Application of terpyridyl ligands to tune the optical and electrochemical properties of a conducting polymer.

We present a simple and effective way of using metal and metal-ligand modifications to tune the electrochemical and optical properties of conducting polymers. To that end, a polyterthiophene functionalized with terpyridine moieties was synthesized and then the resulting film's surface or bulk was modified with different metal ions, namely Fe2+, Zn2+ and Cu2+ and terpyridine. The modification of the terpyridine functionalized polyterthiophene film by Fe2+ increased the absorptivity and electrochemical capacitance of the conducting polymer, and improved its conjugation. Further modification by Zn2+ and Cu2+ resulted in dramatically different spectroelectrochemical properties of the film. Moreover, the influence of the solvents (ACN and 1 : 1 ACN : H2O) in conjunction with the metal ion applied for the modification was found crucial for the electrochemical and optical properties of the films.

Ion-selective electrodes in potentiometric titrations; a new method for processing and evaluating titration data.

A new method to convert the potential of an ion-selective electrode to concentration or activity in potentiometric titration is proposed. The advantage of this method is that the electrode standard potential and the slope of the calibration curve do not have to be known. Instead two activities on the titration curve have to be estimated e.g. the starting activity before the titration begins and the activity at the end of the titration in the presence of large excess of titrant. This new method is beneficial when the analyte is in a complexed matrix or in a harsh environment which affects the properties of the electrode and the traditional calibration procedure with standard solutions cannot be used. The new method was implemented both in a method of linearization based on the Grans's plot and in determination of the stability constant of a complex and the concentration of the complexing ligand in the sample. The new method gave accurate results when using titrations data from experiments with samples of known composition and with real industrial harsh black liquor sample. A complexometric titration model was also developed.

Electro-catalytic oxidation of hemicelluloses at the Au electrode.

The recently reported electro-catalytic reaction mechanism for the oxidation of cellulose is proposed to work also for the electro-oxidation of other polysaccharides (e.g. hemicelluloses). In this report, the electrochemical reactivity of some hemicelluloses (xylan, arabinoxylan, glucomannan, xyloglucan, and glucuronoxylan) in 1.3 M NaOH solution is described. The electrochemical property of each of the studied hemicelluloses at the Au electrode surface was characterized by cyclic voltammetry. Xylan, xyloglucan and glucuronoxylan were found to be electrochemically active. Electrochemical properties of xylan were further studied by electrochemical impedance spectroscopy. The electrochemical reaction products of xylan, obtained by extensive electrolysis of the xylan solution by cyclic voltammetry, were characterized by FTIR spectroscopy, (13)C-NMR spectroscopy, SEM and TEM. The structural studies suggest that the oxidized xylan is a functional material where some of the OH-groups have been oxidized to carboxyl groups making that part of the oxidation product soluble in water under ambient conditions (23 °C, pH 7). The other part remains insoluble in water and contains Au nanoparticles. This work indicates that other polysaccharides than cellulose can also be electrochemically oxidized.

Electrocatalytic oxidation of cellulose at a gold electrode.

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed.

Solid-contact ion-selective electrodes with highly selective thioamide derivatives of p-tert-butylcalix[4]arene for the determination of lead(II) in environmental samples.

Thioamide derivatives of p-tert-butylcalix[4]arene were used as ionophores in the development of solid-contact ion-selective electrodes based on conducting polymer poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT/PSS) which was synthesized by electrodeposition on the glassy carbon electrodes. The typical ion-selective membranes with optionally two different plasticizers [bis(2-ethylhexyl)sebacate (DOS) and 2-nitrophenyl octyl ether (NPOE)] were investigated. The potentiometric selectivity coefficients were determined by separate solution method (SSM) for Pb(2+) over Cu(2+), Cd(2+), Ca(2+), Na(+), and K(+). High selectivity toward Pb(2+) was obtained. By applying two conditioning protocols, a low detection limit log(a(DL)) ≈ -9 was achieved. The fabricated ion-selective electrodes were used to determine Pb(2+) concentration in environmental samples. The obtained results were compared to analysis done by inductively coupled plasma mass spectrometry (ICPMS).

Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction.

Studying electronic transport in polyazulene-ionic liquid systems using infrared vibrational spectroscopy.

