Tailoring Solution Cast Poly(3,4‐dioctyloxythiophene) Transducers for Potentiometric All‐Solid‐State Ion‐Selective Electrodes

A novel concept of tailoring potentiometric responses of all‐solid‐state ion‐selective electrodes was introduced. The effect of composition and resulting properties of the conjugated polymer transducer, placed between the electrode support and ion‐selective membrane, on analytical characteristic of obtained sensors was studied.     

All‐Solid‐State Ion Selective and All‐Solid‐State Reference Electrodes

This paper is aiming to give a brief overview of recent research in the field of all‐solid‐state, internal solution free, ion‐selective electrodes and reference electrodes, employing conducting polymers or nano‐/microstructures as solid contacts beneath the polymeric, ion‐selective or reference membranes. The emphasis is on papers published in the last five years (after 2006). According to the papers published, poly(3‐octylthiophene) conducting polymer transducers offer highly reliable sensors for various applications, involving demanding analytical approaches and miniature sensors. On the other hand, the search for alternative materials continues: the sensors obtained by placing nano‐/microstructures (conducting polymers but also other materials, like, e.g., carbon nanotubes) underneath the receptor membrane are intensively tested. The recent years have also shown how useful the application of advanced instrumental methods is for the investigation of processes occurring within all‐solid‐state ion‐selective electrodes.     

All‐Solid‐State Chloride Sensors with Poly(3‐Octylthiopene) Matrix and Trihexadecylmethylammonium Chlorides as an Ion Exchanger Salt

All‐solid‐state chloride sensors were prepared by incorporation of trihexadecyl‐methylammonium chloride (THMACl) as an ion‐exchanger salt into a conjugated polymer membrane, poly(3‐octylthiophene) (POT). The influence of additional membrane components, such as a lipophilic anion, (potassium tetrakis[3,5‐bis(trifluoromethyl)phenyl] borate), poly(vinyl chloride) (PVC) or a plasticizer, (2‐nitrophenyl octyl ether) were studied. The membrane components were dissolved in chloroform except for PVC, which was dissolved in tetrahydrofuran (THF). The membrane solution was deposited on glassy carbon (GC) by solution casting resulting in all‐solid‐state chloride sensors. The sensor characteristics were determined potentiometrically and with impedance spectroscopy. The addition of plasticizer was found to be crucial in obtaining a well functioning Cl^?‐ISE based on POT and THMACl.     

Voltammetric Properties of All‐solid State Ion‐selective Electrodes with Multiwalled Carbon Nanotubes‐poly(3‐octylthiophene‐2,5‐diyl) Nanocomposite Transducer

Voltammetric response of an all‐solid‐state ion‐selective electrode was studied on example of potassium‐selective sensor with poly(vinyl chloride) based membrane and nanocomposite transducer containing poly(3‐octylthiophene‐2,5‐diyl) and multiwalled carbon nanotubes. Factors limiting the rate of the electrochemical process and the response were discussed. The challenge in voltammetric applications of ion‐selective electrodes is thickness of the plastic membrane. It was found that although a relatively thick ion‐selective membrane was applied, as typically used in potentiometric studies, the position of the reduction peak, corresponding to potassium ions incorporation, was dependent on ions concentration in a Nernstian manner. This opens possibility of deviation from the paradigm of ultrathin membranes in voltammetric applications, thus potentially extending the sensors lifetime. The high resistance of the membrane did not affect the voltammetric characteristics, because the resistance was independent of ions concentration in solution. On the other hand, high resistance results in charge trapping effect in the solid contact material, leading to advantageous retention of the oxidized‐conducting state of the solid contact, independently of the applied electrode potential.     

