A Flexible Platform of Electrochemically Functionalized Carbon Nanotubes for NADH Sensors.

A flexible electrode system entirely constituted by single-walled carbon nanotubes (SWCNTs) has been proposed as the sensor platform for ß-nicotinamide adenine dinucleotide (NADH) detection. The performance of the device, in terms of potential at which the electrochemical process takes place, significantly improves by electrochemical functionalization of the carbon-based material with a molecule possessing an o-hydroquinone residue, namely caffeic acid. Both the processes of SWCNT functionalization and NADH detection have been studied by combining electrochemical and spectroelectrochemical experiments, in order to achieve direct evidence of the electrode modification by the organic residues and to study the electrocatalytic activity of the resulting material in respect to functional groups present at the electrode/solution interface. Electrochemical measurements performed at the fixed potential of +0.30 V let us envision the possible use of the device as an amperometric sensor for NADH detection. Spectroelectrochemistry also demonstrates the effectiveness of the device in acting as a voltabsorptometric sensor for the detection of this same analyte by exploiting this different transduction mechanism, potentially less prone to the possible presence of interfering species.

Chemical Sensors and Biosensors in Italy: A Review of the 2015 Literature.

The contributions of Italian researchers to sensor research in 2015 is reviewed. The analysis of the activities in one year allows one to obtain a snapshot of the Italian scenario capturing the main directions of the research activities. Furthermore, the distance of more than one year makes meaningful the bibliometric analysis of the reviewed papers. The review shows a research community distributed among different scientific disciplines, from chemistry, physics, engineering, and material science, with a strong interest in collaborative works.

Conducting polymers in electrochemical sensing: factors influencing the electroanalytical signal.

The paper highlights the intrinsic role of the conducting polymers (CPs) in CP-based electrochemical sensing devices. The effects of specific parameters of the electrochemical synthesis and overall measurement protocol, such as nature of the solvent and doping ions, the characteristics of the electrochemical polymerisation procedure, the nature of the CP-carrying substrates, and the composition of the medium used for the electroanalytical measurement, are discussed in an attempt to provide guidelines necessary for optimisation of CP-based electrochemical sensing. The lesser stability of CPs is also addressed as one of the main possible drawbacks of these materials in comparison to inorganic-based sensors.

Determination of polyphenol content and colour index in wines through PEDOT-modified electrodes.

Poly(3,4-ethylenedioxythiophene)-modified electrodes have been used for the estimation of the polyphenolic content and of the colour index of different samples of wines. Synthetic wine solutions, prepared with different amount of oenocyanins, have been analysed spectrophotometrically and electrochemically in order to find a correlation between the total polyphenolic content or colour index and the current peak. The regression curves obtained have been used as external calibration lines for the analysis of several commercial wines, ranging from white to dark red wines. In this way, a rapid estimation of the total polyphenolic content and of the colour index may be accomplished from a single voltammetric measurement. Furthermore, principal component analysis has also been used to evaluate the effect of total polyphenolic content and colour index on the whole voltammetric signals within a selected potential range, both for the synthetic solutions and for the commercial products. Graphical abstract Electrochemical sensors for the rapid determination of colour index and polyphenol content in wines.

Ti metal electrode as an unconventional amperometric sensor for determination of Au(III) species.

The control of the noble metal concentration is crucial in order to increase the efficiency of hydrometallurgic processes in mining and in the recovery of precious materials from electronic waste. The present study is devoted to the development of an effective procedure for the quantification of Au(III) species dissolved in aqueous solutions, similar real complex matrices included. In particular, a novel electrode system based on Ti has been studied. This electrode material is still poorly investigated in the framework of electroanalysis, despite its lack of sensitivity to common interfering species, such as oxygen; hence, the determination of metal species can be carried out without performing deaeration of the solution. In addition, the interfering effect due to the presence of other heavy metal ions, such as Ag, Fe and Pb, has been minimised by a proper choice of the conditions adopted for the amperometric measurements. Ti electrodes exhibit reproducible electrochemical responses, even in the presence of high concentration of organic fouling species typical of biosorption processes.

