A tunable mixture solvent for poly(?-caprolactone): Acetone + CO2

We report on a tunable, versatile solvent system for poly(?-caprolactone) (PCL). It is shown that acetone + carbon dioxide mixtures are efficient solvents for this biodegradable polymer. Phase behavior and volumetric properties of PCL + acetone + CO₂ mixtures were determined in a variable-volume view cell. Effect of temperature (323-398 K), pressure (0.1-50 MPa), polymer concentration (1-20 wt%), polymer molecular weight (14k and 65k) and carbon dioxide concentration (0-60 wt%) on the liquid-liquid (L-L) phase boundaries and the densities was explored. Complete miscibility of mixtures with polymer concentrations up to 20 wt% could be achieved in the fluid mixtures containing up to 50 wt% carbon dioxide at modest pressures (5-40 MPa). The solutions all showed LCST-type phase behavior. Comparisons with literature data on the miscibility pressures in other solvent mixtures such as dimethyl ether + carbon dioxide or chlorodifluoromethane + carbon dioxide show that complete miscibilities of PCL in acetone + carbon dioxide mixtures are achievable at much lower pressures.The mixture densities were in the range 0.58-1.20 g/cm³. Mixtures with carbon dioxide content more than 20 wt% showed higher sensitivity and larger change in density with pressure. Densities of the polymer solutions were found to increase significantly with PCL concentration. The densities of solutions with different polymer molecular weights were close to each other, with the lower molecular weight polymer samples showing slightly higher densities.A unique contribution of the present paper is the comparison of compressibility and expansivity of the solutions with the corresponding properties of the solvents. Analysis of the data shows that the compressibilities of PCL solutions are lower than that of the acetone + carbon dioxide solvent mixture at temperatures lower than 373 K. At around 373 K, compressibilities become equal to each other and a switchover is observed at higher temperatures. The difference in the isothermal compressibility of the polymer solution and the solvent decreases with pressure, but reaches a plateau value for pressures greater than 25 MPa. Compared to their solvent mixture, the polymer solutions display a higher isobaric expansivity at the same pressure.     

Polyaniline Langmuir-Blodgett film modified glassy carbon electrode as a voltammetric sensor for determination of Ag ions

A highly sensitive electrochemical sensor made of a glassy carbon electrode (GCE) coated with a Langmuir-Blodgett film (LB) containing polyaniline (PAn) doped with p-toluenesulfonic acid (PTSA) (LB/PAn-PTSA/GCE) has been used for the detection of trace concentrations of Ag⁺. UV-vis absorption spectra indicated that the PAn was doped by PTSA. The surface morphology of the PAn LB film was characterized by atomic force microscopy (AFM). The electrochemical properties of this LB/PAn-PTSA/GCE were studied using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The LB/PAn-PTSA/GCE was used as a voltammetric sensor for determination of trace Ag⁺ at pH 5.0 using linear scanning stripping voltammetry. Under the optimal experimental conditions, the stripping current was proportional to the Ag⁺ concentration over the range from 6.0 × 10⁻¹⁰ mol L⁻¹ to 1.0 × 10⁻⁶ mol L⁻¹, with a detection limit of 4.0 × 10⁻¹⁰ mol L⁻¹. The high sensitivity, selectivity, and stability of this LB/PAn-PTSA/GCE also demonstrated its practical utility for simple, rapid and economical determination of Ag⁺ in water samples.     

Study on the reaction pathway in the vapor-phase hydrogenation of biomass-derived diethyl succinate over CuO/ZnO catalyst

The reactivity of biomass-derived diethyl succinate and its main reaction intermediates was separately investigated in a fixed-bed reactor over CuO/ZnO catalyst, and some interesting results were obtained. Ethyl 4-hydroxybutyl succinate as an intermediate of diethyl succinate hydrogenation reaction was first detected, and it could be converted to 1,4-butanediol or polyesters. Additionally, propanol and butanol are mainly derived from 1,4-butanediol rather than gamma-butyrolactone. A comprehensive reaction pathway for the hydrogenation of diethyl succinate is proposed, which is significant for the design of new catalytic formulations. A CuO/ZnO + HY admixed catalyst exhibiting excellent performance was prepared according to the proposed reaction pathway.     