A Selective Film Based on Poly(3‐octylthiophene) Doped with Dihydroxyanthraquinone Sulfonate

A stable film of poly(3‐octylthiophene)–dihydroxyanthraquinone sulfonate has been synthesized electrochemically in non‐aqueous solution. The incorporation of dihydroxyanthraquinone sulfonate as an anionic complexing ligand into poly(3‐octylthiophene) film during electropolymerization was achieved and copper ions were accumulated by reduction on the electrode surface. The presence of dihydroxyanthraquinone sulfonate during the electrochemical polymerization of 3‐octylthiophene is shown to impact the sensitivity and the stability of the organic conducting film electrode response. The electroanalysis of copper(II) ions using conducting polymer electrode was achieved by differential pulse anodic stripping voltammetry with remarkable selectivity. The analytical performance was evaluated and linear calibration graphs were obtained in the concentration range of 50–400 ng mL^?1 copper(II) ion for 240 seconds accumulation time and the limit of detection was found to be 7.8 ng mL^?1. To check the selectivity of the proposed stripping voltammetric method for copper(II) ion, various metal ions as potential interferents were tested. The developed method was applied to copper(II) determination in certified reference material, NWRI‐TMDA‐61, trace elements in fortified water.     

Highly Selective All‐Plastic,Disposable, Cu2+‐Selective Electrodes

Conducting polymers (CP) remain a promising material to construct stable potential all‐solid‐state ion‐selective potentiometric electrodes. The unique properties of poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrenesulfonate) ions, PEDOT‐PSS: high CP stability and affinity of doping anions towards Cu²⁺ ions, make it highly attractive for construction of all‐solid‐state copper(II)‐selective electrodes with outstanding selectivity. The additional benefits can arise from solution processability of commercially available PEDOT‐PSS system. This material was highly promising for a new sensor arrangement, i.e. to obtain disposable, planar and flexible all‐plastic Cu²⁺‐selective electrodes. These sensors can be obtained by casting a commercially available dispersion of PEDOT‐PSS (Baytron P) on a plastic, non‐conducting support material. The CP being both electrical lead and ion‐to‐electron transducer, was covered with plastic, solvent polymeric Cu²⁺ selective membrane. This extremely simple arrangement, after conditioning in dilute Cu²⁺ solution, was characterized with linear Nernstian responses within the activities range from: 0.1 to 10^?4 M, followed by super‐Nernstian responses for lower activities. The latter result points to effective elimination of primary ions leakage from the plastic membrane / transducer phase and has resulted in significantly improved selectivities. Obtained log K values were equal to ?7.6 for Co²⁺, ?7.4 for Zn²⁺, ?7.2 for Ca²⁺ and ?6.8 for Na⁺, respectively.     

Electrocatalytic Oxidation and Determination of Nitrite at Multi‐walled Carbon Nanotubes Modified Carbon Ceramic Electrode

In the present work, the electrochemical oxidation of nitrite on carbon ceramic electrode (CCE) modified with multi‐walled carbon nanotubes (MWCNTs) was investigated. The modified electrode exhibited catalytic activity toward the electrooxidation of nitrite. Experimental parameters such as solution pH, scan rate, concentration of nitrite and nanotubes amount were studied. It was shown nitrite can be determined by differential pulse voltammetry (DPV) and hydrodynamic amperometry (HA) using the modified electrode. Under the optimized conditions the calibration plots are linear in the concentration ranges of 15‐220 and 50‐3000 μM with limit of detections of 4.74 and 35.8 μM for DPV and HA, respectively. The modified electrode was successfully applied for analysis of nitrite in spinach sample. The results were favorbly compared to those obtained by UV‐Visible spectrophotometric method. The results of the analysis suggest that the proposed method has promise for the routine determination of nitrite in the examined products.     

Multi‐Walled Carbon Nanotubes (MWCNT)‐Ionic Liquid‐Modified Carbon Paste Electrode: Probing FurazolidoneDNA Interactions and DNA Determination

The interactions of furazolidone (Fu) with double‐stranded calf thymus DNA (dsDNA) on the multi‐walled carbon nanotubes‐ionic liquid‐modified carbon paste electrode (MWCNT‐IL‐CPE) have been studied by cyclic voltammetry. In the presence of DNA, the cathodic peak current of Fu decreased and the peak potential shifted to a positive potential, indicating the intercalative interaction of Fu with DNA. The binding constant of Fu with DNA and stoichiometric coefficient has been determined according to the Hill's model. This electrochemical method was further applied to the determination of DNA. Two linear calibration curves were obtained for DNA detection in the concentration ranges of 0.03–0.10 and 0.10–4.0 μg l^?1 with a detection limit of 0.027 μg l^?1. The method was successfully applied to analyze Fu in serum samples.     