Development of a sensor system for the determination of sanitary quality of grapes.

n instrument for the automatic quantification of glycerol in grapes has been developed. We verify here that this analyte can be used as a benchmark of a serious disease affecting the grapevines, namely Botrytis cinerea. The core of the instrument is an amperometric biosensor consisting of a disposable screen printed electrode, generating the analytical signal thanks to a bi-enzymatic process involving glycerol dehydrogenase and diaphorase. The full automation of the analysis is realised by three micropumps and a microprocessor under control of a personal computer. The pumps allow the correct and constant dilution of the grape juice with a buffer solution also containing [Fe(CN)6]3- redox mediator and the injection of NAD+ cofactor when the baseline signal reaches a steady state; the instrument leads to automated reading of the analytical signal and the consequent data treatment. Although the analytical method is based on an amperometric technique that, owing to heavy matrix effects, usually requires an internal calibration, the analyses indicate that a unique external calibration is suitable for giving accurate responses for any grapes, both white and black ones.

Graphene-modified electrode. Determination of hydrogen peroxide at high concentrations.

A gold electrode partially coated by graphene multilayer is developed and tested with respect to high concentrations of hydrogen peroxide. The effective use of conventional electrode materials for the determination of such an analyte by anodic oxidation or cathodic reduction is prevented by the occurrence of adsorptions fouling the electrode surface. This prevents reliable and repeatable voltammetric curves for being recorded and serious problems arise in quantitative analysis via amperometry. The gold-graphene electrode is shown to be effective in quantitative evaluation, by cathodic reduction, of hydrogen peroxide at concentration levels that are of interest in an industrial. Acid, neutral, and basic pH values have been tested through correct adjustment of a Britton Robinson buffer. The experiments have been performed both by cyclic voltammetry and with amperometry at constant potential in unstirred solution. The latter technique has been employed in drawing a calibration linear plot. In particular, the performances of the developed electrode system have been compared with those of both pure gold and pure graphene electrode materials. The bi-component electrode was more sensitive; co-catalytic action by the combination of the two components is hypothesised. The system is stable over many potential cycles, as checked by surface-enhanced Raman spectra recorded over time.

Studies of the interface of conducting polymers with inorganic surfaces.

Many of the properties of multi-material systems and relevant devices depend on the interfaces between the different components. This review focuses on characterization of the interfaces between intrinsically conducting polymers and inorganic materials consisting of metals and metal oxides. These materials are chosen because of their importance in several analytical applications. Although use of conducting polymers and metals or metal oxides in analytical systems, specifically in sensing, is well established, the number of novel materials used for analytical purposes is continuously increasing. This further increases the possible number of effective combinations of different materials within multicomponent systems. As a consequence, innovative characterization techniques have become as important as more conventional techniques. On the other hand, sophisticated characterisation techniques are increasingly widespread and, consequently, also readily accessible. This critical review is not an exhaustive discussion of all possible analytical techniques suitable for characterization of interfaces. It is, instead, limited to an overview of the most effective, relatively widespread techniques, emphasising their most significant recent advances. Critical analysis of the individual techniques is complemented by a few selected examples.

Peptide nucleic acids tagged with four lysine residues for amperometric genosensors.

A homothymine PNA decamer bearing four lysine residues has been synthesized as a probe for the development of amperometric sensors. On one hand, the four amino groups introduced make this derivative nine times more soluble than the corresponding homothymine PNA decamer and, on the other hand, allow the stable anchoring of this molecule on Au nanostructured surface through the terminal -NH 2 moieties. In particular, XPS and electrochemical investigations performed with hexylamine, as a model molecule, indicate that the stable deposition of primary amine derivatives on such a nanostructured surface is possible and involves the free electron doublet on the nitrogen atom. This finding indicates that this PNA derivative is suitable to act as the probe molecule for the development of amperometric sensors. Thanks to the molecular probe chosen and to the use of a nanostructured surface as the substrate for the sensor assembly, the device proposed makes possible the selective recognition of the target oligonucleotide sequence with very high sensitivity.

