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A special issue of Sensors (ISSN 1424-8220). This special issue belongs to the section "Chemical Sensors".

Deadline for manuscript submissions: closed (20 March 2013) | Viewed by 108533

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Prof. Dr. Renato Seeber

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Department of Chemical and Geological Sciences, Università di Modena e Reggio Emilia, Via G. Campi 103, 41125 Modena, Italy
Interests: electrochemical sensors; chemometrics; electrode modifications for electrocatalysis (sensing); molecular electrochemistry
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Special Issue Information

Dear Colleagues,

Electrochemistry often represents an invaluable tool in sensing; as an example, this holds for opaque media, where optical techniques are impractical. In many situations electrochemical sensors alone are suitable to solve the problems, in other cases they complement optics, or other analytical techniques, in giving a complete picture of the system under exam.

The recent realisation and widespread diffusion of novel conducting materials regard i) intrinsically conducting polymers; ii) redox polymers; iii) metallopolymers; iv) carbon nanotubes; v) graphene; vi) metal nanoparticles; vii) metal oxide nanoparticles; etc. A large number of novel materials is potentially well suitable for application in electroanalysis. However, only a minor fraction of them has been tested as electrode materials for sensing, in ‘synthetic’ solutions and, even less, in real matrices. Moreover, a variety of nanocomposites, differently combining two or even more of the components listed above, has also opened new, extremely wide room to electroanalyisis.

In order not to adopt the expensive and time consuming try-and-error approach, full characterisation of the systems realised is necessary, in order to exploit it as a feedback to best material and device performances. With this respect, aiming at defining applicative procedures, the attitude deriving from expertise in analytical sciences is required. Furthermore, the realisation of a complete sensing device, even including features for full automation of the measurement process, requires engineering expertise. Last but not least, in the too often followed ‘empirical’ approach, the lack of a strong enough electrochemical culture is evident, which constitute a heavy drawback when aiming at realising an electrochemical device…

The interdisciplinary science of electrochemical sensing is not only open to disciplines very different from one another but, even more important, forces to melt all the necessary expertises in a common work to a common goal.
The lack of adjectives in front of the Sensors title of the journal and the ensemble of authors collected so far, aim at constituting a strong encouragement to proceed along this direction. The limit to the contributions to this Special Issue is only fixed by the ‘electrochemical’ transduction of the sensing system.

Prof. Dr. Renato Seeber
Guest Editor

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Keywords

Novel materials for

amperometric sensing
potentiometric sensing
conductimetric sensing
electrochemical impedance spectroscopy in sensing

Novel assembly in sensing

microelectrodes
nanoelectrodes (ensemble of)
electrodes and cells with particular geometry, flow cells included

Novel theoretical approaches to complex electrode systems

responses of the different potential controlled or current controlled techniques

Chemometrics

experimental design
statistical treatment of complex signals and signal ensembles
electronic tongues – classification and regression

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Published Papers (12 papers)

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Research

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496 KiB

Open AccessArticle

Impedimetric DNA Biosensor Based on a Nanoporous Alumina Membrane for the Detection of the Specific Oligonucleotide Sequence of Dengue Virus

by Jiajia Deng and Chee-Seng Toh

Sensors 2013, 13(6), 7774-7785; https://doi.org/10.3390/s130607774 - 17 Jun 2013

Cited by 74 | Viewed by 9547

Abstract

A novel and integrated membrane sensing platform for DNA detection is developed based on an anodic aluminum oxide (AAO) membrane. Platinum electrodes (~50–100 nm thick) are coated directly on both sides of the alumina membrane to eliminate the solution resistance outside the nanopores. The electrochemical impedance technique is employed to monitor the impedance changes within the nanopores upon DNA binding. Pore resistance (R_p) linearly increases in response towards the increasing concentration of the target DNA in the range of 1 × 10⁻¹² to 1 × 10⁻⁶ M. Moreover, the biosensor selectively differentiates the complementary sequence from single base mismatched (MM-1) strands and non-complementary strands. This study reveals a simple, selective and sensitive method to fabricate a label-free DNA biosensor. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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600 KiB

Open AccessArticle

Voltammetric Determination of Cocaine in Confiscated Samples Using a Carbon Paste Electrode Modified with Different [UO₂(X-MeOsalen)(H₂O)]·H₂O Complexes

by Laura Siqueira De Oliveira, Ana Paula Dos Santos Poles, Marco Antonio Balbino, Matheus Manoel Teles de Menezes, José Fernando De Andrade, Edward Ralph Dockal, Heloísa Maria Tristão and Marcelo Firmino De Oliveira