Glucose Biosensor Based on Multi‐Walled Carbon Nanotube Modified Glassy Carbon Electrode

An amperometric glucose biosensor based on multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode has been developed. MWCNT‐modified glassy carbon electrode was obtained by casting the electrode surface with multi‐walled carbon nanotube materials. Glucose oxidase was co‐immobilized on the MWCNT‐modified glassy carbon surface by electrochemical deposition of poly(o‐phenylenediamine) film. Enhanced catalytic electroreduction behavior of oxygen at MWCNT‐modified electrode surface was observed at a potential of ?0.40 V (vs. Ag|AgCl) in neutral medium. The steady‐state amperometric response to glucose was determined at a selected potential of ?0.30 V by means of the reduction of dissolved oxygen consumed by the enzymatic reaction. Common interferents such as ascorbic acid, 4‐acetamidophenol, and uric acid did not interfere in the glucose determination. The linear range for glucose determination extended to 2.0 mM and the detection limit was estimated to be about 0.03 mM.     

Optimizing Carbon Nanotubes Dispersing Agents from the Point of View of Ion‐selective Membrane Based Sensors Performance – Introducing Carboxymethylcellulose as Dispersing Agent for Carbon Nanotubes Based Solid Contacts

The influence of dispersing agent used to prepare carbon nanotubes solid‐contact on the performance of all‐solid state ion‐selective electrodes has been evaluated. It is shown that excess of surfactant dispersing agent is leading to deterioration of sensor performance, however, removal of dispersing agent – a typically applied approach – is resulting in substantial change of transducer layer physical properties, which can influence sensor performance. As remedy we propose application of a polymeric dispersing agent – carboxymethylcellulose. Thus obtained ion‐selective electrodes are characterized by high potential readings stability both within day and between days.     

Covalent and Non‐covalent Chemical Modification of Multi‐walled Carbon Nanotubes with Tetra‐(4‐hydroxylphenyl)porphyrin and Its Complexes

Multi‐walled carbon nanotubes (MWNTs) were covalently and non‐covalently functionalized with tetra‐(4‐hydroxylphenyl) porphyrin (THPPH₂) and its complexes (ZnTHPP) forming dispersible nanohybrids in organic solution. The morphology of the nanohybrids was observed with transmission electron microscopy. The structure of the product was characterized by FT‐IR, UV‐Vis spectrophotometer, fluorescence spectroscopy and thermogravimetric analysis. The photo‐induced electron‐transfer process of the nanohybrids in organic solution was also revealed.     

Cyclic Voltammograms of Ferrocene on Multi‐Walled Carbon Nanotubes (MWCNTs)‐Modified Edge Plane Pyrolytic Graphite (EPPG) Electrode in Room Temperature Ionic Liquids (RTILs) of 1‐Ethyl‐3‐Methylimidazolium Tetrafluoroborate (EMIBF4)

In this work, the electrochemical behavior of ferrocene (Fc) was investigated by cyclic voltammetry (CV) in room temperature ionic liquids (RTILs) of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) on glass carbon (GC), edge plane pyrolytic graphite (EPPG) and multi‐walled carbon nanotube (MWCNTs)‐modified EPPG electrodes, respectively. The results demonstrated that on GC electrode, pairs of well‐defined reversible peaks were observed, while for the electrode of EPPG, the peak potential separation (ΔE_p) is obviously larger than the theoretical value of 59 mV, hinting that the electrode of EPPG is distinguished from the commonly used electrode, consistent with the previous proposition that EPPG has many “defects”. To obtain an improved electrochemical response, multi‐walled carbon nanotubes (MWCNTs) were modified on the electrode of EPPG; the increased peak current and promoted peak potential separation not only proved the existence of “defects” in MWCNTs, but also supported that “creating active points” on an electrode is the main contribution of MWCNTs. Initiating the electrochemical research of Fc on the MWCNTs‐modified EPPG electrode in RTILs and verifying the presence of “defects” on both EPPG and MWCNTs using cyclic voltammograms (CVs) of Fc obtained in RTILs of EMIBF₄, is the main contribution of this preliminary work.     

