Solid-contact ion-selective electrodes for aromatic cations based on pi-coordinating soft carriers

Ion-selective electrodes (ISEs) based on pi-coordinating carriers were prepared and investigated as potentiometric sensors for aromatic cations, using N-methylpyridinium as a model aromatic cation. Derivatives of tetraphenylborate were studied as charged carriers in plasticized poly(vinyl chloride) membranes. Furthermore, neutral compounds containing pi-coordinating anthryl groups were studied as neutral carriers. Bis(2-ethylhexyl)sebacate (DOS) and 2-nitrophenyl octyl ether (o-NPOE) were used as non-polar and polar plasticizer, respectively. ISEs were constructed by using poly(3,4-ethylenedioxythiophene) (PEDOT) as solid-contact material. Conventional ISEs with internal filling solution were used for comparison. The potentiometric responses of the ISEs were investigated using N-methylpyridinium as primary ion. The results show that the selectivity of the ISEs is influenced significantly by both the plasticizer and the charged carriers, while the neutral carriers studied have only a minor influence on the selectivity. The role of cation-pi interactions between aromatic cations and the membrane components is discussed.     

Membrane drotaverine-selective electrodes based on tetraphenylborate derivatives: Electrochemical, adsorption, and transport properties and analytical application

The potentiometric response of ion-selective electrodes (ISEs) based on different lipophilic derivatives of tetraphenylborate to drotaverine hydrochloride was studied. The composition of a polymeric membrane was optimized to obtain the best electroanalytical properties of ISEs. The transport properties of selective membranes, the permeability and the flow of ions through the interface, were studied. Linear correlations between the solubility of ionophoric membrane components, membrane transport, and electroanalytical properties were revealed. The kinetic studies of ion-exchange adsorption showed that two limiting stages of transfer, namely, diffusion through the boundary layer and diffusion throug the membrane phase, occurred. Procedures for the potentiometric determination of drotaverine hydrochloride in pharmaceutical forms were proposed.     

Nonionic surfactant-selective electrode and its application for determination in real solutions

A liquid membrane nonionic surfactant sensitive electrode has been prepared, based on a new barium pseudocationic complex of a highly ethoxylated fatty alcohol polyglycol ether and tetraphenylborate as sensing material. The complex has been incorporated into the plasticized PVC-membrane and used as sensing material.The electrode exhibited positive linear non-Nernstian response toward different nonionic surfactants and sub-Nernstian response toward tetraphenylborate with the lower detection limit of 3.3 × 10⁻⁷ mol dm⁻³ in barium chloride solution.The interfering effect of some alkaline, alkaline earth, and heavy metal cations, has been demonstrated by displaying their calibration curves compared with that of Triton X-100.The electrode has been used as an end-point indicator for potentiometric titration of analytical and technical grade polyethoxylated nonionic surfactants, modelled detergent products, and commercial detergents.     

Determination of cationic surfactants in pharmaceutical disinfectants using a new sensitive potentiometric sensor

A new sensitive potentiometric surfactant sensor was prepared based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate antagonist ion. This sensor was used as a sensing material and incorporated into the plasticized PVC-membrane. The sensor responded fast and showed a Nernstian response for investigated surfactant cations: cetylpyridinium chloride (CPC), hexadecyltrimethylammonium bromide (CTAB) and Hyamine with slope 59.8, 58.6 and 56.8 mV/decade, respectively. The sensor served as an end-point detector in ion-pair surfactant potentiometric titrations using sodium tetraphenylborate as titrant. Several technical grade cationic surfactants and a few commercial disinfectant products were also titrated, and the results were compared with those obtained from a two-phase standard titration method. The sensor showed satisfactory analytical performances within a pH range of 2-11, and exhibited excellent selectivity performance for CPC compared to all of the organic and inorganic cations investigated. The influence of the nonionic surfactants on the shape of titration curves was negligible if the mass ratio of ethoxylated nonionic surfactants and cationic surfactants (EONS:CS) was not greater than 5.     