The electrochemical redox processes in PMMA gel electrolytes—behaviour of transition metal complexes

Electrochemical properties of polymer gel electrolytes based on polymethylmethacrylate (PMMA) were studied by cyclic voltammetry and impedance spectroscopy using new solid-state PMMA-Cd-Cd²⁺ reference electrode. The suitable potential window of the PC-PMMA system was estimated from -0.2 to + 1.5 V versus Cd-Cd²⁺. New polymer gels containing ferrocene-ferricinium (Fc-Fc⁺) couple and other transition metal complexes were prepared by the direct polymerisation of methylmethacrylate (MMA) monomer and the solution of metal complex and supporting electrolyte in anhydrous aprotic solvent—propylene carbonate (PC). The half-wave potentials and apparent diffusion coefficients of used complexes and their dependence on the composition of the system (liquid or gel) were estimated. Time dependent electrochemical measurements showed almost three order decrease of the diffusion coefficients of ferrocene (Fc) and ferricinium (Fc⁺) cation from 6 × 10⁻⁵ to 2 × 10⁻⁹ cm² s⁻¹ during the polymerisation from the liquid to the polymer state. The results show that the PC-PMMA gel electrolyte can be described as a system of embedded solvent in the polymer network of PMMA without present monomer.     

Vapor-liquid equilibrium of polymer + solvent systems: Experimental data and thermodynamic modeling

In this work, experimental vapor-liquid equilibrium (VLE) data for binary systems polymer + solvent were obtained using a gravimetric sorption apparatus. The studied systems were benzene + polystyrene, hexane + polystyrene, benzene + poly(methyl methacrylate), benzene + poly(ethyl methacrylate), hexane + poly(vinyl chlorate) and water + poly(vinyl chlorate), in the range of 30-40 °C.The experimental data were modeled with two group contribution models for the activity coefficient, Elbro-FV and UNIFAC-Zhong; the latter method considers the free-volume of molecules of high molecular weight, such as polymers. UNIFAC groups in the literature as well as new groups that were proposed for the monomers were used. The necessary energy interaction parameters between these groups were estimated. There were observed mean deviations between experimental and calculated mass fractions of about 8.5% with Elbro-FV, and about 17% with UNIFAC-Zhong when original groups were used, while there were observed mean deviations of about 7% with Elbro-FV and about 16% with UNIFAC-Zhong when new groups were used. The Elbro-FV model represents the experimental data with better precision in both cases; on the other hand, the data were better correlated with both models when new groups were used.     

Photopolymerization behavior and properties of highly branched poly(thioether-urethane) acrylates used for UV-curing coatings

The highly branched poly(thioether-urethane) acrylate (BPTUA) was synthesized through an “oligomeric A₂ + B₃” approach. The thiol-endcapped difunctional oligomeric A₂ was obtained by the addition reactions of isophorone diisocyanate with 1,4-butanediol, and then further with 1,4-butanediol bis(thioglycolate). Trimethylolpropane triacrylate was used as a B₃ monomer. The addition conduct of 1,6-hexanediol diacrylate with 1,4-butanediol bis(thioglycolate) was introduced into the polymeric chain for preparing the modified BPTUA (m-BPTUA). The molecular structures were characterized with FT-IR and ¹H NMR spectroscopy, and GPC analysis. The number average molecular weights (M_ns) of BPTUA and m-BPTUA were experimentally measured to be 13,500 g mol⁻¹ and 17,900 g mol⁻¹ with the polydispersity indices of 1.86 and 1.94, respectively. A series of UV-curable resins were fabricated based on bisphenol-A epoxy diacrylate (EB600) and tripropylene glycol diacrylate with the addition of either BPTUA or m-BPTUA in different ratios, and exposed to a UV lamp for obtaining the cured films in the presence of 1-hydroxycyclohexylphenyl ketone as a photoinitiator. From the photo-DSC measurements, the polymerization rate at the peak maximum decreased, whereas the final unsaturation conversion in cured film increased, along with the increase of either BPTUA or m-BPTUA. The elastic modulus in the rubbery plateau and the glass transition temperature from DMTA, as well the tensile strength and Young's Modulus of UV-cured film decreased with increasing either BPTUA or m-BPTUA loading, whereas the elongation at break, flexibility and strike performance were greatly enhanced. Moreover, for the m-BPTUA series, the enhancive effects on the properties were much more obviously than the BPTUA series. The water swelling test and thermogravimetric analysis indicated that the water absorption resistance and the oxidative stability of cured films were improved by the incorporation of thioether linkage into the crosslink networks.     