Development of Simple Electrochemical Sensor for Selective Determination of Methadone in Biological Samples Using Multi‐walled Carbon Nanotubes Modified Pencil Graphite Electrode

The electrochemical sensor was developed for determination of methadone (MTD) using multi‐walled carbon nanotubes (MWCNT) modified pencil graphite electrode (MWCNT‐PGE). It was found that the oxidation peak current of MTD at the MWCNT‐PGE was greatly improved compared with that of the bare‐PGE. At the MWCNT‐PGE, well‐defined anodic peak of MTD was observed at about 0.7 V (in pH 7 solution). The influence of several parameters on the determination of MTD was investigated. At optimum experimental conditions, differential pulse voltammetry (DPV) was used for determination of MTD, which exhibited a linear calibration graph of Ip versus MTD concentration in the range of 0.1–15 µM with a correlation coefficient of 0.9992. The calculated detection limit for S/N = 3 was 87 nM. It has been shown that the peaks obtained for oxidation of ascorbic acid (AA), uric acid (UA) and MTD in their mixture could be well resolved by differential pulse voltammetry, permitting us to develop a sensitive and selective electrochemical sensor for determination of MTD in the presence of AA and UA. Finally, MWCNT‐PGE was used for determination of MTD in biological samples, such as human serum and urine, using the standard addition procedure and the results were quite promising.     

Osteoblast Adhesion and Proliferation on Poly(3‐octylthiophene) Thin Films

In this study we assessed the suitability of semiconducting P3OT thin films (30 nm) to sustain attachment, spreading, and proliferation of MC3T3‐E1 osteoblasts. Cell area correlated with surface wettability: area was larger on the more hydrophilic surface (TCPS) and lower on the more hydrophobic surface (P3OT). Cells were rounder, characterized by higher circularity values, on TCPS and Si compared to P3OT. P3OT proliferation rate at 24 h fell twofold after 48 h, then recovered at 72 h to a value significantly higher than that on TCPS. Presoaking experiments showed no evidence of cytotoxic effects or leachants from P3OT. Overall, we conclude that P3OT is a viable substrate for osteoblast attachment and proliferation.

     

Motions of Trimethylphosphine Oxide in Carbon Nanotubes as Revealed by Solid‐state NMR

Trimethylphosphine (TMP) has been adsorbed in carbon nanotubes and oxidized to trimethylphosphine oxide (TMPO). ³¹P spin–lattice relaxation T ₁ measurements at temperatures from 203 to 333 K have been employed to investigate the motions of TMPO. The ³¹P T ₁ is found to be monoexponential and isotropic. The activation energy is measured as 4.4 ± 0.3 kcal•mol⁻¹, which is comparable to that of TMP adsorbed on Lewis acid sites in zeolites.     

Palladium Sub‐Nanoparticle Decorated ‘Bamboo’ Multi‐Walled Carbon Nanotubes Exhibit Electrochemical Metastability: Voltammetric Sensing in Otherwise Inaccessible pH Ranges

A generic approach for the detection of electroactive species in potential ranges that would normally be inhibited due to the stripping of the electrocatalytic material is presented. We demonstrate, via the example of the electrochemical oxidation of hydrazine, that palladium nanoparticle (< 1 nm) decorated bamboo multi‐walled carbon nanotubes exhibit a metastability such that they allow the sensing of hydrazine in the pH range where palladium metal would normally be voltammetrically stripped (oxidized) from the surface of convectional electrodes.     

Electrochemical Determination of Pyrogallol at Conducting Poly(3,4‐ethylenedioxythiophene) Film‐Modified Screen‐Printed Carbon Electrodes

The electrochemical oxidation of pyrogallol at electrogenerated poly(3,4‐ethylenedioxythiophene) (PEDOT) film‐modified screen‐printed carbon electrodes (SPCE) was investigated. The voltammetric peak for the oxidation of pyrogallol in a pH 7 buffer solution at the modified electrode occurred at 0.13 V, much lower than the bare SPCE and preanodized SPCE. The experimental parameters, including electropolymerization conditions, solution pH values and applied potentials were optimized to improve the voltammetric responses. A linear calibration plot, based on flow‐injection amperometry, was obtained for 1–1000 µM pyrogallol, and a slope of 0.030 µA/µM was obtained. The detection limit (S/N=3) was 0.63 µM.     

