Ion-pair Complex Research Articles

Application of ion pair complexes to design novel potentiometric membrane sensors for direct determination of frusemide in pharmaceuticals

BackgroundFabrication of two membrane sensors using two acidic indicators among sulphonthalein dyes, namely bromophenol blue (BPB) and bromocresol green (BCG), and their use as indicative electrodes for the quantification of frusemide (FUR) is presented. The ion pair complexes of FUR with BPB or BCG are used to prepare the membranes in THF solvent, PVC matrix and dibutyl phthalate (DBP) as plasticizer and subsequently to fabricate FUR-BPB (Sensor I) and FUR-BCG (Sensor II) sensors.ResultsSensors I and II are employable to determine 2.4 × 10-5–2.4 × 10-3 mol/L FUR at operative pH of 3.71. The calibration curve between the potentials against the concentration of FUR yielded the slopes of 58.73 ± 1 and 57.66 ± 1 mV/decade, respectively, using Sensors I and II, and this confirmed the Nernstian behaviour. Satisfactory correlation was obtained between the measured potentials and FUR concentration with the proposed sensors, and this was revealed by regression coefficient values of 0.9987 and 0.9980 for Sensors I and II, respectively. The LOD (limit of detection) values were calculated and reported for both the sensors. The experimental parameters were optimised to yield acceptable characteristics of both the sensors in the context of performance. The role of excipients of tablets and interferences were assessed by standard addition protocol. The obtained results confirmed the ineffective role of excipients of tablets and foreign species used as interferents.ConclusionThe designed sensors were validated to confirm the accurate, precise, robust and rugged functioning in determining FUR. The mean of recovered FUR, close to 100%, revealed the acceptable and effective functioning of the proposed sensors. Excellent results were obtained by FUR tablets’ analysis using both the sensors.

Supraamphiphilic Systems Based on Metallosurfactant and Calix[4]resorcinol: Self-Assembly and Drug Delivery Potential.

Metallic amphiphiles are used as building blocks in the construction of nanoscale superstructures, where the hydrophobic effects induce the self-assembly of the nanoparticles of interest. However, the influence of synergizing multiple chemical interactions on an effective design of these structures mostly remains an open question. In this regard, supraamphiphilic systems based on flexible surfactant molecules and rigid macrocycles are being actively developed, but there are few works on the interaction between metallosurfactants and macrocycles. In the present work, the self-assembly and biological properties of a metallosurfactant with calixarene were studied for the first time. The metallosurfactant, a complex between lanthanum nitrate and two 4-aza-1-hexadecylazoniabicyclo[2.2.2]octane bromide units, and calix[4]resorcinol containing sulfonate groups on the upper rim were used to form a novel supraamphiphilic composition. The system formed was studied using a variety of physicochemical methods, including spectrophotometry, NMR, XRF, and dynamic and electrophoretic light scattering. It was found that the most optimal tetraanionic calix[4]resorcinol to dicationic metallosurfactant molar ratio, leading to mixed aggregation upon ion pair complexation, is 2:3. The mixed aggregates formed in the pentamolar concentration range were able to encapsulate hydrophilic substrates, including the anticancer drug cisplatin, the pure form of which is more cytotoxic toward healthy cells than toward diseased cells. Interestingly, the drug loaded into the macrocycle-metallosurfactant particles was less cytotoxic to a healthy Chang liver cell line and more cytotoxic to tumor M-HeLa cells. This selectivity depends on the amount of cisplatin added. The more drug is added to the macrocycle-metallosurfactant composition, the greater the biological activity against cancer cells. Taking into account that the appearance of resistance of cancer cells to drugs, especially to cisplatin, is one of the most important problems in treatment, the results of this work envisage the potential application of a mixed macrocycle-metallosurfactant system for the design of therapeutic cisplatin compositions.