High lithium conductivities in weakly-ionophilic low-dimensional block copolymer electrolytes

The structure of amphiphilic low-dimensional copolymer electrolytes I of similar overall composition but prepared by different synthetic procedures X and Y are described. I are copolymers of poly[2,5,8,11,14-pentaoxapentadecamethylene(5-alkyloxy-1,3-phenylene)] (CmO5) and poly[2,-oxatrimethylene(5-alkyloxy-1,3-phenylene)] (CmO1) where the alkyl side chains having m carbons are hexadecyl or mixed dodecyl/octadecyl (50/50). ¹H NMR shows that the copolymers have 50% (m = 16) or only 18 and 13% of CmO5 units and DSC indicates that the copolymers have ‘block’ sequencing of CmO1 and CmO5 segments. Molecular dynamics modelling indicates that in CmO5 Li⁺ and BF₄⁻ ions are separated by Li⁺ encapsulation in tetraethoxy segments but in ionophobic CmO1 units the salt is mostly present as neutral aggregates decoupled from the polymer. Conductivities of these microphase-separated mixtures with salt-bridge amphiphilic polyethers II and III of each system are similar. They have low temperature dependence over the range 20 °C to 110 °C at ∼10⁻³ S cm⁻¹. ⁷Li NMR linewidth measurements confirm high lithium mobilities at −20 °C. A conduction mechanism is proposed whereby Li⁺ hopping takes place along rows of decoupled aggregates (dimers/quadrupoles) within an essentially block copolymer structure. Subambient measurements to −10 °C gave a conductivity of 4 × 10⁻⁵ S cm⁻¹.     

Modified carbon nanoparticle-chitosan film electrodes: Physisorption versus chemisorption

Surface functionalised carbon nanoparticles of ca. 8 nm diameter co-assemble with chitosan into stable thin film electrodes at glassy carbon surfaces. Robust electrodes for application in sensing or electrocatalysis are obtained in a simple solvent evaporation process. The ratio of chitosan binder backbone to carbon nanoparticle conductor determines the properties of the resulting films. Chitosan (a poly-d-glucosamine) has a dual effect (i) as the binder for the mesoporous carbon composite structure and (ii) as binding site for redox active probes. Physisorption due to the positively charged ammonium group (pK_A ≈ 6.5) occurs, for example, with anionic indigo carmine (a reversible 2e⁻-2H⁺ reduction system in aqueous media). Chemisorption at the amine functionalities is demonstrated with 2-bromo-methyl-anthraquinone in acetonitrile (resulting in a reversible 2e⁻-2H⁺ anthraquinone reduction system in aqueous media). Redox processes within the carbon nanoparticle-chitosan films are studied and at sufficiently high scan rates diffusion of protons (buffer concentration depended) is shown to be rate limiting. The chemisorption process provides a much more stable interfacial redox system with a characteristic and stable pH response over a pH 2-12 range. Chemisorption and physisorption can be employed simultaneously in a complementary binding process.     

Extraction of biologically active compounds from Sideritis ssp. L.

In this study extraction of polyphenols and flavonoids from cultivated hybrid Sideritis scardica × Sideritis syriaca, known for its rich content of phenolics and flavonoids with antioxidant activity, was investigated. Extractions have been done by ethanol and water-ethanol, respectively. High equilibrium values of the extracted species were obtained—17.55 mg/(g solid) total phenolics and 5.7 mg/(g solid) total flavonoids with ethanol as solvent. The influence of the solvent on the total yield and the content of biologically active compounds were studied. Maximum polyphenolics and flavonoids extraction was observed for water-ethanol solvent ratio 20/80. Increase of the content of ethanol in the solvents led to lower total yield of extracts but higher percentage of polyphenolics. The extraction kinetics showed that 90% of the phenolic compounds were extracted during the first 2.5 h. The experimental kinetics was described by a constant effective diffusion coefficient D_e = 1.5 × 10⁻¹² m²/s in the solid, accounting for the actual particle size distribution.     