Sensors 2013, 13(6), 7668-7679; https://doi.org/10.3390/s130607668 - 14 Jun 2013

Cited by 36 | Viewed by 9006

Abstract

A fast and non-destructive voltammetric method to detect cocaine in confiscated samples based on carbon paste electrode modified with methoxy-substituted N,N'-ethylene-bis(salcylideneiminato)uranyl(VI)complexes, [UO₂(X-MeOSalen)(H₂O)]·H₂O, where X corresponds to the positions 3, 4 or 5 of the methoxy group on the aromatic ring, is described. The electrochemical behavior of the modified electrode and the electrochemical detection of cocaine were investigated using cyclic voltammetry. Using 0.1 mol·L⁻¹ KCl as supporting-electrolyte, a concentration-dependent, well-defined peak current for cocaine at 0.62 V, with an amperometric sensitivity of 6.25 × 10⁴ μA·mol·L⁻¹ for cocaine concentrations ranging between 1.0 × 10⁻⁷ and 1.3 × 10⁻⁶ mol·L⁻¹ was obtained. Chemical interference studies using lidocaine and procaine were performed. The position of the methoxy group affects the results, with the 3-methoxy derivative being the most sensitive. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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1712 KiB

Open AccessArticle

Micro-Drilling of Polymer Tubular Ultramicroelectrode Arrays for Electrochemical Sensors

by Jan Kafka, Steen Skaarup, Oliver Geschke and Niels B. Larsen

Sensors 2013, 13(5), 6319-6333; https://doi.org/10.3390/s130506319 - 14 May 2013

Cited by 4 | Viewed by 7208

Abstract

We present a reproducible fast prototyping procedure based on micro-drilling to produce homogeneous tubular ultramicroelectrode arrays made from poly(3,4-ethylenedioxythiophene) (PEDOT), a conductive polymer. Arrays of Ø 100 µm tubular electrodes each having a height of 0.37 ± 0.06 µm were reproducibly fabricated. The electrode dimensions were analyzed by SEM after deposition of silver dendrites to visualize the electroactive electrode area. The electrochemical applicability of the electrodes was demonstrated by voltammetric and amperometric detection of ferri-/ferrocyanide. Recorded signals were in agreement with results from finite element modelling of the system. The tubular PEDOT ultramicroelectrode arrays were modified by prussian blue to enable the detection of hydrogen peroxide. A linear sensor response was demonstrated for hydrogen peroxide concentrations from 0.1 mM to 1 mM. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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705 KiB

Open AccessArticle

A Ferrocene-Porphyrin Ligand for Multi-Transduction Chemical Sensor Development

by Larisa Lvova, Pierluca Galloni, Barbara Floris, Ingemar Lundström, Roberto Paolesse and Corrado Di Natale

Sensors 2013, 13(5), 5841-5856; https://doi.org/10.3390/s130505841 - 7 May 2013

Cited by 36 | Viewed by 8391

Abstract

5,10,15,20-Tetraferrocenyl porphyrin, H₂TFcP, a simple example of a donor-acceptor system, was tested as ligand for the development of a novel multi-transduction chemical sensors aimed at the determination of transition metal ions. The fluorescence energy transfer between ferrocene donor and porphyrin acceptor sub-units was considered. The simultaneously measured optical and potentiometric responses of solvent polymeric membranes based on H₂TFcP permitted the detection of lead ions in sample solutions, in the concentration range from 2.7 × 10⁻⁷ to 3.0 × 10⁻³ M. The detection limit of lead determination was 0.27 μM, low enough to perform the direct analysis of Pb²⁺ in natural waters. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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623 KiB

Open AccessArticle

UV/Vis Spectroelectrochemistry as a Tool for Monitoring the Fabrication of Sensors Based on Silver Nanoparticle Modified Electrodes

by Cristina Fernández-Blanco, Álvaro Colina and Aránzazu Heras

Sensors 2013, 13(5), 5700-5711; https://doi.org/10.3390/s130505700 - 2 May 2013

Cited by 11 | Viewed by 7317

Abstract

A new controlled current multipulse methodology has been developed to modify the screen-printed electrode surface with silver nanoparticles (AgNPs). Spectroelectrochemistry has provided not only information about the type of nanoparticles (NPs) deposited on the electrode surface, but also about the electrosynthesis process. Small NPs without plasmon band are initially generated. Next, these nuclei grow to form bigger NPs in the reduction pulses with a characteristic plasmon band centered at 400 nm. Most of the NPs are generated during the first reduction pulses and a linear growth of the absorbance at a lower reaction rate was obtained in the subsequent pulses. Oxidation pulses do not redissolve completely silver NPs but only partially, meaning that very stable NPs are generated. AgNPs-modified electrodes have been successfully used to determine hydrogen peroxide. Spectroelectrochemistry has also yielded very useful information to understand the voltammetric signal obtained during the reduction of H₂O₂ on silver modified electrodes. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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310 KiB