UPS, XPS, and NEXAFS study of self-assembly of standing 1,4-benzenedimethanethiol SAMs on gold.

We report a study of the self-assembly of 1,4-benzenedimethanethiol monolayers on gold formed in n-hexane solution held at 60 °C for 30 min and in dark conditions. The valence band characteristics, the thickness of the layer, and the orientation of the molecules were analyzed at a synchrotron using high resolution photoelectron spectroscopy and near edge X-ray adsorption spectroscopy. These measurements unambiguously attest the formation of a single layer with molecules arranged in the upright position and presenting a free -SH group at the outer interface. Near edge X-ray absorption fine structure (NEXAFS) measurements suggest that the molecular axis is oriented at 24° with respect to the surface normal. In addition, valence band features could be successfully associated to specific molecular orbital contributions thanks to the comparison with theoretically calculated density of states projected on the different molecular units.

Water-soluble full-length single-wall carbon nanotube polyelectrolytes: preparation and characterization.

HiPco single-wall carbon nanotubes (SWNTs) have been noncovalently modified with ionic pyrene and naphthalene derivatives to prepare water-soluble SWNT polyelectrolytes (SWNT-PEs), which are analogous to polyanions and polycations. The modified nanotubes have been characterized with UV-vis-NIR, fluorescence, Raman and X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The nanotube-adsorbate interactions consist of pi-pi stacking interactions between the aromatic core of the adsorbate and the nanotube surface and specific contributions because of the substituents. The interaction between nanotubes and adsorbates also involves charge transfer from adsorbates to SWNTs, and with naphthalene sulfonates the role of a free amino group was important. The ionic surface charge density of the modified SWNTs is constant and probably controlled by electrostatic repulsion between like charges. The linear ionic charge density of the modified SWNTs is similar to that of common highly charged polyelectrolytes.

3-methylthiophene self-assembled monolayers on planar and nanoparticle Au surfaces.

In this article the adsorption of 3-methylthiophene on planar and nanoparticle Au surfaces is investigated. The resulting systems are compared with a benchmark system based on 1-decanethiol. The characterization data collected evidence the formation of a packed 3-methylthiophene SAM on the planar surface. In particular, spectroscopic investigations suggest that 3-methylthiophene aromatic system is not adsorbed on the surface through the pi-electron system but rather through the S atom alone. On the other hand, the behavior of 3-methylthiophene on nanoparticle surfaces is notably different from that of the alkanethiol. Only a limited fraction of the surface of Au nanoparticles results to be actually coated after purification; this notwithstanding, the nanoparticle growth seems to be strongly influenced by the presence of such a labile encapsulating agent.

A study of the dielectric behaviour and the liquid structure of a ternary solvent system.

The static dielectric constant of the [DMF(1) + ME(2) + DME(3)] ternary mixtures was measured as a function of temperature (25 < or = t/degrees C < or = 80) and composition, over the whole mole fraction range 0 < or = chi,chi2,chi3 < or = 1. The experimental values were processed by an empirical equation accounting for the dependence epsilon = epsilon(T, phi(i)), where phi(t) is the volume fraction of the components. A comparison between calculated and experimental data shows that this fitting relationship can be effectively employed to predict epsilon values in correspondence to experimental data gaps. Starting from the experimental measurements, some derived quantities such as molar polarisation (P), and excess counterpart (PE) were obtained. Both the excess properties, epsilonE and PE, take values partly positive and partly negative under all experimental conditions. The values of the excess quantities are indicative of the presence of specific interactions among different components in the mixtures.

