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A hybrid noble nanoparticle/DNAzyme electrochemical biosensor is proposed for the detection of Pb2+, Cd2+, and Cr3+. The sensor takes advantage of a well-studied material that is known for its selective interaction with heavy metal ions (i.e., DNAzymes), which is combined with metallic nanoparticles. The double-helix structure of DNAzymes is known to dissociate into smaller fragments in the presence of specific heavy metal ions; this results in a measurable change in device resistance due to the collapse of conductive inter-nanoparticle DNAzyme bridging. The paper discusses the effect of DNAzyme anchoring groups (i.e., thiol and amino functionalization groups) on device performance and reports on the successful detection of all three target ions in concentrations that are well below their maximum permitted levels in tap water. While the use of DNAzymes for the detection of lead in particular and, to some extent, cadmium has been studied extensively, this is one of the few reports on the successful detection of chromium (III) via a sensor incorporating DNAzymes. The sensor showed great potential for its future integration in autonomous and remote sensing systems due to its low power characteristics, simple and cost-effective fabrication, and easy automation and measurement.
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In this work a Monte-Carlo tool simulating platinum nanoparticle (NP) based strain-sensors, on flexible substrates, is presented. The tool begins by randomly placing the NPs on the simulation area, with the ability to tune the NP surface coverage. After the calculation of the conductive paths that were generated in the previous step, the whole system is represented with an equivalent circuit; the NPs and the NP clusters act as nodes and the inter-particle gaps as resistances. The effective resistance is then calculated with the use of a Laplacian Matrix, which has proven extremely effective in significantly reducing the overall computational time. The simulation results are then benchmarked with experimental measurements from actual strain-sensing devices. The software is capable of predicting the strain-sensitivity for different NP sizes as well as surface coverages, emerging as a powerful computational tool for design-optimization of NP based devices in polymeric substrates, while it could well be extended to other nanocomposite materials used in flexible or stretchable electronic applications.
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This study presents the experimental testing of a gas-sensing array, for the detection of two commercially available pesticides (i.e., Chloract 48 EC and Nimrod), towards its eventual use along a commercial smart-farming system. The array is comprised of four distinctive sensing devices based on nanoparticles, each functionalized with a different gas-absorbing polymeric layer. As discussed herein, the sensing array is able to identify as well as quantify three gas-analytes, two pesticide solutions, and relative humidity, which acts as a reference analyte. All of the evaluation experiments were conducted in close to real-life conditions; specifically, the sensors response towards the three analytes was tested in three relative humidity backgrounds while the effect of temperature was also considered. The unique response patterns generated after the exposure of the sensing-array to the two gas-analytes were analyzed using the common statistical analysis tool Principal Component Analysis (PCA). The sensing array, being compact, low-cost, and highly sensitive, can be easily integrated with pre-existing crop-monitoring solutions. Given that there are limited reports for effective pesticide gas-sensing solutions, the proposed gas-sensing technology would significantly upgrade the added-value of the integrated system, providing it with unique advantages.
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Nanopartículas , Praguicidas , Polímeros , TemperaturaRESUMO
In this work, the working performance of Platinum (Pt), solvent-free nanoparticle (NP)-based strain sensors made on a flexible substrate has been studied. First, a new model has been developed in order to explain sensor behaviour under strain in a more effective manner than what has been previously reported. The proposed model also highlights the difference between sensors based on solvent-free and solvent-based NPs. As a second step, the ability of atomic layer deposition (ALD) developed Al2O3 (alumina) thin films to act as protective coatings against humidity while in adverse conditions (i.e., variations in relative humidity and repeated mechanical stress) has been evaluated. Two different alumina thicknesses (5 and 11 nm) have been tested and their effect on protection against humidity is studied by monitoring sensor resistance. Even in the case of adverse working conditions and for increased mechanical strain (up to 1.2%), it is found that an alumina layer of 11 nm provides sufficient sensor protection, while the proposed model remains valid. This certifies the appropriateness of the proposed strain-sensing technology for demanding applications, such as e-skin and pressure or flow sensing, as well as the possibility of developing a comprehensive computational tool for NP-based devices.