壬基酚聚氧乙烯醚二聚和三聚表面活性剂的合成及表面性质

合成了系列壬基酚聚氧乙烯醚二聚表面活性剂(DNP)和三聚表面活性剂(TNP), 用核磁共振、红外光谱和元素分析等手段对其结构进行了表征, 并用表面张力法和稳态荧光法对DNP和TNP的表面性能进行了研究. 结果表明, 随着氧乙烯(EO)单元数的增长, DNP和TNP的临界胶束浓度(cmc)值逐渐增大; DNP和TNP的cmc值较相应的单体壬基酚聚氧乙烯醚表面活性剂(NP)明显降低, 显示了较高的表面活性、吸附能力和润湿能力.     

Mercury(II) ion-selective electrodes based on heterocyclic systems

Mercury ion-selective electrodes (ISEs) were prepared with a polymeric membrane based on heterocyclic systems: 2-methylsulfanyl-4-(4-nitro-phenyl)-l-p-tolyl-1H-imidazole (I) and 2,4-diphenyl-l-p-tolyl-1H-imidazole (II) as the ionophores. Several ISEs were conditioned and tested for the selection of common ions. The electrodes based on these ionophores showed a good potentiometric response for Hg2+ ions over a wide concentration range of 5.0 x 10(5-) - 1.0 x 10(-1)M with near-Nernstian slopes. Stable potentiometric signals were obtained within a short time period of 20 s. The detection limits, the working pH range of the electrodes were 1.0 x 10(-5) M and 1.6-4.4 respectively. The electrodes showed better selectivity for Hg2+ ions over many of the alkali, alkaline-earth and heavy metal ions. Also sharp end points were obtained when these sensors were used as indicator electrodes for the potentiometric titration of Hg2+ ions with iodide ions.     

Potentiometric Determination of Non‐Ionic Surfactants by Liquid Membrane Electrodes

It is well known that non‐ionic surfactants (NIS) influence remarkably the potentiometric measurements with liquid membrane ion selective electrodes (ISEs), interfering particularly on performance of ISEs for earth‐alkali metals, for which the loss of selectivity with regard to alkali metals has been documented. These studies indicate that such interferences are due to the extraction of surfactants within the membrane, where a competition takes place between the originally present ionophore and the surfactant which also acts as a ligand for alkali metals. The interpretation of such phenomena enabled one to exploit this interference for analytical purposes by membrane/solution extraction experiment monitored by UV measurements and by impedance FRA analysis on coated wire electrodes. Using Ca/Mg ISEs based on the neutral ionophore ETH 4030, it has been established that the logarithm of the Ca/Mg over Na potentiometric selectivity constant is linearly correlated with the concentration of NIS like Tegopren 5863 and Triton X‐100. The proposed method has been applied for the development of a new potentiometric analytical procedure for the determination of Tegopren 5863 in synthetic seawater (SSW), ranging from 0.25 to 5 ppm. Our procedure consists in the exposure of the electrode to stirred SSW containing the surfactant; the progressive extraction of Tegopren 5863 causes a growth in electrode's sensitivity to Na⁺ and K⁺, losing selectivity for Ca²⁺ and Mg²⁺. In turn this induces an increase of EMF, as all these ions are present in the studied matrix. The potential drift was monitored for 15 hours, showing that the process reaches thermodynamic equilibrium after about 12 hours of exposure. This method presents a value of 210 ppb of Tegopren 5863 as detection limit.     

Determination of the leaching of polymeric ion-selective membrane components by stripping voltammetry

This paper focuses on the quantitative determination of the loss of the components from plastic membranes of ion-selective electrodes (ISEs) during contact with aqueous bathing solutions. The leaching processes, which affect the ISE responses, are rarely characterized by independent methods. For this purpose, differential pulse cathodic stripping voltammetry (DP CSV) is used. This method, owing to its high sensitivity, acceptable recovery and accuracy, is a good tool to characterize the kinetics of leakage of the lipophilic salts. Sodium tetraphenylborate (NaTPB) leakage from the PVC-based sodium-selective membrane containing two different plasticizers, o-nitrophenyl octyl ether (o-NPOE) or di(2-ethylhexyl) sebacate (DOS) is presented. Correlation between the rate of leaching of the lipophilic salt and dielectric constants of the plasticizers is observed. The data obtained by DP CSV correlate well with potentiometric and electrochemical impedance responses. The observed outflow of TPB⁻ is associated with decreasing potentiometric sensitivity to sodium and increasing bulk membrane resistance.     