Thermodynamic modeling of dealcoholization of beverages using supercritical CO2: Application to wine samples

The supercritical removal of ethanol from alcoholic beverages (brandy, wine, and cider) was studied using the GC-EoS model to represent the phase equilibria behavior of the CO₂ + beverage mixture. Each alcoholic drink was represented as the ethanol + water mixture with the corresponding ethanol concentration (35 wt% for brandy, 9-12 wt% for different wines and 6 wt% for cider). The thermodynamic modeling was based on an accurate representation of the CO₂ + ethanol and CO₂ + water binary mixtures, and the CO₂ + ethanol + water ternary mixture.The GC-EoS model was employed to simulate the countercurrent supercritical CO₂ dealcoholization of the referred beverages; the results obtained compared good with experimental data from the literature. Thus, the model was used to estimate process conditions to achieve an ethanol content reduction from ca. 10 wt% to values lower than 1 wt%. The model results were tested by carrying out several extraction assays using wine, in a 3 m height packed column at 308 K, pressures in the range of 9-18 MPa and solvent to wine ratio between 9 and 30 kg/kg.     

Thermal decomposition of pyrotechnic mixtures containing either aluminum or magnesium powder as fuel

Thermal behavior of energetic materials is critical to safe production, storage, handling or even demilitarization. In this work, the thermal behavior of Al, Mg, CuO, KMnO₄ and also three mixtures containing Al + CuO, Mg + CuO and Mg + KMnO₄ were studied experimentally using differential scanning calorimetry and thermogravimetry. These mixtures are sometimes used as pyrotechnic mixtures in military industries. Also, the influence of different heating rates (5, 10, 15 and 20 °C/min) on the DSC behavior of the mixtures was verified. The results showed that as the heating rate was increased, melting points and ignition temperatures of the mixtures were increased. On the other hand, TG-DSC analysis for Mg + KMnO₄ mixture indicates that this mixture melts at 283.0 °C and decomposed at 292.1 °C. By replacing KMnO₄ with CuO as the oxidizer of the magnesium, these temperatures enhanced to 368.7 °C and 408.3 °C, respectively. However, replacing Mg with Al in the Mg/CuO mixture decreases the melting and ignition temperatures of the mixture to 231.4 °C and 271.9 °C, respectively. The activation energy for each pyrotechnic mixture was computed. Also, the values of ΔS^#, ΔH^# and ΔG^# of their reaction were calculated.     

A potentiometric and voltammetric sensor based on polypyrrole film with electrochemically induced recognition sites for detection of silver ion

Conducting polypyrrole membranes were deposited on glassy carbon electrodes by electropolymerizing pyrrole in the presence of Eriochrome Blue-Black B (EBB) as the counter anion. The electrodes were then subjected to several oxidation/reduction potential steps in pure silver nitrate solution for successive accumulation/stripping of silver species. This electrochemically mediated doping/templating generated selective recognition elements in the EBB/PPy film for silver ions. The resulting sensor exhibited a considerable enhancement in the potentiometric and voltammetric response characteristics: extending the linear dynamic range and lowering the detection limit. In the potentiometric mode, the sensor showed highly reproducible response with a Nernstian slope of 58.5 ± 0.3 mV per decade of Ag⁺ activity over a linear range spanning seven orders of magnitude (1 × 10⁻⁸ to 1 × 10⁻¹ M Ag⁺), with a detection limit of ∼6 × 10⁻⁹ M. The electrodes demonstrated high selectivity over a large number of cations including alkali, alkaline earth and several transition and heavy metal ions, and could be used over a wide pH range of 1-8.5. The EBB/PPy modified electrode was also used for preconcentration and differential pulse anodic stripping voltammetric (DPASV) measurements. The DPASV peak current was dependent on the concentration of Ag⁺ over the range 3 × 10⁻¹⁰ to 1 × 10⁻⁴ M. The presence of 1000-fold excess of Cd²⁺, Cu²⁺, Cr³⁺, Co²⁺, Mn²⁺, Fe²⁺, Fe³⁺, Ni²⁺ and Pb²⁺ can be tolerated in the determination of silver ion.     

Adiabatic laminar burning velocities of CH4 + H2 + air flames at low pressures

Experimental measurements of the adiabatic burning velocity in methane + hydrogen + air flames using the Heat Flux method are presented. The hydrogen content in the fuel was varied from 0 to 20%. Non-stretched flames were stabilized on a perforated plate burner from 20 to 100 kPa. The equivalence ratio was varied from 0.8 to 1.4. Adiabatic burning velocities of CH₄ + H₂ + air mixtures were found in good agreement with the literature results at atmospheric pressure. Also low-pressure measurements in CH₄ + air flames performed earlier were accurately reproduced. The effects of enrichment by hydrogen on the laminar burning velocity at low pressures have been studied for the first time. Calculated burning velocities using the Konnov mechanism are in satisfactory agreement with the experiments over the entire range of conditions. Pressure dependences of the burning velocities for the three fuels studied could be approximated by an empirical exponential correlation.     

