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Special Issue "Novel Tools in Electrochemical Sensing"

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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)

Special Issue Editor

Guest Editor
Prof. Dr. Renato Seeber

Department of Chemistry, University of Modena and Reggio Emilia, Modena, Italy
Fax: +39 059 373543
Interests: development and characterisation of novel nanostructured materials for electrochemical sensing; realisation and testing of electrochemical sensors; statistical treatment of data from sensing systems

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

Submission

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. Papers will be published continuously (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are refereed through a peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Sensors is an international peer-reviewed Open Access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs).


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

Published Papers (12 papers)

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Research

Jump to: Review

Open AccessArticle Impedimetric DNA Biosensor Based on a Nanoporous Alumina Membrane for the Detection of the Specific Oligonucleotide Sequence of Dengue Virus
Sensors 2013, 13(6), 7774-7785; doi:10.3390/s130607774
Received: 22 April 2013 / Revised: 7 June 2013 / Accepted: 13 June 2013 / Published: 17 June 2013
Cited by 20 | PDF Full-text (496 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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 (Rp) 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)
Open AccessArticle Voltammetric Determination of Cocaine in Confiscated Samples Using a Carbon Paste Electrode Modified with Different [UO2(X-MeOsalen)(H2O)]·H2O Complexes
Sensors 2013, 13(6), 7668-7679; doi:10.3390/s130607668
Received: 20 April 2013 / Revised: 27 May 2013 / Accepted: 5 June 2013 / Published: 14 June 2013
Cited by 7 | PDF Full-text (600 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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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Open AccessArticle Micro-Drilling of Polymer Tubular Ultramicroelectrode Arrays for Electrochemical Sensors
Sensors 2013, 13(5), 6319-6333; doi:10.3390/s130506319
Received: 12 March 2013 / Revised: 3 May 2013 / Accepted: 7 May 2013 / Published: 14 May 2013
Cited by 1 | PDF Full-text (1712 KB) | HTML Full-text | XML Full-text
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. [...] Read more.
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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Open AccessArticle A Ferrocene-Porphyrin Ligand for Multi-Transduction Chemical Sensor Development
Sensors 2013, 13(5), 5841-5856; doi:10.3390/s130505841
Received: 14 March 2013 / Revised: 19 April 2013 / Accepted: 22 April 2013 / Published: 7 May 2013
Cited by 15 | PDF Full-text (705 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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)
Open AccessArticle UV/Vis Spectroelectrochemistry as a Tool for Monitoring the Fabrication of Sensors Based on Silver Nanoparticle Modified Electrodes
Sensors 2013, 13(5), 5700-5711; doi:10.3390/s130505700
Received: 10 March 2013 / Revised: 23 April 2013 / Accepted: 23 April 2013 / Published: 2 May 2013
Cited by 1 | PDF Full-text (623 KB) | HTML Full-text | XML Full-text
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. [...] Read more.
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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Open AccessArticle A Molecularly Imprinted Polymer with Incorporated Graphene Oxide for Electrochemical Determination of Quercetin
Sensors 2013, 13(5), 5493-5506; doi:10.3390/s130505493
Received: 13 March 2013 / Revised: 11 April 2013 / Accepted: 12 April 2013 / Published: 25 April 2013
Cited by 23 | PDF Full-text (310 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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)
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
Sensors 2013, 13(4), 4979-5007; doi:10.3390/s130404979
Received: 28 February 2013 / Revised: 8 April 2013 / Accepted: 9 April 2013 / Published: 12 April 2013
Cited by 3 | PDF Full-text (2586 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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·mL1)- 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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Open AccessArticle Development of a Sensor System for the Determination of Sanitary Quality of Grapes
Sensors 2013, 13(4), 4571-4580; doi:10.3390/s130404571
Received: 1 March 2013 / Revised: 1 April 2013 / Accepted: 1 April 2013 / Published: 8 April 2013
Cited by 3 | PDF Full-text (317 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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)
Open AccessArticle A Solid-Contact Ion Selective Electrode for Copper(II) Using a Succinimide Derivative as Ionophore
Sensors 2013, 13(4), 4367-4377; doi:10.3390/s130404367
Received: 8 February 2013 / Revised: 21 March 2013 / Accepted: 28 March 2013 / Published: 2 April 2013
Cited by 7 | PDF Full-text (240 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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)
Open AccessArticle Fabrication and Characterisation of the Graphene Ring Micro Electrode (GRiME) with an Integrated, Concentric Ag/AgCl Reference Electrode
Sensors 2013, 13(3), 3635-3651; doi:10.3390/s130303635
Received: 31 January 2013 / Revised: 5 March 2013 / Accepted: 11 March 2013 / Published: 14 March 2013
Cited by 9 | PDF Full-text (1207 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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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Open AccessArticle Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications
Sensors 2013, 13(3), 3432-3444; doi:10.3390/s130303432
Received: 4 January 2013 / Revised: 17 February 2013 / Accepted: 6 March 2013 / Published: 12 March 2013
Cited by 5 | PDF Full-text (663 KB) | HTML Full-text | XML Full-text
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) [...] Read more.
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)

Review

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Open AccessReview Molecular Electric Transducers as Motion Sensors: A Review
Sensors 2013, 13(4), 4581-4597; doi:10.3390/s130404581
Received: 5 March 2013 / Revised: 2 April 2013 / Accepted: 2 April 2013 / Published: 8 April 2013
Cited by 13 | PDF Full-text (1024 KB) | HTML Full-text | XML Full-text
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 [...] Read more.
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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