Development and validation of spectrophotometric methods for estimation of antimigraine drug eletriptan hydrobromide in pure form and pharmaceutical formulations

The present study aims to develop and validate four simple, sensitive, reproducible, and low-cost spectrophotometric methods for the determination of antimigraine drug (eletriptan hydrobromide) in pure form and pharmaceutical formulations. The methods are based on the formation of yellow colored ion-pair complex between eletriptan hydrobromide and four acid dyes, namely, bromocresol purple (BCP), bromocresol green (BCG), bromophenol blue (BPB), and bromothymol blue (BTB) with absorption maxima at 410, 420, 414 and 416nm, respectively. Several parameters such as pH, buffer type and volume, reagent volume, sequence of addition and effect of extracting solvent were optimized. Under the optimum experimental conditions, beer's law is obeyed over the concentration ranges of 1.0-20 and 1.0-16μgmL-1 for (BCP or BCG) and (BPB or BTB), respectively with good correlation coefficients (0.9995-0.9999). The apparent molar absorptivity and Sandell's sensitivity values are reported for all methods. The limit of detection (LOD) and the limit of quantification (LOQ) values are found to be 0.27, 0.28, 0.25, and 0.30μgmL-1 and 0.90, 0.93, 0.83, and 1.0μgmL-1 for BCP, BCG, BPB and BTB, respectively. The stoichiometric ratio of the formed ion-pair complexes was found to be 1:1 (drug: reagent) for all methods. The developed methods were successfully applied for the determination of eletriptan hydrobromide in pharmaceutical formulations with good accuracy and precision. Statistical comparison of the results was performed using Student's t-test and variance ratio F-test at the 95% confidence level and there was no significant difference between the reported and proposed methods regarding accuracy and precision. Further, the validity of the proposed methods was confirmed by recovery studies via standard addition method.

Determination of cefixime in pure form, in pharmaceutical products and biological samples through fluorescence quenching of eosin Y.

A simple, economic and validated spectrofluorimetric method was developed to assay cefixime (CFX). The technique relies on the quenching effect of CFX on the fluorescence intensity of eosin Y in the presence of acetate buffer pH 3.4 to produce an ion-pair complex that is measured at 549 nm using an excitation wavelength of 300 nm. Reaction-influencing factors were carefully investigated and optimized. The fluorescence quenching value was linear to the CFX concentration in the range 0.2-40 μg/ml with a correlation coefficient of 0.992. The calculated limit of detection and limit of quantification were found to be 0.00242 and 0.0080 μg ml-1 , respectively. The selectivity of the method was confirmed by studying the effects of excipients and no interference was distinguished. The developed method was used to determine CFX in marketable products and in biological samples. To validate the method, directives of the International Conference on Harmonization were applied and per cent recoveries obtained ranged from 95.30 to 102.50% for pharmaceutical products and from 97.00 to 103.00% for biological fluids.

Novel spectrofluorimetric determination of brigatinib in bulk powder and human urine samples via ion-pair complex formation using eosin Y

The developed spectrofluorimetric method was successfully applied to the analysis of brigatinib (BRG) in its bulk powder form, and human urine sample.It is based on the investigation of the fluorescence spectrum behavior of the BRG-eosin Y complex. The relative fluorescence intensity (RFI) was recorded at 560 nm after excitation at 480 nm. The principle of the proposed method was thoroughly explained. All experimental parameters affecting method development were optimized. Moreover, the obtained results were fully discussed and statistically analyzed. The molar ratio method was applied to study the stoichiometric relationship between BRG and eosin Y complex. The method revealed a ratio of 1:3 for BRG-eosin Y afforded the highest RFI. The developed method was validated over the concentration range of 62.5–4000 ng mL−1. The results were compared positively with the reported method.

Selective diammonium reagents hosted on nanofibers for recovery of iridium from rhodium: Theoretical and experimental studies