This paper presents an in situ spectroelectrochemical characterization of polyazulene (PAz) and PAz-C(60) composite films using Fourier Transform Infrared Attenuated Total Reflection (FTIR-ATR) spectroscopy. In situ FTIR-ATR spectra were recorded simultaneously as the films were charged and discharged electrochemically. The aim was to clarify how the use of ILs and the addition of C(60) affected the electronic transport and structural changes occurring in PAz during electrochemical charging. We found that electrosynthesis of PAz in an IL lowered the oxidation potential of the film and improved its electroactivity. The FTIR-ATR data also suggest that PAz with a longer effective conjugation length is obtained during electrosynthesis when using ILs. With in situ FTIR-ATR it is possible to quite accurately determine the onset potential for oxidation/reduction. These values are important since they determine the suitability of the polymer for a specific application. Our experiments indicate that two types of charge carriers are formed during electrochemical oxidation of PAz in an IL. Furthermore, their formation is strongly affected by the addition of C(60) into the film. The type of charge carrier formed affects the electronic and possibly also ionic transport within the film. The inclusion of C(60) into PAz influenced the optical and structural properties considerably. In situ FTIR-ATR is also an extremely useful method for studying the potential stability of an IL during electrochemical cycling. We showed that cathodic decomposition of N,N-butyl-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP][Tf(2)N]) occurs at less negative potentials than those determined electrochemically.

Electrochemical determination of NADH and ethanol based on ionic liquid-functionalized graphene.

It is firstly reported that low-potential NADH detection and biosensing for ethanol are achieved at an ionic liquid-functionalized graphene (IL-graphene) modified electrode. A substantial decrease (440 mV) in the overvoltage of the NADH oxidation was observed using IL-graphene/chitosan coating, with oxidation starting at ca. 0 V (vs. Ag|AgCl). And the NADH amperometric response at such a modified electrode is more stable (95.4% and 90% of the initial activity remaining after 10 min and 30 min at 1 mM NADH solution) than that at bare electrode (68% and 46%). Furthermore, the IL-graphene/chitosan-modified electrode exhibited a good linearity from 0.25 to 2 mM and high sensitivity of 37.43 microA mM(-1)cm(-2). The ability of IL-graphene to promote the electron transfer between NADH and the electrode exhibited a novel and promising biocompatible platform for development of dehydrogenase-based amperometric biosensors. With alcohol dehydrogenase (ADH) as a model, the ADH/IL-graphene/chitosan-modified electrode was constructed through a simple casting method. The resulting biosensor showed rapid and highly sensitive amperometric response to ethanol with a low detection limit (5 microM). Moreover, the proposed biosensor has been used to determine ethanol in real samples and the results were in good agreement with those certified by the supplier.

Graphene/AuNPs/chitosan nanocomposites film for glucose biosensing.

A novel glucose biosensor based on immobilization of glucose oxidase in thin films of chitosan containing nanocomposites of graphene and gold nanoparticles (AuNPs) at a gold electrode was developed. The resulting graphene/AuNPs/chitosan composites film exhibited good electrocatalytical activity toward H(2)O(2) and O(2). The wide linear response to H(2)O(2) ranging from 0.2 to 4.2 mM (R=0.998) at -0.2V, high sensitivity of 99.5 microA mM(-1) cm(-2) and good reproducibility were obtained. The good electrocatalytical activity might be attributed to the synergistic effect of graphene and AuNPs. With glucose oxidase (GOD) as a model, the graphene/AuNPs/GOD/chitosan composite-modified electrode was constructed through a simple casting method. The resulting biosensor exhibited good amperometric response to glucose with linear range from 2 to 10 mM (R=0.999) at -0.2V and from 2 to 14 mM (R=0.999) at 0.5 V, good reproducibility and detection limit of 180 microM. Glucose concentration in human blood was studied preliminarily. From 2.5 to 7.5 mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations. The graphene/AuNPs/GOD/chitosan composites film shows prominent electrochemical response to glucose, which makes a promising application for electrochemical detection of glucose.

One-step synthesis of graphene/SnO2 nanocomposites and its application in electrochemical supercapacitors.

A one-step method was developed to fabricate conductive graphene/SnO2 (GS) nanocomposites in acidic solution. Graphite oxides were reduced by SnCl2 to graphene sheets in the presence of HCl and urea. The reducing process was accompanied by generation of SnO2 nanoparticles. The structure and composition of GS nanocomposites were confirmed by means of transmission electron microscopy, x-ray photoelectron and Raman spectroscopy. Moreover, the ultracapacitor characteristics of GS nanocomposites were studied by cyclic voltammograms (CVs) and electrical impedance spectroscopy (EIS). The CVs of GS nanocomposites are nearly rectangular in shape and the specific capacitance degrades slightly as the voltage scan rate is increased. The EIS of GS nanocomposites presents a phase angle close to pi/2 at low frequency, indicating a good capacitive behavior. In addition, the GS nanocomposites could be promisingly applied in many fields such as nanoelectronics, ultracapacitors, sensors, nanocomposites, batteries and gas storage.