Simultaneous potentiometric determination of cationic and ethoxylated nonionic surfactants in liquid cleaners and disinfectants

A sensitive potentiometric surfactant sensor based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate (TPB) antagonist ion was used as the end-point detector in ion-pair potentiometric surfactant titrations using sodium TPB as a titrant. Several analytical and technical grade cationic and ethoxylated nonionic surfactants (EONS) and mixtures of both were potentiometrically titrated.The sensor showed satisfactory analytical performances within a pH range of 3-10 and exhibited satisfactory selectivity for all CS and EONS investigated. Ionic strength did not influence the titration except at 0.1 M NaCl, in which a slight distortion of the second inflexion corresponded with the nonionic surfactant.Two-component combinations of four CS and three EONS were potentiometrically titrated using the sensor previously mentioned as the end-point detector. The quantities of the surfactants varied between 2 and 6 μmol for CS and 2.50 and 7.50 μmol for EONS. The known addition methodology was used for determination of the surfactant with considerably lower concentration in the mixture.Three commercial products containing cationic surfactants as disinfectants and nonionic surfactants were potentiometrically titrated, and the results for both type of surfactants were compared with those obtained with standard conventional methods.     

Solubility of Nonsteroidal Anti-inflammatory Drugs (NSAIDs) in Aqueous Solutions of Non-ionic Surfactants

The solubilities of two nonsteroidal anti-inflammatory (MELOXICAM and CELECOXIB) drugs, were determined in aqueous solutions of nonionic (Tween 20, Tween 80, Brij 30, Brij 35, Triton X 100, Triton X 114) surfactants. These surfactants have different numbers of oxyethylene units and their micelles showed different aggregation numbers. It is shown that these surfactants have different abilities to solubilize NSAIDs drugs. The solubilities of the drugs increased linearly with the increase in concentration of surfactants. The sizes of micelles remained constant with the addition of the drugs, except for Triton type surfactants in which case the size of the micelles decreased. It was observed that the number of oxyethylene units in the surfactants, aggregation number of the micelles and HLB play key roles in solubilizing the drugs.     

Ionic liquid based on a quaternary phosphonium cation as a plasticizer and an electrode-active component of ion-selective electrode membranes

The dodecylethyldiphenylphosphonium bis(trifluoromethylsulfonyl)imide ionic liquid (IL) can behave as both a plasticizer and an electrode-active component in the membranes of ion-selective electrodes (ISEs). A stable potentiometric response to cationic surfactants is observed. The slope of the electrode function is close to the Nernstian value for cetylpyridinium (CP) bromide and cetyltrimethylammonium (CTMA) bromide; the detection limits are (5.0 ± 1.0) × 10^?6 and (1.3 ± 0.3) × 10^?5 mol/l, respectively. The membrane potential does not depend on pH in the range from 3 to 11. The possibility of determining the critical micelle concentration (CMC) with the ISEs is demonstrated.     

Selective synthesis of single-crystalline selenium nanobelts and nanowires in micellar solutions of nonionic surfactants

Single-crystalline nanobelts and nanowires of trigonal selenium (t-Se) have been selectively synthesized in micellar solutions of nonionic surfactants. In particular, t-Se nanobelts about 30 nm in thickness were obtained in micellar solutions of poly(oxyethylene(20)) octadecyl ether (C18EO20), whereas t-Se nanowires were obtained in micellar solutions of poly(oxyethylene(10)) dodecyl ether (C12EO10). The obtained t-Se nanobelts exhibit a low-energy absorption peak that is considerably red shifted from that for t-Se nanowires, which has been presumably attributed to the lower degree of crystal perfection for the t-Se nanobelts with rectangular cross sections.     