Quaternary diammonium-functionalized polyvinyl benzyl chloride nanofibers were done using different diamines such as ethylenediamine (EDA), tetramethylene diamine (TMDA), hexamethylenediamine (HMDA), octamethylenediamine (OMDA), 1,10-diaminodecane (DMDA) and 1,12-diaminododecane (DDMDA) with quaternization using methyl iodide, followed by conversion to a chloride form. These were called F-QUAT EDA, F-QUAT TMDA, F-QUAT HMDA, F-QUAT OMDA, F-QUAT DMDA and F-QUAT DDMDA, respectively. Materials characterization was supported using elemental analysis, FTIR, XPS, SEM-EDS, TG and BET analysis. Langmuir and Freundlich's models were applied to analyze the adsorption of [IrCl6]2− and [RhCl5(H2O)]2− onto the materials, and the Freundlich model was obeyed. The mass transfer kinetics were tested on the pseudo-first-order and pseudo-second-order equations, and the process obeyed the pseudo-second-order kinetics. Column studies for the sorption of [IrCl6]2− using the functional materials were carried out and the loading capacities were 5.98 mg/g, 7.95 mg/g, 15.23 mg/g, 21.71 mg/g, 32.94 mg/g and 9.70 mg/g for F-QUAT EDA, F-QUAT TMDA, F-QUAT HMDA, F-QUAT OMDA, F-QUAT DMDA and F-QUAT DDMDA, respectively. This was the order of an improvement in the methylene chain amongst the two ammonium groups up to ten carbons. Theoretically calculated electrostatic potential energies of the cations, dipole moments and solvation energies of the free cations and anions, energies for replacement of the chloride by [IrCl6]2−, and thermodynamic parameters for the formation of ion-pair complexes were used to explain this trend observed for the capacity of the functional reagents. The functional nanofibers displayed potential for use in selective recovery of iridium from rhodium.

Improvements in the Oral Absorption and Anticancer Efficacy of an Oxaliplatin-Loaded Solid Formulation: Pharmacokinetic Properties in Rats and Nonhuman Primates and the Effects of Oral Metronomic Dosing on Colorectal Cancer.

ObjectiveThe anticancer efficacy of orally administered chemotherapeutics is often constrained by low intestinal membrane permeability and oral bioavailability. In this context, we designed a solid oral formulation of oxaliplatin (OP), a third-generation cisplatin analog, to improve oral bioavailability and investigate its application in metronomic chemotherapy.MethodsAn ion-pairing complex of OP with a permeation enhancer, Nα-deoxycholyl-l-lysyl-methylester (DLM), was successfully prepared and then mixed with dispersing agents (including poloxamer 188 and Labrasol) to form the solid, amorphous oral formulation OP/DLM (OP/DLM-SF; hereafter, ODSF).ResultsThe optimized powder formulation was sized in the nanoscale range (133±1.47 nm). The effective permeability of OP increased by 12.4-fold after ionic complex formation with DLM and was further increased by 24.0-fold after incorporation into ODSF. ODSF exhibited respective increases of 128% and 1010% in apparent permeability across a Caco-2 monolayer, compared to OP/DLM and OP. Furthermore, inhibition of bile acid transporters by actinomycin D and caveola-mediated uptake by brefeldin in Caco-2 cell monolayers reduced the apparent permeability values of ODSF by 58.4% and 51.1%, respectively, suggesting predominant roles for bile acid transporters and caveola-mediated transport in intestinal absorption of ODSF. In addition, macropinocytosis and paracellular and transcellular passive transport significantly influenced the intestinal permeation of ODSF. The oral bioavailabilities of ODSF in rats and monkeys were 68.2% and 277% higher, respectively, than the oral bioavailability of free OP. In vivo analyses of anticancer efficacy in CT26 and HCT116 cell-bearing mice treated with ODSF demonstrated significant suppression of tumor growth, with respective maximal tumor volume reductions of 7.77-fold and 4.07-fold, compared to controls.ConclusionODSF exhibits therapeutic potential, constituting an effective delivery system that increases oral bioavailability, with applications to metronomic chemotherapy.

Molecular recognizable ion-paired complex formation between diclofenac/indomethacin and famotidine/cimetidine regulates their aqueous solubility

This study focused on the physicochemical interactions between acidic and basic drugs in aqueous solutions. Their ion pair interactions were evaluated in an in vitro study. The model non-steroid anti-inflammatory drugs (NSAIDs), indomethacin (INM) and diclofenac (DIC), were used as acidic and hydrophobic drugs, whereas cimetidine (CIM), famotidine (FAM), and imidazole (IMD) were used as basic additives with heterocyclic moieties. The drug mixtures were evaluated by thermal analysis, dissolution test, nuclear magnetic resonance (NMR) spectroscopy, and mass spectroscopy. The fusion enthalpy of DIC-CIM, INM-CIM, and INM-arginine (ARG) sample was calculated based on melting temperature transformation. The DIC mixture with CIM, IMD, antipyrine (ANT), and ARG showed enhanced solubility, whereas the DIC-FAM mixture sample showed a decreased solubility. Electrospray ionization mass spectroscopy was carried out to detect binary mixtures. The interactions in DIC-FAM mixture sample were found between the carboxyl group of DIC and the amine groups of FAM by NMR. These findings were suggested that DIC-FAM mixture samples construct ion pair complexes based on the theory of Bjerrum. Moreover, the acid model drug and basic model drug also can be constructed 1:1 complexes that affects their solubility in the solvent of water type.

