Ion-pair Research Articles

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions.

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN-) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN- binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S-C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency-frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Finally, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the 3LE state (LE: locally excited state). UV-vis absorption spectra indicate electronic coupling between NDI with the phenylene linker as well as the PTZ units, manifested by the appearance of a charge-transfer (CT) absorption band, whereas this coupling is devoid in the triads with conformation restriction imposed. Fluorescence is strongly quenched in the triads compared to the reference compound, indicating electron transfer upon photoexcitation. Femtosecond transient absorption spectra indicate that the CS takes 0.8 ps, and then the 3LE state is formed by charge recombination in 83 ps. Nanosecond transient absorption (ns-TA) spectra show that the 3NDI state was observed in nonpolar solvents such as cyclohexane (triplet state lifetime: 95.7 μs), whereas the CS state was observed in more polar solvents. The CS state lifetimes are up to 1.2 μs (in toluene). Time-resolved electron paramagnetic resonance spectra of the triads in toluene consist of two types of signals: CS states (narrower signals, ∼10 mT) and 3LE states (broader signals, ∼50 to 200 mT). In the spectra of the triads containing PTZ, the CS state signals dominate, whereas for the triads containing oxidized PTZ, the 3NDI signals (zero-field splitting D ≈ 2000 MHz) prevail, both observations being in agreement with the ns-TA spectral studies. The electron spin polarization phase pattern of the 3NDI states of the triads indicates that the intersystem crossing (ISC) mechanism is spin-orbit charge-transfer ISC. Considering the 3CS state as ion pairs, the electron-exchange energy (J) is determined to be -39 to -59 MHz, and the electron spin dipolar interaction is 83-92 MHz.

Laser driven wake wave in pair-ion electron plasma with inclusion of ion dynamics

The generation of laser driven plasma wake wave has been investigated in hydrogen pair-ion electron plasma. The consideration of dynamics of the positive and negative ion pair have been adopted. Inclusion of the ion motion has the effect of modifying the electric field and density profiles of the wake wave. This has been demonstrated by observing the variation of the electron density and electric field profiles with the change in positive ion/negative ion concentration. High density spikes and sawtooth like electric field profiles (indication of wave breaking) are observed to transform into sinusoidal electric field profile and low amplitude density profile when the positive ion density in the plasma system is kept higher. Furthermore, we observe the variation of the electric field amplitude of the wake wave with the laser pulse width. This feature is the indication of the possibility of hybrid acceleration (Direct Laser Acceleration and wake field acceleration) of accelerated beam. The results are quite relevant in laser plasma interaction field in experimental physics and also in planetary environment.

Enantioselective Reduction and Sulfenylation of Isoflavanone Derivatives via Bisguanidinium Hypervalent Silicate.

In this work, we describe an enantioselective reduction and sulfenylation of isoflavanone derivatives by an ion pair strategy. The chiral cationic catalyst bisguanidinium (BG) is capable of chiral induction in catalytic systems. Silane hydride works as a reductant and helps to form an anionic hypervalent silicate complex and intermediates with substrates to pair with chiral catalyst. A series of umpolung sulfur reagents accomplish electrophilic attack in the presence of a silicate anion. Both chemoselectivity and enantioselectivity are good to excellent to afford a wide scope of 4-oxo-4H-chromene-3-carbonitrile and S-electrophilic reagents. Further transformations were completed to introduce more applications.

The use of amines as steel corrosion inhibitors in butanol-gasoline blends

Butanol is an interesting component used for blending gasoline fuels. However, the polar nature of butanol allows the solubility of water and ionic compounds in butanol-gasoline blends (BGBs) making them aggressive to mild steel. Amines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, morpholine, piperazine, and hexamethylenediamine, were tested as corrosion inhibitors for mild steel in BGBs. Additionally, the influence of the acetic acid and sodium chloride concentrations on the inhibition efficiency was examined. Electrochemical impedance spectroscopy andpotentiodynamic polarization were employed for the measurements, complemented by static immersion testing and an XPS surface analysis. The highest inhibition efficiency was demonstrated for diethylenetriamine, triethylenetetramine, andhexamethylenediamine, achieving a value of 95 % or more at aconcentration of 100 mg/L. The formation of ionic pairs involving protonated amines andchlorides was also confirmed. The XPS analysis revealed a very thin passive layer of iron oxides, which may form in the presence of amines, protecting mild steel in BGBs.