Direct electrochemistry of glucose oxidase and biosensing for glucose based on carbon nanotubes@SnO(2)-Au composite.

Multiwalled carbon nanotubes@SnO(2)-Au (MWCNTs@SnO(2)-Au) composite was synthesized by a chemical route. The structure and composition of the MWCNTs@SnO(2)-Au composite were confirmed by means of transmission electron microscopy, X-ray photoelectron and Raman spectroscopy. Due to the good electrocatalytic property of MWCNTs@SnO(2)-Au composite, a glucose biosensor was constructed by absorbing glucose oxidase (GOD) on the hybrid material. A direct electron transfer process is observed at the MWCNTs@SnO(2)-Au/GOD-modified glassy carbon electrode. The glucose biosensor has a linear range from 4.0 to 24.0mM, which is suitable for glucose determination by real samples. It should be worthwhile noting that, from 4.0 to 12.0mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations in human blood. Meanwhile, the resulting biosensor can also prevent the effects of interfering species. Moreover, the biosensor exhibits satisfying reproducibility, good operational stability and storage stability. Therefore, the MWCNTs@SnO(2)-Au/GOD biocomposite could be promisingly applied to determine blood sugar concentration in the practical clinical analysis.

Water-soluble graphene covalently functionalized by biocompatible poly-L-lysine.

Graphene sheets functionalized covalently with biocompatible poly-l-lysine (PLL) were first synthesized in an alkaline solution. PLL-functionalized graphene is water-soluble and biocompatible, which makes it a novel material promising for biological applications. Graphene sheets played an important role as connectors to assemble these active amino groups of poly-l-lysine, which provided a very biocompatible environment for further functionalization, such as attaching bioactive molecules. As an example, an amplified biosensor toward H(2)O(2) based on linking peroxidase onto PLL-functionalized graphene was investigated.

Direct electrochemistry of glucose oxidase and biosensing for glucose based on graphene.

We first reported that polyvinylpyrrolidone-protected graphene was dispersed well in water and had good electrochemical reduction toward O(2) and H(2)O(2). With glucose oxidase (GOD) as an enzyme model, we constructed a novel polyvinylpyrrolidone-protected graphene/polyethylenimine-functionalized ionic liquid/GOD electrochemical biosensor, which achieved the direct electron transfer of GOD, maintained its bioactivity and showed potential application for the fabrication of novel glucose biosensors with linear glucose response up to 14 mM.

The nature of the charge carriers in polyazulene as studied by in situ electron spin resonance-UV-visible-near-infrared spectroscopy.

In situ spectroelectrochemistry is of high importance for the characterization of doping reactions in pi-conjugated polymers. In this paper we present the results of simultaneous ESR and UV-vis-NIR measurements performed in situ during electrochemical p- and n-doping of polyazulene (PAz). In previous studies on p-doping of PAz the assignment of the optical absorption bands to specific charge carriers have been somewhat controversial, therefore the aim of this study is to clarify the nature of the doping-induced charge carriers and their corresponding optical absorption bands by in situ ESR-UV-vis-NIR spectroelectrochemistry. PAz was polymerized in two different potential ranges in order to obtain films with different structures and morphologies. On the basis of our spectroelectrochemical results we propose that polarons and polaron pairs are formed during p-doping in the two different types of PAz films electrodeposited on ITO. For studying n-doping of PAz, a Pt electrode was used. The ESR signal first decreased in intensity at low doping levels and then increased in intensity at higher doping levels pointing to the formation of new paramagnetic species. At high negative potentials there occurred an additional line broadening of the ESR signal indicating the existence of rather localized negative charge carriers.

In situ resonance Raman spectroscopy of polyazulene on aluminum.