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The increased use of pesticides across the globe has a major impact on public health. Advanced sensing methods are considered of significant importance to ensure that pesticide use on agricultural products remains within safety limits. This study presents the experimental testing of a hybrid, nanomaterial based gas-sensing array, for the detection of a commercial organophosphate pesticide, towards its integration in a holistic smart-farming tool such as the "gaiasense" system. The sensing array utilizes nanoparticles (NPs) as the conductive layer of the device while four distinctive polymeric layers (superimposed on top of the NP layer) act as the gas-sensitive layer. The sensing array is ultimately called to discern between two gas-analytes: Chloract 48 EC (a chlorpyrifos based insecticide) and Relative Humidity (R.H.) which acts as a reference analyte since is anticipated to be present in real-field conditions. The unique response patterns generated after the exposure of the sensing-array to the two gas-analytes were analysed using a common statistical analysis tool, namely Principal Component Analysis (PCA). PCA has validated the ability of the array to detect, quantify as well as to differentiate between R.H. and Chloract. The sensing array being compact, low-cost and highly sensitive (LOD in the order of ppb for chlorpyrifos) can be effectively integrated with pre-existing crop-monitoring solutions such as the gaiasense.
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Flexible electronics have gained a lot of attention in recent years due to their compatibility with soft robotics, artificial arms, and many other applications. Meanwhile, the detection of acoustic frequencies is a very useful tool for applications ranging from voice recognition to machine condition monitoring. In this work, the dynamic response of Pt nanoparticles (Pt NPs)-based strain sensors on flexible substrates is investigated. the nanoparticles were grown in a vacuum by magnetron-sputtering inert-gas condensation. Nanoparticle sensors made on cracked alumina deposited by atomic layer deposition on the flexible substrate and reference nanoparticle sensors, without the alumina layer, were first characterized by their response to strain. The sensors were then characterized by their dynamic response to acoustic frequency vibrations between 20 Hz and 6250 Hz. The results show that alumina sensors outperformed the reference sensors in terms of voltage amplitude. Sensors on the alumina layer could accurately detect frequencies up to 6250 Hz, compared with the reference sensors, which were sensitive to frequencies up to 4250 Hz, while they could distinguish between two neighboring frequencies with a difference of no more than 2 Hz.
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Due to rapid industrialization, novel water-quality monitoring techniques for the detection of highly toxic and hazardous heavy metal ions are essential. Herein, a hybrid noble nanoparticle/DNAzyme electrochemical biosensor is proposed for the simultaneous and label-free detection of Pb2+ and Cr3+ in aqueous solutions. The sensor is based on the combination of a two-dimensional naked-platinum nanoparticle film and DNAzymes, whose double-helix configuration disassembles into smaller fragments in the presence of target-specific heavy metal ions. The electrochemical behavior of the fabricated sensor was investigated with non-faradaic electrochemical impedance spectroscopy (EIS), resulting in the successful detection of Pb2+ and Cr3+ well below their maximum permitted levels in tap water. So far, there has been no report on the successful detection of heavy metal ions utilizing the non-faradaic electrochemical impedance spectroscopy technique based on advanced nanomaterials paired with DNAzymes. This is also one of the few reports on the successful detection of chromium (III) via a sensor incorporating DNAzymes.
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Técnicas Biossensoriais , DNA Catalítico , Espectroscopia Dielétrica , Metais Pesados , DNA Catalítico/química , Metais Pesados/análise , Nanopartículas Metálicas/química , Platina/química , Íons , Cromo/análise , Chumbo/análise , Nanopartículas/química , Técnicas EletroquímicasRESUMO
The presence of heavy metal ions in soil, air and water constitutes an important global environmental threat, as these ions accumulate throughout the food chain, contributing to the rise of chronic diseases, including, amongst others, cancer and kidney failure. To date, many efforts have been made for their detection, but there is still a need for the development of sensitive, low-cost, and portable devices able to conduct on-site detection of heavy metal ions. In this work, we combine microfluidic technology and electrochemical sensing in a plastic chip for the selective detection of heavy metal ions utilizing DNAzymes immobilized in between platinum nanoparticles (PtNPs), demonstrating a reliable portable solution for water pollution monitoring. For the realization of the microfluidic-based heavy metal ion detection device, a fast and easy-to-implement fabrication method based on the photolithography of dry photosensitive layers is proposed. As a proof of concept, we demonstrate the detection of Pb2+ ions using the prototype microfluidic device.
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In this paper, we report the demonstration of highly sensitive flexible strain sensors formed by a network of metallic nanoparticles (NPs) grown under vacuum on top of a cracked thin alumina film which has been deposited by atomic layer deposition. It is shown that the sensor sensitivity depends on the surface density of NPs as well as on the thickness of alumina thin films that can both be well controlled via the deposition techniques. This method allows reaching a record strain sensitivity value of 2.6 × 108 at 7.2% strain, while exhibiting high sensitivity in a large strain range from 0.1% to 7.2%. The demonstration is followed by a discussion enlightening the physical understanding of sensor operation, which enables the tuning of its performance according to the above process parameters.