Dynamic Ion Gels from the Complex Coacervation of Oppositely Charged Poly(ionic liquid)s.

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (Tg), ion conducting (σDC), and viscoelastic (elastic moduli (G')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (σDC up to 4.5 × 10-5 S cm-1 at 30 °C) and higher elastic moduli (G' up to 4 kPa at 25 °C and 1 rad s-1), making them highly desirable in many electrochemical applications, including supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.

Dual tobramycin and docosahexaenoic acid loaded nanoemulsions combating Pseudomonas aeruginosa-induced pulmonary infection

Pseudomonas aeruginosa (P. aeruginosa) typically forms biofilms in vivo, which exhibit high resistance and complicate eradication efforts. Additionally, persistent inflammation and excessive oxidative stress can lead to severe lung dysfunction, facilitating bacterial colonization and infection. Herein, we prepared oil-in-water (O/W) nanoemulsions (TD-αT NEs) by using PEG5k-block-PCL5k and α-tocopherol to encapsulate tobramycin (TOB). To enhance TOB’s drug load, a hydrophobic ion pair (TDIP) composed of TOB and docosahexaenoic acid (DHA) was pre-prepared. TD-αT NEs was not only easily prepared and aerosolized, but stable in both physics and chemistry. The negatively charged TD-αT NEs facilitated penetration through mucus, reaching infection sites. Subsequently, TD-αT NEs permeated biofilms due to their small size and released drugs via lipase-triggered carrier dissociation, aiding in eradicating internal bacteria within biofilms (with a 16-fold reduction in CFU vs. free TOB group). TD-αT NEs simultaneously exerted superior anti-inflammatory effects, reducing levels of pro-inflammatory cytokines (NO, IL-6, IL-8, and TNF-α) while increasing the level of anti-inflammatory cytokine (IL-10). It was achieved through the upregulation of PPAR-γ and downregulation of NF-κB signaling, thus mitigating the lung damage. In addition, TD-αT NEs demonstrated strong antioxidant activity, alleviating the oxidative stress induced by P. aeruginosa. Notably, when administered via inhalation, TD-αT NEs significantly reduced the lung bacterial burden, lung inflammation, and oxidative stress in vivo compared to TOB solution. TD-αT NEs could prove beneficial in treating chronic pulmonary infections induced by P. aeruginosa through a comprehensive strategy, specifically enhancing biofilm eradication, reducing inflammation, and alleviating oxidative stress.

Selective Profiling of Carboxylic Acid in Crude Oil by Halogen Labeling Combined with Liquid Chromatography and High-Resolution Mass Spectrometry.

Carboxylic acids are a small but essential compound class within petroleum chemistry, influencing crude oil behaviors in production and processing and causing environmental impacts. Detailed structural information is fundamental to understanding their influence on petroleum characteristics. However, characterizing acids in crude oil remains challenging due to matrix effects, structural diversity, and low abundance. In this work, we present a new methodology for profiling carboxylic acids by liquid-liquid extraction and selective derivatization using 4-bromo-N-methylbenzylamine (4-BNMA) followed by liquid chromatography and electrospray ionization Orbitrap mass spectrometry (LC-ESI-Orbitrap MS). The fragmentation of 4-BNMA derivatives produces a unique product ion pair, m/z 169/171, enabling the identification of chromatographic fractions containing carboxylic acids. The mass spectra of the corresponding fractions are extracted, and the acids are further computationally isolated based on the isotopic pattern. The method was optimized and validated using acid standards and systematic experimental designs, assuring robustness and sensitivity for nontarget screening purposes. This method detected up to 380 carboxylic acids in six Danish North Sea crude oils, with up to two carboxyl and other heteroatom functionalities (NSO). The results indicated that the most populated species are fatty acids (double bond equivalent (DBE) = 1) and small aromatic acids (DBE = 2-6). The predominance and diversities of compound classes in different samples are consistent with their corresponding bulk properties. Polyfunctional acids (Ox, NxOx, and SxOx) were observed due to exposure to oxidation and biodegradation. Also, the approach's applicability benefits high-resolution MS analysis by simplifying data processing for crude oil and potentially other high-organic and aqueous samples.