A-type zeolite containing Ag/Zn as inorganic antifungal for waterborne coating formulations

The biocide cations Ag⁺ and Zn²⁺ were hosted in the cavities of an ordered aluminosiliceous framework. Starting from sodium A-type zeolite (NaA), LTA containing Ag⁺ (AgA), Zn²⁺ (ZnA) and Ag⁺/Zn (AgZnA) at different cation exchanged levels was obtained and its antifungal properties were evaluated. To determine the minimum inhibitory concentration (MIC) of the exchanged zeolites against Aspergillus niger, [Ag⁺] and [Zn²⁺] values ranging from 50 < [Ag⁺] < 1000 mg L⁻¹ to 650 < [Zn²⁺] < 2000 mg L⁻¹, respectively, were used for NaA, and for AgZnA: 30 < Ag⁺ < 250 mg L⁻¹. The zeolite sample having [Ag⁺] = 100 mg L⁻¹, [Zn²⁺] = 90 mg L⁻¹ produces a growth inhibition comparable to that achieved with 230 mg L⁻¹ of Ag⁺¹ (MIC value obtained for the single cation). The antifungal activity of these products after incorporation in waterborne coating formulations was also determined. Results indicate that Ag⁺ and Zn²⁺ supported on A-type zeolite could be a beneficial tool for the development of waterborne coatings with a longer protection against microbiological attack when compared to traditional organic biocides.     

Focused Ion beam implantation of diamond

The interaction between diamond and a 30 kV Ga⁺ focused ion beam, has been studied. Electron backscattered diffraction identified the critical dose for amorphisation of the diamond surface at 2 × 10¹⁴ Ga⁺/cm². Scanning transmission electron microscopy identified a 35 nm amorphous carbon layer which, at higher doses, can swell up to 31% its original volume and accommodate a significant quantity of gallium. Electron energy loss and energy dispersive X-ray spectroscopy further characterised this layer and identified both excess hydrogen and oxygen contained within a stable amorphous carbon structure.     

Prediction of the density and viscosity in biodiesel blends at various temperatures

Biodiesel defined as mono-alkyl esters of vegetable oils and animal fats, has had a considerable development and great acceptance as an alternative fuel for diesel engines. Density and viscosity are two important physical properties to affect the utilization of biodiesel as fuel. In this work, mixtures of biodiesel and ultra low sulfur diesel (ULSD) were used to study the variation of density (ρ) and kinematic viscosity (η) as a function of percent volume (V) and temperature (T), experimental measurements were carried out for six biodiesel blends at nine temperatures in the range of 293.15-373.15 K. Both, density and viscosity increases because of the increase in the concentration of biodiesel in the blend, and both of them decrease as temperature increases. One empirical correlation was proposed to estimate the density: ρ = α·V + β·T + δ; and three empirical correlations were developed to predict the kinematic viscosity: η = exp[ln(γ) + ?·V + ω/T + λ·V/T²], η = exp[ln(γ) + ω/T + λ·V/T²] and η = exp[ln(γ) + ω/T + λ·V/T]. The corresponding parameters were optimized by the Levenberg-Marquardt method. The estimated values of density and viscosity are in good agreement with the experimental data because absolute average prediction errors of 0.02% and 2.10% were obtained in the Biodiesel(1) + ULSD(2) system studied in this work.     

Esterification of ethylene-vinyl alcohol copolymers in homogeneous phase using N,N′-dimethylpropyleneurea as solvent

Ethylene-vinyl alcohol copolymers (EVAL) were esterified with 3,5-dinitrobenzoyl chloride using the cycled urea N,N′-dimethylpropyleneurea (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone) (DMPU) as the solvent. Ethylene-vinyl alcohol-vinyl-3,5-dinitrobenzoate terpolymers (EVALVDNB) and ethylene-vinyl-3,5-dinitrobenzoate copolymers (EVDNB) were obtained. Both EVAL copolymers (6-73 mol% VAL) and esterified polymers, EVDNB, and EVALVDNB dissolve in DMPU. The substitution may become total under the experimental conditions. The degree of transformation was determined by ¹H NMR. EVDNB copolymers were characterised by IR spectroscopy and ¹H and ¹³C NMR. Thermal properties were studied by DSC. The glass transition temperature of the EVDNB copolymers having a low VDNB content (up to 14 mol%) is roughly constant, whereas above 50 mol% increases. Melting temperature decreases as the VDNB content is increased, owing to the fact that the VDNB groups are excluded from the polyethylene crystal lattice.     

