented here.

Impact of the Hydrophobic Phase on the Interfacial Dilational Rheology of Alkoxy Carboxylate/Cetyltrimethyl Ammonium Chloride Mixtures.

Despite extensive investigations on the interfacial activities of mixed anionic and cationic surfactants (Sa/c), the influence of the hydrophobic phase on their interfacial assembly and dilational rheology remains unaddressed. In this study, the interfacial dilational rheology of alkoxy carboxylate (anionic)/cetyltrimethylammonium chloride (cationic) surfactant mixtures was studied at various interfaces. The dilational modulus of Sa/c increases linearly with interfacial pressure at the interfaces of air, n-hexane/n-octane/n-hexadecane, and toluene. The limit elasticity (ε0) is similar at air and alkane interfaces but significantly decreases at the toluene interface. To explain these phenomena, all-atom molecular simulation was carried out to investigate the microscopic features of surfactants at the interface. The findings emphasize the crucial role of anionic/cationic surfactant bound pairs in regulating interfacial rheology. Sa/c tend to form large aggregates at the air/water surface. When mixed with alkanes like octane, most Sa/c remain as ion pairs. However, when toluene is employed, the coordination number between anionic and cationic surfactants sharply decreases due to π-π interactions between the toluene molecules and the phenyl groups in the anionic surfactant. This leads to a much lower interfacial modulus because interactions between oil molecules and surfactants cannot compensate for weakened interactions among anionic/cationic surfactants. These results suggest that Sa/c in this study tolerate alkanes but are not resistant to aromatics, which helps explain why Sa/c demonstrate excellent performance for the chemical enhanced oil recovery of a high-wax reservoir and further provides fundamental knowledge of their potential applications, such as gas well deliquification using foamers in the presence of condensate oil, textiles, etc.

Quantum Molecular Charge-Transfer Model for Multistep Auger-Meitner Decay Cascade Dynamics.

The fragmentation of molecular cations following inner-shell decay processes in molecules containing heavy elements underpins the X-ray damage effects observed in X-ray scattering measurements of biological and chemical materials, as well as in medical applications involving Auger electron-emitting radionuclides. Traditionally, these processes are modeled using simulations that describe the electronic structure at an atomic level, thereby omitting molecular bonding effects. This work addresses the gap by introducing a novel approach that couples Auger-Meitner decay to nuclear dynamics across multiple decay steps, by developing a decay spawning dynamics algorithm and applying it to potential energy surfaces characterized with ab initio molecular dynamics simulations. We showcase the approach on a model decay cascade following K-shell ionization of IBr and subsequent Kβ fluorescence decay. We examine two competing channels that undergo two decay steps, resulting in ion pairs with a total 3+ charge state. This approach provides a continuous description of the electron transfer dynamics occurring during the multistep decay cascade and molecular fragmentation, revealing the combined inner-shell decay and charge transfer time scale to be approximately 75 fs. Our computed kinetic energies of ion fragments show good agreement with experimental data.

Deciphering the Two-Step Hydride Mechanism of Monoamine Oxidase Flavoenzymes.

The complete two-step hydride transfer mechanism of amine oxidation involved in the metabolism of monoamine neurotransmitters was scrutinized by DFT calculations. In living organisms, this process is catalyzed by monoamine oxidase enzymes. Herein, we focus on some intriguing aspects of the reaction that may have been previously noticed but have not been clarified to date. The first step of the reaction includes the C-H bond cleavage on the methylene group vicinal to the amino group of the monoamine substrate and the subsequent transfer of hydrogen to the N5 atom of the flavin prosthetic group of the enzyme. We confirmed the nature of this step to be hydride transfer by evaluation of the pertinent HOMO-LUMO gap together with analysis of orbital contours alongside the intrinsic reaction coordinate profile. Next, we investigated the rather peculiar intermediate adduct that may form between the amine substrate and the flavin molecule, featuring an unusually long C-N bond of ∼1.62 Å. Although this bond is quite stable in the gas phase, the presence of just a few explicit water molecules facilitates its dissociation almost without energy input so that the amine-flavin intermediate can form an ionic pair instead. We attribute the existence of the unusual C-N bond to a fragile balance between opposing electronic structure effects, as evaluated by the natural bond orbital analysis. In line with this, the intermediate in the solution or in the enzyme active site can exist in two energetically almost equivalent forms, namely, as a covalently bound complex or as an ion pair, as suggested by previous studies. Finally, we characterized the transformation of the intermediate to the fully reduced flavin and imine products via proton transfer from the amino group to the flavin N1 atom, completing the reductive part of the catalytic cycle. Although we found that explicit solvation substantially boosts the kinetics of this step, the corresponding barrier is significantly lower than that in the hydride transfer step, confirming hydrogen abstraction as the rate-limiting step of amine oxidation and validating the two-step hydride transfer mechanism of monoamine oxidases.

Specific determination of (-)- and (+)-gossypol in vegetable oil by ultra-performance liquid chromatography-tandem mass spectrometry with chiral pre-column derivatization.