Potentiometric ion-selective electrodes for determination of cyclopentolate hydrochloride and phenylephrine hydrochloride in their challenging ophthalmic formulation

Introduction of potentiometric ion-selective electrodes (ISEs) opened a new bright area in pharmaceutical analysis acknowledged as being an eco-friendly, simple, and energy-saving technique that is well-suited with microfabrication. In this contribution, potentiometric ISEs were employed as an alternative green analytical tool with the crucial goal of expanding the effective application of the potentiometric sensors in different disciplines of drug-stability studies and quality-control investigations. Four novel cyclopentolate hydrochloride and phenylephrine hydrochloride selective membrane sensors were constructed and evaluated. Sensors’ fabrication was achieved using potassium tetrakis (4-chlorophenyl) borate, a cationic exchanger, in a polyvinyl chloride polymeric matrix plasticized with 2-nitrophenyl octyl ether and using 2-hydroxy propyl-β-cyclodextrin as an ionophore. A comparative potentiometric study was implemented using two designs of ISEs; a conventional liquid inner contact and a glassy carbon solid-contact one. Using solid-contact ISEs, detection limit was substantially decreased and the discriminative ability in the presence of the most interfering substances was enhanced. This permits simultaneous estimation of both drugs, in spite of their similar ionic characteristics, abolishing the need for any pretreatment or separation steps in their challenging combined ophthalmic formulation as well as in rabbit aqueous humor and in the presence of their degradation products.     

Oleate Ester-Derived Nonionic Surfactants: Synthesis and Cloud Point Behavior Studies

The synthesis and cloud point behavior of high oleate ester-derived nonionic surfactants are now reported. The effect of various polyethoxylate chain lengths (polyethylene glycol with 7, 11, and 16 units of ethylene oxide (EO) monomer) as the surfactant's hydrophilic head on the cloud point was investigated. The effect of varying amounts of sodium chloride and five different ionic surfactants on the cloud points of the synthesized nonionic surfactants were also presented. When the chain length of polyethoxylate increased, the cloud point of the synthesized nonionic surfactant also increased, ranging from 16°C, 43°C, and 64°C for 7, 11, and 16 EO units, respectively. Increments in sodium chloride concentration depressed the cloud point values of the synthesized nonionic surfactants linearly. The addition of ionic surfactants elevated the cloud points of the synthesized nonionic surfactant. However, in the presence of sodium chloride, the cloud point of the mixed ionic-nonionic solution was suppressed and anincrease in ionic surfactant concentration was required to elevate the cloud point. It was also found that the cloud points of synthesized surfactants can be raised up to 95°C in the presence of 4wt% NaCl solution.     

Plasma-polymerized membrane electrode for the determination of dextromethorphan and dimemorfan

Ion-selective electrodes (ISEs) responsive to the antitussives dextromethorphan and dimemorfan were constructed by the fixation of an ion-exchanger, ammonium tetraphenylborate, on a Millipore membrane by means of a plasma-polymerization technique. The electrodes showed a Nernstian response over the range of 10(-5)-10(-2) M dextromethorphan and dimemorphan, and the working pH range was 5-7. The interference from common cations such as Na+, K+ and Ca2+ was negligible but some organic cations interfered weakly. The electrodes were applied successfully for the determination of the drugs in pharmaceutical preparations.     

Oligocarbazoles as ligands for lead-selective liquid membrane electrodes.

Oligocarbazoles have been applied as new ionophores in liquid membrane electrodes (ISEs) destined for lead(II) determination in water samples. The oligocarbazole-containing ISEs demonstrated a close-to-Nernstian potentiometric response towards Pb2+ in the activity range 10(-7)-10(-2) M. The selectivity coefficients measured by the matched potential method (MPM) confirmed their good selectivity against common interfering mono- and doubly charged cations. The oligocarbazole-containing ISEs do not respond towards protons. Their applicability has been checked by performing the recovery test while using a sample of wastewater.     