Electrochemical Sensor for Sensitive Determination of Ga(III) Ion Based on β‐Cyclodextrin Incorporated Multi‐walled Carbon Nanotubes and Imprinted Sol‐gel Composite Film

A novel sensor for detection of trace gallium ion [Ga(III)] was created by stepwise modification of a gold electrode with β‐cyclodextrin (β‐CD)/multi‐walled carbon nanotubes (MWCNTs) and an ion imprinted polymer (IIP). The sensor surface morphology was characterized by scanning electron microscopy. The electrochemical performance of the imprinted sensor was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The sensor displayed excellent selectivity towards the target Ga(III) ion. Meanwhile, the introduced MWCNTs displayed noticeable catalytic activity, and β‐CD demonstrated significant enrichment capacity. A linear calibration curve was obtained covering the concentration range from 5.0×10^?8 to 1.0×10^?4 mol·L^?1, with a detection limit of 7.6×10^?9 mol·L^?1. The proposed sensor was successfully applied to detect Ga(III) in real urine samples.     

Morphology and Electrical Conductivity of Poly(N‐vinylcarbazole)/Carbon Nanotubes Nanocomposite Synthesized by Solid State Polymerization

This communication describes the morphology and DC conductivity of poly(N‐vinylcarbazole) (PNVC)/multi‐walled carbon nanotubes (MWCNTs) nanocomposite. The nanocomposite has been synthesized by solid state in situ polymerization of N‐vinylcarbazole (NVC) monomer in the presence of MWCNTs at an elevated temperature. Fourier transform infrared (FT‐IR) spectroscopy studies reveal the ability of MWCNTs to promote the in situ polymerization of the NVC monomer. Field‐emission scanning electron microscopy (FE‐SEM) observations show the homogeneous wrapping of MWCNTs' outer surface by PNVC polymer. Transmission electron microscopy (TEM) images and Raman spectroscopy results support the SEM observations. Thermogravimetric analyses reveal a significant improvement of thermal stability of the nanocomposite sample in the higher temperature region. The resulting nanocomposite material exhibits a dramatic improvement of the DC conductivity inherent to the PNVC. For example, the DC conductivity increases from ≈5.9 × 10⁻¹³ S · cm⁻¹ for PNVC to ≈12 S · cm⁻¹ for the nanocomposite, an increase of about 10¹³ in the electrical conductivity.

     

All Solid State Nickel(II)‐Selective Potentiometric Sensor Based on an Upper Rim Substituted Calixarene

A new ionophore, i.e. p‐(2‐thiazolazo)calix[4]arene ( I ) has been explored for its selective behavior towards Ni(II) ions. A poly(vinyl chloride) based membrane containing ( I ) as an electroactive material along with sodiumtetraphenylborate (NaTPB), and nitrophenyloctyl ether in the ratio 10 : 100 : 3 : 150 (I:PVC:NaTPB:NPOE) (w/w) was used to fabricate an all solid state nickel(II)‐selective sensor. The developed sensor exhibited a working concentration range of 1.0×10^?6–1.0×10^?1 M, with a Nernstian slope of 28.9±1.0 mV/decade of activity and a response time of 10–15 s. This sensor shows a detection limit of 9.0×10^?7 M. Its potential response remains unaffected of pH in the range 3.0–7.6, and the cell assembly could be used successfully in partially nonaqueous medium (up to 10 % v/v) without any significant change in the slope value or the working concentration range. The sensor worked satisfactorily for about ten weeks and exhibited excellent selectivity over a number of mono‐, bi‐, and tri‐valent cations including alkali, alkaline earth metal, and transition metal ions. It could be used as an indicator electrode for the end point determination in the potentiometric titration of nickel ions against ethylenediaminetetraacetic acid (EDTA) as well as for the determination of nickel ion concentration in real samples.