Coordination of dissolved transition metals in pristine battery electrolyte solutions determined by NMR and EPR spectroscopy.

The solvation of dissolved transition metal ions in lithium-ion battery electrolytes is not well-characterised experimentally, although it is important for battery degradation mechanisms governed by metal dissolution, deposition, and reactivity in solution. This work identifies the coordinating species in the Mn2+ and Ni2+ solvation spheres in LiPF6/LiTFSI-carbonate electrolyte solutions by examining the electron-nuclear spin interactions, which are probed by pulsed EPR and paramagnetic NMR spectroscopy. These techniques investigate solvation in frozen electrolytes and in the liquid state at ambient temperature, respectively, also probing the bound states and dynamics of the complexes involving the ions. Mn2+ and Ni2+ are shown to primarily coordinate to ethylene carbonate (EC) in the first coordination sphere, while PF6- is found primarily in the second coordination sphere, although a degree of contact ion pairing does appear to occur, particularly in electrolytes with low EC concentrations. NMR results suggest that Mn2+ coordinates more strongly to PF6- than to TFSI-, while the opposite is true for Ni2+. This work provides a framework to experimentally determine the coordination spheres of paramagnetic metals in battery electrolyte solutions.

Crystal structure of the 1:1 co-crystal 4-(dimethylamino)pyridin-1-ium 8-hydroxyquinoline-5-sulfonate–N,N-dimethylpyridin-4-amine

The asymmetric unit of the title compound is composed of two independent ion pairs of 4-(dimethylamino)pyridin-1-ium 8-hydroxyquinoline-5-sulfonate (HDMAP+·HqSA−, C7H11N2 +·C9H6NO4S−) and neutral N,N-dimethylpyridin-4-amine molecules (DMAP, C7H10N2), co-crystallized as a 1:1:1 HDMAP+:HqSA−:DMAP adduct in the monoclinic system, space group Pc. The compound has a layered structure, including cation layers of HDMAP+ with DMAP and anion layers of HqSA− in the crystal. In the cation layer, there are intermolecular N—H...N hydrogen bonds between the protonated HDMAP+ molecule and the neutral DMAP molecule. In the anion layer, each HqSA− is surrounded by other six HqSA−, where the planar network structure is formed by intermolecular O—H...O and C—H...O hydrogen bonds. The cation and anion layers are linked by intermolecular C—H...O hydrogen bonds and C—H...π interactions.

Crystal structure of the 1:1 co-crystal 4-(dimethylamino)pyridin-1-ium 8-hydroxyquinoline-5-sulfonate–N,N-dimethylpyridin-4-amine

The asymmetric unit of the title compound is composed of two independent ion pairs of 4-(dimethylamino)pyridin-1-ium 8-hydroxyquinoline-5-sulfonate (HDMAP+·HqSA−, C7H11N2 +·C9H6NO4S−) and neutral N,N-dimethylpyridin-4-amine molecules (DMAP, C7H10N2), co-crystallized as a 1:1:1 HDMAP+:HqSA−:DMAP adduct in the monoclinic system, space group Pc. The compound has a layered structure, including cation layers of HDMAP+ with DMAP and anion layers of HqSA− in the crystal. In the cation layer, there are intermolecular N—H...N hydrogen bonds between the protonated HDMAP+ molecule and the neutral DMAP molecule. In the anion layer, each HqSA− is surrounded by other six HqSA−, where the planar network structure is formed by intermolecular O—H...O and C—H...O hydrogen bonds. The cation and anion layers are linked by intermolecular C—H...O hydrogen bonds and C—H...π interactions.