Open AccessArticle

A Molecularly Imprinted Polymer with Incorporated Graphene Oxide for Electrochemical Determination of Quercetin

by Si Sun, Mengqi Zhang, Yijun Li and Xiwen He

Sensors 2013, 13(5), 5493-5506; https://doi.org/10.3390/s130505493 - 25 Apr 2013

Cited by 112 | Viewed by 11011

Abstract

The molecularly imprinted polymer based on polypyrrole film with incorporated graphene oxide was fabricated and used for electrochemical determination of quercetin. The electrochemical behavior of quercetin on the modified electrode was studied in detail using differential pulse voltammetry. The oxidation peak current of quercetin in B-R buffer solution (pH = 3.5) at the modified electrode was regressed with the concentration in the range from 6.0 × 10⁻⁷ to 1.5 × 10⁻⁵ mol/L (r² = 0.997) with a detection limit of 4.8 × 10⁻⁸ mol/L (S/N = 3). This electrode showed good stability and reproducibility. In the above mentioned range, rutin or morin which has similar structures and at the same concentration as quercetin did not interfere with the determination of quercetin. The applicability of the method for complex matrix analysis was also evaluated. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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2586 KiB

Open AccessArticle

Study of the Electrocatalytic Activity of Cerium Oxide and Gold-Studded Cerium Oxide Nanoparticles Using a Sonogel-Carbon Material as Supporting Electrode: Electroanalytical Study in Apple Juice for Babies

by M. Yahia M. Abdelrahim, Stephen R. Benjamin, Laura Mª Cubillana-Aguilera, Ignacio Naranjo-Rodríguez, José L. Hidalgo-Hidalgo De Cisneros, Juan José Delgado and José Mª Palacios-Santander

Sensors 2013, 13(4), 4979-5007; https://doi.org/10.3390/s130404979 - 12 Apr 2013

Cited by 22 | Viewed by 11555

Abstract

The present work reports a study of the electrocatalytic activity of CeO₂ nanoparticles and gold sononanoparticles (AuSNPs)/CeO₂ nanocomposite, deposited on the surface of a Sonogel-Carbon (SNGC) matrix used as supporting electrode and the application of the sensing devices built with them to the determination of ascorbic acid (AA) used as a benchmark analyte. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the electrocatalytic behavior of CeO₂- and AuSNPs/CeO₂-modified SNGC electrodes, utilizing different concentrations of CeO₂ nanoparticles and different AuSNPs:CeO₂ w/w ratios. The best detection and quantification limits, obtained for CeO₂(10.0 mg·mL⁻¹)- and AuSNPs/CeO₂(3.25% w/w)-modified SNGC electrodes, were 1.59 × 10⁻⁶ and 5.32 × 10⁻⁶ M, and 2.93 × 10⁻⁶ and 9.77 × 10⁻⁶ M, respectively, with reproducibility values of 5.78% and 6.24%, respectively, for a linear concentration range from 1.5 µM to 4.0 mM of AA. The electrochemical devices were tested for the determination of AA in commercial apple juice for babies. The results were compared with those obtained by applying high performance liquid chromatography (HPLC) as a reference method. Recovery errors below 5% were obtained in most cases, with standard deviations lower than 3% for all the modified SNGC electrodes. Bare, CeO₂- and AuSNPs/CeO₂-modified SNGC electrodes were structurally characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). AuSNPs and AuSNPs/CeO₂ nanocomposite were characterized by UV–vis spectroscopy and X-ray diffraction (XRD), and information about their size distribution and shape was obtained by transmission electron microscopy (TEM). The advantages of employing CeO₂ nanoparticles and AuSNPs/CeO₂ nanocomposite in SNGC supporting material are also described. This research suggests that the modified electrode can be a very promising voltammetric sensor for the determination of electroactive species of interest in real samples. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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317 KiB

Open AccessArticle

Development of a Sensor System for the Determination of Sanitary Quality of Grapes

by Chiara Zanardi, Luca Ferrari, Barbara Zanfrognini, Laura Pigani, Fabio Terzi, Stefano Cattini, Luigi Rovati and Renato Seeber