Electroanalytical properties of membranes based on metal-polyethoxylate-tetraphenylborate compounds

Cationic functions of selective electrodes based on tetraphenylborate salts of polyethoxylate complexes of Pb(II), Ba(II), Ca(II), Cd(II), and Zn(II) (M-PEO-TPB) are studied in solutions of these metal cations and polyethoxylates. It is shown that the linearity range of the electrode response, detection limit, and the slope of the electrode function are governed by the stoichiometry of reaction, stability, and solubility of complex [M-PEO]²⁺ cations in water. Lead-selective electrodes based on a Pb(II)-PEO-TPB compound exhibit the best parameters. The behavior of these electrodes in polyethoxylate solutions is studied and their performance characteristics (response time, potential drift, service life) are determined.     

MICELLE FORMATION IN MIXTURES OF ANIONIC AND NONIONIC SURFACTANTS

The critical micelle concentration of mixtures of anionic and nonionic surfactants was measured. The anionic surfactants were alkylbenzene sulfonates and the nonionic surfactants were polyoxyethylene nonylphenols and a polyoxy-ethylene alcohol. The effect of added electrolyte, the number of ethylene oxide units in the polyethoxylate, and the anionic alkyl chain length were studied. All systems showed substantial negative deviations (lower CMC) from ideal solution theory. The results can be represented by regular solution theory. Charge separation appears to be the source of the nonideality. This considers the reduction of electrostatic repulsion between the ionic surfactant head groups in the mixed micelle, due to the insertion of nonionic hydrophilic groups between these charged groups, to be the cause of enhanced micelle formation. The physical basis of regular solution theory was shown to be consistent with the charge separation effect.     

Recent advances on potentiometric membrane sensors for pharmaceutical analysis

Prime concerns with modern developments are attributed to high level undetected but important biological substances or even toxicants cycled often among individual and populations; which in turn agonizes environmental monitoring, trace-gas detection, water treatment facilities, in vivo detection in biological fluids and other accomplishments. For the detection of such analytes, several analytical devices combined with biological component have been designed with a physiochemical detector component. Here, we essentially focus on drug-based potentiometric membrane sensors known as ion selective electrodes (ISEs). The functionality of ion-selective membrane is quite intricate, challenging, and our understanding is yet to be thrived with more interventions. ISEs have applied explications to enormous variety of analytical inquires as well as informative tools for probing host-guest chemistry. However, expansion of ISEs based applications is aimed to improve the system performance, acquiring enhanced understanding of their response mechanism, and finding new chemical or physical configurations mainly for human welfare. The major strength of ISEs is the precised analytical information, assured by using the ion-selective membrane electrodes used successfully for both in vitro and in vivo assays of pharmaceutical products as well as in clinical analyses. In this review, we attempt to provide a brief prologue to the applicability and advantages of potentiometric sensors in the analysis of pharmaceutically active compounds emphasizing their employment at molecular level for in situ selection of biologically important analytes.     

Structure and composition of cationic-nonionic surfactant mixed adsorbed layers on mica

The composition and morphology of mixed adsorbed layers comprising one of several poly(oxyethylene) alkyl ether nonionic surfactants, C(i)E(j), and two cationic surfactants-dodecyltrimethylammonium bromide (DTAB) and tetradecyltriethylammonium bromide (TTeAB)-at the mica/solution interface have been studied using depletion adsorption and atomic force microscopy. The nonionic surfactants do not themselves adsorb onto mica, but can coadsorb with a cationic surfactant. The extent of their hydrophobic association with the adsorbed cationic surfactant depends on alkyl chain length, while the adsorbed layer morphologies are sensitive to the number of ethoxy groups. Nonionic surfactants with headgroups containing less than eight ethylene oxide units decrease the adsorbed aggregate curvature, gradually transforming globular TTeAB or cylindrical DTAB adsorbed aggregates into a rod, mesh, or bilayer structure. Those with larger headgroups favor globular aggregates. The mechanism by which the nonionic surfactant modifies the adsorbed morphology is the formation of defects in the form of cylinder end-caps or branch-points, leading to adsorbed layer compositions that differ from ideal mixing predictions. All mixed adsorbed films become saturated with the nonionic component when the capacity of the aqueous side of the adsorbed layer is reached.