Understanding Europium and Terbium Speciation and Ion Pairing in Carbonate Complexes Using Advanced Spectroscopy Techniques

Lanthanide (Ln) elements are critical materials that are typically extracted/mined together. Their separation by solvent extraction from acidic media is well known; however, there are few studies in basic media with carbonate anions. We investigated the complexation of Eu(III) and Tb(III) carbonates as solids and solutions in alkaline K2CO3, wherein we sought to access a Tb(IV) carbonate complex through ozonolysis. L3‐edge XANES of Eu and Tb carbonate solids, colorless solutions, and a red‐hued Tb solution (obtained by ozonolysis) all showed Ln(III) cations. The absence of evidence for a Tb(IV) complex was confirmed through XAS and EPR analyses, despite the solution exhibiting a deep red color. For solids and solutions, EXAFS results indicate molecular Ln(III)‐carbonato anions. In terms of the Eu(III) carbonate coordination number, the coordination does not change upon dissolution of the solid sample. Furthermore, EXAFS for the solutions revealed evidence for the association of potassium cations with the Ln(III)‐carbonato anions. This direct observation of contact ion pairing by EXAFS at room temperature is rare. The insights into Ln(III) carbonate complexation and solution speciation afforded by XANES‐EXAFS, FT‐IR, and EPR provides perspectives that serve as benchmarks for future computational and experimental efforts focused on caustic‐side solvent extraction of Ln(III) ions.

Geological and Hydrochemical Processes Driving Karst Development in Southeastern Riyadh, Central Saudi Arabia

This study investigates the processes leading to karst development in the southeastern part of Riyadh city extending up to Al Kharj. Numerous solution features such as sinkholes, collapsed dolines, and solution caverns are common in the area. The role of water in the development of the karst features was investigated using an integrated geological and hydrochemical approach. Geological investigations included the petrographic analysis of rock samples collected from zones of intense karstification with special emphasis on mineral dissolution. The study showed that the Sulaiy Formation is commonly fractured, brecciated, foliated, and contains numerous cavities, vugs, and openings. These features have formed by mineral dissolution by circulating groundwater, which has removed anhydrite beds from the underlying Arab–Hith sequence. Karstification likely started from the tectonically weak zones when there was more groundwater recharge. Studies show that during the early to mid-Holocene period, the climate in the Arabian Peninsula was humid, promoting groundwater recharge and subsequent mineral dissolution, though the process of karstification must have started much earlier. Hydrochemical findings reveal that mineral dissolution (halite and calcium sulfate) is the main process affecting groundwater chemistry. The Piper plot revealed two main hydrochemical facies: the (Ca2+ + Mg2+)–(Cl+ SO42−) Type (Type A) and the (Na+ + K+)–(SO42− + Cl) Type (Type B). Most of the samples belong to Type B, typical of groundwater facies affected by dissolution of halite and anhydrite mineral. The absence of the (Ca2+ + Mg2+)–(CO32− + HCO3−) type of groundwater facies indicates a lack of recent groundwater recharge and the removal of carbonate minerals from the system through precipitation, as evidenced by the saturation indices. Plots of the major ionic pairs (cations vs. anions) in groundwater indicate strong halite and gypsum/anhydrite dissolution. Of the three carbonate minerals, calcite has the highest average saturation index followed by aragonite and dolomite. This suggests significant past rock–water interaction leading to carbonate dissolution. Presently, any additional calcium or carbonate ions introduced into the water lead to calcite precipitation. The study indicates that the process of karst development may not be active today. Currently, groundwater chemistry is mainly influenced by rock–water interaction leading to gypsum/anhydrite dissolution, which has resulted in a high concentration of Na+, Ca2+, Cl− and SO42− ions in groundwater. The dissolution of gypsum and halite from the Hith Formation weakens the structural integrity of the overlying Sulaiy Formation, creating large underground cavities. These cavities increase the risk of roof collapse, leading to cover-collapse sinkholes as the roof becomes too thin to support the weight above.

Geological and Hydrochemical Processes Driving Karst Development in Southeastern Riyadh, Central Saudi Arabia