Comparative studies of the effects of novel excipients amino acids with cyclodextrins on enhancement of dissolution and oral bioavailability of the non-ionizable drug carbamazepine

Despite significant innovations in pharmaceutical industries, low water solubility is still a common biopharmaceutics-related problem that encounters 40% of marketed pharmaceutical products and results in erratic oral absorption and low bioavailability. Poorly soluble non-ionizable drugs pose additional challenges for enhancing solubility of this class of drugs. The effects of small molecular weight carriers such as amino acids (glycine, L-threonine; L-lysine and aspartic acid) on solubilization and enhancing bioavailability of Carbamazepine (Car) were investigated and compared to the more known excipients cyclodextrins (β-CD, HPβ-CD and γ-CD). Drug-carrier PM and Coppt in 1:1 molar ratio were prepared; characterized for docking, solubility, DSC, FTIR, XRD and dissolution rate; and evaluated for their oral bioavailability. Molecular docking calculations, spectral and thermal analysis confirmed Car-Amino acids ion pair complexes and Car-CDs inclusion complexes. While dissolution rate enhancement factors recorded for both CDs and amino acids were up to 12-times; additional permeation enhancing mechanism could explain superior relative bioavailability by approximately 170% for Car: Amino acid complexes and 166% for Car: CDs compared with Car alone. This study warrants the use of amino acids as a promising small molecular weight and versatile water-soluble carrier for enhancing solubility/permeability and bioavailability for this non-ionizable drug. This might endow the formulator flexibility in the design and dosage form with less bulky economic and more patient friendly solid platform for those epileptic patients and/or elderly patients that can experience difficulty in swallowing and need rapid onset of action.

DFT Study of Si/Al Ratio and Confinement Effects on the Energetics and Vibrational Properties of some Aza-Aromatic Molecules Adsorbed on H-ZSM-5 Zeolite

The Si/Al ratio and confinement effects of zeolite framework on energetics and vibrational frequencies of pyridine and 4,4′-bipyridine adsorbed on Brønsted acid sites in the straight channel of H-ZSM-5 are investigated by DFT calculations at the B3LYP and M06-2X+D3 levels. The straight channel of H-ZSM-5 is simulated by a cluster of 32 tetrahedral centers covering the intersection between straight and zigzag channels. Pyridine and 4,4′-bipyridine adsorption at two different sites in the intersection (open region) and/or in the narrow region situated between two intersections (closed region) is studied. For two Si/Al ratios (31, 15), the ion pair complexes formed by proton transfer upon pyridine and 4,4′-bipyridine adsorption in the open region and for the first time in the closed region are characterized. Our results indicate: (i) the stability for all adsorption complexes is essentially governed by the dispersive van der Waals interactions and the open region is energetically more favorable than the closed region owing to the predominance of the dispersive interactions over the steric constraints exerted by the confinement effects; (ii) as the Al centers are sufficiently spaced apart, Si/Al ratio does not influence pyridine adsorption energy, but significantly affects the adsorption energies and the relative stability of 4,4′-bipyridine complexes; (iii) neither Si/Al ratio nor confinement significantly influence pyridine and 4,4′-bipyridine vibrational frequencies within their complexes.

Selective Phase Transfer Reagents (OxP-crowns) for Chromogenic Detection of Nitrates Especially Ammonium Nitrate.