Sensors 2013, 13(4), 4571-4580; https://doi.org/10.3390/s130404571 - 8 Apr 2013

Cited by 11 | Viewed by 6716

Abstract

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. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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240 KiB

Open AccessArticle

A Solid-Contact Ion Selective Electrode for Copper(II) Using a Succinimide Derivative as Ionophore

by Mihaela Dana Tutulea-Anastasiu, Deivy Wilson, Manel Del Valle, Cristina Mihaela Schreiner and Igor Cretescu

Sensors 2013, 13(4), 4367-4377; https://doi.org/10.3390/s130404367 - 2 Apr 2013

Cited by 42 | Viewed by 8542

Abstract

All-solid-state sensors with polyvinyl chloride (PVC)-based membranes using off-the-shelf N-hydroxysuccinimide (NHS) and succinimide (Succ) ionophores were prepared using DOP (dioctyl phthalate) and NPOE (ortho-nitrophenyloctyl ether) as plasticizers. Good responses were obtained when NHS was used. The potentiometric response of the proposed electrode is independent of pH over the range 2–6. The electrode shows a fast response time of 0.25 s. The electrode exhibits a Super-Nernstian response, with 37.5 mV/decade, with a potentiometric detection limit of 4.4 µM. The proposed sensor revealed good selectivity towards a group of transition metal ions. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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1207 KiB

Open AccessArticle

Fabrication and Characterisation of the Graphene Ring Micro Electrode (GRiME) with an Integrated, Concentric Ag/AgCl Reference Electrode

by James W. Dickinson, Michael Bromley, Fabrice P. L. Andrieux and Colin Boxall

Sensors 2013, 13(3), 3635-3651; https://doi.org/10.3390/s130303635 - 14 Mar 2013

Cited by 20 | Viewed by 9166

Abstract

Abstract: We report the fabrication and characterisation of the first graphene ring micro electrodes with the addition of a miniature concentric Ag/AgCl reference electrode. The graphene ring electrode is formed by dip coating fibre optics with graphene produced by a modified Hummers method. The reference electrode is formed using an established photocatalytically initiated electroless deposition (PIED) plating method. The performance of the so-formed graphene ring micro electrodes (GRiMEs) and associated reference electrode is studied using the probe redox system ferricyanide and electrode thicknesses assessed using established electrochemical methods. Using 220 µm diameter fibre optics, a ~15 nm thick graphene ring electrode is obtained corresponding to an inner to outer radius ratio of >0.999, so allowing for use of extant analytical descriptions of very thin ring microelectrodes in data analysis. GRiMEs are highly reliable (current response invariant over >3,000 scans), with the concentric reference electrode showing comparable stability (current response invariant over >300 scans). Furthermore the micro-ring design allows for efficient use of electrochemically active graphene edge sites and the associated nA scale currents obtained neatly obviate issues relating to the high resistivity of undoped graphene. Thus, the use of graphene in ring microelectrodes improves the reliability of existing micro-electrode designs and expands the range of use of graphene-based electrochemical devices. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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663 KiB

Open AccessArticle

Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications

by Heberto Gómez-Pozos, José Luis González-Vidal, Gonzalo Alberto Torres, Jorge Rodríguez-Baez, Arturo Maldonado, María De la Luz Olvera, Dwight Roberto Acosta, Maximino Avendaño-Alejo and Luis Castañeda

Sensors 2013, 13(3), 3432-3444; https://doi.org/10.3390/s130303432 - 12 Mar 2013

Cited by 28 | Viewed by 8499

Abstract

Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C₃H₈) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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Review

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1024 KiB

Open AccessReview

Molecular Electric Transducers as Motion Sensors: A Review

by Hai Huang, Vadim Agafonov and Hongyu Yu

Sensors 2013, 13(4), 4581-4597; https://doi.org/10.3390/s130404581 - 8 Apr 2013

Cited by 82 | Viewed by 10899

Abstract

This article reviews the development of a new category of motion sensors including linear and angular accelerometers and seismometers based on molecular electronic transducer (MET) technology. This technology utilizes a liquid not only as an inertial mass, but also as one of the main elements in the conversion of mechanical motion into electric current. The amplification process is similar to that in a vacuum triode. Therefore, it is possible to achieve signal amplification close to 10⁸. Motion sensors demonstrating wide frequency and dynamic range and sensitivity that are one to two orders of magnitude better than MEMS devices of the same size have been developed. Full article

(This article belongs to the Special Issue Novel Tools in Electrochemical Sensing)

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