This study investigates the processes leading to karst development in the southeastern part of Riyadh city extending up to Al Kharj. Numerous solution features such as sinkholes, collapsed dolines, and solution caverns are common in the area. The role of water in the development of the karst features was investigated using an integrated geological and hydrochemical approach. Geological investigations included the petrographic analysis of rock samples collected from zones of intense karstification with special emphasis on mineral dissolution. The study showed that the Sulaiy Formation is commonly fractured, brecciated, foliated, and contains numerous cavities, vugs, and openings. These features have formed by mineral dissolution by circulating groundwater, which has removed anhydrite beds from the underlying Arab–Hith sequence. Karstification likely started from the tectonically weak zones when there was more groundwater recharge. Studies show that during the early to mid-Holocene period, the climate in the Arabian Peninsula was humid, promoting groundwater recharge and subsequent mineral dissolution, though the process of karstification must have started much earlier. Hydrochemical findings reveal that mineral dissolution (halite and calcium sulfate) is the main process affecting groundwater chemistry. The Piper plot revealed two main hydrochemical facies: the (Ca2+ + Mg2+)–(Cl+ SO42−) Type (Type A) and the (Na+ + K+)–(SO42− + Cl) Type (Type B). Most of the samples belong to Type B, typical of groundwater facies affected by dissolution of halite and anhydrite mineral. The absence of the (Ca2+ + Mg2+)–(CO32− + HCO3−) type of groundwater facies indicates a lack of recent groundwater recharge and the removal of carbonate minerals from the system through precipitation, as evidenced by the saturation indices. Plots of the major ionic pairs (cations vs. anions) in groundwater indicate strong halite and gypsum/anhydrite dissolution. Of the three carbonate minerals, calcite has the highest average saturation index followed by aragonite and dolomite. This suggests significant past rock–water interaction leading to carbonate dissolution. Presently, any additional calcium or carbonate ions introduced into the water lead to calcite precipitation. The study indicates that the process of karst development may not be active today. Currently, groundwater chemistry is mainly influenced by rock–water interaction leading to gypsum/anhydrite dissolution, which has resulted in a high concentration of Na+, Ca2+, Cl− and SO42− ions in groundwater. The dissolution of gypsum and halite from the Hith Formation weakens the structural integrity of the overlying Sulaiy Formation, creating large underground cavities. These cavities increase the risk of roof collapse, leading to cover-collapse sinkholes as the roof becomes too thin to support the weight above.

Organotellurium(II) and ‐(IV) Compounds with Picolinoylbis(thio­ureas): From Simple 1:1 Adducts to Multimetallic Aggregates

Reactions of 2,6‐dipicolinoylbis(N,N‐diethylthiourea) (H2LEt) with common tellurium(IV) starting materials such as PhTeBr3 or TeBr4 yield various tellurium(IV) and tellurium(II) compounds depending on the conditions applied. Equimolar amounts of H2LEt and PhTeBr3 give the 1:1 complex [PhTeIVBr3(H2LEt)], while with an excess of H2LEt, the tellurium compound is partially reduced and a {PhTeII}+ building block coordinates to both sulfur atoms of H2LEt under formation of the ion pair [PhTeII(H2LEt)][PhTeIVBr4]. Similar reactions between H2LEt and TeBr4 give the neutral monomer [TeIIBr2(H2LEt)] or the coordination polymer [TeIIBr2(H2LEt)]∞. The latter compound is also formed with the assistance of Pb2+ ions. While the lead ions do not appear in the isolated product, similar reactions with transition metal ions such as Ni2+, Mn2+, or Co2+ result in the formation of hetero­bimetallic complexes, in which Te(II) building blocks are directed to the sulfur atoms of the deprotonated ligand {H2LEt2‐S,S}2‐, while the transition metal ions occupy central coordination positions between two of the organic ligands using the pyridine nitrogen atom, carbonyl oxygen atom(s) and/or the nitrogen atoms of the thiourea units.

Laser Driven Wake Wave in Pair-ion Electron Plasma with Inclusion of Ion Dynamics

Abstract The generation of laser driven plasma wake wave has been investigated in hydrogen 
 pair-ion electron plasma. The consideration of 
 dynamics of the positive and negative ion pair have been adopted. Inclusion of the ion motion
 has the effect of modifying the electric field and density profiles of the wake wave.
 This has been demonstrated by observing the variation of the 
 electron density and electric field profiles with the change in positive ion/ negative ion concentration.
 High density spikes and sawtooth like electric field profiles (indication of wave breaking) are observed 
 to transform into sinusoidal electric field profile and low amplitude density profile 
 when the positive ion density in the plasma system is kept higher. Furthermore, we observe the variation of 
 the electric field amplitude of the wake wave with the laser pulse width. This feature is the indication of 
 the possibility of hybrid acceleration (Direct Laser Acceleration and wake field acceleration) 
 of accelerated beam. The results are quite relevant in the field Laser plasma interaction field 
 in experimental physics and also in planetary
 environment.