Radical ions from 3,3''',3''''-tris(butylsulfanyl)- 2,2':5',2'':5'',2''',5''',2'''':5'''',2'''''-sexithiophene: an experimental and theoretical study of the p- and n-doped oligomer.

The 3,3''',3'''''-tris(butylsulfanyl)- 2,2':5',2'':5'',2''',5''',2'''':5'''',2'''''-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+. was evidenced by the 1H NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1+., and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 1(2-).

Multicomponent analysis of electrochemical signals in the wavelet domain.

Successful applications of multivariate calibration in the field of electrochemistry have been recently reported, using various approaches such as multilinear regression (MLR), continuum regression, partial least squares regression (PLS) and artificial neural networks (ANN). Despite the good performance of these methods, it is nowadays accepted that they can benefit from data transformations aiming at removing baseline effects, reducing noise and compressing the data. In this context the wavelet transform seems a very promising tool. Here, we propose a methodology, based on the fast wavelet transform, for feature selection prior to calibration. As a benchmark, a data set consisting of lead and thallium mixtures measured by differential pulse anodic stripping voltammetry and giving seriously overlapped responses has been used. Three regression techniques are compared: MLR, PLS and ANN. Good predictive and effective models are obtained. Through inspection of the reconstructed signals, identification and interpretation of significant regions in the voltammograms are possible.

Beta-functionalised polythiophenes as microelectrode modifiers in low conductive media.

A study on polythiophene coated microelectrodes is reported, the goal being that of checking the capability of these electrochemical systems to work in low conductive media. The possibility of electrochemically p-doping the polymer in the presence of very low concentrations or even in the absence of supporting electrolyte in the solution is ascertained, opening the way to the use of similar systems in pure solvent media. This result is obtained in such conditions that the presence of residual charges--and corresponding counterions--trapped inside the film coating can be reasonably hypothesised.

Temperature and composition dependence of the refractive indices of the 2-chloroethanol + 2-methoxyethanol binary mixtures.

Measurements of the refractive index n for the binary mixtures 2-chloroethanol + 2-methoxyethanol in the 0 < or = t/degree C < or = 70 temperature range have been carried out with the purpose of checking the capability of empirical models to express physical quantity as a function of temperature and volume fraction, both separately and together, i.e., in a two independent variables expression. Furthermore, the experimental data have been used to calculate excess properties such as the excess refractive index, the excess molar refraction, and the excess Kirkwood parameter delta g over the whole composition range. The quantities obtained have been discussed and interpreted in terms of the type and nature of the specific intermolecular interactions between the components.

Study of the short-term release of the ionic fraction of heavy metals from dental amalgam into synthetic saliva, using anodic stripping voltammetry with microelectrodes.

The present paper describes a fast and reproducible procedure, employing differential pulse stripping analysis technique with graphite microelectrodes, for the quantitative evaluation of the ionic fraction of heavy metals (namely Hg, Cu, and Zn) released from dental amalgams into synthetic saliva during 6-90 h contact between amalgam and saliva, after completion of the dental restoration (short-term release). The Zn(2+) concentration was evaluated by linear calibration, whereas Cu(2+) and Hg(2+) contents were estimated by the standard additions method. While the concentration of Zn(2+) ion does not increase significantly anymore after a 6-h contact (values from 288+/-12 to 346+/-12 mugdm(-3) at time of contact from 6 to 90 h, respectively), in the same time interval the concentration of both Cu(2+) and Hg(2+) ions progressively increases (from 38+/-6 to 197+/-4 mugdm(-3) and from 15+/-3 to 101+/-2 mugdm(-3), respectively). The results of the release tests reveal that Hg concentration is at the highest level of risk (HBM III), as identified by the three human biomonitoring categories suggested by the Institut für Wasser-, Boden- und Lufthygiene des Umweltbundesamtes (Germany) for the estimation of potential harmful effects on health due to exposure to heavy metals.