Nitrogen and phosphorus-containing ions such as ammonium, nitrates and phosphates are anthropogenic pollutants while ammonium nitrate may be diverted for nefarious purposes in improvised explosive devices. Crown ether-oxoporphyrinogen conjugates (OxP-crowns) are used to selectively detect nitrates, especially their ion pairs with K+ and NH4 + , based on ion pair complexation of OxP-crowns under phase transfer conditions. The presence of phosphate and carbonate lead to deprotonation of OxP-crowns. OxP-1N18C6 is capable of extracting ion pairs with nitrate from aqueous phase leading to a selective chromogenic response. Deprotonation of the OxP moiety leads to [OxP- ]-1N18C6[K+ ] and is promoted by crown ether selective cation binding coupled with hydration of basic oxoanions, which are constrained to remain in the aqueous phase. This work illustrates the utility of molecular design to exploit partitioning and ion hydration effects establishing the selectivity of the chromogenic response.

Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?

It is found by experiment that the cationic halogen bond donors (cationic iodoimidazolium compounds) can activate the Ritter-type solvolysis of benzhydryl bromide, while the cationic hydrogen bond donors (cationic imidazolium compounds) could not. To understand the activation mechanism, various noncovalent interactions between benzhydryl bromide and a series of activators in solution, including halogen bond, hydrogen bond, lone pair···π/π+, and C–H···π/π+, were explored theoretically. Our study revealed that the activation difference can be contributed by the variation of the noncovalent interactions. For halogen bond donors, the successful activation is attributed by halogen bond and lone pair···π. The halogen bonds mainly provide the stabilization energy of the ion-pair complex with the help of lone pair···π. For hydrogen-bond donors, the contribution of the hydrogen bond is unable to compensate the like-charge repulsion arising from the generation of the carbocation, leading to the unsuccessful activation. In general, lone pair···π makes a difference.

Sensitive spectrophotometric determination of vardenafil HCl in pure and dosage forms

The present work aims to develop and validate a simple, rapid, cost-effective, sensitive and extractive spectrophotometric methods for the determination of phosphodiesterase type 5-inhibitor; vardenafil HCl (VARD) in pure and in dosage forms. The developed methods are based on the formation of ion-pair complexes between vardenafil HCl and dyes, namely, bromocresol green (BCG), bromocresol purple (BCP), bromophenol blue (BPB), bromothymol blue (BTB) and eriochrom black T (EBT) in acidic buffer solutions. Different factors affecting the reactions between VARD and the dyes were studied and optimized. The formed complexes were extracted with methylene chloride and measured at 418, 410, 415, 417 and 520nm using BCG, BCP, BPB, BTB and EBT, respectively. The beer's law was obeyed in the ranges 1.0-10, 1.0-16, 0.5-8.0, 2.0-20 and 1.0-14μgmL-1 for BCG, BCP, BPB, BTB and EBT, respectively under the optimum conditions. The composition of the ion-pairs was found 1:1. The molar absorptivity's, Sandell's sensitivity, limits of detection and the limits of quantification were calculated. Other method validation parameters, such as accuracy, intra-day and inter-day precision, robustness, ruggedness and selectivity, have been evaluated. The proposed methods have been applied successfully for the analysis of vardenafil HCl in pure and dosage forms. The reliability of the methods was further ascertained by performing recovery studies using the standard addition method. Statistical comparison of the results with the reported method was performed by applying student's t- and F-tests and no significant statistical differences were obtained.

Development and validation of spectrophotometric methods for the sensitive and selective determination of lamotrigine in pharmaceuticals using bromocresol purple

Three simple, selective and sensitive methods have been developed and validated for the determination of lamotrigine (LMT) in pure drug and in tablets. The first method (method A) is based on the formation of ion-pair complex between LMT and the dye, bromocresol purple (BCP) at pH 2.40±0.01 which was extracted into dichloromethane (DCM) and the absorbance of yellow ion-pair complex was measured at 410 nm. In the second and third methods (method B and method C), the drug-dye ion-pair was dissolved either in ethanol and the resulting acid form of the dye was measured at 410 nm or in ethanolic potassium hydroxide and the resulting base form of the dye was measured at 600 nm. Under the optimized conditions, Beer's law was obeyed over 2.0-20.0 μg/mL, 150-1500 ng/mL and 50-600 ng/mL for method A, method B and method C, respectively, and the corresponding molar absorptivity values were 1.018×104, 1.43×105 and 4.21×105 L/mol/cm. The Sandell sensitivity values of 0.0252, 0.0018 and 0.0006 μg/cm2 for method A, method B and method C, respectively, and the corresponding values for limits of detection and quantification were also reported for all three methods. The molar ratio of the formed ion-pair complex was found to be 1: 1 as deduced by Job's method for method A, and the calculated stability constant was also reported. Over the linear ranges applicable, the accuracy and precision of the methods were evaluated on intra-day and inter-day basis; the reported mean accuracy values are 99.50±1.09%, 99.99±1.11% and 100.72±0.62% for method A, method B, and method C, respectively; the relative error (RE) was ≤ 2.57% and the relative standard deviation (RSD) was ≤ 2.01%. Application of the proposed methods to bulk powder and commercial pharmaceutical tablets are also presented.