Oxidative desulfurization of Gas oil by polyoxometalates catalysts

Several polyoxometalates: Na₂HPM₁₂O₄₀, H₃PM₁₂O₄₀, Na₂HPM₁₂O₄₀, (VO)H[PM₁₂O₄₀] and (n-Bu₄N)₃[PM₁₂O₄₀] (M = Mo and W) as well as (n-Bu₄N)_3 + x[PW_12−xV_xO₄₀] (x = 0–3) were synthesized and characterized. Benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene were used as model sulfur compounds in gas oil. The oxidation reaction was performed using different polyoxometalates as catalyst and H₂O₂/acetic acid. The experimental results show that the W-based polyoxometalate catalysts are more active than the Mo catalysts. The oxidation reactivity of the catalysts depends on the type of countercation: Na⁺ > H⁺ > (VO)⁺ > (n-Bu₄N)⁺. In a series of (n-Bu₄N)_3 + x [PW_12−xV_xO₄₀] (x = 0–3) the order of catalytic activity is V₃ > V₂ > V₁ > V₀. The reactivity order of the sulfur compounds is: dibenzothiophene > 4,6-dimethyldibenzo-thiophene > benzothiophene. The catalytic system in this work was used for the oxidation of gas oil combined with solvent extraction to remove sulfur content in gas oil. Under mild reaction condition, high sulfur removal up to 98% can be achieved with high oil recovery (90%).     

A new fast methodology to measure total diene content in gasoline

The rate constants for the quenching of biacetyl phosphorescence by a series of conjugated dienes were measured. 1,3-cyclohexadiene (k_qP = 2.94 × 10⁹ s⁻¹ mol⁻¹ L), 2,5-dimethyl-2,4-hexadiene (k_qP = 1.91 × 10⁹ s⁻¹ mol⁻¹ L), 2,4-dimethyl-1,3-pentadiene (k_qP = 1.78 × 10⁸ s⁻¹ mol⁻¹ L), 3-methyl-1,3-pentadiene (k_qP = 1.22 × 10⁸ s⁻¹ mol⁻¹ L), 2,4-hexadiene (k_qP = 1.35 × 10⁸ s⁻¹ mol⁻¹ L) and trans-2-methyl-1,3-pentadiene (k_qP = 3.84 × 10⁸ s⁻¹ mol⁻¹ L). Cyclooctene also quenched biacetyl phosphorescence but with a lower rate (k_qP = 1.97 × 10⁷ s⁻¹ mol⁻¹ L). Quenching was not observed with 1-methylnaphthalene. Since conjugated dienes quench biacetyl phosphorescence preferentially, this method was studied using gasoline samples with known diene composition. A good correlation was found between the rate of quenching of biacetyl by the gasoline samples and the quantity of conjugated dienes present.     

Potassium-ion selective solid contact microelectrode based on a novel 1,3-(di-4-oxabutanol)-calix[4]arene-crown-5 neutral carrier

The development of novel potassium-ion selective microelectrodes using microfabrication technologies and electrochemical polymerization is described. The microelectrode is based on electropolymerized polypyrrole films, doped with cobaltabis(dicarbollide) ions ([3,3′-Co(1,2-C₂B₉H₁₁)₂]), as an internal solid contact layer between the platinum surface and the polymeric sensing membrane. The ion selective membranes, which are based on a plasticized PVC membrane, contain 1,3-(di-4-oxabutanol)-calix[4]arene-crown-5 as a novel potassium ionophore, and are deposited on top of a layer of the conducting PPy[3,3′-Co(1,2-C₂B₉H₁₁)₂]. The response of the microelectrode was linear with a Nernstian slope of 51 ± 2 mV decade⁻¹ over a K⁺ ion concentration range of 6 × 10⁻⁶ to 1 × 10⁻¹ M, with a detection limit of 1.8 × 10⁻⁶ M. The microelectrode is suitable for use within the pH range of 3-11. The electrode could be used for at least one month without a considerable alteration in its potential.