As the unique ingredient of cottonseed oil, gossypol is toxic and there are differences between the enantiomers. Although the determination of (-)- and (+)-gossypol in cotton plants or cottonseed was performed, the detection about the gossypol enantiomers in vegetable oil was rarely reported. To develop a specific inspection method for (-)- and (+)-gossypol in vegetable oil by ultra-performance liquid chromatography (UPLC) -tandem mass spectrometry with chiral pre-column derivatization. (-)- and (+)-gossypol were separated on an ACQUITY C18 reverse phase column (100 mm × 2.1 mm, 1.7 μm) maintained at 40 °C on an UPLC system with gradient elution. The mobile phases was composed of methanol (solvent A) and water containing 0.1% formic acid (solvent B). Analytes were detected with Electron Spray Ionization source in the positive mode. The contents of (-)- and (+)-gossypol standard derivatives were quantified by Multiple Reaction Monitoring with the transitions of m/z 633/483 for quantitative ion pairs and m/z 633/558 for qualitative ion pairs. The results indicated that the quantitative analysis could be accomplished within 12.5 minutes and the limits of detection of (-)- and (+)-gossypol were 25.55 μg/kg and 14.67 μg/kg, respectively. When this method was applied to olive oil spiked with gossypol standards, good recoveries (95.37%-105.84% for (-)-gossypol, 98.96%-105.14% for (+)-gossypol) and RSDs (3.41%-6.02% for (-)-gossypol, 4.50%-6.94% for (+)-gossypol) were achieved. The present study confirms the feasibility of determining the gossypol enantiomers and achieves trace determination of (-)- and (+)-gossypol in vegetable oil. These results make this method more suitable for the qualitative identification of whether the vegetable oil has been mixed with cottonseed oil. The trace determination of (-)- and (+)-gossypol in vegetable oils has been achieved. This method provides technical support for further identification of whether commercially available vegetable oil has been mixed with cottonseed oil.

Identification of Cervi cornu pantotrichum and its mixed varieties by UHPLC-QTOF-MS and UHPLC-TQS-MS/MS

Sika deer (Cervus nippon Temminck) and red deer (Cervus elaphus Linnaeus) are the two creatural sources of velvet antlers, which are recorded in the Chinese Pharmacopoeia (2020 edition). However, the counterfeits-moose (Alces alces Linnaeus) antlers are selling as genuine products in the market. In order to strengthen antler quality control and market supervision, a UHPLC-QTOF-MS coupled with chemometrics analysis and UHPLC-TQS-MS were developed and applied to distinguish the Velvet Antler of moose from that of sika deer and red deer. Firstly, the QTOF-MS quantized data obtained from samples treated with trypsin were subjected to principal component analysis (PCA) to classify these three kinds of antlers. Then, the potential differential marker peptides were found with orthogonal partial least-squares discriminant analysis (OPLS-DA). Finally, validation of these differential marker peptides was assessed using UHPLC-QTOF-MS, and the results showed that the specific ion pairs (m/z 724.8 → 518.1, m/z 724.8 → 938.3, m/z 732.8 → 526.3, m/z 732.8 → 784.3) were detected in moose deer antler, not in velvet antler of sika deer (Cervus nippon Temminck) and red deer (Cervus elaphus Linnaeus). The methods in the paper and specific ion pairs could be successfully applied to distinguish moose antlers from sika deer antlers and red deer antlers.

Determination of the extremolyte ectoine in plasma and a pharmacokinetic study in rats by a validated and BAGI-evaluated UPLC-MS/MS method

Ectoine (ECT) has recently gained considerable interest in the healthcare sector due to its promising therapeutic benefits in a variety of human disorders. This research aimed to quantify the ECT plasma level in rats by creating and optimizing a sensitive and validated UPLC-MS/MS method. Prior to analysis, ECT extraction from the plasma samples was conducted via a protein precipitation procedure, using hydroxyectoine as an internal standard (IS). A 1.7 μm UPLC C8 column (100 mm × 2.1 mm) was selected for the chromatographic separation, using a gradient mobile phase consisting of acetonitrile and 0.05% formic acid. The electrospray ionization mass spectrometry (ESI-MS) was used to detect ECT in the positive ion mode. To determine the specific precursor and the product ions of ECT, multiple reaction monitoring (MRM) methods were carried out. The selected ion pair of ECT was 143.1 > 97 and 159.1 > 113.13 for the IS. The ECT’s linearity range in rat plasma was found to be 1-1000 ng/mL, with a recovery rate of 96.48–97.37%. Consistent with FDA guidelines for bio-analytical method validation, the suggested method was validated. The method was efficiently employed to quantify the studied drug in spiked rat plasma with good accuracy and precision with no significant matrix effects. Furthermore, it was effectively used to investigate the pharmacokinetic behavior of ECT in rats after a single oral dose of 30 mg/kg.

Spinel‐Type Structured Phosphor Near‐Infrared‐II Emission: Intervalence Charge Transfer and Hetero‐Valent Chromium Pairs

AbstractNear‐infrared (NIR) emitting phosphors draw much attention because they show great applicability and development prospects in many fields. Herein, a series of inverse spinel‐type structured LiGa5O8 phosphors with a high concentration of Cr3+ activators is reported with a dual emission band covering NIR‐I and II regions. Except for strong ionic exchange interactions such as Cr3+−Cr3+ and Cr3+ clusters, an intervalence charge transfer (IVCT) process between aggregated Cr ion pairs is proposed as the mechanism for the ~1210 nm NIR‐II emission. Comprehensive structural and luminescence characterization points to IVCT between two Cr3+ being induced by structural distortion and further enhanced by irradiation. Construction of the configurational energy level diagram enabled elucidation of this transition within the IVCT process. Therefore, this work provides insight into the emission mechanism within the high Cr3+ concentration system, revealing a new design strategy for NIR‐II emitting phosphors to promote its response.