Spectrophotometric and atomic absorption spectrometric determination of cephalexin and cephradine in dosage forms

This paper describes two simple, sensitive and selective spectrophotometric and atomic absorption spectrometric (AAS) procedures for the determination of two compounds of cephalosporins (Cephalexin monohydrate and Cephradine). These procedures are based on the formation of ion-pair complexes between the drugs and ammonium reineckate. The formed precipitates are quantitatively determined either spectrophotometrically or by AAS procedures. The methods consist of reacting drugs with Reinecke's salt in an acidic medium at a temperature of 25 ± 2°C. The spectrophotometric procedure (procedure I) is based on dissolving the formed precipitate with acetone. The volume was completed quantitatively and absorbance of the solution was measured at 525 nm against blank. Also, the AAS procedures (procedure II) are quantitatively determined directly or indirectly through the chromium precipitate formed or the residual unreacted chromium in the filtrate at 358.6 nm. The optimum conditions for precipitation have been carefully studied. Beer's law is observed for the studied drugs in the ranges 0.1-1.5 mg mL-1 or 5-70 μg mL-1 using spectrophotometric or AAS methods, with correlation coefficients ≥ 0.9965, respectively. Both procedures I and II were accurate and precise when applied to the analysis of the cited cephalosporins in different dosage forms with good recovery percent ranged from 98.90 ± 0.94 to 100.15 ± 0.97 without interference from additives.

Extractive spectrophotometric determination of anti-inflammatory drug nimesulide in pharmaceutical formulations and human plasma

The goal of the present work is to develop simple, rapid, and sensitive extractive spectrophotometric methods for the assay of nimesulide in pharmaceutical formulations and human plasma. The methods depend on the formation of colored ion-pair complexes between nimesulide and five different reagents, bromocresol green (BCG), bromocresol purple (BCP), bromothymol blue (BTB), brilliant blue G (BBG) and methyl orange (MO) in Britton-Robinson buffer solutions of pH 2.0-3.5. The colored products were extracted in chloroform and absorbance measured at 412, 410, 407, 502 and 482 nm, respectively. The analytical parameters and their effects on the reported systems were investigated. The extracts are intensely colored and very stable at room temperature. The calibration graphs were linear over the concentration range of 2-18 μg/mL for BCG, BTB and BBG, 2-16 μg/mL for BCP and 2-14 μg/mL for MO. The stoichiometry of the reaction was found to be 1 : 1 in all cases and the conditional stability constant (K f) of the complexes were calculated. The proposed methods were successfully extended to pharmaceutical preparations in tablet form. Excipients used as additives in commercial formulations did not interfere with the analysis. The proposed methods can be recommended for quality control and routine analysis where time, cost effectiveness and high specificity of the analytical technique are of great importance.

Simple and sensitive spectrophotometric determination of olanzapine in pharmaceutical formulations using two sulphonphthalein acid dyes

Two simple, sensitive and extraction-free spectrophotometric methods have been developed for the determination of olanzapine (OLP) both in pure form and in pharmaceutical formulations. The methods are based on the formation of yellow coloured ion-pair complexes between OLP and two sulphonphthalein acid dyes, bromocresol purple (BCP) and bromothymol blue (BTB) with absorption maximum at 405 nm and 410 nm for BCP and BTB, respectively. The stoichiometry of the complex in either case was found to be 1: 1 and the conditional stability constant (KF) of the complexes has also been calculated. Reaction conditions were optimized to obtain the maximum colour intensity. Beer's law was obeyed in the concentration ranges of 1.0-10.0 and 1.0-8.0 μg/mL with BCP and BTB, respectively. Various analytical parameters have been evaluated and the results have been validated by statistical data. The proposed methods have been applied successfully to the analysis of OLP in pure form and in its dosage forms and no interference was observed from common excipients present in pharmaceutical formulations.