Pnictogen-Bonding Enzymes.

The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a s-hole interaction that is essentially absent in biocatalysis. For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate. Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the s hole on the Sb(V) center, and the emergence of saturation kinetic behavior. Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition. Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product. The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis.

A green, fluorescent probe employing erythrosine-B for tracing the accidental administration of levamisole in milk and plasma samples.

A simple and sensitive fluorescent probe has been developed and optimized to detect the non-intentional administration of levamisole (LVM). LVM is used as an anthelmintic therapy in cows, and hence, its residues appear in the drained milk until 60 hours after administering the drug. Meanwhile, levamisole is known to be an adulterant to cocaine and could be detected in addicts' plasma samples. Owing to its severe side effects, including agranulocytosis, which is lethal in many cases, detection and quantification of LVM in milk and plasma samples are of utmost importance. Therefore, a sensitive and selective analytical method is required for this purpose. This work develops a highly fluorescent probe obtained through the reaction between LVM and erythrosine-B in an acidic medium, where the produced ion pair complex has been measured at 553 nm after excitation at 528 nm. The proposed method provides linearity over the concentration range of 0.5-2.0 μg mL-1 for LVM, with a corresponding detection and quantitation limit of 0.5 and 0.3 μg mL-1. Full validation was performed, permitting the application of the suggested method to perform simple extraction steps. All the applied procedures followed the guidelines offered by green analytical chemistry, where the Green Analytical Procedure Index (GAPI) assessed the greenness of the proposed tool, and the yielded pictograms proved the eco-friendliness of the offered tool.

Quantification of arsenic in real samples using a spectrophotometric cloud point extraction of the formed ion pair with astrazon orange G

A novel cloud-point extraction (CPE) procedure for the determination of ultra-trace amounts of arsenic species in real samples, purchased from the local market by spectrophotometer was developed. Inorganic arsenic species analysis in water, beverages, and foods has become increasingly important in recent years, as arsenic species are considered carcinogenic and are assessed at significant levels in samples. The technique is established on a selective ternary complex of As(V) with astrazon orange G (AOG+) in the presence of tartaric acid and polyethylene glycol tertoctylphenyl ether (Triton X-114) at pH 4.0. The calibration curve developed within range 3.0–160 ng/mL with a correlation coefficient of 0.9988 for As(V) provided a preconcentration factor of 200 and a limit of detection (3S blank/m) of 0.88 ng/mL under optimum investigation conditions. The results of molar absorptivity and Sandell sensitivity are calculated and found to be 4.38 × 105 L/mol cm and 0.018 ng cm−2, respectively. The statistical treatment of data obtained from the proposed and GF-AAS procedures are compared in terms of Student’s t-tests and variance ratio F-tests has revealed no significant differences. The methodology has been effectively confirmed by assessing real samples and comparing it to the GF-AAS method statistically.

Quantification of arsenic in real samples using a spectrophotometric cloud point extraction of the formed ion pair with astrazon orange G

A novel cloud-point extraction (CPE) procedure for the determination of ultra-trace amounts of arsenic species in real samples, purchased from the local market by spectrophotometer was developed. Inorganic arsenic species analysis in water, beverages, and foods has become increasingly important in recent years, as arsenic species are considered carcinogenic and are assessed at significant levels in samples. The technique is established on a selective ternary complex of As(V) with astrazon orange G (AOG+) in the presence of tartaric acid and polyethylene glycol tertoctylphenyl ether (Triton X-114) at pH 4.0. The calibration curve developed within range 3.0–160 ng/mL with a correlation coefficient of 0.9988 for As(V) provided a preconcentration factor of 200 and a limit of detection (3S blank/m) of 0.88 ng/mL under optimum investigation conditions. The results of molar absorptivity and Sandell sensitivity are calculated and found to be 4.38 × 105 L/mol cm and 0.018 ng cm−2, respectively. The statistical treatment of data obtained from the proposed and GF-AAS procedures are compared in terms of Student’s t-tests and variance ratio F-tests has revealed no significant differences. The methodology has been effectively confirmed by assessing real samples and comparing it to the GF-AAS method statistically.