Polyazulene (PAz) has been electrochemically deposited on different electrode substrates. The films were characterized with Raman and UV-vis spectroscopy. The spectroelectrochemical studies were performed in situ during p- and n-doping (electrochemical oxidation and reduction, respectively). The focus of this work was mainly on the charging and discharging reactions of PAz on Al substrates. The results were compared to the corresponding results obtained from PAz on Pt substrates. Three different excitation wavelengths (514, 633, and 780 nm) were used in the Raman experiments and the resonance enhancement effect was observed when changing the wavelength of the excitation line. The vibrational behavior of PAz deposited on Al was very similar to that of PAz deposited on Pt during p-doping. Furthermore, it was found that the vibrational responses during p- and n-doping are different indicating that the electronic structure of PAz is not the same during positive and negative charging. It was concluded that PAz is not reversibly n-doped on Al. The n-doping on Pt was shown to be more reversible. In this paper, the important correlation between UV-vis and Raman spectroscopy is discussed as well as the correlation between doping-induced infrared active bands and Raman bands of neutral PAz.

Applications of ionic liquids in electrochemical sensors.

Ionic liquids (ILs) are molten salts with the melting point close to or below room temperature. They are composed of two asymmetrical ions of opposite charges that only loosely fit together (usually bulky organic cations and smaller anions). The good solvating properties, high conductivity, non-volatility, low toxicity, large electrochemical window (i.e. the electrochemical potential range over which the electrolyte is neither reduced nor oxidized on electrodes) and good electrochemical stability, make ILs suitable for many applications. Recently, novel ion selective sensors, gas sensors and biosensors based on ILs have been developed. IL gels were found to have good biocompatibility with enzymes, proteins and even living cells. Besides a brief discussion of the properties of ILs and their general applications based on these properties, this review focuses on the application of ILs in electroanalytical sensors.

Memory effect in an ionic liquid matrix containing single-walled carbon nanotubes and polystyrene.

We report the use of an ionic liquid (IL) gel matrix containing a blend of single-walled carbon nanotubes (SWNTs) and polystyrene (PS) as a memory device. SWNTs and PS beads were mixed in a room-temperature IL, 1-butyl-3-methyl-hexafluorophosphate ([BMIM][PF(6)]). The composite gel was sandwiched between a bottom ITO glass and a top aluminium electrode. By merely changing the concentrations of SWNTs in the inert insulating PS matrix, we observed several distinct electrical properties of the device, such as an insulator, a memory in terms of switching and negative differential resistance (NDR), and a conductor. The electric bistable switching hops between a higher impedance (OFF) state and a lower impedance (ON) state which is approximately equal to five orders of current decays.

Potassium-selective electrodes with stable and geometrically well-defined internal solid contact based on nanoparticles of polyaniline and plasticized poly(vinyl chloride).

Solid contact potassium-selective electrodes with the internal ion-to-electron transduction layer composed of plasticized poly(vinyl chloride) (PVC) and 2-20% (m/m) of polyaniline (PANI) nanoparticles, with the mean particle size of 8 nm, have been studied in this paper. UV-vis measurements in pH buffer solutions between pH 0 and 12 show that the electrically conducting emeraldine salt (ES) form of PANI has exceptionally good pH stability. Membranes of PANI nanoparticles were mainly in the ES form even at pH 12, in contrast to electrochemically prepared PANI(Cl) films, which are converted completely to the nonconducting form already at pH 6. Long-term UV-vis measurements with the PANI membranes in contact with aqueous buffer solution at pH 7.5 showed no degradation of the ES form. The PANI nanoparticles are homogenously mixed in the PVC-based solid contact (SC) layer. Only the uppermost part of the SC layer is to a minor extent dissolved in the outer potassium-selective PVC membrane. This enabled the preparation of geometrically well-defined inner SC layers, thus improving the reproducibility of the solid contact electrodes and resulting in good mechanical strength between the inner and outer membranes.

Pi-dimer of an aniline dimer: an ESR-UV-vis spectroelectrochemical study.

It is shown for the first time that the most important intermediate formed during aniline polymerization, the p-aminodiphenylamine, forms a pi-dimer under oxidation at room temperature in acidified organic solvents that are used in electropolymerization. N-Phenylquinonediimine, which is generally assumed to be formed under oxidation, is only formed in basic solutions and in ionic liquids. Most of the mechanistic studies reported so far take the formation of N-phenylquinonediimine under consideration, although it is not consistent with the UV-vis spectra measured during oxidation of p-aminodiphenylamine. The formation of a pi-dimer is very well consistent with the electronic spectra of the oxidation product. In this way the pi-dimer is very important for the interpretation of the UV-vis spectra of higher oligomers and polyaniline as well. Furthermore, it offers a new interpretation of the redox behavior of p-aminodiphenylamine as found by cyclic voltammetry and has to be considered in the mechanism of the electrochemical polyaniline formation.