Extractive spectrophotometric determination of cetirizine dihydrochloride in pure and pharmaceutical preparations

A simple and sensitive extractive spectrophotometric method has been described for the assay of cetirizine dihydrochloride in pure and different pharmaceutical preparations. The method was based on the formation of the ion-pair complex from the reaction between cetirizine dihydrochloride and methyl orange in pH 4.0, which gave a yellow color after chloroform extraction and exhibited a maximum absorbance at 424.5 nm. Beer's law was obeyed in the concentration range of 2.5-20 μg/mL. The method was tested and validated for various parameters according to ICH guidelines. The detection and quantification limits were 1.0 and 3.0 μg/mL, respectively. The proposed method was successfully applied for the determination of cetirizine dihydrochloride in pharmaceutical preparations. The results demonstrated that the procedure was accurate, precise and reproducible while statistical analysis of the obtained results showed no significant difference between the proposed method and reference method. No interference was observed for common pharmaceutical preparations.

Novel Potentiometric Screen-printed Carbon Electrodes for Bisphenol S Detection in Commercial Plastic Samples.

Novel miniaturized poly(vinyl chloride) matrix membrane sensors based on screen-printed carbon electrodes and responsive to bisphenol S (BPS) were formulated. Polymeric membranes are based on an ion-pair complex of BPS anion with an Aliquat 336S counter cation. A solid conductive contact of multi-walled carbon nanotubes (MWCNTs) was used on screen-printed carbon platforms. After drop-casting and drying of the MWCNTs on a carbonaceous substrate, it was coated with a layer of polymeric poly(vinyl chloride) PVC sensing membrane containing the recognition complex. Prepared electrodes revealed a near-Nernstian response towards BPS with a -28.2 ± 0.8 mV/decade anionic slope, 0.02 μg/mL detection limit and 2.5 × 10-7 - 1.0 × 10-3 M concentration range (r2 = -0.9994). Signals were recorded in a 30 mM HCO3-/CO32- buffer, pH 10, with fast response times <10 s. A suggested sensing system was effectively applied in the quantitative determination of diminished BPS levels released from plastic bottle samples, and obtained results were statistically assessed against a chromatographic HPLC independent reference method.

The second-order NLO property of a photoswitchable heteroditpioc ion-pair receptor based on 2-pyridyl acylhydrazone linking with 2,6-pyridine bisamide: The impacts of metal cations and anions

A photoswitchable heteroditpioc ion-pair receptor E-1 and its isomeride Z-1 (without the anion binding site), that are based on the 2-pyridyl acylhydrazone linking 2,6-pyridine bisamide, have brought our attention to systematically explore the second-order nonlinear optical (NLO) properties by the density functional theory (DFT). In this work, we mainly studied the influences of metal cations (M = Na+, K+, Mg2+, Ca2+, Hg2+ and Pb2+), anions (X = Cl−, Br− and I−) and ion-pair (NaCl, NaBr and NaI) on NLO responses for the receptor. In addition, the impacts of isomerization and poto-switching processes on NLO response for these systems also have been discussed detailedly. The results show that the isomerization process does not effectively adjust the NLO properties for our studied systems. But the poto-switching process that was triggered by light to capure or release ions plays an important role in improving the NLO properties. The receptors E-1 and Z-1 are excellent candidates to effectively detect metal cation Pb2+, because the first hyperpolarizability (βtot) values of E∗Pb2+ and Z∗Pb2+ increased by 13 times and 20 times relative to that of receptors E-1 (188.06 a.u.) and Z-1 (270.21 a.u.), respectively. In addition, the receptor E-1 has the possibility to detect anion I− due to the larger βtot values compared with other anion-complexes. However, the changes of NLO responses for ion-pair complexes are not obvious compared with corresponding anion-complexes. We are looking forward to the research would be beneficial for further theoretical and experimental studies on recognizing metal cations and anions based on large second-order NLO difference.